2-butene hydroformylation device and method

Abstract

The invention relates to the technical field of petrochemical engineering, in particular to a 2-butene hydroformylation device and method. The invention provides a 2-butene hydroformylation device. The 2-butene hydroformylation device comprises a mixing unit, a supergravity reaction unit and a separation unit, a discharging hole of the mixing unit is connected with a feeding hole of the supergravity reaction unit; a discharging hole of the supergravity reaction unit is connected with a feeding hole of the mixing unit; a discharge port of the supergravity reaction unit is connected with a feed port of the separation unit; a liquid phase discharge port of the separation unit is connected with a feed port of the mixing unit; or the liquid phase discharge port of the separation unit is connected with the feed port of the supergravity reaction unit. According to the 2-butene hydroformylation device disclosed by the invention, the conversion rate and the reaction rate of 2-olefin are improved, and the liquid phase volume and the catalyst dosage of the reaction are reduced.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical engineering, and in particular to a 2-butene hydroformylation device and method. Background Art

[0002] The process of hydroformylating olefins, carbon monoxide and hydrogen to produce aldehydes with one more carbon atom in the presence of a catalyst is a well-known process. Catalysts used for olefin hydroformylation have undergone several generations of development, from high-pressure cobalt catalysts to cobalt-alkylphosphine catalysts, low-pressure rhodium-alkylphosphine catalysts, and rhodium-bisphosphite catalysts with higher activity.

[0003] Aldehydes can be directly hydrogenated to obtain alcohols, or they can be condensed to obtain olefinic aldehydes and then hydrogenated to obtain alcohols. One of the main uses of these alcohols is to use them as plasticizers in PVC after esterification with phthalic acid (or terephthalic acid), such as 2-ethylhexanol (dioctyl terephthalate, i.e. DOP / DOTP) and butanol (dibutyl phthalate, i.e. DBP). An important use of short-chain alcohols such as butanol is to prepare butyl acrylate, which is used commercially on a large scale as a precursor of polybutyl acrylate and is widely used in paints, sealants, coatings, adhesives, fuels, textiles, plastics and caulking agents.

[0004] The 2-propylheptanol obtained by condensing and hydrogenating valeraldehyde prepared by hydroformylation of mixed C4 has better safety performance than 2-ethylhexanol. Due to the cost advantage of mixed C4 over propylene, 2-propylheptanol is the most competitive substitute for 2-ethylhexanol in some toys, food utensils, etc. The mixed C4 raw material used for hydroformylation to prepare valeraldehyde and 2-propylheptanol is usually etherified C4 with isobutylene removed, among which the components that can be used to prepare valeraldehyde are 1-butene and cis- and trans-2-butene. Since 1-butene raw material can usually be used for purposes such as polyolefin monomers, the mixed C4 raw material used for hydroformylation is usually mainly 2-butene.

[0005] Traditional olefin hydroformylation reactors use 2 to 3 stirred tanks in series. In order to enhance the mixing effect and prevent bubbles from coalescing in the reactor, baffles are usually added to the reactor. Since the reaction rate of 2-butene is lower than that of 1-butene and propylene, a production unit of the same scale requires a larger reactor and a higher rhodium concentration. Therefore, more rhodium catalysts are often required. The initial installation of rhodium catalyst for a 60,000 to 80,000-ton 2-propylheptanol unit exceeds 100 million yuan. At the same time, the difficulty in manufacturing stirred tanks with excessively large volumes also limits the upper limit of the production capacity of a single industrial unit.

[0006] In view of this, this invention is proposed. Summary of the invention

[0007] The first object of the present invention is to provide a 2-butene hydroformylation device, which improves the conversion rate and reaction rate of 2-olefins and reduces the liquid phase volume and catalyst dosage of the reaction.

[0008] The second object of the present invention is to provide a method for hydroformylation of 2-butene, which improves the conversion rate and reaction efficiency of 2-olefins.

[0009] In order to achieve the above-mentioned purpose of the present invention, the following technical solutions are particularly adopted:

[0010] In a first aspect, the present invention provides a 2-butene hydroformylation device, comprising: a mixing unit, a supergravity reaction unit and a separation unit;

[0011] The material outlet of the mixing unit is connected to the material inlet of the supergravity reaction unit; the material outlet of the supergravity reaction unit is connected to the material inlet of the mixing unit;

[0012] The discharge port of the supergravity reaction unit is connected to the feed port of the separation unit;

[0013] The liquid phase outlet of the separation unit is connected to the feed inlet of the mixing unit; or, the liquid phase outlet of the separation unit is connected to the feed inlet of the supergravity reaction unit.

[0014] Furthermore, the mixing unit includes at least one of a stirred tank, a buffer tank and a static mixer.

[0015] Furthermore, the supergravity reaction unit includes a plurality of supergravity reactors.

[0016] Furthermore, the rotor structure of the ultra-gravity reactor includes at least one of a filler filling structure, a stator-rotor structure, a baffle structure and a double moving disk structure.

[0017] Furthermore, in the ultra-gravity reactor, the filler void ratio of the filler filling structure is 0.1 to 0.9;

[0018] And / or, in the filler filling structure, the volume of the liquid phase in the filler accounts for 0% to 100% of the total volume of the filler.

[0019] In a second aspect, the present invention further provides a method for hydroformylation of 2-butene, using the 2-butene hydroformylation device as described above, comprising the following steps:

[0020] The materials containing 2-butene and the catalyst are mixed in a mixing unit to obtain a mixture; the mixture, hydrogen and carbon monoxide react in a supergravity reaction unit to obtain a liquid product;

[0021] A portion of the liquid phase product enters a separation unit to separate the gas phase flow containing valeraldehyde and the catalyst solvent; another portion of the liquid phase product enters a mixing unit for mixing;

[0022] The catalyst solution enters a mixing unit for mixing, or the catalyst solution enters a supergravity reaction unit for reaction.

[0023] Furthermore, the catalyst comprises a rhodium catalyst and a phosphine ligand in a molar ratio of 1:(1-15), and the phosphine ligand comprises an organic phosphite and / or an organic phosphoramidite.

[0024] Furthermore, the volume ratio of the mixed material containing the catalyst to the 2-butene is (5-100):1;

[0025] And / or, the mixing time is 2 to 30 minutes.

[0026] Further, in the supergravity reaction unit, the volume ratio of the hydrogen to the carbon monoxide is 1:(0.95-1.2);

[0027] And / or, in the high gravity reaction unit, the concentration of rhodium in the liquid phase is 30 to 400 ppmwt.

[0028] Furthermore, the reaction temperature is 65-110° C., and the reaction pressure is 0.5-3 MPa.

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The 2-butene hydroformylation device provided by the present invention comprises a mixing unit, a supergravity reaction unit and a separation unit. The mixing unit and the supergravity reaction unit constitute a reaction cycle. After being fully mixed in the mixing unit, the reaction raw materials enter the supergravity reaction unit for reaction, thereby improving the reaction rate and the conversion rate of the reaction raw materials, reducing the volume of the reaction liquid phase, and reducing the amount of catalyst required for the reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required for use in the embodiments will be briefly introduced below. It should be understood that the following drawings only show certain embodiments of the present invention and therefore should not be regarded as limiting the scope. For ordinary technicians in this field, other related drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1 It is a schematic structural diagram of the 2-butene hydroformylation device of the present invention.

[0033] Figure 2It is a schematic structural diagram of another 2-butene hydroformylation device of the present invention.

[0034] Figure 3 This is a schematic diagram of the structure of the 2-butene hydroformylation device used in Example 1 of the present invention.

[0035] Figure 4 This is a schematic diagram of the structure of the 2-butene hydroformylation device used in Example 2 of the present invention.

[0036] Figure 5 This is a schematic structural diagram of the 2-butene hydroformylation device used in Comparative Example 1 of the present invention.

[0037] Reference numerals:

[0038] 1-stirring tank; 2-ultra-gravity reactor; 3-heat exchanger; 4-gas-liquid separation tank; 5-condenser; 6-product tank; 7-stirring reactor; 8-evaporator; 9-buffer tank; 101-first pipeline; 102-second pipeline; 103-third pipeline; 104-fourth pipeline; 105-fifth pipeline; 106-sixth pipeline; 107-seventh pipeline; 108-eighth pipeline. DETAILED DESCRIPTION

[0039] The technical scheme of the present invention will be clearly and completely described below in conjunction with the accompanying drawings and specific embodiments, but it will be understood by those skilled in the art that the following described embodiments are part of embodiments of the present invention, rather than all embodiments, and are only used to illustrate the present invention, and should not be considered as limiting the scope of the present invention. Based on the embodiments in the present invention, all other embodiments obtained by those of ordinary skill in the art without making creative work are within the scope of protection of the present invention. If specific conditions are not specified in the embodiments, they are carried out according to normal conditions or conditions recommended by the manufacturer. If the manufacturer is not specified in the reagents or instruments used, they are all conventional products that can be purchased commercially.

[0040] The following is a detailed description of a 2-butene hydroformylation device and method of the present invention.

[0041] In some embodiments of the present invention, a 2-butene hydroformylation device is provided, comprising: a mixing unit, a supergravity reaction unit, and a separation unit;

[0042] The material outlet of the mixing unit is connected to the material inlet of the supergravity reaction unit; the material outlet of the supergravity reaction unit is connected to the material inlet of the mixing unit;

[0043] The discharge port of the supergravity reaction unit is connected to the feed port of the separation unit;

[0044] The liquid phase outlet of the separation unit is connected to the feed port of the mixing unit; or, the liquid phase outlet of the separation unit is connected to the feed port of the supergravity reaction unit.

[0045] The 2-butene hydroformylation device provided by the present invention comprises a mixing unit, a supergravity reaction unit and a separation unit. The mixing unit and the supergravity reaction unit constitute a reaction cycle. After being fully mixed in the mixing unit, the reaction raw materials enter the supergravity reaction unit for reaction, so that the 2-butene is fully contacted with the catalyst solution before the reaction, which is conducive to the coordination between the 2-butene and the catalyst. This allows the reaction in the supergravity reactor to be fully carried out within a short residence time, thereby improving the reaction rate and the conversion rate of the reaction raw materials, reducing the volume of the reaction liquid phase, and reducing the amount of the catalyst required for the reaction.

[0046] The mixing unit of the present invention can be arranged upstream of the supergravity reaction unit, or downstream of the supergravity reaction unit.

[0047] See also Figure 1 , in some embodiments of the present invention, when the mixing unit is disposed upstream from the supergravity reaction unit, the 2-butene hydroformylation device comprises: a mixing unit, a supergravity reaction unit and a separation unit;

[0048] The material outlet of the mixing unit is connected to the material inlet of the supergravity reaction unit; the material outlet of the supergravity reaction unit is connected to the material inlet of the mixing unit;

[0049] The discharge port of the supergravity reaction unit is connected to the feed port of the separation unit; the gas phase outlet of the supergravity reaction unit is connected to the separation unit;

[0050] The liquid phase outlet of the separation unit is connected to the feed inlet of the mixing unit.

[0051] In some embodiments of the present invention, when the mixing unit is disposed upstream of the supergravity reaction unit, the 2-butene hydroformylation unit further comprises a heat exchanger, a condenser, and a product tank;

[0052] The gas phase outlet of the high gravity reaction unit is connected to the heat exchanger, and the material outlet of the high gravity reaction unit is connected to the heat exchanger; the heat exchanger is connected to the separation unit;

[0053] The separation unit, the condenser and the product tank are connected in sequence.

[0054] See also Figure 2 , In some other embodiments of the present invention, when the mixing unit is disposed downstream of the supergravity reaction unit, the 2-butene hydroformylation device comprises: a mixing unit, a supergravity reaction unit and a separation unit;

[0055] The material outlet of the mixing unit is connected to the material inlet of the supergravity reaction unit; the material outlet of the supergravity reaction unit is connected to the material inlet of the mixing unit;

[0056] The mixing unit is connected to the separation unit;

[0057] The discharge port of the supergravity reaction unit is connected to the feed port of the separation unit; the gas phase outlet of the supergravity reaction unit is connected to the separation unit;

[0058] The liquid phase discharge port of the separation unit is connected to the feed port of the supergravity reaction unit.

[0059] In some embodiments of the present invention, when the mixing unit is disposed downstream of the supergravity reaction unit, the 2-butene hydroformylation unit further comprises a heat exchanger, a condenser, and a product tank;

[0060] The mixing unit, the heat exchanger, the separation unit, the condenser and the product tank are connected in sequence; the discharge port of the supergravity reaction unit is connected to the heat exchanger, and the gas phase outlet of the supergravity reaction unit is connected to the mixing unit.

[0061] In some embodiments of the present invention, the mixing unit comprises at least one of a stirred tank, a buffer tank and a static mixer; preferably, the mixing unit comprises a stirred tank.

[0062] In some embodiments of the present invention, the supergravity reaction unit includes a plurality of supergravity reactors; the supergravity reaction unit may be one supergravity reactor or a combination of a plurality of supergravity reactors.

[0063] In some embodiments of the present invention, the rotor structure of the ultra-gravity reactor includes at least one of a filler filling structure, a stator-rotor structure, a baffle structure, and a double-moving disk structure.

[0064] The packing filling structure is that the packing is filled inside the rotor, and the rotor drives the packing to rotate and cut the fluid inside the packing.

[0065] The stator-rotor structure includes a stator and a rotor. The stator is fixed and the rotor rotates driven by the motor. The stator and rotor combination cuts and disperses the fluid.

[0066] The baffle structure includes a rotating plate and a fixed baffle. The rotating plate and the baffle are staggered up and down. The liquid phase material moves centrifugally outward under the drive of the rotating plate, and is baffled up and down through the rotor under the action of the baffle to achieve mixing, contact and reaction of multi-phase materials.

[0067] The double-moving disc structure includes two upper and lower rotors arranged crosswise, and the upper and lower rotors can rotate in the same direction or in opposite directions when driven by the motor.

[0068] In some preferred embodiments of the present invention, the ultra-gravity reactor has a filler filling structure.

[0069] In some embodiments of the present invention, the filler inside the packing filling structure includes but is not limited to structured filler or bulk filler; the structured filler is fixed inside the rotor, including but not limited to at least one of metal mesh filler, plastic mesh filler, foam metal filler and foam ceramic filler; the bulk filler is stacked in bulk inside the rotor, including but not limited to at least one of glass ball filler, ceramic ball filler, plastic ball filler, triangular spiral filler and saddle-shaped filler.

[0070] In some embodiments of the present invention, in the ultragravity reactor, the filler void ratio (porosity) of the filler filling structure is 0.1 to 0.9; typically but not limiting, for example, the filler void ratio of the filler filling structure can be 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or a range of any two thereof; preferably, the filler void ratio is 0.4 to 0.6.

[0071] In some embodiments of the present invention, in the filler filling structure, the volume of the liquid phase in the filler accounts for 0% to 100% of the total volume of the filler; typically but not limiting, for example, the volume of the liquid phase in the filler accounts for 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100% of the total volume of the filler or a range of any two thereof; preferably, in the filler filling structure, the volume of the liquid phase in the filler accounts for 5% to 30% of the total volume of the filler.

[0072] In some embodiments of the present invention, a method for hydroformylation of 2-butene is also provided, using the above-mentioned 2-butene hydroformylation device, comprising the following steps:

[0073] 2-Butene and a material containing a catalyst are mixed in a mixing unit to obtain a mixed material; the mixed material, hydrogen (H2) and carbon monoxide (CO) react in a supergravity reaction unit to obtain a liquid product;

[0074] A portion of the liquid phase product enters a separation unit to separate the gas phase stream containing valeraldehyde and the catalyst solvent; another portion of the liquid phase product enters a mixing unit for mixing;

[0075] The catalyst solution enters the mixing unit for mixing, or the catalyst solution enters the supergravity reaction unit for reaction.

[0076] The 2-butene hydroformylation device provided by the invention improves the conversion rate of 2-butene, shortens the total residence time of the reaction liquid phase in the supergravity reaction unit and the mixing unit, and improves the reaction efficiency.

[0077] The mixing of 2-butene and the catalyst may be carried out upstream of the supergravity reaction unit or downstream of the supergravity reaction unit.

[0078] In some embodiments of the present invention, the method for hydroformylation of 2-butene uses the above-mentioned 2-butene hydroformylation device (see Figure 1 ), specifically including the following steps:

[0079] 2-Butene raw material, liquid phase product and catalyst solution enter the mixing unit, and after mixing in the mixing unit, a mixture is obtained; the mixture and synthesis gas (H2 and CO) enter the high-gravity reaction unit, and the liquid phase containing 2-butene and catalyst in the high-gravity reaction unit is dispersed into tiny droplets, and the synthesis gas is a continuous phase. After full contact and reaction, tail gas and liquid phase products are obtained;

[0080] A portion of the liquid phase product enters the mixing unit for mixing;

[0081] Another part of the liquid phase product enters the separation unit for separation, and a gas phase stream containing valeraldehyde and unreacted 2-butene and a catalyst solution are obtained. The catalyst solution enters the mixing unit for mixing;

[0082] After the tail gas is discharged from the supergravity reaction unit, it can be sent to other reactors for reaction to further convert the unreacted 2-butene into valeraldehyde, or it can be sent to a separation unit together with the liquid product. In the separation unit, the unreacted 2-butene and the product valeraldehyde are vaporized and separated from the catalyst solution. The gaseous 2-butene and valeraldehyde can be further separated after condensation. The separated 2-butene can be used as a by-product, or it can be sent to other reactors for further reaction and conversion into valeraldehyde.

[0083] In some embodiments of the present invention, the method for hydroformylation of 2-butene uses the above-mentioned 2-butene hydroformylation device (see Figure 2 ), comprising the following steps:

[0084] The 2-butene raw material and the liquid phase product enter the mixing unit for mixing to obtain a mixture; the mixture, the catalyst solution and the synthesis gas (H2 and CO) enter the supergravity reaction unit for reaction to obtain tail gas and liquid phase products;

[0085] A portion of the liquid phase product enters the mixing unit for mixing;

[0086] Another part of the liquid phase product enters the separation unit for separation, and obtains a gas phase flow of valeraldehyde and unreacted 2-butene and a catalyst solution, and the catalyst solution enters the supergravity reaction unit for reaction;

[0087] After the tail gas is discharged from the supergravity reaction unit, it can be sent to other reactors for reaction to further convert the unreacted 2-butene into valeraldehyde, or it can be sent to the separation unit together with the liquid phase product (the liquid phase product of the supergravity reaction unit can be partly sent directly to the separation unit, partly sent to the mixing unit, and then returned to the feed port of the supergravity reactor; or all of it can first enter the mixing unit and then partly sent to the separation unit, and partly returned to the feed port of the supergravity reactor). In the separation unit area, the unreacted 2-butene and the product valeraldehyde are vaporized and separated from the catalyst solution. After the gas phase 2-butene and valeraldehyde are condensed, the 2-butene and valeraldehyde can be further separated. 2-butene as a by-product can also be sent to other reactors for further reaction and conversion into valeraldehyde. The liquid phase product entering the separation unit for separation can come from the mixed material of the mixing unit, or from the liquid phase product of the supergravity reaction unit.

[0088] In some embodiments of the present invention, the 2-butene is cis-2-butene and / or trans-2-butene.

[0089] In some embodiments of the present invention, the 2-butene raw material includes 2-butene; or, the 2-butene raw material includes 2-butene and inert components; the inert components include C3 to C10 alkanes; preferably, the 1-butene content in the 2-butene raw material accounts for less than 5% of the total content of butenes (1-butene and 2-butene), preferably less than 2%.

[0090] In some embodiments of the present invention, the catalyst comprises a rhodium catalyst and a phosphine ligand in a molar ratio of 1:(1 to 15), the phosphine ligand comprising an organic phosphite and / or an organic phosphoramidite; preferably, the organic phosphite comprises at least one of a monoorganophosphite, a diorganophosphite and a polyorganophosphite.

[0091] In some embodiments of the present invention, the mixing time is 2 to 30 min; typically but not limitatively, for example, the mixing time can be 2 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min or a range of any two thereof; preferably, the mixing time is 5 to 10 min; more preferably, the mixing stirring rate is 300 to 400 rpm.

[0092] In some embodiments of the present invention, the volume ratio of the mixed material containing the catalyst to 2-butene is (5-100):1; preferably (20-60):1.

[0093] In some embodiments of the present invention, in the supergravity reaction unit, the volume ratio of hydrogen to carbon monoxide is 1:(0.95-1.2).

[0094] In some embodiments of the present invention, in the high gravity reaction unit, the concentration of rhodium in the liquid phase is 30 to 400 ppmwt; typically but not limiting, for example, in the high gravity reaction unit, the concentration of rhodium in the liquid phase may be 30 ppmwt, 50 ppmwt, 100 ppmwt, 150 ppmwt, 200 ppmwt, 250 ppmwt, 300 ppmwt, 350 ppmwt, 400 ppmwt or a range of any two thereof; preferably, in the high gravity reaction unit, the concentration of rhodium in the liquid phase is 150 to 300 ppmwt.

[0095] In some embodiments of the present invention, the reaction temperature is 65-110°C, and the reaction pressure is 0.5-3MPa; typically but not limiting, for example, the reaction temperature can be 65°C, 70°C, 80°C, 90°C, 100°C, 110°C or a range consisting of any two thereof; the reaction pressure can be 0.5MPa, 1MPa, 1.5MPa, 2MPa, 3MPa or a range consisting of any two thereof; preferably, the reaction temperature is 70-85°C, and the reaction pressure is 0.8-1.5MPa.

[0096] In some embodiments of the present invention, in the supergravity reaction unit, the 2-butene feedstock and the synthesis gas are in countercurrent contact or cocurrent contact.

[0097] Example 1

[0098] See also Figure 3 The 2-butene hydroformylation device provided in this embodiment includes: a stirred tank 1, an ultra-gravity reactor 2, a heat exchanger 3, a gas-liquid separation tank 4, a condenser 5, a product tank 6, a first pipeline 101, a second pipeline 102, a third pipeline 103, a fourth pipeline 104, a fifth pipeline 105, a sixth pipeline 106, a seventh pipeline 107, an eighth pipeline 108, a first pumping component, a second pumping component and a third pumping component;

[0099] The first pipeline 101, the first pumping component, the third pipeline 103 and the feed port of the stirring tank 1 are connected in sequence;

[0100] The discharge port of the stirred tank 1, the fourth pipeline 104 and the feed port of the ultra-gravity reactor 2 are connected in sequence;

[0101] The discharge port of the ultra-gravity reactor 2, the second pumping component, the second pipeline 102 and the third pipeline 103 are connected in sequence;

[0102] The gas phase outlet of the ultra-gravity reactor 2, the fifth pipeline 105, the seventh pipeline 107 and the heat exchanger 3 are connected in sequence;

[0103] The discharge port of the ultra-gravity reactor 2, the second pumping component, the sixth pipeline 106 and the seventh pipeline 107 are connected in sequence;

[0104] The heat exchanger 3 is connected to the gas-liquid separation tank 4;

[0105] The gas phase discharge port of the gas-liquid separation tank 4, the condenser 5 and the product tank 6 are connected in sequence;

[0106] The liquid phase discharge port of the gas-liquid separation tank 4, the third pumping component, the eighth pipeline 108 and the second pipeline 102 are connected in sequence.

[0107] The method for hydroformylation of 2-butene provided in this embodiment uses the 2-butene hydroformylation device of this embodiment, and comprises the following steps:

[0108] The 2-butene feedstock (mass composition of trans-2-butene 52%, cis-2-butene 40%, 1-butene 0.5% and butane 7.5%, flow rate of 240 g / hr, density of 0.55-0.6 kg / L) from the first pipeline 101 after being pressurized by the first pumping component and the solution (mainly valeraldehyde and a small amount of butene, rhodium catalyst (metal rhodium) content of 200-220 ppmwt, phosphine ligand (CAS: 138776-88 -2) content is 1500-2000ppmwt, flow rate is 8-10L / hr; wherein, the flow rate of the catalyst solution from the eighth pipeline 108 is 300-400mL / hr, and the rest is the liquid product from the ultra-gravity reactor 2) enters the stirred tank 1 from the feed port of the stirred tank 1 through the third pipeline 103, the liquid volume in the stirred tank 1 is 1L, the stirring speed is 300-400rpm, and the residence time in the stirred tank is 5-7min to obtain a mixed material;

[0109] The mixed material flows out from the discharge port of the stirring tank 1, and enters the supergravity reactor 2 from the feed port at the top of the supergravity reactor 2 through the fourth pipeline 104. The temperature of the mixed material entering the supergravity reactor 2 can be adjusted by a sleeve-type cooling water heat exchanger installed on the pipeline (it can be installed on the second pipeline 102, the third pipeline 103 or the fourth pipeline 104). The control temperature of the mixed material at the feed port of the supergravity reactor 2 is adjusted according to the temperature of the discharge port of the supergravity reactor 2, which is generally 5 to 10°C lower than the liquid phase temperature of the discharge port of the supergravity reactor 2; the synthesis gas (H2 and CO with a volume ratio of 1:1) enters the supergravity reactor 2 from the lower part of the supergravity reactor 2 after the flow rate is measured by a flowmeter (the flow rate of the synthesis gas is regulated according to the required pressure of the supergravity reactor 2). The pressure of the supergravity reactor 2 is 1.4MPa. The liquid phase temperature of the discharge port is 75°C, and 400mL of metal wire mesh filler (porosity is 50%, liquid holding capacity during reaction is about 30% of the total volume of the filler, and the residence time of the reaction liquid in the filler is 2-4s) is filled therein, and the rotation speed is 1200-1400rpm. The mixed material is divided into tiny droplets in the high-speed rotating filler of the supergravity reactor, and the synthesis gas is fully in contact with the mixed material in the filler to react to obtain tail gas and liquid phase products; the tail gas flows into the fifth pipeline 105 from the gas phase outlet at the top of the supergravity reactor 2 after the flow rate is measured by a flowmeter; the liquid phase product flows from the discharge port of the supergravity reactor 2 through the second pumping component, part of which flows into the sixth pipeline 106 and enters the heat exchanger 3, and part of which enters the second pipeline 102, and is mixed with the catalyst solution from the eighth pipeline 108 and the 2-butene raw material and enters the stirred tank 1;

[0110] The tail gas from the fifth pipeline 105 and the liquid product from the sixth pipeline 106 enter the heat exchanger 3 through the seventh pipeline 107 and are heated to 80-95° C. The pressure in the heat exchanger 3 is 0.12 MPa, and then sent to the gas-liquid separation tank 4 for separation to obtain a gas phase stream (unreacted 2-butene raw material and product valeraldehyde) and a catalyst solution;

[0111] The gaseous logistics enters the condenser 5 and is condensed at -15°C and then sent to the product tank 6. The product tank 6 (slightly positive pressure) is maintained at -10°C by a low-temperature cold bath in the jacket, and a small amount of non-condensable gas is discharged through the pipeline; the catalyst solution enters the stirring tank through the third pumping component, the eighth pipeline 108, the second pipeline 102 and the third pipeline 103 in sequence.

[0112] Example 2

[0113] See also Figure 4The 2-butene hydroformylation device provided in this embodiment includes: a buffer tank 9, an ultra-gravity reactor 2, a heat exchanger 3, a gas-liquid separation tank 4, a condenser 5, a product tank 6, a first pipeline 101, a second pipeline 102, a third pipeline 103, a fourth pipeline 104, a fifth pipeline 105, a sixth pipeline 106, a seventh pipeline 107, a first pumping component, a second pumping component and a third pumping component;

[0114] The first pipeline 101, the first pumping component, the third pipeline 103 and the feed port of the buffer tank 9 are connected in sequence;

[0115] The discharge port of the buffer tank 9, the second pumping component, the fourth pipeline 104, the fifth pipeline 105 and the feed port of the ultra-gravity reactor 2 are connected in sequence;

[0116] The discharge port of the ultra-gravity reactor 2, the second pipeline 102 and the third pipeline 103 are connected in sequence;

[0117] The gas phase outlet of the supergravity reactor 2 is connected to the buffer tank 9;

[0118] The discharge port of the ultra-gravity reactor 2 is connected to the heat exchanger 3;

[0119] The discharge port of the stirring tank 1, the second pumping component, the seventh pipeline 107 and the heat exchanger 3 are connected in sequence;

[0120] The heat exchanger 3 is connected to the gas-liquid separation tank 4;

[0121] The gas phase discharge port of the gas-liquid separation tank 4, the condenser 5 and the product tank 6 are connected in sequence;

[0122] The liquid phase discharge port of the gas-liquid separation tank 4, the third pumping component, the sixth pipeline 106 and the fifth pipeline 105 are connected in sequence.

[0123] The method for hydroformylation of 2-butene provided in this embodiment uses the 2-butene hydroformylation device of this embodiment, and comprises the following steps:

[0124] The 2-butene raw material (mass composition of trans-2-butene 99.5% and butane 0.5%, flow rate of 240 g / hr, density of 0.5-0.6 kg / L) from the first pipeline 101 after being pressurized by the first pumping component and the liquid product from the second pipeline 102 (mainly valeraldehyde and a small amount of butene, rhodium catalyst (metal rhodium) content of 200-220 ppmwt, phosphine ligand (CAS: 138776-88-2) content of 1500-2000 ppmwt, flow rate of 15-16 L / hr, wherein the flow rate of the catalyst solution from the sixth pipeline 106 is 300-400 mL / hr) enter the buffer tank 9 from the feed port of the buffer tank 9 through the third pipeline 103, the liquid phase volume in the buffer tank 9 is 1.6 L, and the residence time of the liquid phase feed in the buffer tank 9 is 6 min, to obtain a mixed material;

[0125] The mixed material flows from the discharge port of the buffer tank 9 into the fourth pipeline 104 through the second pumping component (the seventh pipeline 107 is closed at this time), and the mixed material from the fourth pipeline 104 and the catalyst solution from the sixth pipeline 106 enter the supergravity reactor 2 from the feed port at the top of the supergravity reactor 2 through the fifth pipeline 105; the temperature of the mixed material entering the supergravity reactor 2 can be adjusted by a sleeve-type cooling water heat exchanger installed on the pipeline (it can be installed on the fourth pipeline 104 or the fifth pipeline 105), and the control temperature of the mixed material at the feed port of the supergravity reactor 2 is adjusted according to the temperature of the discharge port of the supergravity reactor 2, which is generally 5 to 10°C lower than the liquid phase temperature at the discharge port of the supergravity reactor 2; the synthesis gas (H2 and CO in a volume ratio of 1:1) enters the ultra-gravity reactor 2 from the lower part of the ultra-gravity reactor 2 after the flow rate is measured by a flow meter (the flow rate of the synthesis gas is regulated according to the required pressure of the ultra-gravity reactor 2); the pressure of the ultra-gravity reactor 2 is 0.8MPa, the liquid phase temperature at the discharge port is 72°C, and 400mL of foam metal filler (porosity is 50%, the liquid holding capacity during the reaction is 30% of the total volume of the filler, and the residence time of the reaction liquid in the filler is 2-4s) is filled therein, the rotation speed is 1200-1400rpm, and the mixture is divided into tiny droplets in the high-speed rotating filler of the ultra-gravity reactor, and the synthesis gas is fully in contact with the mixture in the filler, reacts, and obtains tail gas and liquid products;

[0126] The tail gas enters the buffer tank 9 from the gas phase outlet at the top of the high gravity reactor 2, and the gas phase in the buffer tank 9 is discharged after being measured by a flow meter; most of the liquid phase products enter the second pipeline 102 from the discharge port of the high gravity reactor 2, and a small part of the liquid phase products enter the heat exchanger 3 for heating and evaporation (the liquid phase products entering the heat exchanger 3 are measured by the flow meter between the high gravity reactor 2 and the heat exchanger 3, and the flow rate is controlled by the regulating valve in association with the liquid level of the liquid column at the bottom of the high gravity reactor 2), the heat exchanger 3 is heated to 80-95°C, the pressure in the heat exchanger 3 is 0.12MPa, and then sent to the gas-liquid separation tank 4 for separation to obtain a gas phase logistics (unreacted 2-butene raw material and product valeraldehyde) and a catalyst solution;

[0127] The gaseous logistics enters the condenser 5 and is condensed at -15°C and then sent to the product tank 6. The product tank 6 (slightly positive pressure) is maintained at -10°C by a low-temperature cold bath in the jacket, and a small amount of non-condensable gas is discharged; the catalyst solution enters the ultragravity reactor 2 through the third pumping component, the sixth pipeline 106 and the fifth pipeline 105 in turn.

[0128] Example 3

[0129] The method for hydroformylation of 2-butene provided in this embodiment uses the 2-butene hydroformylation device of Example 2, and comprises the following steps:

[0130] The 2-butene raw material (mass composition of trans-2-butene 52%, cis-2-butene 40%, 1-butene 0.5% and butane 7.5%, flow rate of 240 g / hr, density of 0.55-0.6 kg / L) from the first pipeline 101 after being pressurized by the first pumping component and the liquid phase product (mainly valeraldehyde and a small amount of butene, rhodium catalyst (metal rhodium) content of 200-220 ppmwt, phosphine ligand (CAS: 71941-89-4) content of 700-1000 ppmwt, flow rate of 15-16 L / hr, wherein the flow rate of the catalyst solution from the sixth pipeline 106 is 300-400 mL / hr) from the feed port of the buffer tank 9 through the third pipeline 103, the liquid phase volume in the buffer tank 9 is 1.6 L, and the residence time in the buffer tank 9 is 6 min, to obtain a mixed material;

[0131] Most of the mixed material flows from the discharge port of the stirred tank 1 into the fourth pipeline 104 through the second pumping component, and a small part of the mixed material flows into the seventh pipeline 107 and enters the heat exchanger 3; the mixed material from the fourth pipeline 104 and the catalyst solution from the sixth pipeline 106 enter the supergravity reactor 2 from the feed port at the top of the supergravity reactor 2 through the fifth pipeline 105; the temperature of the mixed material entering the supergravity reactor 2 can be adjusted by a sleeve-type cooling water heat exchanger installed on the pipeline (it can be installed on the fourth pipeline 104 or the fifth pipeline 105), and the control temperature of the mixed material at the feed port of the supergravity reactor 2 is adjusted according to the temperature of the discharge port of the supergravity reactor 2, which is generally higher than that of the supergravity reactor 2. The liquid phase temperature at the discharge port of reactor 2 is 5-10°C lower; the synthesis gas (H2 and CO in a volume ratio of 1:1) enters the supergravity reactor 2 from the lower part of the supergravity reactor 2 after the flow rate is measured by a flow meter (the flow rate of the synthesis gas is regulated according to the required pressure of the supergravity reactor 2); the pressure of the supergravity reactor 2 is 2.0MPa, the liquid phase temperature at the discharge port is 85°C, the internal structure is a stator-rotor structure (the residence time of the reaction liquid in the rotor is 3-5s), the rotation speed is 1200-1400rpm, the mixture is divided into tiny droplets in the high-speed rotating turntable of the supergravity reactor, the synthesis gas and the mixture are fully contacted in the turntable, react, and obtain tail gas and liquid products;

[0132] The tail gas enters the buffer tank 9 from the gas phase outlet of the high gravity reactor 2 through the connecting pipe, and the gas phase in the buffer tank 9 is discharged after being measured by the flow meter; all the liquid phase products are mixed with the 2-butene raw material through the second pipeline 102 and enter the buffer tank 9, and the residence time in the buffer tank 9 is 6 minutes;

[0133] The mixed material from the seventh pipeline 107 is heated to 80-95° C. in the heat exchanger 3, and the pressure in the heat exchanger 3 is 0.12 MPa, and then sent to the gas-liquid separation tank 4 for separation to obtain a gas phase stream (unreacted 2-butene raw material and product valeraldehyde) and a catalyst solution;

[0134] The gaseous logistics enters the condenser 5 and is condensed at -15°C and then sent to the product tank 6. The product tank 6 (slightly positive pressure) is maintained at -10°C by a low-temperature cold bath in the jacket, and a small amount of non-condensable gas is discharged; the catalyst solution enters the ultragravity reactor 2 through the third pumping component, the sixth pipeline 106 and the fifth pipeline 105 in turn.

[0135] Comparative Example 1

[0136] See also Figure 5 The 2-butene hydroformylation device provided in this comparative example includes: a stirred reactor 7, an evaporator 8, a gas-liquid separation tank 4, a condenser 5, a product tank 6, a first pipeline 101, a second pipeline 102, a third pipeline 103, a fourth pipeline 104, a fifth pipeline 105, a sixth pipeline 106, a first pumping component, a second pumping component and a third pumping component;

[0137] The first pipeline 101, the first pumping component, the third pipeline 103 and the feed port of the stirring reactor 7 are connected in sequence;

[0138] The discharge port of the stirring reactor 7, the second pumping component, the fourth pipeline 104 and the second pipeline 102 are connected;

[0139] The discharge port of the stirring reactor 7, the second pumping component, the fifth pipeline 105 and the evaporator 8 are connected;

[0140] The evaporator 8 is connected to the gas-liquid separation tank 4;

[0141] The gas phase discharge port of the gas-liquid separation tank 4, the condenser 5 and the product tank 6 are connected in sequence;

[0142] The liquid phase discharge port of the gas-liquid separation tank 4, the third pumping component, the sixth pipeline 106 and the second pipeline 102 are connected in sequence.

[0143] The method for hydroformylation of 2-butene provided in this comparative example uses the 2-butene hydroformylation device of this comparative example, comprising the following steps:

[0144] The 2-butene raw material (composition and flow rate are the same as those in Example 1) from the first pipeline 101 after being pressurized by the first pumping component and the solution from the second pipeline 102 (mainly valeraldehyde and a small amount of butene, the rhodium catalyst (metal rhodium) content is 200-220ppmwt, the phosphine ligand (CAS: 138776-88-2) content is 1500-2000ppmwt, the flow rate is 8-10L / hr, wherein the flow rate of the catalyst solution from the sixth pipeline 106 is 300-400mL / hr, and the rest is the liquid phase product from the stirred reactor 7) enters the stirred reactor 7 from the reactor bottom pipe through the third pipeline 103; the synthesis gas (H2 and CO in a volume ratio of 1:1) enters the stirred reactor 7 from the gas distributor at the bottom of the stirred reactor 7 after the flow rate is adjusted by the flow meter according to the required flow rate. The volume of the stirred reactor 7 is 3L, the operating liquid level in the stirred reactor is 80%, the temperature is 75°C, and the pressure is 1.4MPa. After the reaction, a liquid phase product is obtained;

[0145] Most of the liquid products pass through the second pumping component and the fourth pipeline 104 in sequence and then enter the second pipeline 102; a small part of the liquid products pass through the second pumping component and the fifth pipeline 105 in sequence and enter the evaporator 8 for evaporation, the temperature of the evaporator is 80-95°C, and the pressure is 0.12MPa, and then enter the gas-liquid separation tank 4 for separation to obtain a gas stream (unreacted 2-butene raw material and product valeraldehyde) and a catalyst solution; the gas stream enters the condenser 5 and is condensed at -15°C and then sent to the product tank 6, the product tank 6 (slightly positive pressure) is maintained at -10°C by a low-temperature cold bath in the jacket, and a small amount of non-condensable gas is discharged; the catalyst solution flows into the second pipeline 102 in sequence through the third pumping component and the sixth pipeline 106; the type, concentration and flow rate of the rhodium catalyst and the phosphine ligand in the catalyst solution are the same as those in Example 1.

[0146] Comparative Example 2

[0147] The method for hydroformylation of 2-butene provided in this comparative example refers to comparative example 1, except that the composition and flow rate of the 2-butene raw material are the same as those in Example 2; the temperature of the stirred reactor is 72°C, the operating liquid level is 80%, and the pressure is 0.8MPa; the temperature of the evaporator is 80-95°C, and the pressure is 0.12MPa.

[0148] Comparative Example 3

[0149] The method for hydroformylation of 2-butene provided in this comparative example refers to comparative example 1, except that the 2-butene raw material combination and flow rate are the same as those in Example 3; the temperature of the stirred reactor is 85°C, the operating liquid level is 80%, and the pressure is 2MPa; the temperature of the evaporator is 80-95°C, and the pressure is 0.12MPa.

[0150] Comparative Example 4

[0151] The method for hydroformylation of 2-butene provided in this comparative example refers to Example 1, except that the stirred tank 1 is bypassed, and the 2-butene raw material and the solution from the second pipeline 102 (the flow rate is the same as in Example 1, and the rhodium catalyst and the ligand organophosphine catalyst are the same as in Example 1) are not passed through the stirred tank 1, and directly enter the high-gravity reactor from the feed port at the top of the high-gravity reactor.

[0152] Comparative Example 5

[0153] The method for hydroformylation of 2-butene provided in this comparative example refers to Example 1, except that the liquid phase volume of stirred tank 1 is 0.25 L, and the residence time of the 2-butene raw material and the solution from the second pipeline 102 (the flow rate is the same as that in Example 1, and the rhodium catalyst and the ligand organophosphine catalyst are the same as those in Example 1) in stirred tank 1 is 1.5 to 1.8 min.

[0154] Comparative Example 6

[0155] The method for hydroformylation of 2-butene provided in this comparative example refers to Example 1, except that the liquid phase volume of stirred tank 1 is 5.1 L, and the residence time of the 2-butene raw material and the solution from the second pipeline 102 (the flow rate is the same as that in Example 1, and the rhodium catalyst and the ligand organophosphine catalyst are the same as those in Example 1) in stirred tank 1 is 31 to 38 min.

[0156] Comparative Example 7

[0157] The method for hydroformylation of 2-butene provided in this comparative example refers to Example 1, except that the volume flow rate of the solution from 102 (the rhodium catalyst and the ligand organophosphine catalyst are the same as in Example 1) is 2.0 L / h, the volume ratio of the 2-butene raw material to the solution from the second pipeline 102 is 1:4.8, and the residence time in the stirred tank 1 is 25 min.

[0158] Test example

[0159] The 2-butene single-pass conversion, valeraldehyde yield, valeraldehyde normal-to-iso ratio and liquid phase volume of the 2-butene hydroformylation methods of Examples 1 to 3 and Comparative Examples 1 to 7 are shown in Table 1.

[0160] The product valeraldehyde yield and the ratio of normal valeraldehyde to 2-methylbutyraldehyde (valeraldehyde normal-to-iso ratio) were obtained by weighing the product in the product tank, combined with the tail gas flow rate and analysis results.

[0161] In Table 1, the liquid phase volume of the reaction unit and the mixing unit of Examples 1 to 3 and Comparative Examples 5 to 7 is the total volume of the liquid phase in the stirred tank / buffer tank and the high gravity reactor;

[0162] The liquid phase volumes of the reaction units and mixing units of Comparative Examples 1 to 3 are the liquid phase volumes in the stirred reactor.

[0163] The liquid phase volumes of the reaction unit and the mixing unit of Comparative Example 4 are the liquid phase volumes in the supergravity reactor.

[0164] Table 1

[0165]

[0166]

[0167] From the comparison between Comparative Example 4 and Example 1, it can be seen that under the same reaction conditions, when 2-butene is mixed with the catalyst solution and directly enters the supergravity reactor without being fully mixed, its conversion rate is low, while after mixing in the stirred tank, the conversion rate of 2-butene is significantly improved; although the embodiment adds an additional small-volume stirred tank, the overall liquid phase volume is still significantly reduced compared with the traditional stirred reactor in Comparative Examples 1 to 3, that is, the method of the present invention can improve the conversion rate of the 2-butene hydroformylation reaction while reducing the liquid phase volume of the reaction system, which means that the amount of precious metal rhodium can be reduced accordingly.

[0168] Comparison of Example 1 with Comparative Examples 5 and 6 shows that the mixing time of the 2-butene raw material and the catalyst solution is a relatively important parameter. When the mixing time is less than 2 minutes, the 2-butene cannot fully contact with the catalyst, which will lead to a decrease in the reaction conversion rate. Excessively long mixing time does not increase the conversion rate of 2-butene, but instead leads to a larger volume of the liquid phase retained in the reaction unit and the mixing unit, thereby increasing the occupancy of the precious metal rhodium catalyst.

[0169] Comparison between Example 1 and Comparative Example 7 shows that the volume ratio of the catalyst solution to the 2-butene feedstock is a relatively important parameter. When the volume ratio is less than 5, 2-butene cannot be well dispersed in the supergravity reactor, which will lead to a decrease in the 2-butene conversion rate.

[0170] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A 2-butene hydroformylation device, characterized in that: include: mixing unit, high gravity reaction unit and separation unit; The material outlet of the mixing unit is connected to the material inlet of the supergravity reaction unit; the material outlet of the supergravity reaction unit is connected to the material inlet of the mixing unit; The discharge port of the supergravity reaction unit is connected to the feed port of the separation unit; The liquid phase outlet of the separation unit is connected to the feed inlet of the mixing unit; or, the liquid phase outlet of the separation unit is connected to the feed inlet of the supergravity reaction unit.

2. The 2-butene hydroformylation device according to claim 1, characterized in that: The mixing unit includes at least one of a stirred tank, a buffer tank and a static mixer.

3. The 2-butene hydroformylation device according to claim 1, characterized in that: The supergravity reaction unit includes a plurality of supergravity reactors.

4. The 2-butene hydroformylation device according to claim 3, characterized in that: The rotor structure of the ultra-gravity reactor includes at least one of a filler filling structure, a stator-rotor structure, a baffle structure and a double-moving disk structure.

5. The 2-butene hydroformylation device according to claim 4, characterized in that: In the ultra-gravity reactor, the filler void ratio of the filler filling structure is 0.1 to 0.9; And / or, in the filler filling structure, the volume of the liquid phase in the filler accounts for 0% to 100% of the total volume of the filler.

6. A method for hydroformylation of 2-butene, characterized in that: The 2-butene hydroformylation device according to any one of claims 1 to 5 comprises the following steps: 2-Butene and a material containing a catalyst are mixed in a mixing unit to obtain a mixture; the mixture, hydrogen and carbon monoxide react in a supergravity reaction unit to obtain a liquid product; A portion of the liquid phase product enters a separation unit to separate the gas phase flow containing valeraldehyde and the catalyst solvent; another portion of the liquid phase product enters a mixing unit for mixing; The catalyst solution enters a mixing unit for mixing, or the catalyst solution enters a supergravity reaction unit for reaction.

7. The method for hydroformylation of 2-butene according to claim 6, characterized in that: The catalyst comprises a rhodium catalyst and a phosphine ligand in a molar ratio of 1:(1-15), and the phosphine ligand comprises an organic phosphite and / or an organic phosphoramidite.

8. The method for hydroformylation of 2-butene according to claim 6, characterized in that: The volume ratio of the catalyst-containing material to the 2-butene to be mixed is (5-100):1; And / or, the mixing time is 2 to 30 minutes.

9. The method for hydroformylation of 2-butene according to claim 6, characterized in that: In the supergravity reaction unit, the volume ratio of the hydrogen to the carbon monoxide is 1:(0.95-1.2); And / or, in the high gravity reaction unit, the concentration of rhodium in the liquid phase is 30 to 400 ppmwt.

10. The method for hydroformylation of 2-butene according to claim 6, characterized in that: The reaction temperature is 65-110° C., and the reaction pressure is 0.5-3 MPa.

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