CN110759801B - Method for producing diisobutylene by mixing C4 - Google Patents
Method for producing diisobutylene by mixing C4 Download PDFInfo
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- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
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Abstract
A method for producing diisobutylene by mixing C4, belonging to the technical field of C4 polymerization. The method is characterized in that: mixing C4 in catalyst and inhibitingThe polymerization reaction is carried out in the presence of the agent, the temperature of the polymerization reaction is 20-140 ℃, the reaction pressure is 0.2-4.0 MPa, the mixed C4 contains 1-99.99% of isobutene, the catalyst is macroporous sulfonic acid cation exchange resin, the exchange capacity of the macroporous sulfonic acid cation exchange resin is 4.0-5.5 mmol/g in terms of H < + >, and the using space velocity is 0.2H ‑1 ～8h ‑1 (ii) a The inhibitor is a mixture of acetone and butanone, and the molar ratio of the inhibitor to the isobutene in the mixed C4 is as follows: 0.003 to 1.5:1; and (3) separating a polymerization product after the polymerization reaction to obtain diisobutylene, and recovering the inhibitor by distillation after the polymerization reaction. The invention realizes high conversion rate and high selectivity dimerization, greatly improves the yield of diisobutylene, and has the advantages of no participation of an inhibitor in reaction, easy recovery and cyclic utilization.
Description
Technical Field
A method for producing diisobutylene by mixing C4, belonging to the technical field of C4 polymerization.
Background
The main components of diisobutylene (diisobutylene) are 2, 4, 4-trimethyl-1-pentene and 2, 4, 4-trimethyl-2-pentene, which are colorless transparent liquids and are easy to volatilize. Diisobutylene is increasingly receiving attention as a precious chemical raw material. Can be used for producing various fine chemical products such as octyl phenol, isononanol, octyl diphenylamine and the like. Diisobutylene reacts with phenol to produce octylphenol. The latter is an important fine chemical product, and is a basic raw material for synthesizing surfactant antioxidants, stabilizers, resins and the like.
A large amount of mixed C4 containing 1-99.99% of isobutene is generated in the petroleum processing process, isobutene in the raw materials is polymerized to generate a polymerization product, the main component of the polymerization product is diisobutylene, and a small amount of other C8 olefins are contained, and the polymerization product is separated to obtain the diisobutylene. There are numerous patents and articles relating to the use of isobutylene polymerization in mixed C4 s. US4100220 adds a proper amount of t-butanol to the raw material to improve the polymerization selectivity, and sets the reactor external circulation to take away the reaction heat, because the circulating material contains olefin, the high polymer content in the product is high. CN1087616A discloses a fixed bed series polymerization process of mixed C four, raw materials sequentially pass through a series reactor of two or more stages, a reaction catalyst is small aluminum silicate balls, polymerization is controlled by reaction temperature, and a polymerization inhibitor is not added, so that the content of trimer in a reaction product is high, and the content of dimer and C8 can only reach more than 65%. US4215011 employs a catalytic distillation process for the selective polymerisation of isobutylene in mixed C4 which can solve a problem not easily solved in many fixed beds. The temperature of each point in the distillation tower depends on the boiling point of the material under the set pressure, and the problem of overhigh temperature rise of a reaction bed layer can be avoided. The washing effect of the reflux liquid is strong, and the polymer is prevented from being adhered and gathered on the surface of the catalyst. The separation action causes the dimerization product to leave the catalyst surface quickly, reducing the chance of further polymerization and thus improving the selectivity of the dimerization reaction. This patent does not use water or alcohols to improve the polymerization selectivity, but rather, it is considered that a small amount of water contained in the raw materials is disadvantageous for selective dimerization of isobutylene, which is similar to the industrial examples described in other documents. US4375576 discloses a liquid phase reaction of isobutylene in carbon four, the catalyst is ion exchange resin, MTBE is used as inhibitor, and the generation of by-products such as high polymer, copolymer, etc. is inhibited. US2008242909 discloses a process for the selective dimerization of isobutylene to produce high octane components in the presence of carbon five and an oxygen-containing compound, the oxygen-containing compound being an alcohol or an ether, the second reaction step being a catalytic distillation. CN1210379 discloses that mixed C4 is used as raw material to perform polymerization reaction in the presence of catalyst and inhibitor, wherein the inhibitor is water, tert-butanol or mixture thereof, and the polymerization reaction is followed by washing with water and recovering the inhibitor to obtain a polymerization product, which is subjected to hydrogenation reaction to obtain an alkylated product. The polymerization reaction is carried out by fixed bed prepolymerization reaction and catalytic distillation reaction. The patent ensures that the conversion rate of isobutene in C4 reaches more than 90 percent, the total content of C8 in a hydrogenation product is more than or equal to 92 percent, and the octane number is more than or equal to 95. The above-mentioned technology either does not add the inhibitor, or the inhibitor added is water, alcohol or ether, the diisobutylene content in the polymerization product is not high, or the inhibitor is not easy to be recovered.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a method for producing diisobutylene by mixing C4 with high product selectivity and convenient recovery of an inhibitor.
The technical scheme adopted by the invention for solving the technical problems is as follows: the method for producing diisobutylene by mixing C4 is characterized by comprising the following steps: the mixed C4 is subjected to polymerization reaction in the presence of a catalyst and an inhibitor, the polymerization reaction temperature is 20-140 ℃, the reaction pressure is 0.2-4.0 MPa, the mixed C4 contains 1-99.99 mass percent of isobutene, the catalyst is macroporous sulfonic acid cation exchange resin, the exchange capacity of the macroporous sulfonic acid cation exchange resin is 4.0-5.5 mmol/g in terms of H +, and the use airspeed is 0.2H -1 ～8h -1 (ii) a The inhibitor is a mixture of acetone and butanone, and the molar ratio of the inhibitor to isobutene in the mixed C4 is as follows: 0.003 to 1.5:1; and (3) separating a polymerization product after the polymerization reaction to obtain diisobutylene, and distilling the polymerization product to recover the inhibitor.
The invention aims to solve the technical problem of a method for producing diisobutylene by utilizing mixed C4. Under the condition of an acid catalyst, dimerization reaction of isobutene in mixed C4 is violent, trimerization and even tetramerization reaction can occur at the same time, and in order to inhibit the reaction above trimerization, a certain inhibitor is usually added to improve dimerization reaction selectivity. However, the selectivity of the dimerization reaction is increased and the conversion is inevitably reduced to a great extent. The inventor finds that the mixture of acetone and butanone is added into the reaction system and is matched with a specific resin catalyst, so that higher reaction conversion rate and diisobutylene reaction selectivity can be simultaneously achieved. The invention dimerizes isobutene and a small amount of butene-1 in mixed C4 with high conversion rate and high selectivity under the action of the high-efficiency catalyst and the inhibitor, greatly improves the yield of diisobutylene, obtains diisobutylene through separation after polymerization reaction, and has the advantages of no reaction of the inhibitor, easy recovery and cyclic utilization.
The inhibitor is recovered by distillation after the polymerization reaction. The acetone or butanone does not participate in the reaction process, and the acetone or butanone can be recycled. Compared with other inhibitors, the recovery mode is simpler and more convenient, a water washing mode is not needed, and the industrial wastewater is generated and the equipment corrosion problem exists. And (3) separating and recovering by adopting a rectification or lateral line drawing mode in the separation process of the polymerization product. The flow is simplified, and the cost is saved.
Preferably, the molar ratio of the inhibitor to isobutylene in the mixed C4 is 0.01-1.0. The preferred amount of inhibitor is sufficient to ensure selectivity of the diisobutylene reaction.
Preferably, the temperature of the polymerization reaction is 30-90 ℃, and the reaction pressure is 0.5-1.6 MPa.
Preferably, the mass ratio of acetone to butanone is 0.1-1, more preferably, the mass ratio of acetone to butanone is 0.2-0.4, and the exchange capacity of the macroporous sulfonic acid cation exchange resin is 4.5 mmol/g-5.0 mmol/g in terms of H +. The catalyst may be any type of acid cation exchange resin catalyst commercially available, and more preferably, the catalyst is prepared by a method comprising the steps of:
(1) According to the weight portion, adding a mixture of 15 to 85 portions of pore-forming agent, 0.2 to 10 portions of benzoyl peroxide, 0.2 to 10 portions of tert-butyl peroxyneodecanoate, 60 to 95 portions of styrene monomer and 5 to 40 portions of polyvinyl monomer into water dissolved with 0.1 to 10 portions of hydroxypropyl methyl cellulose, 0.2 to 10 portions of polyacrylamide and 2 to 10 portions of secondary alkyl sodium sulfonate, carrying out polymerization reaction at the reaction temperature of 40 to 90 ℃ to obtain a product copolymer white ball, drying and then extracting the pore-forming agent;
(2) Adding fuming sulfuric acid into the copolymer white spheres at the temperature of 10-85 ℃ under the stirring condition, wherein the weight of the fuming sulfuric acid is 4-10 times of that of the copolymer white spheres, heating to 85-140 ℃, and reacting for 5-11 hours to obtain the cation exchange resin with high-temperature thermal stability.
The amount of water used in step (1) is preferably 300 to 500 parts. The amount of the pore-forming agent used in step (1) is preferably 20 to 50 parts. It can be mutually soluble with the polymerization monomer and insoluble in the aqueous phase, so that there is almost no residual porogen in the polymerization aqueous phase, and the step of recovering the porogen from the polymerization wastewater is omitted. The pore-forming agent is preferably one or a mixture of more than two of C12-C24 saturated alkanes in any proportion. The polyvinyl monomer in step (1) is preferably divinylbenzene or divinyltoluene.
The inhibitor with the optimal proportion can effectively inhibit the high polymerization reaction of more than trimerization, improve the selectivity of the polymerization reaction and improve the yield of the diisobutylene. The preferred catalyst is matched to simultaneously realize better reaction conversion rate.
The polymerization reaction of the present invention is preferably carried out in two or more stages to increase the conversion and selectivity of olefins in C4. The polymerization can be carried out in the following two ways.
Preferably, the polymerization reaction adopts a combined polymerization system of a fixed bed reactor and a catalytic distillation tower, wherein one or more fixed bed reactors are arranged, and the fixed bed reactors are subjected to fixed bed prepolymerization reaction and then are subjected to catalytic distillation reaction. The prepolymerization reaction can improve the selectivity of polymerization reaction, and is carried out in a fixed bed reactor to reduce the generation of high polymer more than trimerization. The fixed bed polymerization reaction and the catalytic distillation reaction may be operated at the same temperature or at different temperatures.
Preferably, when the concentration of isobutene in the C4 is more than 4%, cooling a polymerization reaction product of the fixed bed prepolymerization reaction, partially circulating the cooled polymerization reaction product back to a feed inlet of a fixed bed polymerization reactor to dilute the concentration of the isobutene in the feed and take away the reaction heat, wherein the circulating amount of the polymerization reaction product in parts by weight is 0.1-15 times of that of the mixed C4 feed, and the residual C4 after the reaction is extracted from the top of a catalytic distillation tower; recovering the inhibitor, feeding the polymerization product into a diisobutylene refining tower, and separating and purifying the diisobutylene.
When the isobutene concentration in the mixed C4 s does not exceed 4%, the feed recycle can be dispensed with. The ratio of feed recycled to the fixed bed polymerization reactor to fresh feed is related to the concentration of isobutylene in the feed, with higher isobutylene concentrations requiring greater recycle ratios.
Preferably, the inhibitor is added in two stages of fixed bed prepolymerization and catalytic reaction respectively, wherein the addition amount of the fixed bed prepolymerization stage is more than 60% of the total addition amount of the inhibitor.
Preferably, the mixed C4 is subjected to polymerization reaction in at least two stages of fixed bed reactors connected in series with catalysts, when the concentration of isobutene in the mixed C4 is more than 4%, a part of polymerization reaction products discharged from the first-stage fixed bed polymerization reactor is cooled and then circulated back to the first-stage fixed bed polymerization reactor to dilute the concentration of isobutene in the fed materials and take away reaction heat, the circulation amount of the polymerization reaction products in parts by weight is 0.1-15 times of that of the mixed C4 fed materials, the rest part of the polymerization reaction products enters the second-stage fixed bed polymerization reactor to continue reaction, and the products are sent to a C4 removing tower.
During the polymerization, acetone or butanone or their mixture as polymerization inhibitor exists, and the inhibitor may be added in the first stage or in both stages. The main composition from the first-stage fixed bed polymerization reactor is residual C4, diisobutylene, copolymer of isobutylene and n-butene, and a small amount of polymer with more than three polymers, after cooling, a part of the cooled polymerization product is circulated back to the first-stage fixed bed polymerization reactor to dilute the concentration of isobutylene in the fed material and take away the reaction heat, a part of the cooled polymerization product enters the second-stage fixed bed polymerization reactor for continuous reaction, and the product is sent to a C4 removal tower (a catalytic distillation tower can be used as a separation tower, and the separation is carried out without catalyst). When the isobutene concentration does not exceed 4%, the remaining C4 recycle feed may be omitted. The ratio of the remaining C4 s recycled to the fixed bed polymerization reactor to the fresh feed is related to the concentration of isobutylene in the feed, with higher isobutylene concentrations requiring greater recycle ratios. The operation temperature and pressure of the C4 removing tower are the same as the polymerization reaction conditions.
Preferably, the polymerization reaction temperature of the C4 removing tower is 20-140 ℃, and the reaction pressure is 0.2-4.0 MPa; the residual C4 escapes from the top of the C4 removing tower, the inhibitor is recovered from the polymerization product at the tower bottom, the polymerization product enters a diisobutylene refining tower, and the diisobutylene is separated and purified. And (3) conveying the polymerization product at the bottom of the tower to an inhibitor recovery tower for rectifying and recovering the inhibitor, or extracting a side line from the middle part of a catalytic distillation tower for recovering the inhibitor, conveying the polymerization product mainly containing C8 olefin and a small amount of C12 olefin to a diisobutylene refining tower, and separating and purifying diisobutylene.
Preferably, the total content of C8 in the polymerization product is more than or equal to 95 percent, the content of C12 is less than or equal to 5 percent, and the content of C16 is 0.
The mixed C4 may be a mixed C4 having a low isobutylene content or a high-purity isobutylene C4, such as high-purity isobutylene obtained by MTBE decomposition reaction, wherein the isobutylene content may be up to 99% or more, i.e., the mixed C4 may contain 1 to 99.99% of isobutylene.
Compared with the prior art, the invention has the beneficial effects that: the invention takes mixed C4 generated in the processes of petroleum processing and chemical production as raw materials, leads isobutene and a small amount of butene-1 in the mixed C4 to be dimerized with high conversion rate and high selectivity under the combined action of a high-efficiency catalyst and an inhibitor, and obtains diisobutylene through separation after polymerization reaction. The process can ensure that the conversion rate of isobutene in C4 reaches more than 93 percent, the content of diisobutylene is more than or equal to 80 percent, and the purity of the separated diisobutylene is more than or equal to 98 percent. Meanwhile, the recycling mode of the inhibitor is simple and convenient, industrial wastewater and equipment corrosion are not generated, and the energy consumption is low. The flow is simplified, and the cost is saved. The invention is suitable for olefin polymerization in petroleum hydrocarbon mixtures, is also suitable for high-purity olefin polymerization generated in chemical production processes, and is particularly suitable for the polymerization of olefins in mixed C4 to produce diisobutylene.
Drawings
FIG. 1 is a process flow diagram of the catalytic distillation process of the present invention.
FIG. 2 is a process flow diagram of the series fixed bed process of the present invention.
The system comprises a fixed bed reactor 1, a fixed bed reactor 101, a first-stage fixed bed reactor, a second-stage fixed bed reactor 102, a catalytic distillation tower 3, an inhibitor recovery tower 4, a diisobutylene refining tower 5 and a condenser.
Detailed Description
The present invention is further illustrated by the following specific examples.
The invention is illustrated by combining the process flow chart as follows:
referring to figure 1, a catalytic distillation process: the mixed C4 and the polymerization inhibitor are respectively sent into the fixed bed reactor 1 through a pipeline and a pipeline, the mixed material after prepolymerization is divided into two parts, one part is sent into the catalytic distillation tower 2 through the pipeline, the other part is condensed by the condenser 5 and circulated back to the fixed bed polymerization reactor through the pipeline, so as to dilute the concentration of the fed olefin and reduce the reaction temperature rise. The fixed bed reactor 1 and the catalytic distillation tower 2 are filled with the same polymerization catalyst. The mixed C4 is further polymerized in a catalytic distillation tower 2, the residual C4 after polymerization is discharged from the device through a pipeline, and the polymerization product containing the inhibitor is discharged from the tower kettle through a pipeline and is sent to an inhibitor recovery tower 3. The inhibitor distilled from the tower top of the tower is recycled to the fixed bed polymerization reactor by a pipeline for utilization. The tower bottom liquid is a polymerization product and is sent into a diisobutylene refining tower 4 through a pipeline. Heavy components in the tower bottom are continuously extracted by a pipeline, and diisobutylene at the tower top is extracted out of the device by the pipeline.
The reaction section of the catalytic distillation column may employ any known form of catalytic distillation apparatus.
Referring to the attached figure 2, the indirect alkylation process by the series fixed bed method comprises the following steps: the mixed C4 and the polymerization inhibitor are respectively sent into a first-stage fixed bed reactor 101 through pipelines, the primarily polymerized mixture is sent into a condenser 5 to be condensed and then divided into two parts, and one part is circulated back to the fixed bed polymerization reactor through the pipeline to dilute the concentration of the fed olefin and reduce the reaction temperature rise. A part of the reaction mixture is fed into the second-stage fixed-bed reactor 102 through a line, and an appropriate amount of a polymerization inhibitor is added to the line. The mixed C4 is further polymerized in the second-stage fixed bed reactor 102, the polymerized mixture is sent to the catalytic distillation tower 2 through a pipeline, the rest C4 passes through a pipeline outlet device from the top of the rectifying tower, a side line material is extracted from the middle part of the rectifying tower, wherein the main component is an inhibitor, and the inhibitor is recycled to the fixed bed polymerization reactor for utilization through the pipeline. The tower bottom liquid is a polymerization product and is sent into a diisobutylene refining tower 4 through a pipeline. Heavy components in the tower bottom are continuously extracted by a pipeline, and diisobutylene at the tower top is extracted out of the device by the pipeline.
Example 1
Adopting a catalytic distillation process as shown in figure 1;
the mixed C4 contains 18.5% of isobutene and 16.3% of n-butene, and the feeding amount is as follows: 300g/h;
catalyst loading in fixed bed polymerization reactor: 500ml, the catalyst is macroporous sulfonic acid cation exchange resin, the exchange capacity is 4.5mmol [ H + ]/g; the preparation method of the polymerization catalyst comprises the following steps:
(1) 0.2g of hydroxypropylmethylcellulose, 0.3g of polyacrylamide and 7g of sodium secondary alkylsulfonate were added to 500g of water, and the mixture was heated and stirred to completely dissolve the sodium secondary alkylsulfonate, thereby forming a uniform aqueous solution. Then adding an organic phase mixture consisting of 90g of styrene, 35g of divinylbenzene, 0.9 g of benzoyl peroxide, 24g of n-hexadecane and 6g of tert-butyl peroxyneodecanoate, adjusting the proper stirring speed, heating to 65 ℃, reacting at constant temperature for 2 hours, heating to 80 ℃, and reacting at constant temperature for 4 hours. Filtering the reaction product, placing the reaction product in tap water with the volume being 3 times that of the reaction product, stirring the reaction product for 5 minutes, washing the residual dispersant, filtering the reaction product, airing the reaction product at room temperature (the water content is less than or equal to 3 percent) to obtain dry copolymer white balls, and extracting the pore-foaming agent in the copolymer white balls completely;
(2) Adding 3500g of fuming sulfuric acid into 500g of copolymer white spheres under the conditions of 80 ℃ and stirring, stirring and heating to 80 ℃, reacting for 3 hours at constant temperature, slowly heating to 95 ℃, reacting for 2 hours at constant temperature, slowly heating to 120 ℃, reacting for 4 hours at constant temperature, and centrifugally filtering the product to obtain the cation exchange resin.
Catalyst loading of catalytic distillation column: 200ml;
adding polymerization inhibitor into the raw materials, wherein the molar ratio of the inhibitor to isobutene in fresh feeding is 0.01: 1;
the polymerization product is sent to a diisobutylene refining tower; diisobutylene refining tower pressure 0.2MPa, tower top temperature: 45 ℃;
the fixed bed polymerization temperature is 90 ℃, and the reaction pressure is 0.5 MPa; cooling a polymerization reaction product of the fixed bed prepolymerization reaction, and then partially circulating the cooled polymerization reaction product back to a feed inlet of a fixed bed polymerization reactor to dilute the concentration of isobutene in the feed and take away reaction heat, wherein the circulating amount is 6 times of that of the mixed C4 feed in parts by weight;
the inlet temperature of the catalytic distillation tower bed layer is 90 ℃, and the reaction pressure is 0.5MPa.
Example 2
Adopting a catalytic distillation process as shown in figure 1;
the mixed C4 contains 18.5% of isobutene and 16.3% of n-butene, and the feeding amount is as follows: 300g/h;
catalyst loading in fixed bed polymerization reactor: 300ml of a macroporous sulfonic acid cation exchange resin as a catalyst having an exchange capacity of 5.0mmol [ H + ]/g, which was prepared in the same manner as the polymerization catalyst in example 1 except that: 4g of hydroxypropylmethylcellulose, 0.3g of polyacrylamide and 2g of sodium secondary alkylsulfonate were added to 450g of water, and the mixture was heated and stirred to completely dissolve the sodium secondary alkylsulfonate, thereby forming a uniform aqueous solution. A mixture of organic phases consisting of 60g of styrene, 40g of divinyltoluene, 3g of benzoyl peroxide, 40g of liquid paraffin, 0.6g of tert-butyl peroxyneodecanoate was then added.
Catalyst loading of catalytic distillation column: 200ml;
adding a polymerization inhibitor into the raw materials, wherein the molar ratio of the inhibitor to isobutene in fresh feeding is 1.0;
the polymerization product is sent to a diisobutylene refining tower; diisobutylene refining tower pressure 0.2MPa, tower top temperature: 45 ℃;
the fixed bed polymerization temperature is 30 ℃, and the reaction pressure is 1.6MPa; cooling a polymerization reaction product of the fixed bed prepolymerization reaction, and then partially circulating the cooled polymerization reaction product back to a feed inlet of a fixed bed polymerization reactor to dilute the concentration of isobutene in the feed and take away reaction heat, wherein the circulating amount is 10 times of that of the mixed C4 feed in parts by weight;
the inlet temperature of the catalytic distillation tower bed layer is 30 ℃, and the reaction pressure is 1.6MPa.
Example 3
Adopting a catalytic distillation process as shown in figure 1;
the mixed C4 contains 18.5% of isobutene and 16.3% of n-butene, and the feeding amount is as follows: 300g/h;
catalyst loading in fixed bed polymerization reactor: 400ml of a macroporous sulfonic acid cation exchange resin as a catalyst having an exchange capacity of 5.5mmol [ H + ]/g, which was prepared in the same manner as the polymerization catalyst in example 1 except that: 0.4g of hydroxypropylmethylcellulose, 6g of polyacrylamide and 1g of sodium secondary alkylsulfonate were added to 500g of water, and the mixture was heated and stirred to completely dissolve the sodium secondary alkylsulfonate, thereby forming a uniform aqueous solution. Then adding an organic phase mixture consisting of 80g of styrene, 30g of divinyltoluene, 1.5 g of benzoyl peroxide, 33g of n-dodecane and 4g of tert-butyl peroxyneodecanoate;
catalyst loading of catalytic distillation column: 200ml;
the raw materials are compounded with a polymerization inhibitor, and the molar ratio of the inhibitor to isobutene in fresh feed is 1.5:1;
delivering the polymerization product to a diisobutylene refining tower, wherein the pressure of the diisobutylene refining tower is 0.2MPa, the temperature at the top of the tower is as follows: 45 ℃;
the fixed bed polymerization temperature is 140 ℃, and the reaction pressure is 0.2 MPa; cooling a polymerization reaction product of the fixed bed prepolymerization reaction, and then partially circulating the cooled polymerization reaction product back to a feed inlet of the fixed bed polymerization reactor to dilute the concentration of isobutene in the feed and take away reaction heat, wherein the circulating amount in parts by weight is 9 times of that of the mixed C4 feed;
the inlet temperature of the catalytic distillation column bed layer is 55 ℃, and the reaction pressure is 0.6MPa.
Example 4
Adopting a catalytic distillation process as shown in figure 1;
mixed C4 contains 38.5% isobutylene, 1.63% normal butenes, and the feed rates: 300g/h;
catalyst loading in fixed bed polymerization reactor: 500ml, the catalyst is macroporous sulfonic acid cation exchange resin, the exchange capacity is 4.0 mmol [ H + ]/g;
catalyst loading of catalytic distillation column: 200ml;
the raw materials are compounded with a polymerization inhibitor, and the molar ratio of the inhibitor to isobutene in fresh feed is 0.003:11;
the polymerization product is sent to a diisobutylene refining tower, the pressure of the diisobutylene refining tower is 0.2MPa, the temperature at the top of the tower is as follows: 45 ℃;
the fixed bed polymerization temperature is 20 ℃, and the reaction pressure is 4.0MPa; cooling a polymerization reaction product of the fixed bed prepolymerization reaction, and then partially circulating the cooled polymerization reaction product back to a feed inlet of a fixed bed polymerization reactor to dilute the concentration of isobutene in the feed and take away reaction heat, wherein the circulating amount is 10 times of that of the mixed C4 feed in parts by weight;
the inlet temperature of the catalytic distillation tower bed layer is 25 ℃, and the reaction pressure is 36MPa.
The procedures of comparative examples 1 to 2 were the same as those of example 1.
Examples 1 to 4 and comparative examples 1 to 2 are the results of adding different inhibitors under the above-mentioned operating conditions. The purity of diisobutylene is over 98 percent after the polymerization product is stood by a product refining tower.
The examples 5 to 6 and the comparative examples 3 to 4 adopt the indirect alkylation process of the series fixed bed method as shown in the figure 2;
the mixed C4 contains 48.5 percent of isobutene and 26.3 percent of n-butene;
feeding amount: 400g/h;
the catalyst loading of the first and second fixed bed polymerization reactors are respectively as follows: 400ml and 300ml, the catalyst is macroporous sulfonic acid cation exchange resin, and the exchange capacity is 5.0mmol [ H + ]/g;
respectively adding a proper amount of polymerization reaction inhibitor into the feed of the two-stage reactor, wherein the molar ratio of the total inhibitor to the isobutene in the fresh feed is 0.02: 1, and the adding amount of the first-stage reaction is 70% of the total amount;
the polymerization temperature of the first-stage fixed bed is 50.0 ℃, and the reaction pressure is 1.0MPa; cooling a polymerization reaction product of the prepolymerization reaction of the first-stage fixed bed, and then partially circulating the cooled polymerization reaction product back to a feed inlet of the first-stage fixed bed polymerization reactor to dilute the concentration of isobutene in the fed material and take away reaction heat, wherein the circulating amount is 13 times of that of the mixed C4 fed material in parts by weight;
the polymerization temperature of the second-stage fixed bed is 70.0 ℃, and the reaction pressure is 1.0MPa;
diisobutylene refining tower pressure 0.2MPa, tower top temperature: at 45 ℃.
Examples 5 to 6 and comparative examples 3 to 4 show the results of adding different inhibitors under the above-mentioned operating conditions. The purity of diisobutylene product is above 98% after the polymerization product is stood by a product refining tower.
Examples 7 to 8 adopt the indirect alkylation process of the series fixed bed method as shown in FIG. 2;
the mixed C4 is obtained by washing MTBE decomposition products to remove methanol, and rectifying and refining, wherein the mixed C contains 99.99 percent of isobutene and 0.0003 percent of n-butene;
feeding amount: 450g/h
The catalyst loading of the first and second fixed bed polymerization reactors are respectively as follows: 500ml, 300ml, the catalyst is macroporous sulfonic acid cation exchange resin, the exchange capacity is 5.2mmol [ H + ]/g;
respectively adding a proper amount of polymerization reaction inhibitor into the feed of the two-stage reactor, wherein the molar ratio of the total inhibitor to the isobutene in the fresh feed is 0.3: 1, and the adding amount of the first-stage reaction is 70% of the total amount;
the polymerization temperature of the first-stage fixed bed is 40.0 ℃, and the reaction pressure is 1.0MPa; cooling a polymerization reaction product of the prepolymerization reaction of the first-stage fixed bed, and then partially circulating the cooled polymerization reaction product back to a feed inlet of the first-stage fixed bed polymerization reactor to dilute the concentration of isobutene in the fed material and take away reaction heat, wherein the circulating amount is 15 times of that of the mixed C4 fed material in parts by weight;
the polymerization temperature of the second-stage fixed bed is 50.0 ℃, and the reaction pressure is 1.0MPa;
diisobutylene refining tower pressure 0.2MPa, tower top temperature: at 45 deg.c.
Examples 7 to 8 show the results of the invention with different inhibitors added under the above-mentioned operating conditions. The purity of diisobutylene product is above 98% after the polymerization product is stood by a product refining tower.
While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (8)
1. A method for producing diisobutylene by mixing C4, which is characterized by comprising the following steps: the mixed C4 is subjected to polymerization reaction in the presence of a catalyst and an inhibitor, the polymerization reaction temperature is 20-140 ℃, the reaction pressure is 0.2-4.0 MPa, the mixed C4 contains 1-99.99% of isobutene, the catalyst is macroporous sulfonic acid cation exchange resin, and the macroporous sulfonic acid cation exchange resin is H + The meter exchange capacity is 4.0 mmol/g-5.5 mmol/g, and the use space velocity is 0.2 h -1 ～8h -1 (ii) a The inhibitor is a mixture of acetone and butanone, and the molar ratio of the inhibitor to isobutene in the mixed C4 is as follows: 0.003 to 1.5:1; separating the polymerization product after the polymerization reaction to obtain diisobutylene, and distilling the polymerization product after the polymerization reaction to recover the inhibitor;
the mass ratio of the acetone to the butanone is 0.1-1;
the preparation method of the catalyst in the polymerization reaction comprises the following steps:
(1) According to the weight portion, adding a mixture of 15 to 85 portions of pore-forming agent, 0.2 to 10 portions of benzoyl peroxide, 0.2 to 10 portions of tert-butyl peroxyneodecanoate, 60 to 95 portions of styrene monomer and 5 to 40 portions of polyvinyl monomer into water dissolved with 0.1 to 10 portions of hydroxypropyl methyl cellulose, 0.2 to 10 portions of polyacrylamide and 2 to 10 portions of secondary alkyl sodium sulfonate, carrying out polymerization reaction at the reaction temperature of 40 to 90 ℃ to obtain a product copolymer white ball, drying and then extracting the pore-forming agent;
(2) Adding fuming sulfuric acid into the copolymer white spheres at the temperature of 10-85 ℃ under the stirring condition, wherein the weight of the fuming sulfuric acid is 4-10 times of that of the copolymer white spheres, then heating to 85-140 ℃, and reacting for 5-11 hours to obtain the cation exchange resin with high-temperature thermal stability.
2. The method for producing diisobutylene by mixing C4's according to claim 1, wherein: the molar ratio of the inhibitor to the isobutene in the mixed C4 is 0.01-1.0.
3. The method for producing diisobutylene by mixing C4's according to claim 1, wherein: the temperature of the polymerization reaction is 30-90 ℃, and the reaction pressure is 0.5-1.6 MPa.
4. The method for producing diisobutylene by mixing C4's according to claim 1, wherein: the mass ratio of acetone to butanone is 0.2-0.4, and the macroporous sulfonic acid cation exchange resin is H + The measured exchange capacity is 4.5 mmol/g-5.0 mmol/g.
5. The method for producing diisobutylene by mixing C4's according to claim 1, wherein: the polymerization reaction adopts a combined polymerization system of a fixed bed reactor and a catalytic distillation tower, wherein one or more fixed bed reactors are used for performing fixed bed prepolymerization reaction and then performing catalytic distillation reaction.
6. The method for producing diisobutylene by mixing C4's according to claim 5, wherein: when the concentration of isobutene in C4 is more than 4%, cooling a polymerization reaction product of fixed bed prepolymerization reaction, and then partially circulating the cooled polymerization reaction product back to a feed inlet of a fixed bed polymerization reactor, wherein the circulating amount of the polymerization reaction product is 0.1-15 times of that of the mixed C4 feed in parts by weight, and extracting the residual C4 after reaction at the top of a catalytic distillation tower; recovering the inhibitor, feeding the polymerization product into a diisobutylene refining tower, and separating and purifying the diisobutylene.
7. The method for producing diisobutylene by mixing C4's according to claim 5, wherein: the inhibitor is respectively added in two stages of fixed bed prepolymerization reaction and catalytic reaction, wherein the addition amount of the fixed bed prepolymerization reaction stage is more than 60 percent of the total addition amount of the inhibitor.
8. The method for producing diisobutylene by mixing C4's according to claim 1, wherein: and (2) carrying out polymerization reaction on the mixed C4 in at least two stages of fixed bed reactors connected in series with catalysts, when the concentration of isobutene in the mixed C4 is more than 4%, cooling a part of polymerization reaction products discharged from the first-stage fixed bed polymerization reactor, circulating a part of the cooled polymerization reaction products back to the first-stage fixed bed polymerization reactor, wherein the circulating amount of the polymerization reaction products calculated by weight parts is 0.1-15 times of that of the mixed C4, allowing the rest part of the cooled polymerization reaction products to enter the second-stage fixed bed polymerization reactor for continuous reaction, and delivering the products to a C4 removal tower.
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