Aggregation method and apparatus therefor

Abstract

The invention relates to an aggregation method and an apparatus therefor. A method of assembling and / or operating an apparatus 110 for performing a chemical reaction is disclosed. The apparatus 110 comprises a housing 112 in which a precursor of the reservoir 14 is disposed. A fluid (F1) may be introduced into the precursor to cause the precursor to inflate.

Description

[0001] This application is a divisional application of the invention patent application with the application date of January 31, 2020, application number 202080025757.X, and name “Polymerization method and apparatus thereof”. Technical Field

[0002] The present invention relates to chemical reactions and particularly, but not exclusively, to reactions for making polymers. Preferred embodiments relate to the assembly and / or operation of apparatus for carrying out chemical reactions, such as polymerization reactions. Preferred embodiments relate to drag reducing polymers and their use in reducing drag, such as reducing the effects of friction ("drag") experienced by liquid hydrocarbons flowing through hydrocarbon transport pipelines. Background Art

[0003] The use of polymers and / or copolymers of alpha-olefins to reduce the effects of friction ("drag") experienced by liquid hydrocarbons flowing through hydrocarbon transport pipelines is well known in the art. Reducing drag reduces the amount of energy required to achieve such flow, and therefore also reduces the costs associated with pumping. These materials, commonly referred to as drag reducing agents (DRAs), can take various forms, including certain polymers in oil-soluble suspensions, emulsions, pellets, gels, micronfine powders, and particulate slurries (e.g., containing aqueous, organic, or mixed aqueous / organic solvents). In some cases, the DRA may include a "true" solution (e.g., a dilute polymer solution product produced in a solution polymerization process) in an appropriate carrier solvent. However, particulate slurries containing ground polymers are often the cheapest form.

[0004] The polymers most commonly used to prepare DRAs are poly(alpha-olefins) with carbon chain lengths ranging from 2 to about 40. Typically, these polymers are prepared using Ziegler-Natta catalysts and often also using co-catalysts such as alkylaluminum compounds. These polymerization reactions tend to be very efficient, producing relatively high yields when carried out in batches. However, they also tend to be highly exothermic. The exotherm itself can create problems that reduce product availability if it is not effectively managed. These problems include, but are not necessarily limited to, a significant reduction in polymer molecular weight. This can significantly reduce the effectiveness of the polymer in a drag reducer formulation.

[0005] As described below, various different types of apparatus for producing polymers and / or copolymers of alpha-olefins have been described.

[0006] US5504132 and US5504131 describe the preparation and use of non-crystalline high molecular weight hydrocarbon soluble drag reducing polymers. The literature describes suitable polymerization reaction containers as polymer bottles and bags. It is said that the invention described here has been demonstrated with bottles and bags containing five to seven layers, the layers comprising impermeable polyolefins (such as polypropylene, polyethylene, polybutylene), bonding polymers and ethylene-vinyl alcohol copolymer oxygen barriers, another bonding polymer, and the outside is coated with polyethylene, polypropylene or polybutylene. The use of polyethylene terephthalate as an additional layer to increase the strength of the reactor at high temperatures is stated to be the most preferred. One disadvantage of using the bottles and bags is that the poly(alpha-olefin) polymer produced is very easy to adhere to the wall of the reactor container. As a result, the polymer container cannot be separated from the poly(alpha-olefin) polymer. Instead, the bottle or bag is ground together with the polymer when forming the drag reducing material. However, this is disadvantageous and undesirable-the material of the bottle or bag can contaminate downstream processes or products, such as in a refinery. When contamination reaches refined fuels, adverse effects such as filter plugging can occur in final fuel applications.

[0007] US7534403, US7582708, US8105547 and US8110150 describe polymerization reactors for producing drag reducing polymers. The reactors are said to solve the problem of removing heat from a DRA polymerization reactor without adding cooling additives. The solution to the problem involves using a reactor including a reservoir that incorporates an array of plates defining a heat exchanger. In one embodiment, seventeen 4-foot heat exchanger plates are spaced 4 13 / 16 inches apart. Disadvantageously, due to the size, it is difficult to achieve consistent product quality using the equipment, and it can be difficult to separate the polymer from the heat exchanger plates.

[0008] US6649670B describes a continuous polymerization and environmental grinding process for polyolefin drag reducers. In one embodiment, a continuous polymerization process is described, which includes a "form, fill and seal" packaging process. The polymerization equipment may include a continuous stirred tank reactor (CSTR), in which raw materials (such as monomers and catalysts) are continuously charged, allowing a suitable residence or residence time in the reactor system to maintain sufficient molecular weight or viscosity, and then discharged in a continuous manner into a "form, fill and seal" packaging device. The packaging device can form a bag that acts as a temporary and separated reactor container, collects it, maintains it in the presence of an inert atmosphere, and allows the reactants to polymerize to a high conversion rate.

[0009] US6906150 discloses a method for preparing a drag reducer polymer. The method includes allowing a polymerization mixture to polymerize in at least one closed reaction chamber, the reaction chamber being configured as a linear void space having a linear axis and a cross section and a first and second end, wherein the linear void space is surrounded by a chamber wall having an inner chamber surface and an outer heat exchange surface. A coolant passes over the outer heat exchange surface to remove heat from the surface. The ends of the reaction chambers are open, and substantially all of the polymer is removed from each reaction chamber with a harvesting plunger. The harvesting plunger travels along the linear axis of the void space from its first end to its second end. However, the use of a harvesting plunger is impractical because the equipment including such a plunger is expensive to manufacture, the plunger is not very effective in removing solid polymer from the reaction chamber, and in addition, cleaning the equipment to prepare for refilling the reaction chamber is time-consuming and difficult.

[0010] It is an object of the present invention to solve the problems associated with producing drag reducing polymers, which may be advantageous. Summary of the invention

[0011] According to a first aspect of the present invention, there is provided a method of assembling and / or operating an apparatus for carrying out a chemical reaction, the method comprising the following steps: (i) selecting a housing in which a precursor of the reservoir is disposed; and (ii) introducing a fluid (F1) into said precursor in said reservoir to cause the precursor to expand (eg inflate) to define an expanded reservoir for receiving a reagent to react in the device.

[0012] The housing is preferably arranged to support the precursor of the reservoir and / or the expanded reservoir. In step (i), the precursor of the reservoir is preferably substantially relaxed. Preferably, the relaxed reservoir rests on a housing surface that appropriately supports it. The surface is preferably a substantially horizontal surface, or at a height of at least 10° above the horizontal. o (For example, up to 5 o Preferably, the relaxation reservoir rests on one or more surfaces of the housing which suitably support it. The one or more surfaces are preferably substantially horizontal surfaces or surfaces which are at an angle of up to 45°, such as up to 40°, or 30° or most preferably up to 10° to the horizontal. o (For example, up to 5 o ) angle.

[0013] Preferably, the precursor of the reservoir has a length (L), and preferably in the combination described in step (i), at least 60%, at least 80% or at least 90% of the length (L) of the precursor of the reservoir is in contact with and / or supported by the shell surface.

[0014] Preferably, the shell is elongated and, in the combination described in step (i), the length (L) of the reservoir precursor extends at least 60%, at least 80% or at least 90% along the elongated extent of the shell interior region, in which the reservoir precursor is arranged.

[0015] Preferably, the housing has a volume in which the precursor of the reservoir is arranged, wherein in the combination described in step (i), the precursor of the reservoir occupies less than 70%, such as less than 55%, or less than 30% of the volume. In some embodiments, the precursor of the reservoir occupies less than 20%, suitably less than 10% or less than 5% of the volume.

[0016] In the combination described in step (i), the said precursor of the reservoir is preferably suitably fixed in position relative to the housing. It is preferably fixed in position at one end of the precursor of the reservoir, which end is preferably the open end of the precursor of the reservoir and / or the end of the precursor of the reservoir into which the fluid can be introduced, for example in step (ii) of the method.

[0017] The precursor of the reservoir is preferably not self-supporting. It is preferably relaxed unless inflated or otherwise supported by external means (such as a supporting surface of the housing).

[0018] The precursor of the reservoir preferably comprises a plastics material (eg a polymeric material), such as a plastics film material.The film material may have a thickness of at least 20 μm, suitably at least 50 μm, preferably at least 100 μm.

[0019] The thickness of the film material may be less than 2000 μm, preferably less than 1000 μm, more preferably less than 500 μm. The inner wall area of ​​the precursor of the reservoir (and / or the expanded reservoir of step (ii)) may be defined as the reservoir area arranged to contain the material (e.g. the polymer used). Suitably, at least 50%, preferably at least 75%, more preferably at least 90%, especially about 100% of the inner wall area is defined by the plastic film material having a thickness within the defined range. The thickness of the film material may be from 20 μm to 1000 μm, preferably from 50 μm to 500 μm.

[0020] The inner wall region of the precursor of the reservoir is as described preferably defined by a plastic film material, which consists of a single layer. Thus, the precursor of the reservoir preferably does not contain laminated materials and / or multilayer materials. The inner wall region of the precursor of the reservoir preferably has a substantially smooth surface.

[0021] The outer wall region of the reservoir precursor (i.e. the wall region of the reservoir precursor on the side of the membrane material opposite the inner wall region) preferably has a substantially smooth surface, as described for the inner wall region. The inner wall region and the outer wall region preferably consist of the same material and are preferably represented as opposite surfaces of the same material.

[0022] Preferably, as stated, substantially the entire said precursor of the receptacle comprises said plastics material, more preferably said plastics film material.

[0023] As stated, said precursor of the reservoir preferably comprises a plastics material, such as a plastics film material. Suitably, at least 90% by weight, preferably at least 95% by weight, more preferably 100% by weight of said precursor of the reservoir is made of said plastics material.

[0024] The plastic material is suitably strong and inert enough to withstand the polymerization reaction and does not significantly adhere to the polymer when it is formed. It is also preferably relatively cheap so that it can be discarded after use. The plastic material is preferably heat sealable. It is preferably a thermoplastic polymer. It is preferably compatible with the reagents used in the polymerization reaction and the polymer chemistry produced. The plastic material preferably comprises optionally substituted, preferably unsubstituted alkylene (e.g. ethylene) repeating units, which can be components of homopolymers or copolymers. The plastic material preferably comprises optionally substituted, preferably unsubstituted polyolefin polymers, such as polyalkylene polymers, such as polyethylene.

[0025] The precursor of the reservoir preferably comprises a first end and a second end which are spaced apart along the elongate extent of the precursor of the reservoir. The first end is preferably a closed end, and more preferably is substantially permanently closed - that is, it is preferably not openable except by, for example, destroying the precursor of the reservoir. The first end preferably comprises a sealed, for example heat-sealed, area whereby opposing walls of the precursor of the reservoir are suitably secured together, for example heat-bonded together, thereby defining a closed end.

[0026] In the context of this specification and unless the context requires otherwise, the diameter of a reservoir refers to the longest straight line from one side to the opposite side of a cross-section of the reservoir when the reservoir is in an expanded (e.g. inflated) state and / or when it is configured to define its maximum cross-sectional area.

[0027] In the case of a reservoir having a substantially symmetrical cross-sectional shape (e.g., having a substantially circular cross-sectional shape), the diameter of the reservoir refers to a straight line from one side of the reservoir through the center of the cross-section to the opposite side of the reservoir when the reservoir is in an expanded (e.g., inflated) state and / or when it is configured to define its maximum cross-sectional area.

[0028] Preferably, the precursor of the reservoir does not comprise a seam between the first and second ends, apart from any means of arranging the first end of the precursor of the reservoir to define a closed end. The precursor of the reservoir is preferably formed of lay-flat tubing. It is preferably sealed at the first end as described and suitably expanded (e.g. by opening) at the second end as described herein.

[0029] Prior to step (i), the method may include a step (i)* comprising selecting said housing and introducing said precursor of said reservoir into the housing to appropriately define the combination described in step (i).

[0030] When the precursor of the reservoir comprises first and second ends spaced apart along the elongate extent of the precursor of the reservoir and wherein the first end is suitably a closed end, the method may comprise the step of selecting the precursor of the reservoir comprising a region adjacent the expanded (or suitably flared) second end, suitably such that an opening of the reservoir at the second end (through which fluid may suitably be introduced into the precursor in step (ii) of the method) has a larger diameter than a region of the precursor inwardly of the second end.

[0031] The length of the reservoir is suitably the linear distance between the first end and the second end. Preferably, the diameter of the precursor of the reservoir is substantially constant over at least 80% (preferably at least 90% or 95%) of the distance from the first end to the second end. In a preferred embodiment, the region of the precursor of the reservoir adjacent to the second end is expanded (or suitably opened) so that the diameter of the opening of the precursor of the reservoir at the second end is greater than the diameter of the region of the precursor of the reservoir inwardly at the second end. Such an arrangement facilitates fixing and sealing the second end in place in a manner that minimizes the creation of air gaps during use.

[0032] The diameter of the precursor of the reservoir may be from 1 cm to 45 cm throughout its entire extent. When the second end is expanded as described, the maximum diameter of the expanded region may be up to 30% greater than the diameter of the reservoir upstream of the expanded region. The length of the precursor of the reservoir may be from 15 cm to 60 m.

[0033] In step (i)*, the method may comprise clamping a precursor of the reservoir in place. Suitably clamping in place such that the position of the precursor of the reservoir is fixed relative to the position of the housing. Suitably clamping in place the expanded tip of the precursor of the reservoir.

[0034] Step (ii) of the method may comprise introducing an inert fluid (F1), for example an inert gas such as nitrogen, into said precursor in said reservoir to cause said precursor in said reservoir to expand and suitably define an expanded reservoir. The volume of the expanded reservoir may be 4000cm 3 Up to 0.5 m 3 Preferably, the diameter of the expansion reservoir (suitably over at least 80% of the length of the reservoir) is less than 30 cm. It is more preferably less than 11 cm. It may be at least 5 cm or at least 7 cm. The length of the expansion reservoir is preferably 3 m to 15 m, especially 4 m to 11 m. The volume of the reservoir is preferably 4000 cm 3 Up to 0.5 m 3 , for example, 10000 cm 3 Up to 0.15 m 3 , more preferably 20000cm 3 Up to 0.12 m 3 The diameter, length and / or volume are suitably selected as described to optimize the polymerization process and / or solidification of the polymer in the reservoir. It has been found that if the diameter, length and / or volume are too large, there may be insufficient heat transfer during the polymerization process. This may mean that the degree of polymerization may vary unacceptably over the diameter and / or within the volume, which may result in the production of an inferior drag reducing polymer.

[0035] The aspect ratio of the expanded reservoir may be defined as the length of the reservoir internal volume divided by the diameter of the reservoir internal volume. The aspect ratio may be at least 10, suitably at least 20, preferably at least 30. The aspect ratio may be less than 600, preferably less than 300, more preferably less than 150. The aspect ratio is preferably from 10 to 300, more preferably from 30 to 150.

[0036] The method preferably comprises introducing said inert fluid (F1), suitably such that it purges fluid (e.g. gas such as oxygen) from the precursor in said reservoir, such that the level of oxygen in the expanded reservoir after introduction of said fluid (F1) is less than a predetermined level. Thus, initially in step (ii), said inert fluid (F1) may expel gas (e.g. oxygen) therefrom as the precursor in said reservoir expands (e.g. inflates). Thus, a portion of the fluid (F1) introduced into the precursor in said reservoir may be expelled from the precursor in said reservoir in step (ii), suitably together with entrained oxygen.

[0037] Step (ii) may comprise introducing said fluid (F1 ) via said second end of the precursor of the reservoir.

[0038] The method may comprise an optional step (iii) comprising introducing a fluid (F2) into the housing, suitably between a wall of the housing and an outer surface of the precursor of the reservoir and / or the expanded reservoir.

[0039] The fluid (F2) may be an inert fluid, for example an inert gas such as nitrogen.

[0040] Fluid (F2) is suitably arranged to inert the area around the precursor and / or expansion reservoir - that is to say to inert the area outside the volume of the precursor and / or expansion reservoir receiving fluid (F1 ) and / or reagents for a reaction in the apparatus.

[0041] Step (iii) may be performed before, simultaneously with or after step (ii).

[0042] The housing is preferably arranged to support a reservoir, the reservoir being suitably arranged within the housing.

[0043] The housing preferably comprises cooling means for cooling the reagents and polymer contained in the device when in use.

[0044] The housing preferably comprises inerting means for introducing and / or maintaining an inert atmosphere in and / or around the reservoir.

[0045] The housing is preferably elongated. The elongated housing preferably comprises a first elongated tube in which the precursor of the reservoir and / or the expansion reservoir are located. When in use (e.g., when inflated and / or when containing reagents for preparing the polymer described herein), the expansion reservoir preferably contacts the inner surface of the first elongated tube. At least 60%, at least 75%, or at least 90% of the area of ​​the outer wall area of ​​the expansion reservoir preferably contacts the inner surface. The expansion reservoir preferably has a substantially circular cross-section, such as at least 50%, at least 75%, at least 90%, or at least 95% along its length. The cross-sectional area of ​​the expansion reservoir may be substantially constant, such as at least 50%, at least 75%, at least 90%, or at least 95% along its length.

[0046] Preferably, the first elongate tube has a circular cross-section and the expansion reservoir has a circular cross-section. The ratio of the maximum diameter of the expansion reservoir divided by the diameter of the first elongate tube (suitably in the region where the first elongate tube and the reservoir are opposite each other) may be at least 0.8, preferably at least 0.9, more preferably at least 0.95. The ratio may be 1.2 or less, preferably less than 1.1, more preferably less than 1.05. Suitably, the aforementioned ratio applies along at least 50% or at least 80% of the length of the expansion reservoir. Thus, in a preferred embodiment, the ratio of the maximum diameter of the expansion reservoir (measured at any position along at least 50% or at least 80% of the length of the reservoir) divided by the inner diameter of the first elongate tube at a position opposite to the position where the diameter of the first elongate tube is measured is 0.8 to 1.2, preferably 0.95 to 1.1.

[0047] The interior surface of the first elongated tube is preferably a substantially smooth surface; and / or preferably comprises a relatively low coefficient of friction to enable the expansion reservoir to slide on the interior surface (when required to do so). The interior surface is preferably uninterrupted over a majority of its area (e.g. greater than 80% or greater than 90%). The interior surface is preferably cylindrical, preferably circularly cylindrical. The interior surface preferably has a constant cross-section along substantially its entire extent.

[0048] The first elongated tube is preferably cylindrical, such as cylindrical. The first elongated tube is preferably rigid and / or self-supporting. It can be made of metal, such as steel.

[0049] The first elongate tube may comprise a port (A) through its wall to allow fluid to flow into and / or out of the first tube in use. The elongate tube may comprise one or more such ports.

[0050] The elongate housing preferably comprises a second elongate tube, suitably coaxial with the first tube, and the first tube suitably being located within the second tube. The first and second tubes are preferably radially spaced apart so as to define an annular gap between the first and second tubes, suitably spacer means are present to maintain the gap. The annular gap preferably defines a fluid passage for a coolant fluid.

[0051] The annular gap preferably extends around substantially the entire surface area of ​​the first tube, so that in use the coolant fluid suitably contacts at least 20%, at least 50%, at least 70%, at least 80%, at least 90%, especially substantially all, of the surface area of ​​the first tube, thereby cooling the first tube (and hence the reservoir therein). The arrangement may thereby define part of a cooling device for cooling a reagent in an expansion reservoir (e.g. a reservoir containing a reagent as described herein) in use, or the cooling device.

[0052] The second tube is preferably cylindrical, such as circular cylindrical.

[0053] The second elongated tube is preferably rigid and / or self-supporting. It may be made of metal, such as steel.

[0054] The second elongate tube may comprise one or preferably a plurality of ports (e.g. port (B) and port (C)) through the wall of the second tube to allow fluid to flow into and out of the second tube (and suitably into and / or out of the annular gap) in use. The method may comprise the step of introducing a fluid (e.g. a coolant liquid, such as a mixture of ethylene glycol and water) via one or more of the ports (e.g. port (B) and / or port (C)).

[0055] The first elongate tube is preferably closed at a first end (which is suitably adjacent to a first end of the precursor and / or expansion reservoir) by a first end plate. The first end plate may include a port (e.g., port (D)) extending through the first end plate to allow fluid to flow into and out of the first and / or second tubes.

[0056] The elongate housing preferably comprises fixing means for removably fixing the precursor and / or expansion reservoir in place, suitably within the first and / or second tube as described. Thus, the housing is preferably arranged so that the elongate reservoir is suitably removed from the housing after the polymer has been produced in the elongate reservoir. In a preferred embodiment in which the housing comprises the first tube as described, the housing and / or the first tube may be arranged so that the reservoir slides out of the first tube and is thereby removed and / or detached from the first tube.

[0057] The fixing means may comprise a clamp for holding the precursor of the reservoir and / or the expansion reservoir in place. When the precursor of the reservoir comprises a second end section (which is suitably flared as described), the fixing means may hold the second end and / or an area adjacent thereto in place. The clamp may comprise a second end plate suitably arranged to be operatively connected to the first elongate tube of the elongate housing (when provided).

[0058] The second end plate may comprise one or preferably a plurality of ports (eg port (E) and port (F)) extending through the second end plate to allow fluid to flow into and out of the elongate housing and / or the precursor of the reservoir and / or the expansion reservoir in use.

[0059] Preferably, in the method, the same port (e.g. port (E)) is used at different times for both introducing fluid (F1) into the precursor of the reservoir to cause its expansion (e.g. inflation) and subsequently delivering reagents (e.g. monomers and / or catalysts) into the expanded reservoir.

[0060] When the apparatus comprises the cooling device, the apparatus may comprise a container (C1) for containing a coolant fluid, wherein the apparatus is arranged so as to convey the coolant fluid from the container (C1) to an area outside the expansion reservoir and / or outside the reservoir containing the reagent. When the apparatus comprises a first and a second tube and an annular gap as described, the apparatus is preferably arranged to convey the coolant fluid from the container (C1) into the annular gap. The coolant fluid may circulate during use. The method preferably comprises circulating a coolant fluid in the apparatus (e.g. in the annular gap), thereby cooling the reagent, e.g. a monomer and a polymer formed therefrom. In the event that it is necessary to heat the reagent in the reservoir, a heating fluid (e.g. having a temperature higher than the ambient temperature) may be used instead of the coolant fluid. In some cases, a coolant fluid may be supplied at a certain time during a polymerization reaction using the apparatus, and a heating fluid may be supplied at another time.

[0061] As an alternative to providing a second elongate tube cooperating with the first elongate tube to define an annular gap for circulating coolant fluid as described, an alternative cooling arrangement may be used. This may include a cooling assembly comprising an elongate (e.g. substantially rectangular cross-section) tube arranged to be fixed (e.g. removably fixed) adjacent to an outer surface of the first elongate tube. The cross-section is suitably configured so that its face may be in intimate thermal contact (e.g. face-to-face contact) with the first elongate tube. The coolant fluid may be circulated through the rectangular cross-section tube in use, thereby cooling the first elongate tube and hence the reservoir in thermal contact therewith.

[0062] In one embodiment, the container (C1) contains a coolant fluid for cooling the reagent and / or polymer in the expansion reservoir and / or the reservoir containing the reagent in use. The container (C1) is preferably operatively arranged, suitably via a conduit, to deliver the coolant fluid into the annular gap.

[0063] The apparatus may comprise a container (C2) for containing the monomer, wherein the apparatus is arranged so as to deliver the monomer to the reservoir. In one embodiment, the container (C2) contains the monomer for delivery to the reservoir. After step (ii), the method preferably comprises introducing one or more monomers into an expansion reservoir, suitably defining a reservoir for containing the reagent. The container (C2) is preferably operatively arranged, suitably via a conduit, so as to deliver the monomer to the reservoir.

[0064] The apparatus may comprise a container (C3) for containing a catalyst, wherein the apparatus is arranged so as to deliver the catalyst to a reservoir. In one embodiment, the container (C3) contains a catalyst for delivery to a reservoir. After step (ii), the method preferably comprises introducing the catalyst into an expansion reservoir, suitably defining a reservoir for containing a reagent. The container (C3) is preferably operatively arranged, suitably via a conduit, so as to deliver the catalyst to the reservoir.

[0065] Vessels (C2) and (C3) may be arranged to deliver monomer and catalyst respectively to a mixing zone where they contact and mix, wherein the mixing zone is upstream of said reservoir. Suitably, a conduit is operatively arranged to deliver a mixture comprising monomer and catalyst from said mixing zone to said reservoir. Thus, the method preferably comprises mixing monomer and catalyst upstream of said expansion reservoir and introducing said mixture into the expansion reservoir after step (iii).

[0066] The apparatus may comprise mixing means for mixing monomer and catalyst, and preferably said mixing means is provided upstream of said expansion reservoir.

[0067] The apparatus may comprise a container (C4) for containing an inert fluid (e.g. an inert gas, such as nitrogen), wherein the apparatus is arranged to deliver the inert fluid into the apparatus and / or into the reservoir for inerting the apparatus and / or the reservoir. In one embodiment, the container (C4) contains the inert fluid. The container (C4) is preferably operatively arranged, suitably via a conduit, to deliver the inert fluid for inerting the apparatus and / or the reservoir.

[0068] The method may comprise a step (iv) comprising introducing reagents for preparing a polymer (eg at least one monomer and at least one catalyst) into said expansion reservoir of said apparatus.

[0069] The method may include controlling conditions surrounding the expansion reservoir so as to control polymerization of the agent therein.

[0070] The method may comprise step (v) comprising operating the cooling means to cool the reagent and / or polymer in the reservoir containing the reagent during polymerisation.

[0071] The method is preferably used to carry out a polymerization reaction.

[0072] The total weight of the reagents introduced into the expansion reservoir may be at least 12 g, suitably at least 1000 g, preferably at least 10000 g, more preferably at least 20000 g, and especially at least 30000 g. The total weight may be less than 3300 kg, suitably less than 1000 kg, preferably less than 500 kg, more preferably less than 250 kg, especially less than 100 kg. The total weight of the reagents introduced into the expansion reservoir may be from 1000 g to 250 kg, preferably from 10000 g to 100 kg.

[0073] The polymer produced in the method can be any conventional or known polymer drag reducer (DRA), including but not limited to poly (alpha-olefins), polychloroprene, vinyl acetate polymers and copolymers, polyalkylene oxide (PAO) and mixtures thereof, etc. In one embodiment, the monomer can be any monomer that forms a suitable drag reducer (DRA) when polymerized. The at least one monomer can include an alpha-olefin. Preferred alpha-olefins can have a carbon chain length of 2 to 40 carbon atoms, preferably 4 to 25, and more preferably 6 to 12 carbon atoms. The at least one monomer can be selected from: 1-hexene, 1-heptene, 1-nonene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, isobutylene; alkyl acrylates; alkyl methacrylates; styrene and alkyl styrene. Copolymers of these monomers (which may include two or more different monomers) can also prepare suitable drag reducers. Preferred monomers include alpha-olefins with carbon chain lengths of 4 to 25, more preferably 6 to 12 carbon atoms. Preferred monomers are selected from the group consisting of: 1-hexene, 1-heptene, 1-nonene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, isobutylene. A particularly preferred monomer is 1-decene.

[0074] Preferred copolymer drag reducers may comprise repeating units derived from 1-decene, optionally (but preferably) in combination with repeating units from one or more other monomers. Such other monomers may be selected from 1-hexene, 1-octene and 1-dodecene, for example in a molar ratio of 1:9 to 9:1. Particularly preferred copolymer drag reducers may be prepared from a monomer mixture comprising 1-hexene and 1-decene.

[0075] Any known suitable catalyst and / or cocatalyst can be used in the process, provided that they sufficiently catalyze the reaction to a sufficient degree. Metallocenes are useful catalysts for polymerizing certain monomers. In the case of α-olefins, polymerization can be carried out by adding a mixture of a Ziegler-Natta catalyst and one or more cocatalysts to the monomers. Catalysts for the polymerization of α-olefins include, but are not necessarily limited to, powdered catalysts TiCl3.AA (aluminum activated titanium trichloride); one or more cocatalysts, diethylaluminum chloride (DEAC) and diethylaluminum ethoxide (DEALE); TEAL (triethylaluminum chloride), trimethylaluminum, triisobutylaluminum, MAO (methylaluminoxane), alkyl halides (e.g., 1,2-dichloroethane), and the like. Of course, the cocatalyst must be matched to the primary catalyst so that the catalytic activity of the primary catalyst is triggered only by the presence of a particular cocatalyst or class thereof.

[0076] After introducing the reagent into the expansion reservoir in step (iv), the method may include closing the access to the reservoir containing the reagent (e.g. sealing), optionally except for an inlet through which an inert fluid, e.g. an inert gas such as nitrogen, is introduced into the reservoir, e.g. at a relatively low pressure (e.g. about 0.5 psi). After step (iv), the method suitably includes a polymerization reaction, which may be carried out for a period of at least 10 hours, at least 1 day, at least 2 days, at least 3 days, at least 4 days or at least 5 days. The time period is suitably measured from the completion of the introduction of the reagent into the expansion reservoir (to define the reservoir containing the reagent thereby). The polymerization reaction is preferably carried out for less than 20 days. After a selected time, the polymer may be removed from the apparatus.

[0077] The method preferably comprises the step of removing the reservoir containing the polymer from the housing, suitably after step (iv). The method may comprise releasing the fixing means, such as the clamp holding the reservoir in place. Thus, preferably, after the polymer has been prepared in the reservoir containing the reagent, the reservoir containing the polymer may be withdrawn from the housing.

[0078] The method preferably comprises sliding the reservoir containing the polymer out of the housing. It may be slidable from the housing in the direction of the elongate extent of the housing. For example, when the housing comprises the first elongate tube, the reservoir may be slid on the inner surface of the first tube, thereby removing it from the first tube, suitably completely disengaging the reservoir from all other components of the device.

[0079] The process is preferably a batch process, for example producing from 12 g to 3300 kg, preferably from 20 kg to 100 kg, more preferably from 30 kg to 50 kg of polymer, for example in said precursor in said reservoir.

[0080] The method may comprise the step of removing the polymer from the reservoir in which the polymer was prepared. The method may comprise detachment, for example peeling the reservoir film from the polymer. Advantageously, this can be achieved without leaving any film derived from the reservoir on the polymer. Thus, in a preferred embodiment, at least 95% by weight, preferably at least 99% by weight, more preferably 100% by weight of the reservoir film is detached from the polymer. Thus, the polymer can be separated from the reservoir and therefore preferably comprises less than 1% by weight, more preferably less than 0.1% by weight, especially substantially 0% by weight of the film derived from the reservoir.

[0081] The method preferably comprises reusing the housing. For example, the method may comprise joining a new said reservoir precursor to said housing and repeating said steps to prepare a polymer in a new said reservoir precursor. Said new said reservoir precursor may have any of the features of said reservoir precursor mentioned above.

[0082] In embodiment (I), the method of the first aspect may include the following steps: (i) selecting a housing in which a precursor of the reservoir is disposed; and (ii) introducing a fluid (F1) into said precursor in said reservoir to cause the precursor to expand (e.g. inflate) to define an expanded reservoir for receiving a reagent to react in the device; wherein the precursor of the reservoir comprises a single layer of polyalkylene film; The polyalkylene film has a thickness of 50 µm to 500 µm (e.g., 125 µm to 500 µm); The diameter of the reservoir precursor in its expanded (e.g. inflated) state is 7 cm to 25 cm (e.g. 7 cm to 11 cm); The length of the precursor of the receptacle is between 300 cm and 1500 cm; and The reservoir precursor has an expansion region (eg, at the second end of the reservoir precursor as described herein) having a maximum diameter that is at most 30% greater than the diameter of the reservoir precursor upstream of the expansion region.

[0083] In said embodiment (I), the method may comprise introducing reagents for reaction (eg polymerisation) in the device, wherein the reagents are suitably as described herein.

[0084] According to a second aspect of the invention, there is provided an apparatus for carrying out a chemical reaction, such as a polymerisation reaction, e.g. to prepare a drag reducing polymer, the apparatus comprising a housing in which an expansion (e.g. inflation) reservoir is arranged, wherein the expansion reservoir is arranged to receive a reagent for reacting (e.g. polymerising) in the apparatus.

[0085] The expansion reservoir suitably comprises a fluid (F1 ) which is suitably contained in the expansion reservoir and / or which causes expansion (eg inflation) of the reservoir.

[0086] The apparatus may be as described in the first aspect.

[0087] The housing may be as described in the first aspect.

[0088] The expansion reservoir and the precursor of the expansion reservoir may be as described in the first aspect.

[0089] The apparatus may comprise any features of the apparatus of the first aspect and / or any features for use in the method of the first aspect.

[0090] In one embodiment, the apparatus comprises a container (C1) for containing a coolant fluid, wherein the apparatus is arranged to convey the coolant fluid from the container (C1) to an area outside the expansion reservoir. In one embodiment, the container (C1) contains a coolant fluid for cooling the reagent and / or polymer in the reservoir in use.

[0091] The apparatus may comprise a container (C2) for containing the monomer, wherein the apparatus is arranged to deliver the monomer to the reservoir. In one embodiment, the container (C2) contains the monomer for delivery to the reservoir.

[0092] The apparatus may comprise a container (C3) for containing the catalyst, wherein the apparatus is arranged for delivering the catalyst to the reservoir. In one embodiment, the container (C3) contains the catalyst for delivery to the reservoir.

[0093] Vessels (C2) and (C3) may be arranged to deliver monomer and catalyst, respectively, to a mixing zone where they contact and mix, wherein the mixing zone is upstream of the reservoir.

[0094] The apparatus may comprise mixing means for mixing the monomer and the catalyst and preferably said mixing means is provided upstream of said reservoir.

[0095] The apparatus may comprise a container (C4) for containing an inert fluid (e.g. an inert gas, such as nitrogen), wherein the apparatus is arranged to deliver the inert fluid into the apparatus and / or into the reservoir for inerting the apparatus and / or the reservoir. In one embodiment, the container (C4) contains an inert fluid.

[0096] The volume of the expansion reservoir can be 12 cm 3 Up to 4 m 3 Preferably, the diameter of the expansion reservoir (suitably over at least 80% of the length of the reservoir) is less than 30 cm. It is more preferably less than 11 cm. It may be at least 7 cm. The length of the expansion reservoir is preferably 3 m to 15 m, especially 4 m to 11 m. The volume of the reservoir is preferably 10000 cm 3Up to 0.15 m 3 , more preferably 20000 cm 3 Up to 0.12 m 3 .

[0097] Any feature of any aspect of any invention or embodiment described herein may be combined with any feature of any aspect of any other invention described herein, mutatis mutandis. BRIEF DESCRIPTION OF THE DRAWINGS

[0098] Specific embodiments of the present invention will now be described by way of example with reference to the accompanying drawings, in which: Figure 1 is a schematic diagram of an apparatus for producing a polymer; Figures 2(a) to 2(d) show in schematic cross-section the steps involved in producing a plastic reaction tube of an apparatus; 3(a) to 3(d) illustrate the steps involved in assembling the apparatus, including the plastic reaction tube; Figures 4(a) and 4(b) illustrate the steps involved in preparing the assembled apparatus of Figure 3(d) for use in a polymerization process; Figure 5 An apparatus for charging for bulk polymerization is shown; Figure 6 and 7 showing the steps of removing the plastic reaction tube from the rest of the apparatus; and Figure 8 A sealed tube containing a polymer is shown; Fig. 9 The log of polymer removed from the reaction tube is shown (log); Figure 10(a) is Figure 1 but additionally including a thermocouple for monitoring temperature during the polymerization process; Figure 10(b) is a side view of the thermocouple; FIG. 10( c ) is an end view in the direction of arrow X(c) of FIG. 10( b ); and Fig.11 is a schematic diagram of a simplified apparatus for producing polymers.

[0099] In the drawings, the same or similar components are marked with the same reference numerals. DETAILED DESCRIPTION

[0100] Reference Figure 1The apparatus 2 for carrying out a polymerization reaction involving one or more monomers and a catalyst to produce, for example, DRA comprises a rigid elongated support tube assembly 4 including a cooling jacket 6 for containing a coolant. The jacket 6 comprises a coolant inlet 8 and a coolant outlet 10. An inflatable plastic reaction tube 12 (in the support tube assembly 4) is arranged. Figure 1 ), which is adjacent to the interior wall 14 of the support tube assembly 4. An end fitting 16 at one end of the support tube assembly 4 includes a fluid port 18 through which the inert gas can leave the device. An end fitting 20 at the opposite end of the support tube assembly 4 includes fluid ports 22, 24, wherein fluids (e.g., one or more monomers and / or one or more catalysts and / or an inert gas) can be introduced into the device and / or removed from the device during operation. When the device is in use, polymer is produced in the plastic reaction tube 12 while the tube 12 is cooled by contact with the interior wall 14 of the support assembly 4 cooled by a coolant passing through the cooling jacket 6, and while a positive pressure of inert gas is maintained around the tube 12. By applying an inert gas through ports 22 and / or 24 while the polymerization process is in progress, the contents of the plastic reaction tube can be maintained under inert gas conditions. After the polymerization is completed, the end fitting 20 is removed and the plastic reaction tube 12 containing the produced polymer is withdrawn from the assembly 4. The reactor tube 12 (ie, the plastic material of which it is composed) is detached (eg, peeled) from the polymer to separate the polymer from the reactor tube. The polymer may then be comminuted and formulated for use as a drag reducing additive.

[0101] Features of the apparatus and associated methods are described in more detail below.

[0102] Figures 2(a) to (d) show the steps involved in producing the inflatable plastic reaction tube 12, which is shown in its finished state in Figure 2(d).

[0103] The reaction tube 12 is formed from a 125 μm (500 Ga.) lay-flat polyethylene tube 26, which is initially unsealed at either end. When the tube is in its flattened state shown in FIG. 2( a ), the tube has a length of approximately 600 cm plus an additional 5 cm to 10 cm (to enable it to be clamped in place as described below) and a width of approximately 153 mm ± 5 mm.

[0104] In the first step shown in Figure 2(b), a section of the tube is heat sealed, as indicated by numeral 28, thereby completely closing the end and defining a closed end of the reservoir for the polymerizable mixture.

[0105] In the second step shown in Fig. 2(c), the open end (opposite the closed end) of the tube 26 is stretched over the heated cone 30 (as indicated by reference numeral 27), thereby causing the tube to expand in the region toward its open end. As a result, the diameter of the tube 26 adjacent its open end gradually increases as it moves from region 32 (inwardly of the open end) to region 34 located at the open end.

[0106] In a third step, shown in FIG. 2( d ), the cone 30 is detached from the tube 26 , thereby leaving behind a flared open end 35 , which has been permanently deformed by heat treatment using the heated cone 30 .

[0107] The open end is flared as previously described to facilitate securing the open end within the apparatus in a manner that minimizes air gaps between the plastic reaction tube 12 and associated fittings of the apparatus. Such air can be detrimental to the polymerization process and / or reagents used therein if it becomes trapped within the folds of the plastic reaction tube 12. In addition, the flaring facilitates creating a fluid-tight seal between the plastic tube and the fittings of the apparatus.

[0108] The apparatus 2 may be assembled as described with reference to Figures 3(a) to 3(d).

[0109] 3( a ), the support tube assembly 4 includes an inner rigid tube 38 disposed in an outer rigid tube 40. A spacer (not shown) is provided between the tubes 38 , 40 to maintain a spacing therebetween, thereby defining a channel 42 (in which a cooling fluid can flow) between the tubes 38 , 40. The end of the outer rigid tube is welded to the outer surface of the inner rigid tube to close the end of the jacket assembly. The coolant inlet 8 is in communication with the channel 42 so that a cooling fluid flows into the channel 42 from the outside via the inlet 8 and flows out of the channel via the outlet 10. The cooling fluid can flow in the channel around substantially the entire tube 38 before leaving the channel via the coolant outlet 10. Thus, a cooled jacketed support tube assembly is arranged around the plastic reaction tube 12.

[0110] The inner tube 38 may suitably be made of stainless steel (e.g., SS304L) having a thickness of 0.083" (2.1 mm) and may have an outer diameter of 4" (101.6 mm). The length may be 20 ft (609.6 cm). An inlet 13 ( Figure 1 ) so that gas can be introduced into the interior of the inner tube 38 as described below.

[0111] The outer tube 40 may suitably be made of stainless steel (eg SS304L) having a thickness of 0.12" (3 mm) and may have an inner diameter of 108 mm and an outer diameter of 4.5" (114.3 mm). The length may be 19 ft 7½" (598.2 cm).

[0112] The coolant inlet 8 and outlet 10 may be made from 0.5" NPT Weldolet (trademark). Push fit adaptors may be used to allow easy connection or removal of the tubes for the coolant.

[0113] The end fitting 16 may include a suitable gasket and a sanitary stainless steel end plate having a single tapped thread for the port 18 .

[0114] At the left end of Figure 3(a), a 4" (101.6mm) Viton (trademark) tri-clamp gasket 44 and end plate 46 are shown. The end plate 46 incorporates inlet / outlet ports 22, 24 that are accessible to the end plate. Push-on adapters may be provided to allow for easy connection and removal of polyethylene (PE) tubing. The inlet / outlet 24 incorporates a ½" NPT ball valve. As described below, during the process, the inlet / outlet 24 is used in three different steps - (a) charging and inert gas purging of the reaction tube 12; (b) charging of the monomer / catalyst mixture; and (c) purging with inert gas after charging of the monomer / catalyst mixture (to clean transfer lines and provide additional inertization of the apparatus contents).

[0115] As also described below, during the process, inlet / outlet 22 can be used as an inert gas outlet during the aeration, inerting and monomer / catalyst charging of reaction tube 12; and subsequently as an inlet for inert gas (in order to maintain a small positive pressure inside reaction tube 12 during the remainder of the bulk polymerization process).

[0116] Although the apparatus is shown in the figures with the elongated axes of the tubes 38, 40 supporting the tube assembly 4 being horizontal, it is preferred that the tubes be elevated at the left end of Figures 3(a) to (d) to facilitate the flow of fluids from their introduction locations and into the reaction tube 12 defined by the tube 26; and to avoid loss of monomer / catalyst during loading via the port 22. Typically, the angle defined by the tubes 38, 40 with the horizontal plane is about 2 to 3° (or a gradient of about 1 / 20).

[0117] The reaction tube 12 made of tube 26 as described in FIG. 2( d ) is inserted into the inner tube 38 and pushed therein so that its heat-sealed end 28 is adjacent to the end fitting 16 . As shown in FIG. 3( b ), the flared open end 35 initially extends from the inner tube 38 . Next, as shown in FIG. 3( c ), the flared open end 35 is turned up over the flange 48 shown on the inner tube 38 . Subsequently, as shown in FIG. 3( d ), the gasket 44 and the end plate 46 are fixed in place, thereby holding the open end 35 securely (and sealingly) in place as shown in FIG. 3( d ). Note that in FIG. 3( d ), the sanitary fitting clamp is omitted for clarity.

[0118] As will be noted from Figure 3(d), after insertion of the tube 12 (and before its expansion), the tube is relaxed, as shown in Figure 3(d).

[0119] After the apparatus has been assembled as described with reference to Figures 3(a) to 3(d), the apparatus can be prepared for use by inflating the tube 12 and inerting any areas of the apparatus that may contact monomer / catalyst subsequently introduced into the apparatus, including indirect contact via diffusion of gas through the tube, as described with reference to Figures 4(a) and 4(b).

[0120] Referring to FIG4(a), the volume within the apparatus outside of tube 12 and within inner tube 38 is initially inerted to a specific level (e.g., less than 0.3% oxygen by volume by introducing an inert gas (e.g., nitrogen) via port inlet 13 as indicated by the arrows in FIG4(a)). The inert gas exits via port 18. The oxygen content of the gas exiting inner tube 38 can be monitored at a downstream sampling point (not shown) using standard methods.

[0121] Next, as shown in FIG4( b ), the tube 12 is charged with an inert gas (e.g., nitrogen). The inert gas is passed through the tube until the inert gas discharged through port 22 has an oxygen content (e.g., less than 0.3% by volume) measured at a downstream sampling point (not shown). The charging includes introducing the inert gas into the tube 12 through port 24.

[0122] The gas is circulated in the tube 12 to inflate it and is exhausted through port 22. During the inflation of the tube 12, the supply of inert gas through port 13 is stopped. The inflation of the tube 12 can be determined by observing the gas flow from port 18, which is caused by the displacement of the gas volume from the outside of the tube 12 due to the inflation of the tube 12. Once the inflation of the tube 12 is completed as shown in Figure 4 (b), the port 18 is temporarily closed while the inerting of the tube 12 is completed to prevent the entry of air through the port 18. Before the monomer(s) / catalyst(s) are loaded into the apparatus, the port 18 is reopened.

[0123] As an alternative to the order of steps described with reference to Figures 4(a) and 4(b), the order of the steps may be interchanged - for example, tube 12 may be inflated first and then sealed before the area outside of tube 12 is inerted, or, the steps of Figures 4(a) and 4(b) may be performed substantially simultaneously, with a slightly higher gas pressure being employed within tube 12 to maintain it in an inflated state.

[0124] After step 4(b) is completed, the apparatus is ready to be loaded with reagents and polymerized. Figure 5, by introducing the coolant into the channel 42 via the inlet 8 and removing the coolant therefrom via the outlet 10, the coolant is caused to flow in the channel 42 between the tubes 38 and 40. Next, the monomer / catalyst mixture is introduced into the gas charging tube 12 via the port 24, thereby filling the tube 12. The polymerization reaction is then allowed to proceed for an appropriate length of time (usually about 6 days). During this process, the coolant flows continuously and the temperature can be monitored. For example, some equipment may include a properly positioned thermocouple 91 (Figure 10). In addition, a relatively low pressure (about 0.5 psi) of inert gas is applied via ports 22 and 13 to ensure that the tube 12 (and its polymerized contents) remains under an inert atmosphere.

[0125] The monomer(s) / catalyst(s) mixture is suitably arranged to produce an ultra high molecular weight polymer for drag reduction.The polymer may suitably be a polymer and / or copolymer of one or more alpha-olefins.

[0126] The polymer was prepared from 1-decene monomer as described in Example 1 using the equipment.

[0127] Example 1 – Production of polymers 1-Decene monomer (31.6 kg) was purged with nitrogen for 60 minutes to remove dissolved oxygen, which would otherwise poison the catalyst used. The monomer was passed through a pre-treatment column containing 1.5 kg of a 50:50 mixture of 13X and 5Å molecular sieves, which had been pre-dried in vacuum at elevated temperature. After the pre-treatment column, the monomer was pumped into a 90-liter stirred and jacketed glass-lined reactor, which had been pre-dried and inerted to 0.3% oxygen by volume or less.

[0128] 1-Decene was cooled to 5°C and then 25 wt% diethylaluminium chloride (DEAC) (80.45 g) in heptane was transferred to a Swagelok (trademark) high pressure gas storage cylinder in a glove box. It was then added to 1-decene under an inert atmosphere to purge any remaining water or proton impurities. The mixture was then stirred in a 90 liter reactor for 20-30 minutes.

[0129] Inside the glove box, titanium trichloride aluminium activated TiCl3(AAD) (3.7888 g) was dispersed in anhydrous heptane (157.6 ml) with stirring, and anhydrous 1,2-dichloroethane (1.37 ml) and isobutylaluminoxane (IBAO) in heptane (3.5 wt% aluminum content in heptane) (41.4 ml) were added to the catalyst dispersion. The mixture was stirred and then transferred to a Swagelok high pressure gas storage tank and then transferred to a 90 liter reactor while maintaining an inert atmosphere to initiate Ziegler-Natta polymerization.

[0130] It has been found that upon mixing the monomers and catalyst, polymerization is initiated immediately and thus proceeds rapidly. Figure 5 As described, the mixture is rapidly introduced into the inflation tube 12 via port 24 using inert gas pressure.

[0131] like Figure 5 As shown in FIG. 1 , the reaction mixture was maintained in the tube 12 at a jacket temperature of 5° C. Cooling water flowed in the channel 42. After 24 hours, the fluid temperature in the channel 42 increased, and the reaction continued.

[0132] Throughout the process, both the exterior and interior of tube 12 were maintained at a nitrogen pressure of approximately 0.5 psi by introducing nitrogen through ports 13 and 22 to help limit the ingress of oxygen into the polymerizing mixture.

[0133] At the end of the aforementioned 6-day reaction time, if Figure 6 As shown, the gasket 44 and the end plate 46 are disengaged to provide access to the tube 12 containing the polymer 50. The end plate 16 can also be optionally removed to allow visual inspection of the polymer in the tube 12. Figure 7 As shown in , the tube 12 (and polymer) is then manually extracted from the inner tube 38. During the extraction process, the open end of the tube 26 is closed by a tightened cable tie 52 (or the like). The tube is then completely removed to isolate the sealed tube 12, as shown in FIG. Figure 8 As shown in FIG. 1 , the sealed tube 12 contains approximately 20 feet (610 centimeters) of polymer 50 log.

[0134] like Fig. 9As shown in FIG. 1 , the tube 12 (which is made of polyethylene as described) can be easily separated, e.g., cut and / or peeled, from the round of polymer 50, thereby producing a separate round of polymer 50 as a single piece. After removing the tube 12, there is substantially no PE residue contaminating the polymer, which can minimize contamination of the polymer and, in turn, can facilitate its downstream applications. While not wishing to be bound by any theory, the ease with which the tube can be cut from the polymer 50 may be related to the fact that the polymer has a lower density than 1-decene (density 0.74 g / cm 3 ) Higher bulk density of raw materials (about 0.85g / cm 3 ), which means that the polymer tends to shrink from the reservoir wall as it forms.

[0135] Fig. 9 The polymer 50 pellets can be processed by known methods and contacted with a carrier to produce a formulation containing DRA.

[0136] Other procedures undertaken are described in Examples 2 to 7. Examples 2 to 6 describe procedures used to evaluate the properties of polymers produced as described herein and the results of such evaluations.

[0137] Example 2 – Determine the percent polymer conversion in the polymer produced A disposable aluminum pan is weighed to four decimal places and the weight is recorded (A). A sample (2-3 grams) of the test material is placed in the pan, and the combined weight of the pan and sample is also weighed to four decimal places (B). The sample is dried in a vacuum oven (200°C, 0.04 Torr) for 1 hour, removed and reweighed. This process is repeated until a constant weight is reached (C).

[0138] The percent polymer conversion was calculated as follows: % Conversion = (C – A) / ((B - A)*D) Where D is equivalent to the percent purity of the commercial alpha-olefin monomer used / 100. For example, commercial 1-decene with a purity of 99.4% has a D = 0.994.

[0139] Example 3 – Determine the percent drag reduction of the resulting polymer Step 1 - Prepare working solution n-Hexane (~ 80 ml) was charged to a 250 ml bottle. A piece of the test polymer was sampled directly from the polymer round prepared in the bulk polymerization and accurately weighed to four decimal places (0.0150-0.0200 g). The polymer was then dissolved in n-hexane by mixing under low shear conditions for 2 days to provide solution (A).

[0140] The solution (A) was subsequently transferred to a clean pre-weighed 500 mL bottle and accurately filled with more n-hexane to provide a final polymer concentration of 100 mg / kg (100 ppm w / w). The sample was mixed manually, avoiding vigorous shaking, to provide a partially diluted solution (B).

[0141] An aliquot of solution (B) (4 g) was accurately weighed into a clean pre-weighed 1000 ml bottle and then accurately filled with more n-hexane to the target sample weight (400 g). The sample was manually mixed as above to provide a 1 mg / kg (1 ppmw / w) working solution (C).

[0142] Step 2 – Drag Reduction Test Procedure Clean, pre-weighed collection bottles (1000 mL) are used to collect liquids during the test.

[0143] The test apparatus consisted of a 2-liter pressure vessel equipped with a loading inlet for the solvent, a run off (for cleaning purposes at the end of the experiment), and a dipleg connected to a length of stainless steel tubing (7 feet long, 6.35 mm OD, 0.89 mm wall thickness) outside the vessel. The tubing was equipped with a control valve at the outlet. The pressure vessel was also equipped with an inert gas inlet, which was connected to the supply line via a precision pressure control valve. This was set to a constant pressure (2.6 psi) for all experiments.

[0144] The vessel was charged with ~400 g of the working solution (C) prepared in step 1 or untreated n-hexane (control sample), then sealed and pressurized with inert gas (2.6 psi) with the outlet control valve closed. The valve was then opened to allow liquid to purge the external tube, then closed (discarding the liquid). A pre-weighed collection bottle (1000 ml) was placed at the outlet, then the valve was reopened for 12-13 seconds to allow liquid to flow again, and the elapsed time was recorded using a stopwatch. The remaining liquid in the vessel was then discarded and the vessel was thoroughly rinsed with untreated n-hexane (for the test cycle using solution (C)).

[0145] The percentage flow improvement (%FI) and the percentage drag reduction (%DR) were calculated from the hexane blank flow rate (F0) and the treated sample (solution (C)) flow rate (Fa) as follows: F0 in grams / second = (collected weight in grams) / (valve opening time in seconds) Fa in grams / second = (collected weight in grams) / (valve opening time in seconds) Afterwards %FI = 100*(Fa – F0) / F0 %DR = [(1 + %FI) 1.9 – 1] / (1 + %FI) 1.9 .

[0146] Examples 4 to 6 – Production of polymers using different catalyst amounts Using the above equipment, three separate bulk polymerization reactions (Examples 4 to 6, respectively) were carried out with 1-decene as the monomer. The synthetic procedure was the same as described in Example 1, except that the charges of TiCl3 (AAD), 1,2-dichloroethane, isobutylaluminoxane solution, and heptane diluent were varied to provide different levels of catalyst loading (expressed as ppm w / w Ti relative to the weight of the monomer charge). After the bulk polymerization was complete, the reaction tube containing the polymer was removed according to the above procedure, and the sampled polymer was used for analysis as described in Examples 2 and 3.

[0147] For each polymer product, the percent polymer conversion was determined for 10 samples taken from different points in the polymer log. These points were chosen to provide information about the uniformity of the polymerization along both the long axis and the cross-sectional diameter of the polymer log.

[0148] For each polymer product, the percent drag reduction (%DR) was determined for four samples taken from different points in the polymer log as described in Example 3. These points were chosen to provide information about the consistency of product performance characteristics along the long axis of the polymer log.

[0149] The results of these experiments are shown in Table 1.

[0150] The results show that when bulk polymerization is performed using the apparatus, products with excellent performance characteristics are obtained. The data show that polymerization can be successfully achieved using the apparatus over a range of catalyst concentrations typical for this application. Furthermore, for each individual experiment, the data show excellent consistency in both chemical composition and performance characteristics throughout the polymerization reaction volume.

[0151] Examples 7 to 9 – Production of copolymers Using the above equipment, three separate bulk polymerization reactions (Examples 7 to 9, respectively) were carried out with a monomer mixture of 1-hexene and 1-decene. The synthetic procedure was the same as described in Example 1 (120 ppm w / w Ti relative to the monomer charge weight) except for the choice of monomers. After the bulk polymerization was complete, the reaction tube 12 containing the polymer was removed according to the above procedure, and the sampled polymer was used for analysis as described in Examples 2 and 3.

[0152] In the same manner as Examples 4 to 6, percent polymer conversion and percent drag reduction (%DR) measurements were made from various points in the polymer log and reported.

[0153] The results of these tests are shown in Table 2.

[0154] The results show that when bulk polymerization is performed using the apparatus to prepare copolymers, products with excellent performance properties are also obtained. Similar to Examples 4 to 6, the data show excellent consistency in both chemical composition and performance properties throughout the polymerization reaction volume.

[0155] An alternative simplified apparatus 110 is shown in FIG. 11. The apparatus 110 for performing a chemical reaction comprises an elongated housing 112 and a reservoir 114. The elongated housing 112 comprises a cooling device 116 and end fittings 118, 120, which comprise ports through which fluids can be introduced and / or removed. When the apparatus 110 is used, a chemical reaction product is formed in the reservoir 114. Subsequently, the reservoir 114 containing the chemical reaction product is withdrawn from the elongated housing 112.

[0156] Although only one apparatus 2, 110 is described, an assembly comprising a plurality of apparatuses 2, 110 may be provided to produce larger quantities of polymer. Such reactors may be filled sequentially or simultaneously, optionally by using a manifold system.

[0157] exist Fig.11 In another embodiment shown in , an apparatus for conducting a polymerization reaction may include a plurality of assemblies, each of which includes a reaction tube 2 in a rigid tube 38. The assemblies may be collectively surrounded by a single cooling jacket, which is arranged to cool all the reaction tubes simultaneously. For example, two or more assemblies (each including a reaction tube 2 in a rigid tube 38) may be axially aligned, and a single cooling jacket may surround the tube. In an alternative, a plurality of assemblies (each including a reaction tube 2 in a rigid tube 38) may be stacked, with a single cooling device arranged to cool a plurality of assemblies (plurality).

[0158] The invention is not limited to the details of one or more of the above described embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel step or any novel combination of steps in any method or process so disclosed.

[0159] The present application may also include the following implementation schemes.

[0160] Scheme 1. A method of assembling and / or operating an apparatus for performing a chemical reaction, the method comprising the following steps: (i) selecting a housing in which a precursor of the reservoir is disposed; and (ii) introducing a fluid (F1) into said precursor in said reservoir to cause the precursor to expand (eg inflate) to define an expanded reservoir for receiving a reagent to react in the device.

[0161] Option 2. The method according to Option 1, wherein in step (i), the precursor of the reservoir is substantially relaxed.

[0162] Option 3. A method according to Option 1 or Option 2, wherein the housing has a volume in which the precursor of the reservoir is arranged, wherein in the combination described in step (i), the precursor of the reservoir occupies less than 70%, preferably less than 5%, of the volume.

[0163] Scheme 4. The method according to any one of the preceding schemes, wherein: The housing supports the precursor of the reservoir and / or the expansion reservoir; and / or The housing is elongated and, in the combination described in step (i), the length (L) of the front body of the reservoir extends at least 60% (or at least 90%) along the elongated extent of the housing interior region in which the front body of the reservoir is arranged; and / or The housing is elongate and includes securing means for removably securing the precursor and / or expansion reservoir in position.

[0164] Aspect 5. The method according to any one of the preceding aspects, wherein in the combination described in step (i), the precursor of the reservoir is fixed in position relative to the housing.

[0165] Option 6. A method according to any one of the preceding options, wherein the precursor of the reservoir comprises a plastic material.

[0166] Option 7. A method according to Option 6, wherein the plastic material of the film comprises optionally substituted alkylene units and is preferably polyethylene.

[0167] Option 8. A method according to any of the preceding options, wherein the reservoir comprises a first end and a second end, which are spaced apart along the elongated extent of the reservoir, wherein the first end is a closed end and comprises a sealed, such as a heat-sealed area.

[0168] Option 9. A method according to any of the preceding options, wherein the length of the reservoir is the straight-line distance between its first end and the second end, wherein the diameter of the reservoir is substantially constant over at least 80% (preferably at least 90% or 95%) of the distance from the first end to the second end; and wherein the area of ​​the reservoir adjacent to the second end expands so that the diameter of the opening of the reservoir at the second end is greater than the diameter of the area of ​​the reservoir inward from the second end.

[0169] Item 10. The method of item 8 or item 9, wherein the precursor of the reservoir does not include a seam between the first end and the second end, other than any means for arranging the first end of the precursor of the reservoir to define a closed end.

[0170] Scheme 11. A method according to any one of the preceding schemes, wherein the diameter of the reservoir is 1 cm to 45 cm throughout its entire range; and / or the length of the reservoir is 3 m to 15 m (and preferably 4 m to 11 m); and / or the volume of the reservoir is 4000 cm 3 Up to 0.5 m 3 (preferably 10000 cm 3 Up to 0.15 m 3 ).

[0171] Item 12. A method according to any one of the preceding items, wherein the method comprises clamping the precursor of the reservoir in place to define the combination described in step (i).

[0172] Embodiment 13. The method according to any one of the preceding embodiments, wherein step (ii) comprises introducing an inert fluid (F1) into the precursor of the reservoir to cause the precursor of the reservoir to expand and define an expanded reservoir.

[0173] Option 14. The method according to Option 13, comprising introducing the inert fluid (F1) so that it is purged of fluid by the precursor of the reservoir, so that the level of oxygen in the expansion reservoir after the introduction of the fluid (F1) is less than a predetermined level.

[0174] Option 15. A method according to any of the preceding options, comprising step (iii), which comprises introducing a fluid (F2) into the housing, between the wall of the housing and the outer surface of the reservoir precursor and / or the expansion reservoir.

[0175] Option 16. A method according to any of the preceding options, wherein the housing includes a cooling device for cooling the reagents and polymers contained in the device in use.

[0176] Option 17. A method according to any of the preceding options, wherein the elongated shell includes a first elongated tube in which the precursor of the reservoir is located, wherein preferably after step (ii), the expanded reservoir contacts the inner surface of the first tube, wherein at least 60% of the area of ​​the outer wall area of ​​the expanded reservoir contacts the inner surface.

[0177] Option 18. A method according to Option 15, wherein the elongated shell includes a second elongated tube, which is coaxial with the first tube, and the first tube is positioned in the second tube, and the first and second tubes are radially spaced apart to define an annular gap between the first and second tubes, wherein the annular gap defines a fluid channel for a coolant fluid.

[0178] Option 19. A method according to Option 18, wherein the annular gap extends around substantially the entire first elongated tube so that in use the coolant fluid can contact at least 20% (preferably at least 70%) of the first elongated tube to cool the first elongated tube.

[0179] Option 20. A method according to Option 18 or Option 19, wherein the first and second tubes are cylindrical.

[0180] Item 21. A method according to any one of the preceding items, wherein in the method the same port is used at different times for both introducing a fluid (F1) into the precursor of the reservoir to cause its expansion and subsequently delivering a reagent into the expanded reservoir.

[0181] Option 22. A method according to any of the preceding options, wherein the equipment used in the method includes a cooling device, which includes a container (C1) for containing a coolant fluid, and the method includes conveying the coolant fluid from the container (C1) to an area outside the expansion reservoir and / or outside the reservoir containing the reagent.

[0182] Embodiment 23. The method according to any one of the preceding embodiments, wherein the apparatus comprises a container (C2) for containing monomers, and the method comprises conveying the monomers into the expansion reservoir.

[0183] Option 24. A method according to any one of the preceding options, wherein the apparatus comprises a container (C3) for containing a catalyst, wherein the method comprises conveying the catalyst into the expansion reservoir.

[0184] Embodiment 25. The method according to any of the preceding embodiments, wherein the vessels (C2) and (C3) are arranged so as to deliver the monomer and the catalyst, respectively, to a mixing zone where they contact and mix, wherein the mixing zone is upstream of the expansion reservoir.

[0185] Option 26. A method according to any of the preceding options, comprising step (iv), comprising introducing reagents for preparing a polymer into the expansion reservoir, wherein the total weight of the reagents introduced into the expansion reservoir is at least 1000 grams (and may be at least 10,000 grams; and may be less than 3,300 kilograms or less than 1,000 kilograms).

[0186] Scheme 27. A method according to any one of the preceding schemes, comprising step (iv), wherein step (iv) comprises introducing a reagent for preparing a polymer into the expansion reservoir, wherein the prepared polymer is selected from: poly(α-olefins), polychloroprene, vinyl acetate polymers and copolymers, polyalkylene oxide (PAO) and mixtures thereof.

[0187] Item 28. The method of item 27, comprising closing the passage to the reservoir containing the reagent after introducing the reagent into the expansion reservoir in step (iv).

[0188] Item 29. The method according to Item 28, comprising carrying out the reaction for a period of at least 10 hours (e.g., at least 3 days), and subsequently comprising the step of removing the reservoir containing the polymer from the housing.

[0189] Option 30. A method according to any of the preceding options, wherein a polymer is prepared in the method, and the method includes withdrawing a reservoir containing the polymer from a shell, and then joining a new reservoir precursor to the shell and producing a polymer in the new reservoir precursor.

[0190] 31. A device for performing a chemical reaction, such as a polymerization reaction, such as for producing a drag reducing polymer, the device comprising a housing in which an expansion reservoir is arranged, wherein the expansion reservoir is arranged to receive a reagent for a reaction in the device.

[0191] Option 32. An apparatus according to Option 31, wherein the expansion reservoir comprises a fluid (F1) which is contained in the expansion reservoir and / or which causes expansion; the apparatus comprises a container (C1) for containing a coolant fluid, wherein the apparatus is arranged so as to convey the coolant fluid from the container (C1) to an area outside the expansion reservoir; the apparatus comprises a container (C2) for containing a monomer, wherein the apparatus is arranged so as to convey the monomer to the expansion reservoir; wherein the apparatus comprises a container (C3) for containing a catalyst, wherein the apparatus is arranged so as to convey the catalyst to the reservoir; the apparatus comprises a mixing device for mixing the monomer and the catalyst upstream of the expansion reservoir; and the volume of the expansion reservoir is 4000cm 3 Up to 0.5m 3 (Preferably 20000cm 3 Up to 0.12m3 ）。

Claims

1. A method for assembling and / or operating an apparatus for carrying out a chemical reaction, the method comprising the following steps: (i) selecting a housing in which a precursor of the reservoir is disposed; and (ii) introducing a fluid (F1) into said precursor in said reservoir to cause the precursor to expand (eg inflate) to define an expanded reservoir for receiving a reagent to react in the device.

2. The method according to claim 1, wherein: The housing is arranged to support a front body of the reservoir; the housing is elongated and comprises a first elongated tube in which the precursor of the reservoir is located, wherein after step (ii), the expanded reservoir contacts an interior surface of the first tube, wherein at least 60% of the area of ​​the exterior wall of the expanded reservoir contacts the interior surface; wherein the elongated housing includes a second elongated tube coaxial with the first tube and the first tube is positioned within the second tube, the first and second tubes being radially spaced apart to define an annular gap between the first and second tubes, wherein the annular gap defines a fluid passage for a coolant fluid; Wherein the apparatus comprises a container (C2) containing monomer, the method comprises delivering the monomer into the expansion reservoir.

3. The method of claim 2, wherein the first and second tubes are cylindrical.

4. The method according to claim 2 or 3, wherein the monomer is selected from the group comprising: 1-hexene, 1-heptene, 1-nonene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, isobutylene; alkyl acrylates; alkyl methacrylates; styrene and alkyl styrenes.

5. The method according to any one of claims 2 to 4, wherein: The first elongate tube comprises a port (A) through its wall to allow fluid to flow into and / or out of the first tube in use; and The second elongated tube includes one or more ports.

6. A method according to any one of the preceding claims, wherein in step (i), the precursor of the reservoir is substantially relaxed and the relaxed reservoir rests on a housing surface supporting it, wherein the surface is substantially horizontal or at an angle of at most 45° to the horizontal. o angle.

7. The method according to any of the preceding claims, wherein the precursor of the reservoir has a length (L), and in the combination described in step (i), at least 90% of the length (L) of the precursor of the reservoir is supported by the housing surface.

8. A method according to any one of the preceding claims, wherein before step (i), the method comprises a step (i)* comprising selecting the housing and introducing the precursor of the reservoir into the housing to define the combination described in step (i).

9. Method according to any of the preceding claims, comprising a step (iii) comprising introducing a fluid (F2) into the housing, between the wall of the housing and the outer surface of the precursor of the reservoir and / or the expansion reservoir.

10. The method according to any one of the preceding claims, wherein the housing has a volume in which the precursor of the reservoir is arranged, wherein in the combination described in step (i), the precursor of the reservoir occupies less than 70% of the volume.

11. A method according to any preceding claim, wherein in the combination described in step (i), the precursor of the reservoir is fixed in position relative to the housing.

12. A method according to any preceding claim, wherein the precursor of the reservoir comprises polyethylene.

13. A method according to any preceding claim, wherein the reservoir comprises a first end and a second end spaced apart along the elongate extent of the reservoir, wherein the first end is a closed end and comprises a sealed region.

14. The method of claim 13, wherein the reservoir precursor does not include a seam between the first and second ends other than any means for arranging the first end of the reservoir precursor to define a closed end.

15. A method according to any one of the preceding claims, wherein the diameter of the reservoir is from 1 cm to 45 cm throughout its extent; and / or the length of the reservoir is from 3 m to 15 m; and / or the volume of the reservoir is 4000 cm 3 Up to 0.5m 3 .

16. A method according to any preceding claim, wherein the method comprises clamping a precursor of the reservoir in position to define the combination described in step (i).

17. A method according to any preceding claim, wherein step (ii) comprises introducing an inert fluid (F1 ) into the precursor of the reservoir to cause the precursor of the reservoir to expand and define an expanded reservoir.

18. A method according to any preceding claim, wherein the housing comprises cooling means for cooling reagents and polymers contained in the device in use.

19. A method according to any preceding claim, wherein the annular gap extends around substantially the entire first elongate tube such that, in use, coolant fluid may contact at least 20% of the first elongate tube to cool the first elongate tube.

20. A method according to any one of the preceding claims, wherein in the method the same port is used at different times for both introducing a fluid (F1 ) into the precursor of the reservoir to cause its expansion and subsequently delivering a reagent into the expanded reservoir.

21. A method according to any of the preceding claims, wherein the apparatus used in the method comprises a cooling device comprising a container (C1) for containing a coolant fluid, the method comprising conveying the coolant fluid from the container (C1) to a region outside the expansion reservoir and / or outside the reservoir containing the reagent.

22. The method according to any of the preceding claims, wherein the apparatus comprises a container (C3) for containing a catalyst, wherein the method comprises conveying the catalyst into the expansion reservoir.

23. A method according to any one of the preceding claims, comprising step (iv) comprising introducing into the expansion reservoir a reagent for preparing a polymer, wherein the polymer prepared is selected from the group consisting of: poly(alpha-olefins), polychloroprene, vinyl acetate polymers and copolymers, polyalkylene oxides (PAOs) and mixtures thereof.

24. A method according to claim 23, comprising closing the access to the reservoir containing the reagent after introducing the reagent into the expansion reservoir in step (iv).

25. A method according to any preceding claim, comprising carrying out the reaction for a period of at least 10 hours and subsequently comprising the step of removing the polymer containing reservoir from the housing.

26. A method according to any preceding claim, wherein a polymer is produced during the method and the method comprises withdrawing the reservoir containing the polymer from the housing.

27. Apparatus for carrying out a polymerisation reaction to produce a drag reducing polymer, the apparatus comprising a housing in which an expansion reservoir is arranged, wherein the expansion reservoir is arranged to receive a reagent for reaction in the apparatus.

28. The apparatus of claim 27, wherein the housing is elongated and comprises a first elongated tube in which the expansion reservoir is located, wherein the expansion reservoir contacts an interior surface of the first elongated tube; wherein at least 60% of the area of ​​the exterior wall region of the expansion reservoir contacts the interior surface; wherein the elongated housing includes a second elongated tube coaxial with the first tube and the first tube is positioned within the second tube, the first and second tubes being radially spaced apart to define an annular gap between the first and second tubes, wherein the annular gap defines a fluid passage for a coolant fluid; The expansion reservoir comprises a fluid (F1) which is contained in the expansion reservoir and / or which causes expansion; The device comprises a container (C1) for containing a coolant fluid, wherein the device is arranged to convey the coolant fluid from the container (C1) to a region outside the expansion reservoir; The apparatus comprises a container (C2) containing monomer, wherein the apparatus is arranged to deliver monomer into the expansion reservoir.

29. The apparatus according to claim 28, wherein the apparatus comprises a container (C3) for containing a catalyst, wherein the apparatus is arranged so as to deliver the catalyst into the reservoir; the apparatus comprises mixing means for mixing monomer and catalyst upstream of the expansion reservoir; and the volume of the expansion reservoir is 20000 cm 3 Up to 0.12m 3 .

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