CN107474174B - Method for producing butadiene rubber - Google Patents
Method for producing butadiene rubber Download PDFInfo
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- CN107474174B CN107474174B CN201610398538.1A CN201610398538A CN107474174B CN 107474174 B CN107474174 B CN 107474174B CN 201610398538 A CN201610398538 A CN 201610398538A CN 107474174 B CN107474174 B CN 107474174B
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F136/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F136/06—Butadiene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F2/04—Polymerisation in solution
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Abstract
The invention relates to the field of polymers, and discloses a method for producing butadiene rubber, which comprises the following steps: under the condition of solution polymerization, 1, 3-butadiene monomer and solvent are introduced into a polymerization reactor for polymerization reaction, part of butadiene rubber liquid obtained at the outlet of the polymerization reactor is circulated back to the inlet of the polymerization reactor, and the rest butadiene rubber liquid is introduced into a subsequent processing unit as a crude product. According to the invention, the polymerized glue solution is returned to the polymerization reactor to reduce the solvent consumption in the polymerization process and reduce the solvent consumption of ton dry glue, so that the steam consumption for solvent recovery is reduced, and a better energy-saving effect is achieved.
Description
Technical Field
The invention relates to the field of polymers, in particular to a method for producing butadiene rubber.
Background
The cis-butadiene rubber is a synthetic rubber with a regular structure and polymerized by a butadiene monomer, and the cis-structure content of the cis-butadiene rubber is more than 95 weight percent. Depending on the catalyst, it can be classified into a nickel-based, cobalt-based, titanium-based and rare earth-based (neodymium-based) butadiene rubber.
Butadiene rubber is the second largest synthetic rubber second only to styrene butadiene rubber. Compared with natural rubber and styrene butadiene rubber, the vulcanized butadiene rubber has particularly excellent cold resistance, wear resistance and elasticity, less heat generation under dynamic load and good aging resistance, and is easy to be used together with natural rubber, chloroprene rubber or nitrile rubber. The butadiene rubber is especially suitable for manufacturing automobile tires and cold-resistant products, and can also be used for manufacturing buffer materials, various rubber shoes, adhesive tapes, sponge rubbers and the like.
In the prior art, the butadiene rubber glue solution produced by a multi-kettle series process route contains a solvent and unreacted butadiene monomers besides polybutadiene, and a high-purity butadiene rubber product can be obtained only by the working procedures of coagulation, drying and the like.
The energy consumption and the cost of the method for producing the butadiene rubber in the prior art are higher, so that the reduction of the production energy consumption of the butadiene rubber is always the target pursued by business industry and technologists. United states combined carbon chemicals and plastics technology company reported gas phase polymerization of butadiene (see CN1297952A) to reduce energy consumption for production. The company of Enizamel Erastomi Italy reports that the energy consumption and the preparation cost are greatly reduced in the production of butadiene rubber in the absence of a solvent or in the presence of a small amount of a solvent with respect to the bulk polymerization technique of butadiene (see CN86103327A, CN 86103350A).
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a novel energy-saving method for producing butadiene rubber on the premise of keeping and even improving the concentration of butadiene rubber glue solution obtained by production.
The inventor of the invention finds that a large amount of polymerization heat is generated during the polymerization reaction of butadiene, the viscosity of the butadiene rubber solution obtained by polymerization is high, and if the butadiene rubber is prepared only in a temperature control mode of jacket heat removal, the heat transfer of a reactor is quite difficult. For improvement, polymerization can generally be carried out using a polymerization technique combining low temperature feeding (even large solvent feeding) with jacket heat removal. However, when the polymerization is carried out by a polymerization technique combining low-temperature feeding and jacket heat removal, 5 tons or more of solvent is required to be charged into the polymerization reactor for absorbing a large amount of polymerization heat per one ton of dry rubber produced, and if the solvent is recovered, a large amount of energy is required. Moreover, when the method provided by the prior art is adopted to produce the butadiene rubber, the concentration of the obtained butadiene rubber liquid is lower.
In order to overcome the above-mentioned drawbacks of the prior art, the inventors of the present invention have provided, through inventive studies, the following process for producing butadiene rubber, the process comprising:
under the condition of solution polymerization, 1, 3-butadiene monomer and solvent are introduced into a polymerization reactor for polymerization reaction, part of butadiene rubber liquid obtained at the outlet of the polymerization reactor is circulated back to the inlet of the polymerization reactor, and the rest butadiene rubber liquid is introduced into a subsequent processing unit as a crude product.
Aiming at the problem of high energy consumption of the butadiene rubber production process in the prior art, the invention provides a novel method for producing butadiene rubber, which is characterized in that the polymerized glue solution is returned to a polymerization reactor to replace part of solvent to remove polymerization heat, so that the addition amount of the solvent in the polymerization reactor is correspondingly reduced, the steam consumption for recovering the solvent is further reduced, and a better energy-saving effect is achieved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a schematic process flow diagram for producing butadiene rubber in accordance with a preferred embodiment of the present invention.
Description of the reference numerals
1. 1, 3-butadiene monomer 2 and solvent
3. Part of the butadiene rubber cement recycled to the inlet of the polymerization reactor
4. Butadiene rubber cement as the remainder of the crude product introduced into a subsequent processing unit
A. A first reactor B and a second reactor
C. Third reactor
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for producing butadiene rubber, which comprises the following steps: under the condition of solution polymerization, 1, 3-butadiene monomer and solvent are introduced into a polymerization reactor for polymerization reaction, part of butadiene rubber liquid obtained at the outlet of the polymerization reactor is circulated back to the inlet of the polymerization reactor, and the rest butadiene rubber liquid is introduced into a subsequent processing unit as a crude product.
In the method for producing butadiene rubber according to the present invention, the solution polymerization reaction may be carried out by removing heat from the jacket to control the reaction temperature, or may be carried out by adiabatic polymerization, and preferably, the solution polymerization reaction is adiabatic polymerization.
The polymerization reactor may be a conventional tank polymerization reactor or other type of polymerization reactor commonly used in the art, and preferably, the polymerization reactor is a tank polymerization reactor. The polymerization reactor of the present invention may be one reactor, i.e., a one-pot reactor; or at least two reactors connected in series, namely a multi-kettle reactor; preferably, the polymerization reactor of the present invention is a two-pot reactor formed by two reactors connected in series, or a three-pot reactor formed by three reactors connected in series. The volume of the polymerization reactor is not particularly limited and may be various sizes conventionally used in the art, and preferably, when the polymerization reactor is formed of at least two reactors connected in series, the volume of each reactor forming the polymerization reactor is equal.
The outlet of the polymerization reactor means the outlet of the entire polymerization reactor, that is, if there are two or more reactors, the outlet of the polymerization reactor means the outlet of the last reactor.
The inlet of the polymerization reactor refers to the inlet of the whole polymerization reactor, that is, if there are two or more reactors, the inlet of the polymerization reactor refers to the inlet of the first reactor.
The partial butadiene rubber cement liquid is a part of the whole butadiene rubber cement liquid obtained from the outlet of the polymerization reactor.
The residual part of the cis-butadiene rubber liquid is the part of the cis-butadiene rubber liquid left after subtracting the part of the cis-butadiene rubber liquid circulated to the inlet of the polymerization reactor from the whole cis-butadiene rubber liquid obtained at the outlet of the polymerization reactor.
The specific process of the solution polymerization is well known to those skilled in the art, and the present invention will not be described in detail herein.
The inventor of the present invention finds that, because the viscosity of the butadiene rubber cement solution obtained at the outlet of the polymerization reactor is relatively high, when all or a large amount of the butadiene rubber cement solution obtained at the outlet of the polymerization reactor is circulated to the inlet of the polymerization reactor, the viscosity of the polymerization reaction feed is greatly increased to affect the efficiency of the polymerization reaction, and therefore, in order to obtain a better energy saving effect on the premise of ensuring the efficient progress of the polymerization reaction, the present invention preferably uses the total weight of all the butadiene rubber cement solution obtained at the outlet of the polymerization reactor as a reference, and the butadiene rubber cement solution circulated to the inlet of the polymerization reactor is 5-35 wt%.
More preferably, the amount of the butadiene rubber cement circulated back to the inlet of the polymerization reactor is 15 to 30% by weight, based on the total weight of all the butadiene rubber cement obtained at the outlet of the polymerization reactor. The inventor of the present invention found that when the amount of the butadiene rubber cement circulated back to the inlet of the polymerization reactor is in the range of 15 to 30% by weight based on the total weight of all the butadiene rubber cement obtained at the outlet of the polymerization reactor, the method for producing butadiene rubber of the present invention can be easily operated and has a more significant energy saving effect.
Preferably, the temperature of the portion of the cis-butadiene rubber cement recycled to the inlet of the polymerization reactor is 20-70 ℃.
More preferably, the temperature of the portion of the butadiene rubber cement that is recycled to the inlet of the polymerization reactor is between 35 and 55 ℃. The inventor of the present invention found that when the temperature of the butadiene rubber cement solution circulating back to the inlet of the polymerization reactor is controlled within the above-mentioned range of 35 to 55 ℃, the method for producing butadiene rubber of the present invention can be easily operated and has a more significant energy saving effect.
In order to ensure that the temperature of the portion of the butadiene rubber solution circulated back to the inlet of the polymerization reactor is within the aforementioned range, a person skilled in the art may use a method commonly used in the art to cool the portion of the butadiene rubber solution circulated back to the inlet of the polymerization reactor, for example, may use a method of heat exchange, and specifically, may use a refrigerant to exchange heat with the portion of the butadiene rubber solution circulated back to the inlet of the polymerization reactor.
Preferably, the 1, 3-butadiene monomer and the solvent are used in a weight ratio of 1: 2.5-5. More preferably, the 1, 3-butadiene monomer and the solvent are used in a weight ratio of 1: 3.5-4.5. By adopting the method for circulating part of the butadiene rubber liquid to the inlet of the polymerization reactor, the usage amount of the solvent is obviously lower than that of the method in the prior art, so that the production cost is saved; moreover, the amount of the solvent used is reduced, and the amount of steam consumed by recovering the solvent can be reduced, so that the production energy consumption is saved.
Preferably, the solution polymerization conditions include: the polymerization reaction temperature is 50-100 ℃, preferably 65-95 ℃; the polymerization time is from 45 to 150 minutes, preferably from 60 to 90 minutes. The inventor of the present invention finds that when the conditions of the solution polymerization reaction are controlled within the above parameter range of the present invention, the solvent usage amount of the process method for producing butadiene rubber of the present invention can be significantly reduced on the premise of ensuring that a butadiene rubber product with the quality equivalent to that of the prior art is obtained by matching with the process of circulating part of the butadiene rubber liquid to the inlet of the polymerization reactor. Further, when the polymerization reactor is a polymerization reactor formed by connecting at least two reactors in series, the solution polymerization reaction conditions in the respective reactors may be the same or different, and preferably the solution polymerization reaction conditions in the respective reactors are different.
Preferably, the temperature of the 1, 3-butadiene monomer and the solvent is not higher than 10 ℃ before entering the polymerization reactor for polymerization; more preferably, the temperature of the 1, 3-butadiene monomer and the solvent is from-15 ℃ below zero to-5 ℃ above zero.
Preferably, the solvent is selected from at least one of pentane, isopentane, hexane, cyclohexane, methylcyclohexane, heptane, octane.
The method for producing the butadiene rubber can adopt a batch process operation mode and a continuous process operation mode, and specifically, the method for batch process operation is to step the 1, 3-butadiene monomer, the solvent and the catalyst into a polymerization reactor in the production process, and the polymerization reactor does not have feeding and discharging operations in the reaction process. And when the reaction is finished, discharging a part of glue solution obtained in the polymerization reactor out of the polymerization reactor, and taking the residual glue solution as circulating glue solution to be left in the polymerization reactor to replace the solvent so as to reduce the addition of the solvent in the polymerization reaction of the next batch, thereby realizing energy conservation and consumption reduction.
In addition, the continuous process operation method is to continuously add the 1, 3-butadiene monomer, the solvent and the catalyst in the production process and continuously produce the butadiene rubber glue solution at the same time, so that the total amount of materials in the polymerization reactor is kept relatively stable, and the method for producing butadiene rubber preferably adopts a continuous process operation mode and ensures that the average residence time of the 1, 3-butadiene monomer in the polymerization reactor is 20-50 min.
Preferably, the process of the invention is carried out in a system comprising at least three polymerization reactors connected in series, and part of the butadiene rubber cement obtained at the outlet of the last polymerization reactor is recycled to the inlet of the first polymerization reactor.
Preferably, the process of the invention is carried out in a system comprising three polymerization reactors connected in series.
According to a preferred embodiment, the process for producing butadiene rubber according to the invention is carried out according to the schematic process flow diagram shown in fig. 1, specifically, the polymerization reactor consists of three reactors connected in series in sequence, the 1, 3-butadiene monomer 1 and the solvent 2 sequentially pass through the first reactor a, the second reactor B and the third reactor C, and the part of the butadiene rubber cement 3 recycled to the inlet of the polymerization reactor obtained at the outlet of the third reactor C is returned to the inlet of the first reactor a, and the remaining part of the butadiene rubber cement 4 introduced as a crude product into the subsequent processing unit is subjected to desolventizing treatment.
The concentration of the butadiene rubber cement obtained from the outlet of the polymerization reactor can reach 18 to 23 weight percent by adopting the method for producing butadiene rubber. Moreover, the method of the invention obviously reduces the addition amount of the solvent, reduces the consumption of the solvent, further reduces the consumption of steam for recovering the solvent, and has certain energy-saving effect.
The method of the present invention is not particularly limited in the kind of the catalyst used in the production of the butadiene rubber, and various catalysts conventionally used in the art may be used.
Preferably, the catalyst is at least one selected from the group consisting of a nickel-based catalyst, a cobalt-based catalyst, and a rare earth-based catalyst.
The nickel-based catalyst may be, for example, the nickel-based catalyst disclosed in CN 103172789A.
The cobalt-based catalyst may be, for example, a cobalt-based catalyst disclosed in CN 104151454A.
The rare earth catalyst may be, for example, a rare earth catalyst disclosed in CN 105524197A.
The solvent amount required to be added for producing each ton of dry glue by adopting the method can be reduced to 60-80 wt% in the prior art.
The present invention will be described in detail below by way of examples.
Unless otherwise specified, various raw materials used below are commercially available.
The solvents used below are all hexane.
The catalyst used below was a nickel-based catalyst, which was a Ni-a L-B three-way catalyst in which Ni was nickel naphthenate, Al was triisobutylaluminum, B was boron trifluoride diethyl etherate, and Ni: Al: B was 1: 5.3: 10 (molar ratio) and Ni/1, 3-butadiene monomer (molar ratio) was 1.5 × 10 at the time of feeding-5。
In order to more clearly illustrate the process for producing cis-butadiene rubber of the present invention, the following examples and comparative examples were all subjected to adiabatic polymerization using the operating temperature and outlet conversion shown in Table 1.
TABLE 1
| Operating temperature/. degree.C | Outlet conversion/weight% | |
| First reactor | 70 | 56 |
| Second reactor | 90 | 77 |
| Third reactor | 96 | 85 |
Examples 1 to 8 are intended to illustrate the process for producing cis-butadiene rubber of the present invention.
Example 1
This example used three polymerization reactors shown in FIG. 1 connected in series in sequence, each having a volume of 120L, for solution polymerization, and was operated in a continuous process.
In the first reactor in this example, the total material feed rate was 150kg/h, wherein the 1, 3-butadiene monomer feed rate was 25.2kg/h, the solvent feed rate was 82.8kg/h, the catalyst feed rate was 10kg/h, and the feed temperatures of the three streams of materials cooled by low-temperature water were all 0 ℃. The operating temperatures and outlet conversions for the three reactors were controlled as shown in table 1. And the amount of the butadiene rubber cement liquid circulated back to the inlet of the first reactor was 32kg/h, and the temperature of the circulated cement liquid from the third reactor was cooled to 40 ℃ by circulating cooling water before entering the inlet of the first reactor. The average residence time of the materials in each reactor was 30min, and after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 13.7 wt%, 17.4 wt% and 18.8 wt%, respectively, and the solvent amount required in the polymerization process was 4t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
Example 2
This example was carried out using the same polymerization reactor as in example 1.
In the first reactor in this example, the total material feed rate was 150kg/h, wherein the 1, 3-butadiene monomer feed rate was 24.5kg/h, the solvent feed rate was 72.5kg/h, the catalyst feed rate was 10kg/h, and the feed temperatures of the three streams of materials cooled by low-temperature water were all 0 ℃. The operating temperatures and outlet conversions for the three reactors were controlled as shown in table 1. And the amount of the butadiene rubber cement liquid circulated back to the inlet of the first reactor was 43kg/h, and the temperature of the circulated cement liquid from the third reactor was cooled to 45 ℃ by circulating cooling water before entering the inlet of the first reactor. The average residence time of the materials in each reactor was 30min, and after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 15.8 wt%, 19.4 wt% and 20.8 wt%, respectively, and the solvent amount required in the polymerization process was 3.8t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
Example 3
This example was carried out using the same polymerization reactor as in example 1.
In the first reactor in this example, the total feed rate of the materials was 150kg/h, wherein the feed rate of 1, 3-butadiene monomer was 24.9kg/h, the feed rate of solvent was 76.6kg/h, the feed rate of catalyst was 10kg/h, and the feed temperatures of the three materials after cooling with low-temperature water were all 0 ℃. The operating temperatures and outlet conversions for the three reactors were controlled as shown in table 1. And the amount of the butadiene rubber cement liquid circulated back to the inlet of the first reactor was 38.5kg/h, and the temperature of the circulated cement liquid from the third reactor was cooled to 50 ℃ by circulating cooling water before entering the inlet of the first reactor. The average residence time of the materials in each polymerization reactor was 30min, and after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 14.9 wt%, 18.5 wt% and 19.9 wt%, respectively, and the solvent amount required in the polymerization process was 4t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
Example 4
This example was carried out using the same polymerization reactor as in example 1.
In the first reactor in this example, the total material feed rate was 150kg/h, wherein the 1, 3-butadiene monomer feed rate was 25.1kg/h, the solvent feed rate was 81.9kg/h, the catalyst feed rate was 10kg/h, and the feed temperatures of the three streams of materials cooled by low-temperature water were all 2.5 ℃. The operating temperatures and outlet conversions for the three reactors were controlled as shown in table 1. And the amount of the cis-butadiene rubber cement circulated back to the inlet of the first reactor was 33kg/h, and the temperature of the circulating cement from the third reactor was cooled to 50 ℃ by circulating cooling water. The average residence time of the materials in each reactor was 30min, and after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 13.9 wt%, 17.6 wt% and 18.9 wt%, respectively, and the solvent amount required in the polymerization process was 4.2t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
Example 5
This example was carried out using the same polymerization reactor as in example 1.
In the first reactor in this example, the total feed rate of the materials was 150kg/h, wherein the feed rate of the 1, 3-butadiene monomer was 24.7kg/h, the feed rate of the solvent was 73.3kg/h, the feed rate of the catalyst was 10kg/h, and the feed temperatures of the three materials after cooling with low-temperature water were all-5 ℃. The operating temperatures and outlet conversions for the three reactors were controlled as shown in table 1. And the amount of the butadiene rubber cement liquid circulated back to the inlet of the first reactor was 42kg/h, and the temperature of the circulated cement liquid from the third reactor was cooled to 40 ℃ by circulating cooling water before entering the inlet of the first reactor. The average residence time of the materials in each reactor was 30min, and after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 15.6 wt%, 19.3 wt% and 20.7 wt%, respectively, and the solvent amount required in the polymerization process was 3.8t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
Example 6
This example was carried out using the same polymerization reactor as in example 1.
In the first reactor in this example, the total feed rate of the materials was 150kg/h, wherein the feed rate of 1, 3-butadiene monomer was 25kg/h, the feed rate of solvent was 78kg/h, the feed rate of catalyst was 10kg/h, and the feed temperatures of the three materials after cooling with low-temperature water were all 2.5 ℃. The operating temperatures and outlet conversions for the three reactors were controlled as shown in table 1. And the amount of the butadiene rubber cement liquid circulated back to the inlet of the first reactor was 37kg/h, and the temperature of the circulated cement liquid from the third reactor was cooled to 45 ℃ by circulating cooling water before entering the inlet of the first reactor. The average residence time of the materials in each reactor was 30min, and after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were 14.6 wt%, 18.3 wt% and 19.7 wt%, respectively, and the solvent amount required in the polymerization process was 4.1t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
From the results of the above examples 1-6, it can be seen that the glue solution obtained by the method of the present invention has a high concentration, and the amount of the solvent used in the polymerization process is low, even significantly lower than the solvent usage level of the prior art, thus demonstrating that the method of the present invention has a significant energy saving effect.
Example 7
This example was carried out in a similar manner to example 1, except that:
the amount of the cis-butadiene rubber cement circulated back to the inlet of the first reactor in this example was 15 kg/h.
Specifically, in this example, the total material feeding amount is 150kg/h, wherein the feeding amount of the 1, 3-butadiene monomer is 25.2kg/h, the feeding amount of the solvent is 99.8kg/h, the feeding amount of the catalyst is 10kg/h, and the feeding temperatures of the three materials after being cooled by the low-temperature water are all 0 ℃.
The rest is the same as in example 1.
As a result: the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 13.2 wt%, 18.0 wt% and 19.1 wt%, respectively, and the amount of solvent required in the polymerization process was 4.5t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
From the results of this example, it can be seen that the solvent consumption in the polymerization process can be reduced compared to the prior art by using the method of the present invention while ensuring the obtained glue solution has a higher concentration.
While comparing the results of this example with those of example 1, it can be seen that by adding a larger amount of fresh solvent at 0 ℃ when the amount of the butadiene rubber cement recycled to the inlet of the first reactor is smaller, although the concentration of the cement obtained at the outlet of the reactor is comparable to that of example 1, the solvent consumption is significantly higher than that of example 1.
Example 8
This example was carried out in a similar manner to example 2, except that:
the temperature of the circulating cement from the third reactor was cooled to 20 ℃ by circulating cooling water before entering the inlet of the first reactor.
The rest is the same as in example 2.
As a result: the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 15.6 wt%, 18.8 wt% and 19.9 wt%, respectively, and the amount of solvent required in the polymerization process was 4t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
From the results of this example, it can be seen that the solvent consumption during the polymerization process can be made lower by the process of the present invention while ensuring the obtained dope concentration is higher.
Comparing the results of this example with those of example 2, it can be seen that even if the temperature of the circulating dope from the third reactor is lowered more, the solvent consumption cannot be saved to a greater extent, and the concentration of the dope obtained at the outlet of the reactor is not as high as that of example 2.
Comparative example 1
This comparative example was carried out in a similar manner to example 1, except that no circulating glue was provided in this comparative example, that is, the butadiene rubber glue obtained from the outlet of the third polymerization reactor in this comparative example was entirely introduced as a crude product into the subsequent processing unit. The total material feeding amount is 150kg/h, wherein the feeding amount of the 1, 3-butadiene monomer is 25.2kg/h, the feeding amount of the solvent is 114.8kg/h, the feeding amount of the catalyst is 10kg/h, and the feeding temperatures of the three materials after being cooled by low-temperature water are all 0 ℃.
Then, after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 10.6 wt%, 14.5 wt% and 15.8 wt%, respectively, and the amount of the solvent required in the polymerization process was 5.3t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
Comparative example 2
This comparative example was carried out in a similar manner to comparative example 1, except that in this comparative example, the feed rate of 1, 3-butadiene monomer was 30kg/h, the feed rate of solvent was 110kg/h, the feed rate of catalyst was 10kg/h, and the feed temperatures of the three streams of material cooled with low-temperature water were all 0 ℃.
Then, after the polymerization in the adiabatic solution, the concentrations of the glue solutions at the outlets of the first reactor, the second reactor and the third reactor were measured to be 11.2 wt%, 15.3 wt% and 16.7 wt%, respectively, and the amount of the solvent required in the polymerization process was 5.2t/t dry glue. The results of the mass analysis of the obtained butadiene rubber product are shown in the following table 2.
TABLE 2
As can be seen from the results of the comparative examples and the comparative examples, when the method is used for producing the butadiene rubber, the solvent consumption in the polymerization process can be obviously reduced, the solvent consumption per ton of dry rubber is reduced, the steam consumption for solvent recovery is further reduced, and a better energy-saving effect is achieved. Moreover, the quality of the butadiene rubber product obtained by the method of the example of the invention is comparable to, or even better than, that of the butadiene rubber product obtained by the method of the comparative example.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (13)
1. A process for producing butadiene rubber, the process comprising: under the condition of solution polymerization, introducing a 1, 3-butadiene monomer and a solvent into a polymerization reactor for polymerization reaction, circulating part of butadiene rubber liquid obtained at an outlet of the polymerization reactor back to an inlet of the polymerization reactor, and introducing the rest part of butadiene rubber liquid serving as a crude product into a subsequent processing unit; the temperature of the butadiene rubber liquid circulating back to the inlet of the polymerization reactor is 20-70 ℃; the total weight of all the butadiene rubber liquid obtained at the outlet of the polymerization reactor is taken as the reference, the butadiene rubber liquid circulated back to the inlet of the polymerization reactor is 5-35 wt%, and the method is carried out by adopting a continuous operation process.
2. The process according to claim 1, wherein the temperature of the portion of the butadiene rubber cement recycled to the inlet of the polymerization reactor is 35-55 ℃.
3. A process according to claim 1 or 2, wherein the butadiene rubber cement recycled back to the inlet of the polymerization reactor is from 15 to 30% by weight, based on the total weight of all butadiene rubber cement obtained at the outlet of the polymerization reactor.
4. The process according to claim 1 or 2, wherein the 1, 3-butadiene monomer and the solvent are used in a weight ratio of 1: 2.5-5.
5. The process according to claim 1 or 2, wherein the 1, 3-butadiene monomer and the solvent are used in a weight ratio of 1: 3.5-4.5.
6. The method according to claim 1 or 2, wherein the solution polymerization reaction is carried out in the presence of a catalyst selected from at least one of a nickel-based catalyst, a cobalt-based catalyst, and a rare earth-based catalyst.
7. The process of claim 1 or 2, wherein the conditions of the solution polymerization reaction comprise: the polymerization reaction temperature is 50-100 ℃; the polymerization time is 45-150 minutes.
8. The process of claim 1 or 2, wherein the conditions of the solution polymerization reaction comprise: the polymerization reaction temperature is 65-95 ℃; the polymerization time is 60 to 90 minutes.
9. The process of claim 1 or 2, wherein the temperature of the 1, 3-butadiene monomer and the solvent is no greater than 10 ℃ prior to entering the polymerization reactor for polymerization.
10. The process of claim 1 or 2, wherein the temperature of the 1, 3-butadiene monomer and the solvent is from-15 ℃ to-5 ℃ prior to entering the polymerization reactor for polymerization.
11. The process according to claim 1, wherein the process is carried out in a system comprising at least three polymerization reactors connected in series, and part of the butadiene rubber cement obtained at the outlet of the last polymerization reactor is recycled to the inlet of the first polymerization reactor.
12. The process according to claim 11, wherein the process is carried out in a system comprising three polymerization reactors connected in series.
13. The method of claim 1, wherein the solvent is selected from at least one of pentane, isopentane, hexane, cyclohexane, methylcyclohexane, heptane, and octane.
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| US3250757A (en) * | 1961-05-18 | 1966-05-10 | Phillips Petroleum Co | Method and apparatus for controlling feed to a polymerization reaction |
| CN102504066A (en) * | 2011-11-11 | 2012-06-20 | 茂名鲁华化工有限公司 | Method for solvent refining during isoprene rubber production |
| CN104159928A (en) * | 2012-03-12 | 2014-11-19 | 埃克森美孚化学专利公司 | Processes and apparatus for continuous solution polymerization |
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| RU2288235C1 (en) * | 2005-08-12 | 2006-11-27 | Открытое акционерное общество "Нижнекамскнефтехим" | Method for producing synthetic rubber |
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| US3250757A (en) * | 1961-05-18 | 1966-05-10 | Phillips Petroleum Co | Method and apparatus for controlling feed to a polymerization reaction |
| CN102504066A (en) * | 2011-11-11 | 2012-06-20 | 茂名鲁华化工有限公司 | Method for solvent refining during isoprene rubber production |
| CN104159928A (en) * | 2012-03-12 | 2014-11-19 | 埃克森美孚化学专利公司 | Processes and apparatus for continuous solution polymerization |
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