Polyalphaolefin production apparatus and preparation method

Abstract

The present invention provides an apparatus and method for producing polyα-olefins. The apparatus for producing polyα-olefins of the present invention comprises a mixing unit, a microchannel reaction unit, a high-pressure separation unit, a low-pressure separation unit, a gas circulation unit, a post-treatment unit, and a pressure control unit. The mixing unit, the microchannel reaction unit, the high-pressure separation unit, and the low-pressure separation unit are connected in series; a BF gas inlet is disposed in the gas circulation unit and the microchannel reaction unit; an auxiliary feedstock inlet and an olefin feedstock inlet are disposed in the mixing unit; the gas circulation unit is connected to the BF gas inlet; the low-pressure separation unit is further connected to the post-treatment unit; and the high-pressure separation unit, the pressure control unit, and the gas circulation unit are further connected in series. The apparatus and method of the present invention have a high polymerization reaction rate, a high reaction conversion, and good product selectivity, and are suitable for large-scale industrial production.

Description

Detailed Description of the Invention

[0001] [Technical Field] The present invention relates to an apparatus and method for producing poly-α-olefins, and more particularly to an apparatus and method for producing poly-α-olefins using a continuous process.

[0002] [Background technology] Polyα-olefins are typically obtained by the polymerization of one or more linear α-olefins via an oligomerization reaction under the action of a catalyst. Hydrogenated polyα-olefins, obtained by separation and hydrogenation of polyα-olefins, can be used for blending into high-quality synthetic base oils. Polyα-olefin synthetic base oils, also known as PAO synthetic base oils, have a wide range of applications due to their excellent properties, such as high viscosity index, ultra-low pour point, excellent thermal and oxidative stability, and high flash point. PAO synthetic base oils are classified according to their kinematic viscosity at 100°C. Mainstream products include PAO4, PAO6, PAO8, PAO10, PAO40, and PAO100. Among them, low-viscosity PAOs with kinematic viscosities between 4 and 8 cSt at 100°C are the most widely used and are primarily used for blending into various high-quality engine oils. The use of low-viscosity PAOs can extend drain intervals, improve fuel economy, and reduce low-temperature torque loss in engines.

[0003] Traditional methods for preparing poly-α-olefins typically use a Lewis acid catalyst system to allow α-olefins to undergo oligomerization, resulting in the formation of polymers with different degrees of polymerization. Currently, the catalyst used in the industrial production of low-viscosity poly-α-olefins is primarily a BF3 cocatalyst. Typical production processes involve batch or continuous stirred-tank reactors. In BF3-catalyzed oligomerization reactions, the BF3 must be fully dispersed in the gas phase, and the coagent and α-olefin must be mixed in the liquid phase, where a portion of the coagent dissolves to form the active cationic catalyst, which then initiates the α-olefin oligomerization reaction. The dissolution and interphase mass transfer of BF3 determine the macroscopic reaction rate, conversion, etc. Furthermore, too short a reaction time tends to result in low olefin conversion and low product yield. Too long a reaction time can lead to side reactions of the formed α-olefin oligomers, such as secondary polymerization, which increases the degree of polymerization, and isomerization, which reduces the viscosity index.

[0004] US4045508A discloses a continuous method for preparing poly-α-olefins, which is characterized by combining a stirred reactor and a tubular reactor to control a multi-stage polymerization process. However, this method leads to more secondary polymerization reactions of oligomers, and the content of trimers is greatly reduced.

[0005] CN104370675B discloses a continuous method for preparing polyα-olefins, which involves introducing α-olefins into a continuous glass microchannel reactor in a continuous manner and carrying out a polymerization reaction in the presence of an aluminum compound catalyst and an auxiliary to produce polyα-olefins. This process consumes a large amount of catalyst and requires a higher reaction temperature.

[0006] On the other hand, after reactions using boron trifluoride or its complexes as catalysts, it is often necessary to remove boron trifluoride or its complexes from the product. To achieve this, a method of neutralizing the product with an alkaline substance, such as aqueous sodium hydroxide or aqueous ammonia, followed by water washing is typically used. However, this method can cause serious environmental pollution problems and the catalyst cannot be recycled. The resulting waste alkali and fluorine- and boron-containing wastewater are very difficult to treat. At the same time, water washing treatment can result in the consumption of large amounts of water resources. Furthermore, with the strengthening of national environmental protection policies, many polluting enterprises have been closed, and projects without appropriate pollution treatment methods cannot be implemented.

[0007] Various methods for removing and recovering boron trifluoride have been proposed to date, but all have various limitations.

[0008] U.S. Patent Application No. US4433197A discloses a method for regenerating BF3 by using SiO2 particles to adsorb BF3 in a low-temperature polymerization reaction solution and then heating at low pressure. U.S. Patent Application No. US2997371A discloses adhering polyacrylonitrile to the surface of inert particles such as activated carbon or activated alumina, which are then used to adsorb BF3. U.S. Patent Application No. US5846429A discloses using polyacrylonitrile fibers to adsorb BF3 and then releasing the BF3 by heating after adsorption reaches saturation. Chinese Patent Application No. CN1289344A discloses a method for separating and recovering BF3 using metal fluorides. First, the metal fluoride and BF3 are chemically reacted to produce tetrafluoroborate. After separating the BF3, the tetrafluoroborate is decomposed under high-temperature heating conditions to release the BF3. US Patent Application No. US4454366A introduced a method for removing BF3 by forming a stable complex with polyvinyl alcohol and BF3.

[0009] US Patent US6939943B2 discloses a method for recovering BF3 using methanol and ethanol, in which methanol or ethanol is added to the polymerization reaction solution at low temperature, and BF3 is extracted into the alcohol phase and separated.

[0010] Chinese patent application CN1217726A discloses a separation method of electroprecipitation, in which an electric field is applied to the polymerization solution to separate boron trifluoride complexes from the polymerization product.

[0011] Taking advantage of the instability of boron trifluoride complexes, US Patent Application No. 3929749A employs a heating method to thermally decompose the complex in the polymerization solution, resulting in the overflow of BF3 gas, which allows the catalyst to be separated.

[0012] In reactions using boron trifluoride as one of the catalyst components, the complex formed by boron trifluoride and a ligand plays a catalytic role. These boron trifluoride complexes are usually selected for a specific ligand, and the molar ratio between boron trifluoride and the ligand is also a specific molar ratio. Therefore, when recycling and reusing the catalyst, it is necessary to do so without changing the coordination state between boron trifluoride and the ligand, because a change in the coordination state can reduce the catalytic activity of the catalyst or even deactivate the catalyst.

[0013] However, whether it is an adsorption method using the formation of a complex between BF3 and an adsorbent, an extraction method using the principle of mutual solubility, an electrolytic precipitation method using an electric field, or a thermal decomposition method, there are various problems, such as disadvantages such as poor separation efficiency, destruction of the catalyst structure, and the large influence of side reactions, which limit its application to industrial scale-up production.

[0014] Furthermore, the batch-type stirred tank reaction processes reported in the prior art have drawbacks such as large stirred tank reactor volume, large occupied area, strict requirements for process parameter control, complicated process operation, long reaction time and production period, etc., and continuous tank preparation processes can ensure batch stability, but cannot achieve ideal conversion and selectivity, and neither process can fully treat the catalyst in the product. Therefore, the art needs an apparatus and preparation method for α-olefin oligomers that has high conversion and selectivity, a simple process, low investment cost, and is safe and environmentally friendly.

[0015] It should be noted that the information disclosed in the Background section above is intended merely to enhance understanding of the background of the present invention and may therefore include information that does not constitute prior art already known to those skilled in the art.

[0016] Summary of the Invention The present invention provides an apparatus and method for producing polyalphaolefins.

[0017] Specifically, the present invention includes the following aspects.

[0018] In a first aspect, the present invention provides an apparatus for producing polyalphaolefins.

[0019] The poly-α-olefin production apparatus of the present invention comprises a mixing unit 1, a microchannel reaction unit 2, a high-pressure separation unit 3, a low-pressure separation unit 4, a gas circulation unit 5, a post-treatment unit 6, and a pressure control unit 7. The mixing unit 1, the microchannel reaction unit 2, the high-pressure separation unit 3, the low-pressure separation unit 4, and the gas circulation unit 5 are connected in series. The microchannel reaction unit 2 has a BF gas inlet 01. The mixing unit 1 has an auxiliary feedstock inlet 02 and an olefin feedstock inlet 03. The gas circulation unit 5 is connected to the BF gas inlet 01. The low-pressure separation unit 4 is further connected to the post-treatment unit 6. The high-pressure separation unit 3, the pressure control unit 7, and the gas circulation unit 5 are further connected in series. Preferably, the mixing unit 1 further has a BF gas inlet. Optionally, the gas circulation unit 5 is connected to the BF gas inlet provided in the mixing unit 1. Optionally, the post-treatment unit 6 is connected to the mixing unit 1 to recycle the complex of the auxiliary feedstock and BF and the unreacted olefin feed.

[0020] According to the apparatus of the present invention, the mixing unit 1 can uniformly mix the streams flowing therein (the mixing unit 1 is preferably a mixer, more preferably a static mixer and / or a dynamic mixer). The streams flowing into the mixing unit 1 include the auxiliary material and the olefinic material, and optionally include a recycled complex of the auxiliary material with BF3 and unreacted olefinic material. Preferably, the streams flowing into the mixing unit 1 may contain BF3 gas, so that the auxiliary material, the olefinic material, and the BF3 gas can be mixed in the mixing unit. Optionally, the structure and parameters of the mixer are such that the operating temperature is 20 to 200°C and the upper limit of the operating pressure is 20 MPa or less; the mixer is preferably a static mixer, more preferably a static mixer with enhanced mixing; and the number of mixers can be one or more. When two or more mixers are used, these mixers can be connected in parallel, in series, or both in parallel and in series. The mixer may optionally have a heat exchange layer. The mixer may optionally have a filler; the filler in the mixer may be selected from Pall rings, ceramic balls, regular fillers, corrugated fillers, wire mesh, or plastic rings. When the stream flowing into the mixing unit 1 contains BF3 gas, the mixing unit 1 includes a first mixer for mixing any two of the auxiliary feedstock, the olefin feedstock, and the BF3 gas, and a second mixer for further mixing the mixture with the remaining one of the feedstocks; more preferably, the mixing unit 1 includes a first mixer for mixing one of the olefin feedstock and the BF3 gas with the auxiliary feedstock, and a second mixer for further mixing the mixture with the other of the olefin feedstock and the BF3 gas. For example, the mixing unit 1 includes a first mixer for mixing the olefin feedstock with the auxiliary feedstock and a second mixer for mixing the mixture with BF gas; or the mixing unit 1 includes a first mixer for mixing the BF gas with the auxiliary feedstock and a second mixer for mixing the mixture with the olefin feedstock; or the mixing unit 1 includes a mixer for simultaneously mixing the BF gas, the auxiliary feedstock, and the olefin feedstock.

[0021] The microchannel reaction unit 2 allows a microchannel reaction between the BF gas from the BF gas inlet 01 and a mixed stream of the auxiliary material and olefin feedstock and optional BF gas from the mixing unit 1. Preferably, the microchannel reaction unit 2 allows a microchannel reaction between the BF gas from the BF gas inlet 01 and a mixed stream of the auxiliary material, olefin feedstock, and BF gas from the mixing unit 1. Preferably, the microchannel reaction unit is a microchannel reactor. The number of microchannel reactors may be one or more, preferably one, two, three, four, five, or six. When two or more microchannel reactors are used, these microchannel reactors may be connected in series, parallel, or both parallel and series.

[0022] The high-pressure separation unit 3 allows the intermediate stream flowing therein to undergo gas-liquid separation, and the separated gas phase flows into the gas circulation unit 5 via the pressure control unit 7, while the separated liquid phase flows into the low-pressure separation unit 4. The high-pressure separation unit 3 is preferably a high-pressure separator. The number of high-pressure separators may be one or more, preferably one, two, three, four, five, or six. When two or more high-pressure separators are used, these high-pressure separators may be connected in series, parallel, or both parallel and series.

[0023] The low-pressure separation unit 4 allows the intermediate stream flowing therein to undergo gas-liquid separation, and the separated gas phase flows into the gas circulation unit 5, and the separated liquid phase flows into the post-treatment unit 6. The low-pressure separation unit 4 is preferably a low-pressure separator. The number of low-pressure separators may be one or more, preferably one, two, three, four, five, or six. When two or more low-pressure separators are used, these low-pressure separators may be connected in series, in parallel, or both in parallel and in series.

[0024] The gas circulation unit 5 allows for the recovery of BF3 gas flowing therein and for the delivery of the recovered BF3 gas to the microchannel reaction unit 2 via the BF3 gas inlet 01 for recycling. The gas circulation unit 5 can be one or more of a compressor, a gas circulation pump, and a vacuum pump. The number of compressors, gas circulation pumps, and vacuum pumps can be one or more, so that the gas circulation unit can achieve single-stage or multi-stage circulation. Optionally, the gas circulation unit 5 is connected to the BF3 gas inlet of the mixing unit 1 and delivers the recovered BF3 gas to the mixing unit for mixing with auxiliary materials and olefin feedstocks.

[0025] The post-treatment unit 6 allows the stream entering therein to be post-treated to produce a polyolefin product. The post-treatment unit can be one or more of an adsorption unit, an extraction unit, a distillation unit, a centrifuge, a settling unit, an alkali wash unit, and a water wash unit. Preferably, the post-treatment unit 6 is a settling unit or a centrifuge. The settling unit or the centrifuge allows the stream entering therein to be separated into a light liquid phase and a heavy liquid phase, the heavy liquid phase being a complex of the auxiliary feedstock with BF3 and unreacted olefin feedstock, which can optionally be returned to the mixing unit 1 to continue participating in the continuous reaction. The light liquid phase is a crude polyolefin product and can be subjected to further post-treatment.

[0026] The pressure control unit 7 can control the pressures of the microchannel reaction unit 2 and the high-pressure separation unit 3 to promote the smooth progress of the microchannel reaction and the smooth progress of gas-liquid separation of the stream in the high-pressure separation unit 3. The pressure control unit 7 may be one or more of a backpressure valve, a throttle valve, and a pressure reducing valve. Optionally, the pressure control unit 7 may independently control the operating pressure of the microchannel reaction unit 2 and the operating pressure of the high-pressure separation unit 3. Optionally, the pressure control unit 7 may control the operating pressure of the microchannel reaction unit 2 to be the same as the operating pressure of the high-pressure separation unit 3.

[0027] According to the apparatus of the present invention, a gas purification unit 8 is preferably provided between the low-pressure separation unit 4 and the gas circulation unit 5, and / or between the pressure control unit 7 and the gas circulation unit 5. The gas purification unit 8 allows the BF3 gas flowing therein to be dried and / or purified. The gas purification unit 8 may be one or more of a gas filter, an adsorption dryer, a freeze dryer, and a cyclone separator, preferably an adsorption dryer, and may be filled with a filler, which may be one or more of silica gel, anhydrous calcium sulfate, anhydrous calcium chloride, and activated carbon.

[0028] According to the apparatus of the present invention, the microchannel reaction unit 2 is optionally a single microchannel reactor or a combination of two or more microchannel reactors. The structure and parameters of the microchannel reactor are as follows: the reaction channels are 2 to 10,000 channels in parallel, the operating temperature range is -70 to 300°C, the maximum allowable reaction pressure does not exceed 20 MPa, the maximum allowable heat transfer medium pressure does not exceed 10 MPa, the fluid channel volume without mixing inserts is 0.1 to 20,000 L, and the volumetric flow rate is 1 to 50,000 L / h. More preferably, the reaction channels are 2 to 5,000 channels, and more preferably 2 to 500 channels. For example, the reaction channels can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 channels, etc. In the microchannel reactor of the present invention, each reaction channel is 1 mm or less. 2 ~150mm 2and a length of 50 mm to 5000 mm. Preferably, each reaction channel is provided with a mixing element capable of promoting mixing of the reaction stream. The mixing element is a element known in the art that can promote mixing of the reaction stream and enhance turbulence, and may be a mixing disk, as well as the first and second mixing elements of the present invention. Preferably, the microchannel reactor of the present invention comprises a header pipe for introducing a reaction gas and branch pipes for distributing the reaction gas to each reaction channel.

[0029] According to the apparatus of the present invention, a preferred microchannel reactor (hereinafter also referred to as a preferred microchannel reactor of the present invention) comprises: a shell 003, wherein a feed zone 023, a mixing zone 008, a reaction zone 009, and a collection zone 024 are arranged and communicated successively along a first direction within the shell 003, the shell 003 comprising a feed pipe 002 communicating with the feed zone 023 and a discharge pipe 001 communicating with the collection zone 024, and the mixing zone 008 comprising a mixing channel 014 extending along the first direction; a fluid distribution pipe 017, the fluid distribution pipe 017 extending from the exterior of the shell 003 into the mixing channel 014, the fluid distribution pipe 017 connected to a fluid distributor 016 at an end of the mixing channel 014; The feed pipe 002 is connected to the mixing unit 1 and can be used to input a mixture of olefin feedstock and auxiliary feedstock, the fluid distribution pipe 017 is connected to the BF3 inlet 01 and can be used to input BF3 gas, and the discharge pipe 001 is connected to the high-pressure separation unit 3.

[0030] In the present invention, the first direction is the flow direction of the stream, which may be a horizontal direction, an upward direction, etc. The upward direction is preferred, and an upward direction from bottom to top is more preferred.

[0031] In the present invention, the mixing zone 008 and the feeding zone 023 can be separated by a first partition plate 019. The first partition plate 019 is provided with a plurality of through-holes, each of which is aligned with a mixing channel 014, and thus the mixing zone 008 communicates with the feeding zone 023.

[0032] According to the apparatus of the present invention, in a preferred microchannel reactor: In one embodiment of the present invention, the fluid distributor 016 is at least one selected from a sintered powder compact having micropores, a mesoporous foam material, a wire mesh, and a tube having microslits or micropores.

[0033] Preferably, the fluid distributor is a cylindrical sintered powder body having micropores.

[0034] In one embodiment of the present invention, the fluid distributor 016 has a diameter of 0.01 cm. 2 ~200cm 2 The mixing channel has a cross-sectional area of 0.05 cm and a length of 1 mm to 2000 mm. 2 ~400cm 2 and a length of 50 mm to 5000 mm. In the present invention, the length and cross-sectional area of the mixing channel 014 are both greater than the length and cross-sectional area of the fluid distributor 016.

[0035] In one embodiment of the present invention, the mixing zone comprises 1 to 100 (preferably 1 to 50, more preferably 2 to 10) mixing channels, and the fluid distribution pipe 017 includes a main pipe extending from the exterior of the shell to the supply zone, and branch pipes extending from the supply zone to each mixing channel 014 and having fluid distributors 016 connected to their ends.

[0036] In one embodiment of the present invention, in the mixing channel 014, the first mixing element 015 is positioned downstream of the fluid distributor 016.

[0037] In one embodiment of the present invention, the first mixing element 015 includes alternating main flow sections and diverging flow sections that communicate along a first direction. The main flow section includes a single main flow channel, and the diverging flow sections include multiple diverging flow channels. A collection cavity communicating with the multiple diverging flow channels is located downstream of the diverging flow section. The first mixing element 015 can be formed by joining multiple plate-like elements (2 to 100 elements, preferably 2 to 50 elements, and more preferably 10 to 30 elements) (each having a thickness of approximately 0.2 mm to 10 mm) arranged along the first direction. Each plate-like element may have hollows, cavities, or other structures corresponding to the main flow channel 0001, the diverging flow channels 0002, and the collection cavity 0003. This structure is convenient for processing and manufacturing.

[0038] In one embodiment of the present invention, the mixing zone may include a first heat exchange cavity 013 disposed within the shell, the mixing channel being disposed within the first heat exchange cavity, and the shell comprising a first heat exchange medium inlet 004 and a first heat exchange medium outlet 005 in communication with the first heat exchange cavity.

[0039] In one embodiment of the present invention, the volume ratio of the first heat exchange cavity to the mixing channel is 2 to 50; preferably, the volume ratio of the first heat exchange cavity to the mixing channel is 5 to 30. In the mixing zone 008, the mixing channel 014 and the first heat exchange cavity 013 are isolated from each other and do not communicate with each other, but heat conduction can be achieved between them, and a pipe fitting with good thermal conductivity can be used for the mixing channel 014.

[0040] In one embodiment of the present invention, a transition zone 020 is provided between the mixing zone and the reaction zone, and the transition zone comprises a stabilization channel 021 having a constant cross-sectional area and a diffusion channel 022 having a gradually expanding cross-sectional area, arranged along and communicating with the first direction, wherein the stabilization channel is connected to the mixing channel and the diffusion channel is connected to the reaction zone.

[0041] In one embodiment of the present invention, an exhaust pipe 018 that extends outside the shell is connected to the stabilization channel.

[0042] In one embodiment of the present invention, the diffusion channel comprises a diffusion plate having a mesh or slits.

[0043] In one embodiment of the present invention, the two ends of the transition zone 020 are provided with partition plates having through holes so that they are isolated from the mixing zone 008 (mainly the first heat exchange cavity 013) and the reaction zone 009 (mainly the second heat exchange cavity 012), respectively, and are connected to the mixing channel 014 and the reaction channel 010 through the through holes on the partition plates, and the diffusion channel 022 and the stabilization channel 021 can be pipe fittings provided between the two partition plates.

[0044] In one embodiment of the present invention, the reaction zone includes a plurality of parallel reaction channels extending along a first direction and communicating with a mixing channel via a stabilization channel 021 and a diffusion channel 022. The reaction channels have at least one cross section of a circular, rectangular, or triangular shape. The number of reaction channels is, for example, 2 to 10,000 channels, preferably 2 to 5,000 channels, and more preferably 2 to 500 channels.

[0045] In one embodiment of the present invention, the reaction channel comprises a second mixing element, the second mixing element including a base strip extending along a first direction, and a tooth element connected to the base strip and extending transversely relative to the base strip; the tooth element has at least one of a triangular, arcuate, wavy, and spiral shape. Preferably, the tooth element is triangular, one side of the triangle is adjacent to the base strip, one end is connected to the base strip, and the other end is 0.01 mm to 20 mm away from the base strip.

[0046] In one embodiment of the present invention, each of the reaction channels is independently provided with a plurality of spaced apart second mixing elements (the number of second mixing elements may be 2 to 100, preferably 2 to 50, more preferably 10 to 30), and the tooth elements of the second mixing elements are arranged alternately.

[0047] Preferably, the reaction channel has a rectangular cross section and the tooth elements extend between a pair of opposing rectangular sections.

[0048] In one embodiment of the present invention, the reaction channel is 1 mm 2 ~150mm 2 and a length of 50 mm to 5000 mm, the shortest distance between reaction channels is 1 mm to 50 mm, the second mixing element has a thickness of 0.1 mm to 3 mm, and the spacing between adjacent tooth elements is 1 mm to 50 mm, preferably the reaction channels have a length of 100 mm to 3000 mm, the shortest distance between reaction channels is 3 mm to 30 mm, the second mixing element has a thickness of 0.2 mm to 2 mm, and the spacing between adjacent tooth elements is 1.5 mm to 20 mm.

[0049] In one embodiment of the present invention, the reaction zone may comprise a second heat exchange cavity 012 disposed within the shell, the reaction channel being disposed within the second heat exchange cavity, and the shell comprising a second heat exchange medium inlet 006 and a second heat exchange medium outlet 007 in communication with the second heat exchange cavity.

[0050] In one embodiment of the present invention, the volume ratio of the second heat exchange cavity to the reaction channel is 2-50, preferably the volume ratio of the second heat exchange cavity to the reaction channel is 5-30.

[0051] In one embodiment of the present invention, the second heat exchange cavity 012 may be formed mainly by the shell 003, and the two ends are a second partition plate 025 between the reaction zone 009 and the collection zone 024, and a partition plate between the reaction zone 009 and the transition zone 020, respectively.

[0052] The poly-α-olefin production apparatus of the present invention can be used for the continuous synthesis of poly-α-olefin synthetic oil, and has the advantages of high reaction rate, high reaction conversion rate, and good product selectivity.

[0053] The poly-α-olefin production apparatus using the preferred microchannel reactor of the present invention can achieve continuous and efficient mixing of the reaction system, maintain fluid flow in a plug flow mode, maximize consistency in the residence time of the reaction fluid, and avoid undesirable product selectivity due to residence time distribution.

[0054] In a second aspect, the present invention provides a method for preparing a polyalphaolefin.

[0055] The method for preparing poly-α-olefins of the present invention comprises: after mixing olefin raw material and auxiliary raw material in mixing unit, the mixed stream and BF3 gas obtained are respectively introduced into microchannel reaction unit; the intermediate stream formed after polymerization reaction in microchannel reaction unit is introduced into high-pressure separation unit; the intermediate material undergoes first gas-liquid separation in high-pressure separation unit, the separated liquid phase is introduced into low-pressure separation unit, the second gas-liquid separation in low-pressure separation unit, the liquid phase separated from low-pressure separation unit is introduced into post-treatment unit, and after processing in post-treatment unit, obtain polyolefin product; the gas phase (BF3 gas) separated from high-pressure separation unit and low-pressure separation unit is introduced into gas circulation unit, and BF3 gas is recovered for recycling.Preferably, BF3 gas is further supplied to mixing unit, so that after mixing unit, BF3 gas, olefin raw material and auxiliary raw material are mixed, the mixed stream and BF3 gas are respectively introduced into microchannel reaction unit. Optionally, the heavy liquid phase obtained after treatment in the post-treatment unit, which contains the complex of auxiliary feedstock with BF3 and unreacted olefin feedstock, is recycled to the mixing unit.

[0056] In one embodiment of the present invention, when BF gas is supplied to the mixing unit, the order in which the BF gas, olefin raw material, and auxiliary raw material are mixed is not particularly limited, and the mixing method can be as follows: any two of the BF gas, olefin raw material, and auxiliary raw material are mixed and then mixed with the remaining raw material, or the BF gas, olefin raw material, and auxiliary raw material are mixed simultaneously. For example, the BF gas and the auxiliary raw material can be mixed to form a complex and then mixed with the olefin raw material, or the auxiliary raw material and olefin raw material can be mixed and then mixed with BF gas, or the BF gas, olefin raw material, and auxiliary raw material can be mixed simultaneously.

[0057] In one embodiment of the present invention, the olefins in the olefin feedstock are C3 to C 20 One or more α-olefins, preferably C5 to C 15 One or more of the α-olefins, more preferably C7 to C 14 For example, the olefin may be one or more of the α-olefins commonly used in the preparation of PAO synthetic base oils, such as nonene and decene.

[0058] In one embodiment of the present invention, the olefin raw material is a C5 to C6 olefin as a solvent. 20 Alkanes and / or C1-C 20 It may further contain an oxygen-containing compound. 20 The mass fraction of alkanes can be 0-80%, preferably 0.5-50%, and most preferably 1-30% relative to the total mass of the olefin feedstock. 20 The mass fraction of oxygen-containing compounds can be 0-20%, preferably 0-10%, and most preferably 0.001-5%. 20 The alkane may be one or more of an n-alkane, an isoalkane, and a cycloalkane; C1-C 20 The oxygen-containing compound may be one or more of an n-alkanol, an isoalcohol, and a ketone. The Fischer-Tropsch olefin feedstock is a C3 to C6 20 α-olefins, C5-C 20Alkanes and C1-C 20 The mixture of oxygen-containing compounds (i.e., olefin feedstock) can be used.

[0059] In one embodiment of the present invention, the auxiliary raw material may be a commonly used auxiliary agent that can be used as an electron donor for BF3, and may be one or more of alcohols having 1 to 20 carbon atoms, ethers having 1 to 20 carbon atoms, aldehydes having 1 to 20 carbon atoms, ketones having 1 to 20 carbon atoms, esters having 1 to 30 carbon atoms, carboxylic acids having 1 to 20 carbon atoms, and phenols having 1 to 20 carbon atoms, preferably alcohols having 1 to 10 carbon atoms, more preferably alcohols having 3 to 5 carbon atoms, such as one or more of n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, and isopentanol.

[0060] According to the method of the present invention, the mixing unit can uniformly mix the streams flowing therein. It is preferably a mixer, more preferably a static mixer and / or a dynamic mixer. The stream flowing into the mixing unit includes an auxiliary material and an olefinic material, optionally including a recycled complex of the auxiliary material with BF3 and unreacted olefinic material. Preferably, the stream flowing into the mixing unit may contain BF3 gas, so that the auxiliary material, olefinic material, and BF3 gas can be mixed in the mixing unit. As mentioned above, the mixing order of the BF3 gas, olefinic material, and auxiliary material in the mixing unit is not particularly limited. The mixing unit is preferably a mixer, and the structure and parameters of the mixer are preferably as follows: the operating temperature is 20 to 200°C, and the upper limit of the operating pressure is 20 MPa or less. The mixer is preferably a static mixer, more preferably a static mixer with enhanced mixing. The number of mixers may be one or more. When two or more mixers are used, these mixers can be connected in parallel, in series, or both in parallel and in series. The mixer may optionally have a heat exchange layer. The mixer may optionally have a filler. The filler in the mixer may be selected from Pall rings, ceramic balls, regular fillers, corrugated fillers, wire mesh, or plastic rings. When the stream entering the mixing unit contains BF3 gas, the mixing unit includes a mixer for mixing any two of the auxiliary feedstock, the olefin feedstock, and the BF3 gas, and a mixer for further mixing the mixture with the remaining one of the feedstocks; more preferably, the mixing unit includes a mixer for mixing one of the olefin feedstock and the BF3 gas with the auxiliary feedstock, and a mixer for further mixing the mixture with the other of the olefin feedstock and the BF3 gas.For example, the mixing unit includes a mixer for mixing the olefin feedstock and the auxiliary feedstock, and a mixer for mixing the mixture with BF3 gas; or the mixing unit 1 includes a mixer for mixing the BF3 gas and the auxiliary feedstock, and a mixer for mixing the mixture with the olefin feedstock; or the mixing unit includes a mixer for simultaneously mixing the BF3 gas, the auxiliary feedstock, and the olefin feedstock.

[0061] The microchannel reaction unit allows for the microchannel reaction of a mixed stream of BF3 gas, auxiliary feedstock, and olefin feedstock therein. Preferably, the microchannel reaction unit allows for the microchannel reaction of BF3 gas from the BF3 gas inlet with a mixed stream of auxiliary feedstock, olefin feedstock, and optional BF3 gas from the mixing unit. Preferably, the microchannel reaction unit is a microchannel reactor. The number of microchannel reactors may be one or more, preferably one, two, three, four, five, or six. When two or more microchannel reactors are used, these microchannel reactors may be connected in series, parallel, or both parallel and series. Any of the microchannel reactors as described in the first embodiment above may be used in the microchannel reaction unit. The structure and parameters of the microchannel reactor are preferably as follows: 2 to 10,000 parallel reaction channels, an operating temperature range of -70 to 300°C, a maximum allowable reaction pressure not exceeding 20 MPa, a maximum allowable heat transfer medium pressure not exceeding 10 MPa, a fluid channel volume without mixing inserts of 0.001 to 20,000 L, and a volumetric flow rate of 1 to 5,000 L / h. More preferably, the number of reaction channels is 2 to 5,000, more preferably 2 to 500. For example, the number of reaction channels may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, etc. In the microchannel reactor of the present invention, each reaction channel is 1 mm or less. 2 ~150mm 2and a length of 50 mm to 5000 mm. Preferably, each reaction channel is provided with a mixing element capable of promoting mixing of the reaction stream. The mixing element is a element known in the art that can promote mixing of the reaction stream and enhance turbulence, and may be a mixing disk, as well as the first and second mixing elements of the present invention. Preferably, the microchannel reactor of the present invention comprises a header pipe for introducing a reaction gas and branch pipes for distributing the reaction gas to each reaction channel.

[0062] The high-pressure separation unit allows the intermediate stream flowing therein to undergo gas-liquid separation, and the separated gas phase flows into the gas circulation unit via the pressure control unit, while the separated liquid phase flows into the low-pressure separation unit. The high-pressure separation unit is preferably a high-pressure separator. The number of high-pressure separators may be one or more, preferably one, two, three, four, five, or six. When two or more high-pressure separators are used, these high-pressure separators may be connected in series, parallel, or both parallel and series.

[0063] The low-pressure separation unit allows the intermediate stream flowing therein to undergo gas-liquid separation, with the separated gas phase flowing into the gas circulation unit and the separated liquid phase flowing into the post-treatment unit. The low-pressure separation unit is preferably a low-pressure separator. The number of low-pressure separators may be one or more, preferably one, two, three, four, five, or six. When two or more low-pressure separators are used, these low-pressure separators may be connected in series, in parallel, or both in parallel and in series.

[0064] The gas circulation unit allows for the recovery of the BF3 gas flowing therein and the delivery of the recovered BF3 gas to the microchannel reaction unit for recycling. The gas circulation unit can be one or more of a compressor, a gas circulation pump, and a vacuum pump. The number of compressors, gas circulation pumps, and vacuum pumps can be one or more, so that the gas circulation unit can achieve single-stage or multi-stage circulation. Optionally, the gas circulation unit delivers the recovered BF3 gas to a mixing unit for mixing with auxiliary materials and olefin feedstocks.

[0065] The post-treatment unit allows the stream flowing therein to be post-treated to produce a polyolefin product. The post-treatment unit is preferably one or more of an adsorption unit, an extraction unit, a distillation unit, a centrifuge unit, a settling unit, an alkali washing unit, and a water washing unit. Preferably, the heavy liquid phase containing the complex of the auxiliary feedstock and BF3 and the unreacted olefin feedstock obtained from the post-treatment unit are returned to the mixing unit to continue participating in the continuous reaction.

[0066] The pressure control unit can control the pressure of the microchannel reaction unit and the high-pressure separation unit to promote smooth progress of the microchannel reaction and smooth progress of gas-liquid separation of the stream in the high-pressure separation unit. The pressure control unit can be one or more of a backpressure valve, a throttle valve, and a pressure reduction valve. Optionally, the pressure control unit can independently control the operating pressure of the microchannel reaction unit and the operating pressure of the high-pressure separation unit. Optionally, the pressure control unit can control the operating pressure of the microchannel reaction unit to be the same as the operating pressure of the high-pressure separation unit.

[0067] In one embodiment of the present invention, according to the method of the present invention, the flow rate of the olefin feedstock into the mixing unit is 10 to 5,000 L / h, preferably 20 to 4,000 L / h, and more preferably 40 to 2,500 L / h. The flow rate of the auxiliary feedstock into the mixing unit is 0.01 to 1,000 L / h, preferably 0.1 to 800 L / h, and more preferably 0.2 to 500 L / h. The flow rate of BF3 gas (including the initially injected BF3 gas and optionally recycled BF3 gas) into the microchannel reaction unit is 5 to 200,000 L / h, preferably 50 to 100,000 L / h, and more preferably 100 to 50,000 L / h. Generally, the flow rate of BF3 gas into the microchannel reaction unit is controlled to a constant value or within a certain range. As long as the total amount of both is a constant value or within a certain range, the amount of BF3 gas initially injected can be adjusted according to the amount of recycled BF3 gas. When BF3 gas is further supplied to the mixing unit, the flow rate of the BF3 gas into the mixing unit is 4 to 180,000 L / h, preferably 45 to 90,000 L / h, and more preferably 90 to 45,000 L / h.

[0068] In one embodiment of the present invention, according to the method of the present invention, the reaction temperature in the microchannel reaction unit is preferably 0 to 120°C, preferably 10 to 80°C, and more preferably 20 to 60°C. The reaction pressure in the microchannel reaction unit is 0.01 to 10 MPa, preferably 0.01 to 8 MPa, and more preferably 0.1 to 6 MPa. The residence time of the olefin raw material in the microchannel reaction unit is 1 to 3600 seconds, preferably 10 to 1800 seconds, and more preferably 15 to 1000 seconds. In the microchannel reaction unit, the mass ratio of the auxiliary material:olefin raw material:total amount of BF3 gas is 1:1 to 1000:1 to 500 (preferably 1:1 to 500:1 to 200, and most preferably 1:10 to 250:1.5 to 100). When the microchannel reaction unit is the above-mentioned microchannel reactor, the mass ratio of the auxiliary feedstock: the olefin feedstock: the total amount of BF gas refers to the mass ratio of the feedstocks when all the feedstocks are fed into the microchannel reactor, that is, it may be the proportion of the reactant feedstocks in the stream immediately downstream of the fluid distributor.

[0069] In one embodiment of the present invention, according to the method of the present invention, the high-pressure separation unit is preferably a high-pressure separator. The pressure of the high-pressure separator may be 0.01 to 10 MPa, preferably 0.01 to 8 MPa, more preferably 0.1 to 6 MPa. The temperature of the high-pressure separator may be 0 to 120°C, preferably 10 to 80°C, more preferably 20 to 60°C. The volume of the high-pressure separator may be 0.1 to 20,000 L, preferably 0.2 to 2,000 L.

[0070] In one embodiment of the present invention, the low-pressure separation unit is preferably a low-pressure separator. The pressure of the low-pressure separator may be -0.1 to 1 MPa, preferably -0.1 to 0.9 MPa, more preferably -0.1 to 0.1 MPa. The temperature of the low-pressure separator may be 0 to 120°C, preferably 10 to 80°C, more preferably 20 to 60°C. The volume of the low-pressure separator may be 0.1 to 20,000 L, preferably 0.2 to 2,000 L.

[0071] In one embodiment of the present invention, the pressure of the recycled BF3 gas passing through the gas circulation unit can be 0.01 to 10 MPa, preferably 0.01 to 8 MPa, more preferably 0.1 to 6 MPa.

[0072] In one embodiment of the present invention, the pressure of the pressure control unit is 0.01 to 10 MPa, preferably 0.01 to 8 MPa, and more preferably 0.1 to 6 MPa.

[0073] In one embodiment of the present invention, according to the method of the present invention, the post-treatment method used in the post-treatment unit may be a post-treatment method known to those skilled in the art, such as one or more of adsorption, extraction, distillation, centrifugation, sedimentation, alkaline washing, and water washing. Preferably, the post-treatment method is sedimentation or centrifugation. Sedimentation or centrifugation allows the stream entering the post-treatment unit to be separated into a light liquid phase and a heavy liquid phase, the heavy liquid phase being the complex of the auxiliary feedstock with BF3 and the unreacted olefin feedstock, which can optionally be returned to the mixing unit to continue participating in the continuous reaction. The light liquid phase is the crude polyolefin product and can be subjected to further post-treatment.

[0074] In one embodiment of the present invention, according to the method of the present invention, a gas purification unit is preferably provided between the low-pressure separation unit and the gas circulation device, and / or between the pressure control unit and the gas circulation device. The gas purification unit allows the BF3 gas flowing therein to be dried and / or purified. The gas purification unit may be one or more of a gas filter, an adsorption dryer, a freeze dryer, and a cyclone separator, preferably an adsorption dryer, and may be filled with a filler, which may be one or more of silica gel, anhydrous calcium sulfate, anhydrous calcium chloride, and activated carbon.

[0075] In one embodiment of the present invention, according to the method of the present invention, when BF3 gas is further mixed in the mixing unit in addition to the olefin raw material and the auxiliary raw material, the mass ratio of the BF3 gas mixed in the mixing unit to the BF3 gas directly flowing into the microchannel reaction unit is 100-10:0-90, based on the total mass of all BF3 in the microchannel reaction unit.

[0076] According to the method of the present invention, the resulting polyolefin product is further preferably subjected to fractionation, hydrogenation, and optional blending operations to obtain a polyolefin product (synthetic oil) that meets a viscosity grade.

[0077] The method of the present invention has the advantages of high polymerization reaction rate, high reaction conversion rate, and good product selectivity, and is suitable for large-scale industrial production.

[0078] In a third aspect, the present invention provides a method for preparing polyalphaolefins using any of the devices described in the first aspect.

[0079] According to the present invention, a method for preparing polyalphaolefins using any of the devices according to the first aspect comprises the steps of: The method includes: separately feeding the mixed stream and BF gas obtained after mixing the olefin feedstock and auxiliary feedstock in the mixing unit 1 into the microchannel reaction unit 2; feeding the intermediate stream formed after the polymerization reaction in the microchannel reaction unit 2 into the high-pressure separation unit 3; subjecting the intermediate stream to a first gas-liquid separation in the high-pressure separation unit 3, feeding the separated liquid phase into the low-pressure separation unit 4, and subjecting the second gas-liquid separation in the low-pressure separation unit 4; feeding the liquid phase separated from the low-pressure separation unit 4 into the post-treatment unit 6 to obtain a polyolefin product after treatment in the post-treatment unit; and feeding the gas phase (BF gas) separated from the high-pressure separation unit 3 and the low-pressure separation unit 4 into the gas circulation unit 5, and recovering the BF gas for recycling. Preferably, BF gas is further supplied to the mixing unit 1, so that after the BF gas, the olefin feedstock, and the auxiliary feedstock are mixed in the mixing unit 1, the mixed stream and BF gas separately flow into the microchannel reaction unit 2. Optionally, the heavy liquid phase obtained after treatment in post-treatment unit 6, comprising the complex of auxiliary feedstock with BF3 and unreacted olefin feedstock, is recycled to mixing unit 1.

[0080] In one embodiment of the present invention, the olefins in the olefin feedstock are C3 to C 20 One or more α-olefins, preferably C5 to C 15 One or more of the α-olefins, more preferably C7 to C 14 For example, the olefin may be one or more of the α-olefins commonly used in the preparation of PAO synthetic base oils, such as nonene and decene.

[0081] In one embodiment of the present invention, the olefin raw material is a C5 to C6 olefin as a solvent. 20 Alkanes and / or C1-C 20 It may further contain an oxygen-containing compound. 20The mass fraction of alkanes can be 0-80%, preferably 0.5-50%, and most preferably 1-30% relative to the total mass of the olefin feedstock. 20 The mass fraction of oxygen-containing compounds can be 0-20%, preferably 0-10%, and most preferably 0.001-5%. 20 The alkane may be one or more of an n-alkane, an isoalkane, and a cycloalkane; C1-C 20 The oxygen-containing compound may be one or more of an n-alkanol, an isoalcohol, and a ketone. The Fischer-Tropsch olefin feedstock is a C3 to C6 20 α-olefins, C5-C 20 Alkanes and C1-C 20 The mixture of oxygen-containing compounds (i.e., olefin feedstock) can be used.

[0082] In one embodiment of the present invention, the auxiliary raw material may be a commonly used auxiliary agent that can be used as an electron donor for BF3, and may be one or more of alcohols having 1 to 20 carbon atoms, ethers having 1 to 20 carbon atoms, aldehydes having 1 to 20 carbon atoms, ketones having 1 to 20 carbon atoms, esters having 1 to 30 carbon atoms, carboxylic acids having 1 to 20 carbon atoms, and phenols having 1 to 20 carbon atoms, preferably alcohols having 1 to 10 carbon atoms, more preferably alcohols having 3 to 5 carbon atoms, such as one or more of n-propanol, isopropanol, n-butanol, isobutanol, n-pentanol, and isopentanol.

[0083] According to the method of the present invention, the flow rate of the olefin raw material flowing into the mixing unit 1 is 10 to 5,000 L / h, preferably 20 to 4,000 L / h, and more preferably 40 to 2,500 L / h. The flow rate of the auxiliary raw material flowing into the mixing unit 1 is 0.01 to 1,000 L / h, preferably 0.1 to 800 L / h, and more preferably 0.2 to 500 L / h. The flow rate of the BF gas (including the initially injected BF gas and the recycled BF gas) flowing into the microchannel reaction unit 2 is 5 to 200,000 L / h, preferably 50 to 100,000 L / h, and more preferably 100 to 50,000 L / h. Generally, the flow rate of the BF gas flowing into the microchannel reaction unit 2 is controlled to a constant value or within a certain range. As long as the total amount of both is a constant value or within a certain range, the amount of the initially injected BF gas can be adjusted according to the amount of recycled BF gas. When BF3 gas is further supplied to the mixing unit 1, the flow rate of the BF3 gas into the mixing unit 1 is 4 to 180,000 L / h, preferably 45 to 90,000 L / h, and more preferably 90 to 45,000 L / h.

[0084] According to the method of the present invention, the reaction temperature in the microchannel reaction unit 2 is preferably 0 to 120°C, preferably 10 to 80°C, and more preferably 20 to 60°C. The reaction pressure in the microchannel reaction unit 2 is 0.01 to 10 MPa, preferably 0.01 to 8 MPa, and more preferably 0.1 to 6 MPa. The residence time of the olefin raw material in the microchannel reaction unit 2 is 1 to 3600 seconds, preferably 10 to 1800 seconds, and more preferably 15 to 1000 seconds. In the microchannel reaction unit 2, the mass ratio of the auxiliary material:olefin raw material:total amount of BF3 gas is 1:1 to 1000:1 to 500 (preferably 1:1 to 500:1 to 200, and most preferably 1:10 to 250:1.5 to 100). When the microchannel reaction unit 2 is the above-mentioned microchannel reactor, the mass ratio of the auxiliary feedstock: the olefin feedstock: the total amount of BF gas refers to the mass ratio of the feedstocks when all the feedstocks are fed into the microchannel reactor, that is, it may be the proportion of the reactant feedstocks in the stream immediately downstream of the fluid distributor.

[0085] According to the method of the present invention, the high-pressure separation unit 3 is preferably a high-pressure separator. The pressure of the high-pressure separator may be 0.01 to 10 MPa, preferably 0.01 to 8 MPa, more preferably 0.1 to 6 MPa. The temperature of the high-pressure separator may be 0 to 120°C, preferably 10 to 80°C, more preferably 20 to 60°C. The volume of the high-pressure separator may be 0.1 to 20,000 L, preferably 0.2 to 2,000 L.

[0086] The low-pressure separation unit 4 is preferably a low-pressure separator. The low-pressure separation unit 4 is preferably a low-pressure separator. The pressure of the low-pressure separator may be -0.1 to 1 MPa, preferably -0.1 to 0.9 MPa, more preferably -0.1 to 0.1 MPa. The temperature of the low-pressure separator may be 0 to 120°C, preferably 10 to 80°C, more preferably 20 to 60°C. The volume of the low-pressure separator may be 0.1 to 20,000 L, preferably 0.2 to 2,000 L.

[0087] The pressure of the recycled BF3 gas passing through the gas circulation unit 5 can be 0.01 to 10 MPa, preferably 0.01 to 8 MPa, more preferably 0.1 to 6 MPa.

[0088] The pressure of the pressure control unit 7 can be 0.01 to 10 MPa, preferably 0.01 to 8 MPa, and more preferably 0.1 to 6 MPa.

[0089] The method of the present invention has the advantages of high polymerization reaction rate, high reaction conversion rate, and good product selectivity, and is suitable for large-scale industrial production.

[0090] BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of the apparatus of the present invention.

[0091] FIG. 2 is a schematic diagram of a preferred apparatus of the present invention.

[0092] FIG. 3 is a schematic diagram of a preferred apparatus of the present invention.

[0093] FIG. 4 is a schematic diagram of a preferred microchannel reactor of the present invention.

[0094] FIG. 5 is a cross-sectional view of a first mixing element according to an embodiment of the present invention.

[0095] FIG. 6 is a structural diagram of a second mixing element according to an embodiment of the present invention.

[0096] FIG. 7 is a structural diagram of a stack of a plurality of second mixing elements according to an embodiment of the present invention.

[0097] FIG. 8 is a schematic diagram of a comparative device of the present invention.

[0098] [Explanation of symbols] 1: Mixing unit (preferably a mixer) 2: Microchannel reaction unit (preferably a microchannel reactor) 3: High-pressure separation unit (preferably a high-pressure separator) 4: Low pressure separation unit (preferably a low pressure separator) 5: Gas circulation unit 6: Post-processing unit 7: Pressure control unit 8: Gas purification unit 01: BF3 gas inlet 02: Auxiliary raw material entrance 03: Olefin raw material inlet 04~09: Pipeline 001: Exhaust pipe 002: Supply pipe 003: Shell 004: First heat exchange medium inlet 005: First heat exchange medium outlet 006: Second heat exchange medium inlet 007: Second heat exchange medium outlet 008: Mixed Zone 009: Reaction Zone 010: Reaction channel 011: Second mixing element 012: Second heat exchange cavity 013: First heat exchange cavity 014: Mixed Channel 015: First mixing element 016:Fluid distributor 017: Fluid distribution pipe 018:Exhaust pipe 019: First partition 020:Transition Zone 021: Stabilization channel 022: Diffusion Channel 023: Supply Zone 024: Collection Zone 025: Second partition 0001: Main channel 0002: Branch flow path 0003:Collecting cavity 0004: Base Strip 0005: Tooth Element

[0099] Detailed Description The invention is further described below by way of example and in conjunction with the accompanying drawings, in which:

[0100] It should be noted that in some embodiments of the present invention, the polyα-olefin production apparatus can achieve continuous production as long as the temperature and pressure of the microchannel reaction unit can be controlled, and therefore, the process parameters or process conditions for all operational units in the apparatus of the present invention are not listed, and are not necessarily listed.

[0101] FIG. 1 is a schematic diagram of a poly-α-olefin production apparatus according to the present invention. The apparatus comprises a mixing unit 1, a microchannel reaction unit 2, a high-pressure separation unit 3, a low-pressure separation unit 4, a gas circulation unit 5, a post-treatment unit 6, and a pressure control unit 7. The mixing unit 1, the microchannel reaction unit 2, the high-pressure separation unit 3, the low-pressure separation unit 4, and the gas circulation unit 5 are connected in series. The microchannel reaction unit 2 is equipped with a BF gas inlet 01. The mixing unit 1 is equipped with an auxiliary feedstock inlet 02 and an olefin feedstock inlet 03. The gas circulation unit 5 is connected to the BF gas inlet 01. The low-pressure separation unit 4 is further connected to a post-treatment unit 6. The high-pressure separation unit 3, the pressure control unit 7, and the gas circulation unit 5 are further connected in series.

[0102] Figure 2 is a schematic diagram of a polyalphaolefin production apparatus of the present invention, which is based on the apparatus of Figure 1 and is formed by commonly disposing one gas purification unit 8 between the pressure control unit 7 and the gas circulation unit 5, and between the low-pressure separation unit 4 and the gas circulation unit 5.

[0103] 3 is a schematic diagram of an apparatus for producing poly-α-olefins according to the present invention, which differs from the apparatus of FIG. 2 in that a post-treatment unit 6 is connected to the mixing unit 1. In this figure, the post-treatment unit 6 is a settler or a centrifuge, which allows the stream flowing therein to be separated into a light liquid phase and a heavy liquid phase, and the heavy liquid phase (containing the complex of the auxiliary material with BF3 and the unreacted olefin material) is returned to the mixing unit 1 to continue the continuous reaction.

[0104] The microchannel reaction unit 2 of the present invention is preferably a microchannel reactor shown in FIG.

[0105] A preferred microchannel reactor of the present invention comprises: a shell 003, wherein a feed zone 023, a mixing zone 008, a reaction zone 009, and a collection zone 024 are arranged and communicated successively along a first direction within the shell 003, the shell 003 comprising a feed pipe 002 communicating with the feed zone 023 and a discharge pipe 001 communicating with the collection zone 024, and the mixing zone 008 comprising a mixing channel 014 extending along the first direction; A fluid distribution pipe 017, the fluid distribution pipe 017 extending from the exterior of the shell 003 into the mixing channel 014, the fluid distribution pipe 017 connected to a fluid distributor 016 at an end of the mixing channel 014.

[0106] The shell 003 is the main vessel for containing the reactants and products, and the feed zone 023, mixing zone 008, reaction zone 009, and collection zone 024 are different zones in the interior space of the shell 003 (all of which can store streams), and these zones are linearly arranged so that the reactants (and products) advance linearly. In the present invention, the flow direction of the streams is referred to as the first direction. Preferably, as shown in Figure 4, the shell 003 is arranged so that the first direction is the upward direction, and the feed zone 023, mixing zone 008, reaction zone 009, and collection zone 024 are arranged from bottom to top.

[0107] The first group of reaction streams (streams from the mixing unit 1) can be supplied into the supply zone 023 through the supply pipe 002 on the shell 003. The supply zone 023 has a relatively large cavity and can serve to store the first group of reaction streams, which can then flow into the adjacent mixing zone 008, i.e., the mixing channel 014. The fluid distribution pipe 017 is connected to the BF3 gas inlet 01, so that the input of the second group of reaction streams (individually supplied BF3 gas) can be provided to the mixing channel 014 through the fluid distribution pipe 017, thereby allowing the first group of reaction streams and the second group of reaction streams to mix with each other in the mixing channel 014 of the mixing zone 008. In particular, the outlet end of the fluid distribution pipe 017 is equipped with a fluid distributor 016. The fluid distributor 016 can form the second group of reaction streams into smaller droplets or bubbles, so that the second group of reaction streams can be more uniformly distributed relative to the first group of reaction streams in the mixing channel 014. In particular, the mixing structure in the mixing channel 014 is more suitable for mixing a liquid phase stream and a gas phase stream. In this case, the first group of reaction streams is a liquid phase stream, and the second group of reaction streams is a gas phase stream. The gas phase stream is formed into dispersed microbubbles through the fluid distributor 016, which can increase the contact area with the liquid phase stream and at the same time significantly affect the liquid phase stream, thereby increasing the uniformity of mixing between the two.

[0108] Furthermore, as shown in FIG. 4, the mixing channel 014 is a cavity extending along a first direction, i.e., the mixing channel 014 has a substantially tubular structure, thereby allowing the stream therein to flow along the first direction to form a stable plug flow.

[0109] The preferred microchannel reactor provided by the present invention can achieve continuous and efficient mixing of the reaction streams by designing the structure of the mixing channel and the mixing pattern therein, and at the same time, can maintain the reaction fluids flowing in a plug flow pattern, thereby ensuring the consistency of the residence time of the reaction fluids as much as possible and avoiding undesirable product selectivity due to the distribution of residence time.

[0110] More specifically, the fluid distributor 016 is at least one selected from a microporous sintered powder, a mesoporous foam material, a wire mesh, and a tube with microslits or micropores. The microporous sintered powder can be obtained by sintering powder into a microporous structure using powder metallurgy. The hollow / mesoporous foam material is a hollow microchannel with a network skeleton. The wire mesh is a microporous network structure. The tube has microslits or microholes. All of these can disperse the fluid from the fluid distribution pipe 017 into smaller bubbles or droplets.

[0111] Preferably, the fluid distributor 016 is a cylindrical sintered powder body having micropores, and the mixing channel 014 has a circular cross section. The fluid distributor 016 may have a structure having substantially the same outer diameter as the fluid distribution pipe 017, and the cross-sectional shape of the fluid distributor 016 substantially corresponds to the cross-sectional shape of the mixing channel 014, and the fluid distributor 016 is disposed coaxially with the mixing channel 014, which allows the fluid stream dispersed by the fluid distributor 016 to be more uniformly mixed with the stream in the mixing channel 014, forming a stable and uniform plug flow and avoiding mismatch in the residence times of the streams.

[0112] In particular, the fluid distributor 016 has a diameter of 0.01 cm 2 ~200cm 2 The mixing channel 014 has a cross-sectional area of 0.05 cm and a length of 1 mm to 2000 mm. 2~400cm 2 and a length of 50 mm to 5000 mm. The length and cross-sectional area of the mixing channel 014 are both greater than the length and cross-sectional area of the fluid distributor 016.

[0113] The mixing zone 008 further includes 1 to 100 (preferably 1 to 50, more preferably 2 to 10) mixing channels 014. The fluid distribution pipe 017 includes a main pipe extending from the outside of the shell 003 into the feed zone 023 and branch pipes extending from the feed zone 023 into each mixing channel 014 and having fluid distributors 016 connected to the ends of the branch pipes. Each of the multiple mixing channels 014 is connected to the feed zone 023. The first group of reaction streams is divided into multiple portions within the mixing channels, which serve to disperse the first group of reaction streams, allowing the first group of reaction streams to form a stable, uniform plug flow. The fluid distribution pipe 017 includes a main pipe and branch pipes. The main pipe is connected to the BF3 gas inlet 01 and extends from a position in the shell 003 corresponding to the feed zone 023 into the feed zone 023. The branch pipes extend from the feed zone 023 into the mixing channels 014. That is, the fluid distribution pipe 017 extends from the feed zone 023 into the mixing channel 014. The mixing zone 008 and the feed zone 023 can be separated by a first partition plate 019. The first partition plate 019 is provided with a plurality of through-holes, and each mixing channel 014 is aligned with a respective through-hole, so that the mixing zone 008 communicates with the feed zone 023.

[0114] Furthermore, in the mixing channel 014, the first mixing element 015 is disposed downstream of the fluid distributor 016. In the mixing channel 014, downstream of the fluid distributor 016 refers to a position downstream in the fluid flow direction (i.e., downstream of the fluid distributor 016 in the first direction), i.e., a position closer to the reaction zone 009 than the fluid distributor 016. Through the first mixing element 015, the fluids can be further mixed to increase the mixing uniformity of the two groups of streams.

[0115] Specifically, the first mixing element 015 has a main flow section and a diverging flow section that are alternately arranged and communicate with each other along a first direction. The main flow section has one main flow path 0001, and the diverging flow section has multiple diverging flow paths 0002. As shown in FIG. 5, one or more main flow sections / diverging flow sections may be provided and arranged alternately, with only one main flow path 0001 provided in the main flow section and multiple diverging flow paths 0002 provided in the diverging flow section. The fluid merges into the main flow path 0001 and is dispersed into the diverging flow paths 0002 of each diverging flow section. This merging and dispersion process can sufficiently increase the degree of turbulence and improve the uniformity of fluid mixing.

[0116] Furthermore, in the first mixing element 015, a collection cavity 0003 communicating with the multiple branch channels 0002 is disposed downstream of the branch section 0002. As shown in Fig. 5, the volume (particularly the cross-sectional area) of the collection cavity 0003 is larger than the volume (particularly the cross-sectional area) of the main channel 0001, and the collection cavity 0003 can merge the multiple upstream branch channels 0002, and communicates with the next main channel 0001, or the next stage, the reaction zone 009 or the transition zone 020.

[0117] As shown in Figure 5, a first mixing member 015 according to an embodiment of the present invention is shown, and the first mixing member 015 is formed by joining a plurality of plate-like members (2 to 100, preferably 2 to 50, more preferably 10 to 30) (approximately 0.2 mm to 10 mm thick) arranged along a first direction, and each plate-like member is formed with structures such as holes and cavities corresponding to a main flow path 0001, branch flow paths 0002, and collection cavities 0003, making it convenient to process and manufacture.

[0118] Furthermore, the mixing zone 008 includes a first heat exchange cavity disposed in the shell 003, the mixing channel 014 is disposed in the first heat exchange cavity 013, and the shell 003 has a first heat exchange medium inlet 004 and a first heat exchange medium outlet 005 communicating with the first heat exchange cavity 013. In the mixing zone 008, the mixing channel 014 and the first heat exchange cavity 013 are isolated from each other and do not communicate with each other, but can achieve heat conduction with each other, and a pipe fitting with good thermal conductivity can be used for the mixing channel 014. By supplying the heat exchange medium to the first heat exchange medium inlet 004 and discharging the heat exchange medium through the first heat exchange medium outlet 005, a circulating flow of the heat exchange medium can be formed in the first heat exchange cavity 013 to realize heat exchange between the mixing channel 014 and the fluid therein, i.e., to realize heat dissipation between the mixing channel 014 and the fluid therein, and to ensure that the heat generated by the mixing and dissolving of the fluid in the mixing channel 014 is dissipated in a timely manner so that the fluid therein is in an appropriate temperature range.

[0119] In particular, the volume ratio of the first heat exchange cavity 013 to the mixing channel 014 is 2 to 50, and preferably, the volume ratio of the first heat exchange cavity 013 to the mixing channel 014 is 5 to 30. Because the volume of the first heat exchange cavity 013 is larger than the volume of the mixing channel 014, the heat generated by the mixing and dissolving of the first group of reaction streams and the second group of reaction streams can be guided out in a timely manner.

[0120] Furthermore, a transition zone 020 is provided between the mixing zone 008 and the reaction zone 009. The transition zone 020 includes a stabilization channel 021 having a constant cross-sectional area and a diffusion channel 022 having a gradually expanding cross-sectional area and arranged along a first direction and communicating with each other. The stabilization channel 021 communicates with the mixing channel 014, and the diffusion channel 022 communicates with the reaction zone 009. The transition zone 020 can merge mixed fluids from multiple mixing channels 014 in the stabilization channel 021 to achieve another uniform mixing, and then deliver the mixed fluid into the reaction zone 009 via the diffusion channel 022. In particular, the transition region 020 includes the stabilization channel 021 and the diffusion channel 022. The stabilization channel 021 mainly realizes the merging and mixing of fluids, and the diffusion channel 022 has a bell-mouth shape and can diffuse. For example, the mixed fluid can be dispersed into multiple reaction channels 010, as described below. The two ends of the transition zone 020 are provided with partition plates having through holes so as to isolate the transition zone 020 from the mixing zone 008 (mainly the first heat exchange cavity 013) and the reaction zone 009 (mainly the second heat exchange cavity 012), respectively, and are connected to each mixing channel 014 and each reaction channel 010 through each through hole of each partition plate, and the diffusion channel 022 and the stabilization channel 021 can be pipe joints provided between the two partition plates.

[0121] Furthermore, the stabilization channel 021 may be connected to a discharge pipe 018 extending outside the shell 003. As described above, the stabilization channel 021 has the functions of merging and mixing, and the discharge pipe 018 can discharge bubbles and streams accumulated in the stabilization channel 021 to avoid the effects of bubble accumulation on the uniformity of the mixture and blockage of the stream. A valve may be installed in the discharge pipe 018, and the valve can be opened when bubbles or streams need to be discharged.

[0122] Furthermore, the diffusion channel 022 is provided with a diffuser plate having a mesh or slits. The diffuser plate may be substantially perpendicular to the first direction. The fluid in the diffusion channel 022 can flow through the mesh or slits on the diffuser plate, thereby dispersing the fluid and improving the uniformity of the mixed fluid.

[0123] The reaction zone 009 includes multiple parallel reaction channels 010 extending along a first direction and communicating with a mixing channel 014 via stabilization channels 021 and diffusion channels 022. The reaction channels 010 provide a reaction space for the mixed fluid and support the mixed fluid as it flows along the first direction to the next stage, the collection region 024. As a result, the mixed fluid reacts within the reaction channels 010 while forming a stable plug flow, avoiding undesired products due to inconsistent residence time distribution. As described above, a transition zone 020 may be provided between the reaction zone 009 and the mixing zone 008. The multiple reaction channels 010 may communicate with the diffusion channel 022, thereby uniformly distributing the mixed fluid within the diffusion channel 022 to the multiple reaction channels 010. The number of reaction channels may be, for example, 2 to 10,000 channels, preferably 2 to 5,000 channels, and more preferably 2 to 500 channels. The reaction channels 010 may have at least one cross-section of a circular, rectangular, or triangular shape.

[0124] Furthermore, the reaction channel 010 includes a second mixing element 011, which includes a base strip 0004 extending along the first direction and tooth elements 0005 connected to the base strip 0004 and extending transversely to the base strip 0004. In the second mixing element 011, the base strip 0004 provides support for the tooth elements 0005, so that the tooth elements 0005 can be stably held within the reaction channel 010, and the tooth elements 0005 extend in a direction substantially transverse to the reaction channel 010, which increases the turbulence of the fluid within the reaction channel 010 and thereby increases the mixing uniformity between the reaction streams.

[0125] Furthermore, the tooth element 0005 is one of a triangular, arcuate, wavy, and spiral shape. The tooth element 0005 can have various shapes as long as it extends transversely to the reaction channel 010 and can achieve the function of increasing the turbulence of the fluid.

[0126] Preferably, the tooth element 0005 is triangular, one side of the triangle is adjacent to the base strip 0004, one end is connected to the base strip 0004, and the other end is 0.01 mm to 20 mm away from the base strip 0004. The tooth element 0005 may be a triangular plate-like member, and only one end is connected to the base strip 0004.

[0127] Preferably, the reaction channel 010 is provided with a plurality of second mixing elements 011 (2 to 100, preferably 2 to 50, more preferably 10 to 30) arranged at intervals, and the plurality of second mixing elements 011 are arranged at intervals, and the tooth elements 0005 are also arranged at intervals correspondingly, and the tooth elements 0005 of different second mixing elements 011 are arranged alternately, so that the different second mixing elements 011 are arranged more irregularly, which can better increase the degree of turbulence of the fluid in the reaction channel 010.

[0128] Preferably, the cross section of the reaction channel 010 is rectangular, and the tooth element 0005 extends between a pair of opposing rectangular shapes. Specifically, the reaction channel 010 includes four side walls, i.e., two pairs of opposing parallel side walls, the base strip 0004 is disposed on one side wall of the reaction channel 010, and the tooth element 0005 extends toward the other opposing side wall, so that the multiple second mixing elements 011 can be well accommodated by the rectangular prism-shaped internal cavity structure of the reaction channel 010.

[0129] Reaction channel 010 is 1 mm 2 ~150mm 2 and a length of 50 mm to 5000 mm, the shortest distance between the reaction channels 010 is 1 mm to 50 mm, the second mixing member 011 has a thickness of 0.1 mm to 3 mm, and the spacing between adjacent tooth elements 0005 is 1 mm to 50 mm.

[0130] Preferably, the reaction channels 010 have a length of 100 mm to 3000 mm, the minimum spacing between the reaction channels 010 is 3 mm to 30 mm, the second mixing element 011 has a thickness of 0.2 mm to 2 mm, and the spacing between adjacent tooth elements 0005 is 1.5 mm to 20 mm. The minimum spacing between the reaction channels 010 reflects the density of the reaction channels 010 in the reaction zone 009. Preferably, in the second mixing element 011, the tooth elements 0005 are plate-like elements that may be flush with the base strip 0004, and the thickness of the second mixing element 011 is approximately the same as the thickness of the tooth elements 0005.

[0131] Furthermore, the reaction zone 009 may include a second heat exchange cavity 012 disposed within the shell 003, the reaction channel 010 being disposed within the second heat exchange cavity 012, and the shell 003 including a second heat transfer medium inlet 006 and a second heat transfer medium outlet 007 communicating with the second heat exchange cavity 012. The second heat exchange cavity 012 may be primarily formed by the shell 003, with a second partition plate 025 between the reaction zone 009 and the collection zone 024 and a partition plate between the reaction zone 009 and the transition zone 020 at its two ends, respectively. A heat exchange medium may be introduced into the second heat exchange cavity 012 via the second heat exchange medium inlet 006 and the second heat exchange medium outlet 007 to realize the heat exchange process of the reaction channel 010, thereby ensuring that the fluid in the reaction channel 010 reacts within an appropriate temperature range and avoids the production of undesired products.

[0132] Furthermore, the first heat exchange cavity 013 and the second heat exchange cavity 012 may be connected in series to each other and arranged in one heat exchange circulation flow path, or may be arranged in parallel in one heat exchange circulation flow path, or may be arranged in two different heat exchange circulation flow paths, respectively.

[0133] In particular, the volume ratio of the second heat exchange cavity 012 to the reaction channel 010 is 2 to 50, and preferably the volume ratio of the second heat exchange cavity 012 to the reaction channel 010 is 5 to 30. The volume of the second heat exchange cavity 012 is larger than the volume of the reaction channel 010, so that the heat in the reaction channel 010 can be discharged in a timely manner to ensure that the reaction channel 010 is at an appropriate temperature.

[0134] Unless otherwise specified, in the embodiments of the present invention, preferred structural elements or parameters are used without repetition when using the preferred microchannel reactor.

[0135] A preferred microchannel reactor of the present invention can be used to synthesize poly-α-olefin synthetic oil. The feed pipe 002 can be used to input a mixture of an olefin feedstock and an auxiliary feedstock, and the fluid distribution pipe 017 can be used to input BF3 gas. The mixture of the olefin feedstock and the auxiliary feedstock is used as a continuous phase and flows into the feed zone 023 of the microchannel reactor through the feed pipe 002. BF3 gas (with a weight ratio of BF3 gas to α-olefin of 0.1% to 4%) is used as a dispersed phase and flows into the mixing channel 014 of the reactor through the fluid distribution pipe 017. BF3 is supplied in gaseous form and partially dissolved in the continuous phase through the fluid distributor 016. The mixed fluid after the reaction in the reaction channel 010 flows into the recovery area 024 and is finally discharged through the discharge pipe 001. Preferably, the olefin feedstock, auxiliary feedstock, and BF3 gas are supplied through the feed pipe 002.

[0136] FIG. 8 is a schematic diagram of a comparative device of the present invention, which differs from the device in that it has only one high-pressure separation unit 3 and no low-pressure separation unit 4, and the high-pressure separation unit 3 is directly connected to a pressure control unit 7.

[0137] Example 1 Polymerization of an olefin feedstock was carried out by using the apparatus shown in Figure 1. In this apparatus, the mixing unit 1 was a mixer, the microchannel reaction unit 2 was a general microchannel reactor packed with mixing sheets (not the preferred microchannel reactor of the present invention), the high-pressure separation unit 3 was a high-pressure separator, the low-pressure separation unit 4 was a low-pressure separator, the gas circulation unit 5 was a compressor, the post-treatment unit 6 was a water washing device, and the pressure control unit 7 was a back-pressure valve.

[0138] The mixer had the following structure and parameters: allowable process fluid temperature range: 20–200°C, upper limit of operating pressure (25°C): 10 MPa; the microchannel reactor had eight parallel channels, a process fluid temperature range: -20–200°C, a maximum allowable reaction pressure: 6 MPa, a maximum allowable heat transfer medium pressure: 2 MPa, two temperature probes for measuring the temperature in the reaction system, a fluid channel volume (without mixing disk): 50 mL, a reaction volume (when mixing sheet is packed): 30 mL, a volumetric flow rate: 3–30 L / h, and a header pipe for introducing the reaction gas and a branch pipe for distributing the reaction gas to each channel. The high-pressure separator had a volume of 1 L and a diameter of 10 cm, and the low-pressure separator had a volume of 15 L and a diameter of 50 cm. The compressor had the following operating parameters: suction pressure: -0.1–0.03 MPa, discharge pressure: 10 MPa, and volumetric flow rate: 3 m / s. 3 / h, the pressure of the back pressure valve was 6 MPa; the dryer had an effective volume of 10 L, and was equipped with a gas distributor at the bottom and a silica gel filler placed in the upper layer.

[0139] The mixed stream obtained by mixing 1-nonene and n-butanol in a mixer and BF gas were each independently introduced into a microchannel reactor. BF was introduced into the microchannel reactor through a reaction gas header pipe. The volumetric flow rates of BF, 1-nonene, and n-butanol were 52 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The intermediate stream thus formed was introduced into a high-pressure separator. The intermediate stream underwent a first gas-liquid separation in the high-pressure separator at a separation temperature of 20°C and a separation pressure of 4 MPa. The separated liquid phase was then introduced into a low-pressure separator for a second gas-liquid separation at a separation temperature of 20°C and a separation pressure of -0.01 MPa. The liquid phase separated from the low-pressure separator was washed with water in a water washing device to obtain a polyolefin product. The BF3 gas separated from the high-pressure and low-pressure separators was recycled by a compressor. The compressor's gas outlet pressure was 4 MPa. After the system was in stable operation, a small sample of the polyolefin product in the low-pressure separator was taken, washed with water, and the content of each component in the product was measured by gas chromatography. The recovery rate of BF3 gas was 40%. The test results are shown in Table 1.

[0140] [Table 1]

[0141] (Comparative Example 1) The low-pressure separator was removed from the apparatus used in Example 1, and the high-pressure separator was directly connected in series to the back pressure valve and the compressor, and the high-pressure separator was directly connected to the water washing device, which is a post-treatment unit.

[0142] Polymerization of olefin feedstock was carried out using the above-mentioned apparatus. The mixer had the following structure and parameters: allowable process fluid temperature range: 20–200°C, upper limit of operating pressure (25°C): 10 MPa; the microchannel reactor had the following structure and parameters: eight parallel channels, process fluid temperature range: -20–200°C, maximum allowable reaction pressure: 6 MPa, maximum allowable heat transfer medium pressure: 2 MPa, including two temperature probes for measuring the temperature in the reaction system, fluid channel volume (without mixing disk): 50 mL, reaction volume (with mixing sheet): 30 mL, volumetric flow rate: 3–30 L / h, header pipe for introducing reaction gas and branch pipe for distributing reaction gas to each channel; the high-pressure separator had a volume of 1 L and a diameter of 10 cm; and the compressor had the following operating parameters: suction pressure: -0.1–0.03 MPa, discharge pressure: 10 MPa, volumetric flow rate: 3 m / s. 3 / h, the pressure of the back pressure valve was 6 MPa; the dryer had an effective volume of 10 L, and was equipped with a gas distributor at the bottom and a silica gel filler placed in the upper layer.

[0143] The mixed stream obtained by mixing 1-decene and isopropanol in a mixer and BF3 gas were each independently introduced into a microchannel reactor. BF3 was introduced into the microchannel reactor through a reaction gas header pipe. The volumetric flow rates of BF3, 1-nonene, and isopropanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 25°C and a pressure of 4 MPa. The intermediate stream thus formed was introduced into a high-pressure separator, where it underwent gas-liquid separation. The separation temperature was 20°C and the separation pressure was 4 MPa. The separated liquid phase was washed with water in a water washing device to obtain the polyolefin product. The BF3 gas separated from the high-pressure separator was recycled through a compressor. The gas outlet pressure of the compressor was 4 MPa. Test results showed that the separation efficiency of the high-pressure separator was relatively low, with a BF3 gas recovery rate of only 20%. After the system was in stable operation, a small amount of polyolefin product was sampled from the high-pressure separator, washed with water, and the content of each component in the product was measured by gas chromatography. The test results are shown in Table 2.

[0144] [Table 2]

[0145] (Comparative Example 2) The polymerization of the olefin raw material was carried out using the poly-α-olefin production apparatus shown in Example 1.

[0146] The mixer had the following structure and parameters: allowable process fluid temperature range: 20–200°C, upper limit of operating pressure (25°C): 10 MPa; the microchannel reactor had eight parallel channels, a process fluid temperature range: -20–200°C, a maximum allowable reaction pressure: 6 MPa, a maximum allowable heat transfer medium pressure: 2 MPa, two temperature probes for measuring the temperature in the reaction system, a fluid channel volume (without mixing disk): 50 mL, a reaction volume (when mixing sheet is packed): 30 mL, a volumetric flow rate: 3–30 L / h, and a header pipe for introducing the reaction gas and a branch pipe for distributing the reaction gas to each channel. The high-pressure separator had a volume of 1 L and a diameter of 10 cm, and the low-pressure separator had a volume of 15 L and a diameter of 50 cm. The compressor had the following operating parameters: suction pressure: -0.1–0.03 MPa, discharge pressure: 10 MPa, and volumetric flow rate: 3 m / s. 3 / h, the pressure of the back pressure valve was 6 MPa; the dryer had an effective volume of 10 L, and was equipped with a gas distributor at the bottom and a silica gel filler placed in the upper layer.

[0147] The mixed stream obtained by mixing 1-nonene and n-butanol in a mixer and BF3 gas were each independently introduced into a microchannel reactor. BF3 was introduced into the microchannel reactor through a reaction gas header pipe. The volumetric flow rates of BF3, 1-nonene, and n-butanol were 26 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The intermediate stream thus formed was introduced into a high-pressure separator. The intermediate stream underwent a first gas-liquid separation in the high-pressure separator. The separation temperature was 20°C and the separation pressure was 4 MPa. The separated liquid phase was introduced into a low-pressure separator for a second gas-liquid separation at a separation temperature of 20°C and a separation pressure of -0.01 MPa. The liquid phase separated from the low-pressure separator was washed with water in a water washing device to obtain a polyolefin product. The BF3 gas separated from the high-pressure and low-pressure separators was recycled by a compressor. The compressor gas outlet pressure was 4 MPa. The BF3 gas recovery rate was 40%. After the system was in stable operation, a small sample of the polyolefin product in the low-pressure separator was taken, washed with water, and the content of each component in the product was measured by gas chromatography. The test results are shown in Table 3.

[0148] [Table 3]

[0149] Example 2 Polymerization of the olefin raw material was carried out using the apparatus shown in FIG.

[0150] In the apparatus used in this example, the mixing unit 1 was a mixer, the microchannel reaction unit 2 was a general microchannel reactor packed with mixing sheets (not the preferred microchannel reactor of the present invention), the high-pressure separation unit 3 was a high-pressure separator, the low-pressure separation unit 4 was a low-pressure separator, the gas circulation unit 5 was a compressor, the post-treatment unit 6 was a water washing device, the pressure control unit 7 was a back-pressure valve, and the gas purification unit 8 was a dryer.

[0151] The mixer had the following structure and parameters: allowable process fluid temperature range: 20–200°C, upper limit of operating pressure (25°C): 10 MPa; the microchannel reactor had eight parallel channels, a process fluid temperature range: -20–200°C, a maximum allowable reaction pressure: 6 MPa, a maximum allowable heat transfer medium pressure: 2 MPa, two temperature probes for measuring the temperature in the reaction system, a fluid channel volume (without mixing disk): 50 mL, a reaction volume (when mixing sheet is packed): 30 mL, a volumetric flow rate: 3–30 L / h, and a header pipe for introducing the reaction gas and a branch pipe for distributing the reaction gas to each channel. The high-pressure separator had a volume of 1 L and a diameter of 10 cm, and the low-pressure separator had a volume of 15 L and a diameter of 50 cm. The compressor had the following operating parameters: suction pressure: -0.1–0.03 MPa, discharge pressure: 10 MPa, and volumetric flow rate: 3 m / s. 3 / h, the pressure of the back pressure valve was 6 MPa; the dryer was an adsorption dryer with an effective volume of 10 L, equipped with a gas distributor at the bottom and a silica gel filler placed in the upper layer.

[0152] The mixed stream obtained by mixing 1-decene and n-butanol in a mixer and BF3 gas were each independently introduced into a microchannel reactor. BF3 was introduced into the microchannel reactor via a reaction gas header pipe. The volumetric flow rates of BF3, 1-decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The intermediate stream thus formed was introduced into a high-pressure separator. The intermediate stream underwent a first gas-liquid separation in the high-pressure separator at a separation temperature of 20°C and a separation pressure of 4 MPa. The separated liquid phase was introduced into a low-pressure separator for a second gas-liquid separation at a separation temperature of 20°C and a separation pressure of -0.01 MPa. The liquid phase separated by the low-pressure separator was washed with water in a water washing device (post-treatment unit 6) to obtain the final polyolefin product. The gas phase (BF3 gas) separated from the high-pressure and low-pressure separators was dried in a dryer and recycled through a compressor. The compressor gas outlet pressure was 4 MPa. After the system was in stable operation, a small sample of the polyolefin product in the low-pressure separator was taken, washed with water, and the content of each component in the product was measured by gas chromatography. The recovery rate of BF3 gas was 54%. The test results are shown in Table 4.

[0153] [Table 4]

[0154] Example 3 Polymerization of the olefin raw material was carried out using the apparatus shown in FIG.

[0155] In the apparatus used in this example, the mixing unit 1 is a mixer, the microchannel reaction unit 2 is a general microchannel reactor packed with mixing sheets (not the preferred microchannel reactor of the present invention), the high-pressure separation unit 3 is a high-pressure separator, the low-pressure separation unit 4 is a low-pressure separator, the gas circulation unit 5 is a compressor, the post-treatment unit 6 is a settler, the pressure control unit 7 is a backpressure valve, and the gas purification unit 8 is a dryer; the mixer, microchannel reactor, high-pressure separator, low-pressure separator, compressor, and dryer were the same as those in Example 1.

[0156] The settler allows the stream flowing therein to be separated into a light liquid phase and a heavy liquid phase, and the heavy liquid phase (containing the complex of auxiliary material and BF3, and unreacted olefin material) is returned to the mixing unit 1 to continue participating in the continuous reaction. The apparatus is a horizontal gravity settler, and the tank of the apparatus contains a rectangular parallelepiped container measuring 3000 mm x 300 mm x 1500 mm, in which there are compound inclined and horizontal plates, and 10 horizontal plates are connected to every 10 compound inclined plates. The spacing between the compound inclined plates is 30 mm, the inclination angle is 30°, and the length of the inclined plates is 34 mm. The length of the horizontal plates is 30 mm, and the spacing is 30 mm.

[0157] The mixed stream obtained by mixing 1-decene and n-butanol in a mixer and BF3 gas were each independently introduced into a microchannel reactor. BF3 was introduced into the microchannel reactor via a reaction gas header pipe. The volumetric flow rates of BF3, 1-decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The intermediate stream thus formed was introduced into a high-pressure separator. The intermediate stream underwent a first gas-liquid separation in the high-pressure separator at a separation temperature of 20°C and a separation pressure of 4 MPa. The separated liquid phase was introduced into a low-pressure separator for a second gas-liquid separation at a separation temperature of 20°C and a separation pressure of -0.01 MPa. The liquid phase separated by the low-pressure separator was introduced into a settler (post-treatment unit 6) where it was separated into a light liquid phase and a heavy liquid phase through settling. The light liquid phase was the crude polyolefin product, which was washed with water to produce the final polyolefin product; the heavy liquid phase contained the complex of auxiliary feedstocks and BF3, as well as unreacted olefin feedstock, and was returned to the mixing unit 1. The gas phases separated from the high-pressure and low-pressure separators were dried in a dryer, compressed in a compressor, and recycled for reuse. The compressor gas outlet pressure was 4 MPa. After the system was operated stably, a small sample of the polyolefin product in the low-pressure separator was taken and washed with water, and the contents of each component in the product were measured by gas chromatography. The recovery rate of the complex catalyst was 65%, and the recovery rate of the BF3 gas was 75.45%. The test results are shown in Table 5.

[0158] [Table 5]

[0159] Example 4 The polymerization of the olefin raw material was carried out using the polyolefin production apparatus shown in FIG.

[0160] In the equipment used in this example, the mixing unit 1 was a mixer, the microchannel reaction unit 2 was a general microchannel reactor packed with mixing sheets (not the preferred microchannel reactor of the present invention), the high-pressure separation unit 3 was a high-pressure separator, the low-pressure separation unit 4 was a low-pressure separator, the gas circulation unit 5 was a compressor, the post-treatment unit 6 was a centrifugal separator, the pressure control unit 7 was a backpressure valve, and the gas purification unit 8 was a dryer with a working volume of 10 L and a gas distributor at the bottom and a silica gel filler on top; the mixer, microchannel reactor, high-pressure separator, low-pressure separator, and compressor were the same as those in Example 1.

[0161] The centrifugal separator allowed the stream entering it to be separated into a light liquid phase and a heavy liquid phase, and the heavy liquid phase (containing the complex of auxiliary feedstock with BF3 and unreacted olefin feedstock) was returned to the mixing unit 1 to continue participating in the continuous reaction.

[0162] In particular, the centrifugal device is a tubular high-speed separator, the rotation speed of the rotating drum is 10-30,000 r / min, the separation degree is above 15,000 G; the centrifugation temperature is 10-60°C, and the centrifugation residence time is 10-1,000 s.

[0163] The mixed stream obtained by mixing 1-decene and n-butanol in the mixer and BF3 gas were each independently introduced into a microchannel reactor. BF3 was introduced into the microchannel reactor via a reaction gas header pipe. The volumetric flow rates of BF3, 1-decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The intermediate stream thus formed flowed into a high-pressure separator. The intermediate stream underwent a first gas-liquid separation in the high-pressure separator at a separation temperature of 20°C and a separation pressure of 4 MPa. The separated liquid phase flowed into a low-pressure separator for a second gas-liquid separation at a separation temperature of 20°C and a separation pressure of -0.01 MPa. The liquid phase separated by the low-pressure separator flowed into a centrifugal separator, which was the post-treatment unit 6. The separated light liquid phase from the centrifugal separator was the crude polyolefin product and was washed with water to produce the final polyolefin product; the separated heavy liquid phase contained the complex of auxiliary feedstocks and BF3, as well as unreacted olefin feedstock, and was returned to the mixing unit 1 to continue participating in the continuous reaction. The gas phase (BF3 gas) separated from the high-pressure and low-pressure separators was dried in a dryer, compressed in a compressor, and recycled for reuse. The compressor gas outlet pressure was 4 MPa. After the system was operated stably, a small sample of the polyolefin product in the low-pressure separator was taken and washed with water, and the content of each component in the product was measured by gas chromatography. The recovery rate of the complex catalyst was 80%. The total recovery rate of BF3 gas was 80.4%. The test results are shown in Table 6.

[0164] [Table 6]

[0165] (Comparative Example 3) The polymerization of the olefin raw material was carried out using only the mixer, microchannel reactor, and centrifugal separator that were the same as those used in the poly-α-olefin production apparatus of Example 4.

[0166] The mixed stream obtained by mixing 1-decene and n-butanol in the mixer and BF3 gas were introduced into the microchannel reactor. BF3 was introduced into the microchannel reactor through a reaction gas header pipe. The volumetric flow rates of BF3, 1-decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The intermediate product from the microchannel reactor flowed directly into a centrifuge, without recovering BF3 gas. The separated light liquid phase in the centrifuge was the crude polyolefin product, which was washed with water to produce the final polyolefin product; the separated heavy liquid phase, containing the complex of auxiliary materials with BF3 and unreacted olefin feedstock, was returned to the mixing unit 1 to continue participating in the continuous reaction. The recovery rate of the complex catalyst was 80%. The total recovery rate of BF3 gas was 26.4%. A small amount of the polyolefin product sample was taken and the content of each component in the product was measured by gas chromatography. The test results are shown in Table 7.

[0167] [Table 7]

[0168] Example 5 The polymerization of the olefin raw material was carried out using the polyolefin production apparatus shown in Figure 2.

[0169] In this apparatus, the mixing unit 1 was a mixer, the microchannel reaction unit 2 was the preferred microchannel reactor shown in FIG. 4 (the preferred microchannel reactor of the present invention), the high-pressure separation unit 3 was a high-pressure separator, the low-pressure separation unit 4 was a low-pressure separator, the gas circulation unit 5 was a compressor, the post-treatment unit 6 was a water washing device, the pressure control unit 7 was a backpressure valve, the gas purification unit 8 was a dryer, and the mixer, the high-pressure separator, the low-pressure separator, and the compressor were the same as those in Example 1.

[0170] In this device, the microchannel reactor contains five reaction channels 010 in parallel, each of which has a diameter of 20 mm. 2 The reaction channel 010 had a rectangular cross section with a cross-sectional area of 1000 mm, and the reaction channel 010 had a length of 2000 mm. The second mixing element 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. As shown in Figure 7, a total of four layers of second mixing elements 011 were arranged in the reaction channel 010, stacked one on the other. In this device, the high-pressure separator had a volume of 1 L and a diameter of 10 cm, and the low-pressure separator had a volume of 15 L and a diameter of 50 cm; the compressor had a suction pressure of -0.1 to 0.03 MPa, a discharge pressure of 10 MPa, and a volumetric flow rate of 3 m 3 / h; the back pressure valve had a pressure of 6 MPa, and the dryer had an effective volume of 10 L, with a gas distributor at the bottom and a silica gel filler placed in the upper layer.

[0171] The microchannel reactor was fed with a mixed stream obtained by mixing 1-decene and n-butanol in a mixer via feed pipe 002, and BF3 gas via fluid distribution pipe 017; the volumetric flow rates of BF3, decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The BF3 gas separated from the high-pressure and low-pressure separators was dried in a dryer, compressed in a compressor, and recycled for reuse. The compressor gas outlet pressure was 4 MPa. The recovery rate of BF3 gas was 54%. After the system was operated stably, a small sample of the polyolefin product in the low-pressure separator was taken and washed with water. The contents of each component in the product were measured by gas chromatography. The test results are shown in Table 8.

[0172] [Table 8]

[0173] Comparative Example 4 The polymerization of the olefin raw material was carried out using the polyolefin production apparatus shown in Figure 2.

[0174] In this apparatus, the mixing unit 1 was a mixer, the microchannel reaction unit 2 was the preferred microchannel reactor shown in FIG. 4 (a preferred microchannel reactor of the present invention), but the reactor was not provided with a mixing channel 014 and a fluid distributor 016, the high-pressure separation unit 3 was a high-pressure separator, the low-pressure separation unit 4 was a low-pressure separator, the gas circulation unit 5 was a compressor, the post-treatment unit 6 was a water washing device, the pressure control unit 7 was a backpressure valve, the gas purification unit 8 was a dryer, and the mixer, the high-pressure separator, the low-pressure separator, and the compressor were the same as those in Example 1.

[0175] In this device, the microchannel reactor contains five reaction channels 010 in parallel, each of which has a diameter of 20 mm. 2 The reaction channel 010 had a rectangular cross-section with a cross-sectional area of 1 mm, and the reaction channel 010 had a length of 2000 mm. The second mixing element 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. A total of four layers of second mixing elements 011 were arranged in the reaction channel 010, stacked on top of each other, as shown in Figure 7.

[0176] In this device, the high-pressure separator has a volume of 1 L and a diameter of 10 cm, and the low-pressure separator has a volume of 15 L and a diameter of 50 cm; the compressor has a suction pressure of -0.1 to 0.03 MPa, a discharge pressure of 10 MPa, and a volume flow rate of 3 m 3 / h; the back pressure valve had a pressure of 6 MPa, and the dryer had an effective volume of 10 L, with a gas distributor at the bottom and a silica gel filler placed in the upper layer.

[0177] The microchannel reactor was fed with a mixed stream obtained by mixing 1-decene and n-butanol in a mixer via feed pipe 002, and BF3 gas via fluid distribution pipe 017; the volumetric flow rates of BF3, decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The BF3 gas separated from the high-pressure and low-pressure separators was dried in a dryer, compressed in a compressor, and recycled for reuse. The compressor gas outlet pressure was 4 MPa. The recovery rate of BF3 gas was 58%. After the system was operated stably, a small sample of the polyolefin product in the low-pressure separator was taken and washed with water. The contents of each component in the product were measured by gas chromatography. The test results are shown in Table 9.

[0178] [Table 9]

[0179] Example 6 The polymerization of the olefin raw material was carried out using the polyolefin production apparatus shown in Figure 2.

[0180] In this apparatus, the mixing unit 1 was a mixer, the microchannel reaction unit 2 was the preferred microchannel reactor shown in FIG. 4 (the preferred microchannel reactor of the present invention), the high-pressure separation unit 3 was a high-pressure separator, the low-pressure separation unit 4 was a low-pressure separator, the gas circulation unit 5 was a compressor, the post-treatment unit 6 was a water washing device, the pressure control unit 7 was a backpressure valve, the gas purification unit 8 was a dryer, and the mixer, the high-pressure separator, the low-pressure separator, and the compressor were the same as those in Example 1.

[0181] In this device, the microchannel reactor contains five reaction channels 010 in parallel, each of which has a diameter of 20 mm. 2The reactor had a rectangular cross section with a cross-sectional area of 1000 mm, and the reaction channel 010 had a length of 2000 mm. The second mixing element 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. As shown in Figure 7, a total of four layers of second mixing elements 011 were arranged in the reaction channel 010. The reactor had a diameter of 10 cm. 2 The fluid distributor 016 contained one mixing channel 014 with an average pore size of 5 microns, a cross-sectional area of 8.5 cm, and a length of 800 mm. 2 The mixing channel 014 was provided with three first mixing members 015. The first mixing member 015 was a sintered metal powder compact having micropores and a length of 150 mm.

[0182] In this device, the high-pressure separator has a volume of 1 L and a diameter of 10 cm; the low-pressure separator has a volume of 15 L and a diameter of 50 cm; the compressor has a suction pressure of -0.1 to 0.03 MPa, a discharge pressure of 10 MPa, and a volumetric flow rate of 3 m 3 / h, the back pressure valve had a pressure of 6 MPa, the dryer had an effective volume of 10 L, a gas distributor at the bottom, and a silica gel filler placed in the upper layer.

[0183] The microchannel reactor was fed with a mixed stream obtained by mixing 1-decene and n-butanol in a mixer via feed pipe 002, and BF3 gas via fluid distribution pipe 017; the volumetric flow rates of BF3, decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The BF3 gas separated from the high-pressure and low-pressure separators was dried in a dryer, compressed in a compressor, and recycled for reuse. The compressor gas outlet pressure was 4 MPa. The BF3 gas recovery rate was 55%. After the system was stably operated, a small sample of the polyolefin product in the low-pressure separator was taken and washed with water. The contents of each component in the product were measured by gas chromatography. The test results are shown in Table 10.

[0184] [Table 10]

[0185] Example 7 The polymerization of the olefin raw material was carried out using the polyolefin production apparatus shown in Figure 2.

[0186] In this apparatus, the mixing unit 1 was a mixer, the microchannel reaction unit 2 was the preferred microchannel reactor shown in FIG. 4 (the preferred microchannel reactor of the present invention), the high-pressure separation unit 3 was a high-pressure separator, the low-pressure separation unit 4 was a low-pressure separator, the gas circulation unit 5 was a compressor, the post-treatment unit 6 was a water washing device, the pressure control unit 7 was a backpressure valve, the gas purification unit 8 was a dryer, and the mixer, the high-pressure separator, the low-pressure separator, and the compressor were the same as those in Example 1.

[0187] In this device, the microchannel reactor contains five reaction channels 010 in parallel, each of which has a diameter of 20 mm. 2 The reactor had a rectangular cross section with a cross-sectional area of 1000 mm, and the reaction channel 010 had a length of 2000 mm. The second mixing element 011 in the reaction channel 010 had triangular tooth elements 0005, and the spacing between adjacent tooth elements 0005 was 5 mm. The reaction channel 010 had a total of four layers of second mixing elements 011 stacked on top of each other, as shown in Figure 7. The reactor included two mixing channels 014, each of which was 10 cm 2 The mixing channel 014 had a cross-sectional area of 8.5 cm and a length of 800 mm. Three first mixing elements 015 were provided in each mixing channel 014. The fluid distributor 016 was made of micro / mesoporous tubular material, and the hollow microchannels constituting the network framework of the micro / mesoporous tubular material were 8.5 cm in diameter. 2 The tube had a cross-sectional area of 100 mm, an average pore size of 2 microns, and a length of 150 mm.

[0188] In this device, the high-pressure separator has a volume of 1 L and a diameter of 10 cm; the low-pressure separator has a volume of 15 L and a diameter of 50 cm; the compressor has a suction pressure of 0.1 to 0.03 MPa, a discharge pressure of 10 MPa, and a volume flow rate of 3 m 3 / h, the back pressure valve had a pressure of 6 MPa, the dryer had an effective volume of 10 L, a gas distributor at the bottom, and a silica gel filler placed in the upper layer.

[0189] The microchannel reactor was fed with a mixed stream obtained by mixing 1-decene and n-butanol in a mixer via feed pipe 002, and BF3 gas via fluid distribution pipe 017; the volumetric flow rates of BF3, decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The BF3 gas separated from the high-pressure and low-pressure separators was dried in a dryer, compressed in a compressor, and recycled for reuse. The compressor gas outlet pressure was 4 MPa. The recovery rate of BF3 gas was 54%. After the system was operated stably, a small sample of the polyolefin product in the low-pressure separator was taken and washed with water. The contents of each component in the product were measured by gas chromatography. The test results are shown in Table 11.

[0190] [Table 11]

[0191] (Comparative Example 5) The same equipment as in Example 2 was used, except that the microchannel reactor was not packed with a mixing sheet.

[0192] The mixed stream obtained by mixing 1-decene and n-butanol in a mixer and BF3 gas were each independently introduced into a microchannel reactor. BF3 was introduced into the microchannel reactor via a reaction gas header pipe. The volumetric flow rates of BF3, 1-decene, and n-butanol were 78 L / h, 10 L / h, and 0.1 L / h, respectively. The polymerization reaction was carried out in the microchannel reactor at a reaction temperature of 20°C and a pressure of 4 MPa. The intermediate stream thus formed was introduced into a high-pressure separator. The intermediate stream underwent a first gas-liquid separation in the high-pressure separator at a separation temperature of 20°C and a separation pressure of 4 MPa. The separated liquid phase was introduced into a low-pressure separator for a second gas-liquid separation at a separation temperature of 20°C and a separation pressure of -0.01 MPa. The liquid phase separated by the low-pressure separator was washed with water in a water washing device (post-treatment unit 6) to obtain the final polyolefin product. The gas phase (BF3 gas) separated from the high-pressure separator and the low-pressure separator was dried in a dryer and recycled by a compressor. The gas outlet pressure of the compressor was 4 MPa. After the system was operated stably, a small sample of the polyolefin product in the low-pressure separator was taken, washed with water, and the content of each component in the product was measured by gas chromatography. The recovery rate of BF3 gas was 53%. The test results are shown in Table 12.

[0193] [Table 12]

[0194] The polyolefin products of Examples 1 to 7 and Comparative Examples 1 to 5 were each distilled and fractionated to obtain poly-α-olefin synthetic oils at temperatures above 280°C, and the kinematic viscosity and viscosity index at 100°C were tested. The test results are shown in Table 13.

[0195] [Table 13]

[0196] From the above examples, it can be seen that the poly-α-olefin production apparatus of the present invention can recover BF3 and BF3 complexes at a high recovery rate, thereby avoiding environmental pollution and reducing reaction costs.

[0197] Furthermore, as can be seen from the table above, the preferred microchannel reactor of the present invention enabled the production of poly-α-olefin synthetic oil with a high conversion rate. This is because the reaction channel 010 and the mixing channel 014 are axially arranged in a tubular structure, allowing the mixed fluid to form a stable plug flow along the first direction, improving the consistency of the mixed fluid's residence time and preventing or reducing the formation of undesired products. Furthermore, the reaction channel 010 is equipped with a second mixing element 011, and the mixing channel 014 is equipped with a fluid distributor 016 and a first mixing element 015, further improving the turbulence of the mixed fluid, improving the mixing uniformity, and further preventing or reducing the formation of undesired products and improving the conversion rate of the target product. Furthermore, the resulting poly-α-olefin synthetic oil had a low kinematic viscosity and a high viscosity index.

[0198] Although the preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, the present invention is not limited thereto. Within the technical spirit of the present invention, various simple modifications may be made to the technical solutions of the present invention, including the combination of various specific technical features in any suitable manner. These simple modifications and combinations should also be considered as the content of the disclosed invention, and all belong to the protection scope of the present invention. [Brief explanation of the drawings]

[0199] [Figure 1] FIG. 1 is a schematic diagram of the apparatus of the present invention. [Figure 2] FIG. 2 is a schematic diagram of a preferred apparatus of the present invention. [Figure 3] FIG. 3 is a schematic diagram of a preferred apparatus of the present invention. [Figure 4]FIG. 4 is a schematic diagram of a preferred microchannel reactor of the present invention. [Figure 5] FIG. 5 is a cross-sectional view of a first mixing element according to an embodiment of the present invention. [Figure 6] FIG. 6 is a structural diagram of a second mixing element according to an embodiment of the present invention. [Figure 7] FIG. 7 is a structural diagram of a stack of a plurality of second mixing elements according to an embodiment of the present invention. [Figure 8] FIG. 8 is a schematic diagram of a comparative device of the present invention.

Claims

1. A poly-α-olefin production apparatus comprising a mixing unit (1), a microchannel reaction unit (2), a high-pressure separation unit (3), a low-pressure separation unit (4), a gas circulation unit (5), a post-treatment unit (6), and a pressure control unit (7), wherein the mixing unit (1), the microchannel reaction unit (2), the high-pressure separation unit (3), the low-pressure separation unit (4), and the gas circulation unit (5) are connected in series, and the microchannel reaction unit (2) is used to produce BF ３ The gas circulation unit (5) is provided with a gas inlet (01), the mixing unit (1) is provided with an auxiliary feedstock inlet (02) and an olefin feedstock inlet (03), and the BF ３ The apparatus for producing poly-α-olefins is connected to a gas inlet (01), and the low-pressure separation unit (4) is further connected to the post-treatment unit (6), and the high-pressure separation unit (3), the pressure control unit (7), and the gas circulation unit (5) are further connected in series, and the post-treatment unit (6) is one of an adsorption apparatus, an extraction apparatus, a distillation apparatus, a centrifuge apparatus, a sedimentation apparatus, an alkali washing apparatus, and a water washing apparatus.

2. The device according to claim 1, characterized in that it satisfies one or more of the following (i) to (vi): (i) The mixing unit (1) is used to uniformly mix the streams flowing therein, and the mixing unit (1) is a static mixer and / or a dynamic mixer; (ii) The microchannel reaction unit (2) contains the BF ３ BF from gas inlet (01) ３ The gas and the mixed stream of auxiliary feedstock and olefin feedstock from the mixing unit (1) are allowed to react in the microchannel therein, and the microchannel reaction unit (2) is a microchannel reactor; (iii) the high-pressure separation unit (3) allows the intermediate stream flowing therein to undergo gas-liquid separation, the separated gas phase flows into the gas circulation unit (5) via the pressure control unit (7), and the separated liquid phase flows into the low-pressure separation unit (4), and the high-pressure separation unit (3) is a high-pressure separator; (iv) the low-pressure separation unit (4) allows the intermediate stream flowing therein to undergo gas-liquid separation, the separated gas phase flows into the gas circulation unit (5), and the separated liquid phase flows into the post-treatment unit (6), and the low-pressure separation unit (4) is a low-pressure separator; (v) The gas circulation unit (5) is configured to circulate the BF ３ Recovering the gas and the recovered BF ３ The BF gas ３ and delivery of the gas to the microchannel reaction unit (2) for recycling via a gas inlet (01), wherein the gas circulation unit (5) is one or more of a compressor, a gas circulation pump, and a vacuum pump; (vi) The pressure control unit (7) controls the pressure of the microchannel reaction unit (2) and the high-pressure separation unit (3), and the pressure control unit (7) is one or more of a back pressure valve, a throttle valve, and a pressure reducing valve.

3. 2. Apparatus according to claim 1, characterized in that the post-treatment unit (6) is connected to the mixing unit (1) and is a settler or centrifuge, which allows the stream entering it to be separated into a light liquid phase and a heavy liquid phase, and returns the heavy liquid phase to the mixing unit (1) to continue the continuous reaction.

4. 2. The apparatus according to claim 1, wherein the pressure control unit (7) controls the working pressure of the microchannel reaction unit (2) to be the same as the working pressure of the high-pressure separation unit (3).

5. A gas purification unit (8) is provided between the low pressure separation unit (4) and the gas circulation unit (5), and / or a gas purification unit (8) is provided between the pressure control unit (7) and the gas circulation unit (5), and the gas purification unit (8) is configured to purify the BF flowing therein. ３ 2. Apparatus according to claim 1, which allows drying and / or purifying the gas, characterized in that the gas purification unit (8) is one or more of a gas filter, an adsorption dryer, a freeze dryer and a cyclone separator.

6. 10. The apparatus of claim 1, wherein the microchannel reaction unit (2) is a microchannel reactor or a combination of two or more microchannel reactors, the structure and parameters of the microchannel reactor are as follows: the reaction channels are 2 to 10,000 channels in parallel, the operating temperature range is -70 to 300°C, the maximum allowable reaction pressure is not more than 20 MPa, and the maximum allowable heat transfer medium pressure is not more than 10 MPa; the fluid channel volume without mixing inserts is 0.1 to 20,000 L, and the volumetric flow rate is 1 to 50,000 L / h; each reaction channel is provided with a mixing element to promote mixing of the reaction streams; and the microchannel reactor is equipped with a header pipe for introducing reaction gases and branch pipes for distributing reaction gases to each reaction channel.

7. The microchannel reactor comprises: a shell (003), wherein a feed zone (023), a mixing zone (008), a reaction zone (009), and a collection zone (024) are arranged and communicated successively along a first direction of the shell (003), the shell (003) comprising a feed pipe (002) communicating with the feed zone (023) and a discharge pipe (001) communicating with the collection zone (024), the mixing zone (008) comprising a mixing channel (014) extending along the first direction; a fluid distribution pipe (017), said fluid distribution pipe (017) extending from the exterior of said shell (003) into said mixing channel (014), said fluid distribution pipe (017) being connected to a fluid distributor (016) at an end of said mixing channel (014); Including, The feed pipe (002) is connected to the mixing unit (1) and is used to feed a mixture of olefin feedstock and auxiliary feedstock, and the fluid distribution pipe (017) is used to feed the BF ３ Connected to the gas inlet (01), BF ３ Used to introduce gas, 7. Apparatus according to claim 6, characterized in that the discharge pipe (001) is connected to the high pressure separation unit (3).

8. The device according to claim 7, characterized in that it satisfies one or more of the following (i) to (xviii): (i) the fluid distributor is at least one selected from a powder sintered body having micropores, a mesoporous foam material, a wire mesh, and a tube having microslits or micropores; (ii) the mixing zone comprises 1 to 100 mixing channels, the fluid distribution pipes including a main pipe extending from the exterior of the shell to the feed zone and branch pipes extending from the feed zone to each mixing channel and having a fluid distributor connected to an end thereof, the mixing channels having a circular cross section; (iii) a first mixing element is disposed in the mixing channel downstream of the fluid distributor; (iv) the first mixing element includes a main flow section and a branch flow section that are alternately arranged and communicate with each other along a first direction, the main flow section including a single main flow path, and the branch flow section including a plurality of branch flow paths; (v) a collection cavity communicating with the plurality of branch channels is disposed downstream of the branch section; (vi) the mixing zone includes a first heat exchange cavity within the shell, the mixing channel is disposed within the first heat exchange cavity, and the shell includes a first heat exchange medium inlet and a first heat exchange medium outlet in communication with the first heat exchange cavity; (vii) a volume ratio of the first heat exchange cavity to the mixing channel is 2 to 50; (viii) a transition zone is provided between the mixing zone and the reaction zone, the transition zone comprising a stabilization channel having a constant cross-sectional area and a diffusion channel having a gradually expanding cross-sectional area, the stabilization channel communicating with the mixing channel and the diffusion channel communicating with the reaction zone, the stabilization channel communicating with the mixing channel and the diffusion channel communicating with the reaction zone; (ix) a discharge pipe extending to the exterior of the shell is connected to the stabilization channel; (x) the diffusion channel comprises a diffusion plate having a mesh or slits; (xi) the reaction zone comprises 2 to 10,000 parallel reaction channels extending along the first direction and communicating with the mixing channel through the transition zone; (xii) the reaction channel comprises a second mixing element, the second mixing element including a base strip extending along the first direction and a tooth element connected to the base strip and extending transversely relative to the base strip; (xiii) the tooth element is at least one of triangular, arcuate, wavy, and spiral; (xiv) each reaction channel independently comprises a plurality of the second mixing elements arranged at intervals, and the tooth elements of the second mixing elements are staggered; (xv) the reaction channel has a cross section of at least one of a circle, a rectangle, and a triangle; (xvi) the reaction channel is 1 mm ２ ~150mm ２ and a length of 50 mm to 5000 mm, the shortest distance between the reaction channels is 1 mm to 50 mm, the second mixing element has a thickness of 0.1 mm to 3 mm, and the spacing between adjacent tooth elements is 1 mm to 50 mm; (xvii) the reaction zone comprises a second heat exchange cavity disposed within the shell, the reaction channel being disposed within the second heat exchange cavity, and the shell comprising a second heat exchange medium inlet and a second heat exchange medium outlet communicating with the second heat exchange cavity; (xviii) the volume ratio of the second heat exchange cavity to the reaction channel is 2-50;

9. The mixing unit (1) is BF ３ The gas inlet further includes a gas inlet for supplying the auxiliary feedstock, the olefin feedstock, and BF ３ 10. The apparatus of claim 1, wherein a mixture of gases is fed to the microchannel reaction unit.

10. The gas circulation unit (5) is the BF ３ 10. The apparatus of claim 1 further connected to a gas inlet.

11. The mixed stream obtained after mixing the olefin feedstock and auxiliary feedstock in the mixing unit and BF ３ and the gas are each independently introduced into a microchannel reaction unit, an intermediate stream formed after the polymerization reaction in the microchannel reaction unit is introduced into a high-pressure separation unit, the intermediate stream is subjected to a first gas-liquid separation in the high-pressure separation unit, the separated liquid phase is introduced into a low-pressure separation unit, the second gas-liquid separation is performed in the low-pressure separation unit, the liquid phase separated from the low-pressure separation unit is introduced into a post-treatment unit, and a polyolefin product is obtained after treatment in the post-treatment unit; ３ gas) into a gas circulation unit, ３ The gas is recovered for recycling, and the post-treatment method used in the post-treatment unit is one or more of adsorption, extraction, distillation, centrifugation, sedimentation, alkaline washing, and water washing; A method for preparing a poly-α-olefin, comprising:

12. 12. The method according to claim 11, characterized in that: (i) the olefin in the olefin feedstock is C ３ ~C ２０ α-olefins; optionally, the olefin feedstock is one or more of ５ ~C ２０ Alkanes and / or C １ ~C ２０ further comprising a mixture of oxygen-containing compounds; (ii) The auxiliary material is one or more of an alcohol having 1 to 20 carbon atoms, an ether having 1 to 20 carbon atoms, an aldehyde having 1 to 20 carbon atoms, a ketone having 1 to 20 carbon atoms, an ester having 1 to 30 carbon atoms, a carboxylic acid having 1 to 20 carbon atoms, and a phenol having 1 to 20 carbon atoms.

13. The rate of the olefin feedstock flowing into the mixing unit is 10 to 5000 L / h; the rate of the auxiliary feedstock flowing into the mixing unit is 0.01 to 1000 L / h; the rate of the BF flowing into the microchannel reaction unit is ３ The method according to claim 11, wherein the gas inflow rate of the gas is 5 to 200,000 L / h.

14. The reaction temperature in the microchannel reaction unit is 0 to 120°C; the reaction pressure in the microchannel reaction unit is 0.01 to 10 MPa; The residence time of the olefin feedstock in the microchannel reaction unit is 1 to 3600 seconds; In the microchannel reaction unit, the auxiliary feedstock: the olefin feedstock: the BF ３ The method according to claim 11, characterized in that the mass ratio of the total amount of

15. The method according to claim 11, characterized in that one or more of the following (i) to (iv) are satisfied: (i) the high-pressure separation unit is a high-pressure separator, the pressure of the high-pressure separator is 0.01 to 10 MPa; the temperature of the high-pressure separator is 0 to 120°C; and the volume of the high-pressure separator is 0.1 to 20,000 L; (ii) the low-pressure separation unit is a low-pressure separator, the pressure of the low-pressure separator is -0.1 to 1 MPa; the temperature of the low-pressure separator is 0 to 120°C; and the volume of the low-pressure separator is 0.1 to 20,000 L; (iii) recycled BF through the gas circulation unit ３ The pressure of the gas is 0.01 to 10 MPa; (iv) The pressure of the pressure control unit is 0.01 to 10 MPa.

16. The method described in claim 11, characterized in that the post-treatment method is sedimentation or centrifugation, which allows the stream flowing into the post-treatment unit to be separated into a light liquid phase and a heavy liquid phase, and the heavy liquid phase is returned to the mixing unit to continue participating in the continuous reaction.

17. A gas purification unit is provided between the low-pressure separation unit and the gas circulation unit, and / or a gas purification unit is provided between the pressure control unit and the gas circulation unit, and the gas purification unit is configured to purify the BF ３ 12. The method according to claim 11, wherein the gas is dried and / or purified, and the gas purification unit is one or more of a gas filter, an adsorption dryer, a freeze dryer, and a cyclone separator.

18. In the mixing unit, in addition to the olefin feedstock and the auxiliary feedstock, ３ The gases are further mixed and the BF ３ The method according to claim 11, characterized in that the gas velocity is between 4 and 180,000 L / h.

19. The gas phase (BF) separated from the high-pressure separation unit and the low-pressure separation unit ３ 19. The method of claim 18, wherein a gas is introduced into the mixing unit.

20. The BF in the microchannel reaction unit ３ Based on the total mass of the BF mixed in the mixing unit, ３ The BF gas flows directly into the microchannel reaction unit. ３ The mass ratio of the gas is 100-10:0-90, and the BF ３ When supplying the gas, the BF ３ 20. The method of claim 18, wherein any two of the gas, the olefin feedstock, and the auxiliary feedstock are mixed together and then mixed with the remaining one feedstock.

21. The method according to claim 11, wherein a poly-α-olefin is prepared using the apparatus according to any one of claims 1 to 10.

22. The device according to claim 8, wherein one or more of the following (i) to (ix) are satisfied: (i) the fluid distributor is a cylindrical powder sintered body having micropores; (ii) the fluid distributor has a cross-sectional area of 0.01 cm 2 to 200 cm 2 and a length of 1 mm to 2000 m; (iii) the mixing channel has a cross-sectional area of 0.05 cm 2 to 400 cm 2 and a length of 50 mm to 5000 mm; (iv) the volume ratio of the first heat exchange cavity to the reaction channel is 5 to 30; (v) the reaction zone comprises 2 to 500 parallel reaction channels extending along the first direction and communicating with the mixing channel through the transition zone; (vi) the tooth element is triangular, one side of the triangle is adjacent to the base strip, one end is connected to the base strip, and the other end is 0.01 mm to 20 mm away from the base strip; (vii) the cross-section of the reaction channel is rectangular, and the tooth element extends between opposing pairs of the rectangles; (viii) the reaction channel has a cross-sectional area of 1 mm 2 to 150 mm 2 and a length of 100 mm to 3000 mm, the shortest distance between the reaction channels is 3 mm to 30 mm, the second mixing member has a thickness of 0.2 mm to 2 mm, and the spacing between adjacent tooth elements is 1.5 mm to 20 mm; (ix) the volume ratio of the second heat exchange cavity to the mixing channel is 5-30;

23. The apparatus described in claim 9, characterized in that the mixing unit (1) further has a BF3 gas inlet, and a mixture of auxiliary raw material, olefin raw material, and BF3 gas is supplied to the microchannel reaction unit, and the mixing unit (1) includes a mixer for mixing one of the olefin raw material and the BF3 gas with the auxiliary raw material, and a mixer for further mixing the mixture with the other of the olefin raw material and the BF3 gas.

24. The method according to claim 11, wherein one or more of the following (i) to (ix) are satisfied: (i) the flow rate of the olefin raw material flowing into the mixing unit is 40 to 2500 L / h; the flow rate of the auxiliary raw material flowing into the mixing unit is 0.2 to 500 L / h; and the flow rate of the BF 3 gas flowing into the microchannel reaction unit is 100 to 50000 L / h; (ii) the reaction temperature in the microchannel reaction unit is 20 to 60°C, and the reaction pressure in the microchannel reaction unit is 0.1 to 6 MPa; (iii) the residence time of the olefin feedstock in the microchannel reaction unit is 15 to 1000 seconds; (iv) in the microchannel reaction unit, the mass ratio of the auxiliary feedstock: the olefin feedstock: the total amount of the BF 3 gas is 1:10-250:1.5-100; (v) the high-pressure separation unit is a high-pressure separator, the pressure of the high-pressure separator is 0.1 to 6 MPa, the temperature of the high-pressure separator is 20 to 60°C, and the volume of the high-pressure separator is 0.2 to 2000 L; (vi) the low-pressure separation unit is a low-pressure separator, the pressure of the low-pressure separator is -0.1 to 0.1 MPa, the temperature of the low-pressure separator is 20 to 60°C, and the volume of the low-pressure separator is 0.2 to 2000 L; (vii) the pressure of the recycled BF 3 gas passing through the gas circulation unit is 0.1-6 MPa; (viii) the pressure of the pressure control unit is 0.1 to 6 MPa; (ix) In addition to the olefin feedstock and the auxiliary feedstock, the BF 3 gas is further mixed, and the flow rate of the BF 3 gas flowing into the mixing unit is 90 to 45,000 L / h.

25. A method as described in claim 18, characterized in that, based on the total mass of the BF3 in the microchannel reaction unit, the mass ratio of the BF3 gas mixed in the mixing unit to the BF3 gas flowing directly into the microchannel reaction unit is 100-10:0-90, and when the BF3 gas is supplied to the mixing unit, the BF3 gas and the auxiliary raw material are mixed to form a complex and then mixed with the olefin raw material; or the auxiliary raw material and the olefin raw material are mixed and then mixed with the BF3 gas; or the BF3, the olefin raw material, and the auxiliary raw material are mixed simultaneously.

Images