CN113929550A - Mixed carbon four-superposition reaction method and device - Google Patents
Mixed carbon four-superposition reaction method and device Download PDFInfo
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- 238000000926 separation method Methods 0.000 claims abstract description 92
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- 238000006116 polymerization reaction Methods 0.000 claims abstract description 82
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- 239000002994 raw material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 238000006471 dimerization reaction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/177—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by selective oligomerisation or polymerisation of at least one compound of the mixture
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a mixed carbon four-polymerization reaction method, which comprises S1, carrying out a first polymerization reaction on mixed carbon four in a first reactor to obtain a first polymerization reactant, wherein a first catalyst is arranged in the first reactor; and S2, introducing the first superposed reactant obtained in the step S1 into a second reaction separation tower, wherein the second reaction separation tower is provided with a separation section and a reaction section, the reaction section is provided with a second catalyst, and the first superposed reactant is subjected to gas-liquid separation in the separation section, so that the obtained first gas phase is subjected to a second superposed reaction in the reaction section to obtain a second superposed reactant. The method can ensure that the conversion rate of isobutene in the mixed C4 is more than 97 percent and the conversion rate of 1-butene is less than 10 percent by using the two catalysts in a compatible manner, thereby realizing the separation of isobutene and 1-butene and obtaining the residual C4 which meets the requirements of raw materials of a 1-butene separation device.
Description
Technical Field
The invention belongs to the technical field of comprehensive utilization of carbon four, and particularly relates to a mixed carbon four-polymerization reaction method and a mixed carbon four-polymerization reaction device.
Background
1-butene is alpha-olefin with active chemical property, is an important chemical raw material and is mainly used as a comonomer for producing Linear Low Density Polyethylene (LLDPE), High Density Polyethylene (HDPE) and polybutene-1 (PB) plastics. In addition, the method can also be used for producing fine chemical products such as sec-butyl alcohol \ methyl ethyl ketone and butylene oxide, preparing butadiene, 1-octene, dodecene, valeraldehyde and derivatives thereof by oxidative dehydrogenation, high-grade plasticizer alcohol, special solvent oil and the like.
The 1-butene is generally prepared by reacting the raffinate C4 from the butadiene extraction unit with commercially available methanol to produce MTBE and chemically reacting the isobutylene. The remaining ether post C4 was used to purify polymerization grade butene-1, the product was used in downstream polyethylene units for comonomer or export. With the vigorous popularization and implementation of the embodiment on expanding the production of biofuel ethanol and popularizing and using the ethanol gasoline for vehicles, the MTBE synthesis device faces production stop and transfer, and how to realize the separation of 1-butene and isobutene is a difficult problem for enterprises.
The selective polymerization of mixed C4 is the main way to realize the separation of isobutene and 1-butene, isobutene is reacted through isobutene polymerization reaction, and the residual C4 is used as the raw material of a 1-butene separation device, thereby realizing the transformation of an MTBE synthesis device. Resin is generally adopted as a catalyst for the polymerization of the mixed C4, but in the polymerization reaction process, the 1-butene is easy to generate double bond isomerization and polymerization, the loss is more, and the loss amount reaches 50-70%. In order to control the conversion rate of 1-butene, the prior art mainly adopts adding an inhibitor to control the conversion degree of the polymerization reaction.
CN101190860A is that C4 raw material and methanol are simultaneously fed, the polymerization-etherification reaction is carried out in the presence of solid acid, the weight conversion rate of n-butene is controlled to be less than 10% by controlling the reaction conditions, but the MTBE content in the product is more than 50%, the isobutene reaction conversion rate is low, and the like.
Disclosure of Invention
At present, the carbon tetra-polymerization reaction has defects, the loss of 1-butene in the reaction process is too high, and the carbon tetra-polymerization reaction cannot be combined with a downstream 1-butene separation device. Therefore, there is a need for improvement and research on the selective polymerization process to explore its potential, so as to achieve the purposes of reducing 1-butene loss and improving economic benefits. Therefore, according to the first aspect of the invention, a mixed carbon four-polymerization reaction method is provided, and the method realizes that the conversion rate of isobutene is more than 97% and the conversion rate of 1-butene is less than 10% by using a resin catalyst and a molecular sieve catalyst together. The second aspect of the invention provides an application of a mixed carbon four-stacking reaction method in mixed carbon four separation. In a third aspect, the invention provides an apparatus for use in a hybrid carbon-four metathesis process.
According to a first aspect, the present invention provides a mixed carbon tetra-stacking reaction process comprising the steps of:
s1, carrying out a first polymerization reaction on the mixed C4 in a first reactor to obtain a first polymerization reactant, wherein the first reactor is provided with a first catalyst;
s2, introducing the first superposed reactant obtained in the step S1 into a second reaction separation tower, wherein the second reaction separation tower is provided with a separation section and a reaction section, the reaction section is provided with a second catalyst, the first superposed reactant is subjected to gas-liquid separation in the separation section, and a first gas phase obtained by the gas-liquid separation is subjected to a second superposed reaction in the reaction section to obtain a second superposed reactant;
wherein the first catalyst is selected from one or more of cation exchange resins in the hydrogen form and the second catalyst is selected from one or more of molecular sieve catalysts.
According to some embodiments of the invention, the first polymerization reactant comprises dimerization and oligomerization products of isobutylene.
According to some embodiments of the invention, the second polymerization reactant comprises dimerization and oligomerization products of isobutylene.
According to some preferred embodiments of the invention, eight of the carbons in the dimerization and oligomerization product of isobutene constitutes 80% to 90% and more than twelve carbons constitutes 10% to 20%.
According to some embodiments of the invention, the reaction section is disposed in an upper portion of the second reactive separation column and the separation section is disposed in a lower portion of the second reactive separation column.
According to some embodiments of the present invention, the first polymerization reactant is first introduced into the separation section of the second reaction-separation tower to be separated, so as to obtain a gas phase material containing isobutylene, and the gas phase material containing isobutylene is introduced into the reaction section to be subjected to a second polymerization reaction, so as to obtain a second polymerization reactant.
According to some embodiments of the present invention, the upper part of the second reaction-separation tower is a reaction section, and the lower part of the second reaction-separation tower is a separation section, so that the reaction and the separation are performed simultaneously, the equilibrium conversion rate of isobutene is further improved, and the investment cost of the device is saved.
According to some embodiments of the invention, the mass ratio of the first catalyst to the second catalyst is 1 (1-10), such as 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.5, 1:7, 1:7.5, 1:8, 1:8.5, 1:9, 1:9.5, 1:10, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the first catalyst to the second catalyst is 1 (1-10), the mass ratio is too high, the retention time of mixed C4 on the resin catalyst is too long, the conversion rate of 1-butene is increased, and more 1-butene is lost; the mass ratio is too low, on one hand, the use amount of the molecular sieve catalyst is increased, which increases the cost of the molecular sieve catalyst, and on the other hand, too much isobutene is polymerized on the molecular sieve, and too much oligomer is generated.
According to some embodiments of the invention, the mass ratio of the first catalyst to the second catalyst is 1 (2-7).
According to some embodiments of the invention, the cation exchange resin in hydrogen form is selected from one or more of the group consisting of strong acid cation exchange resins.
According to some embodiments of the invention, the hydrogen cation exchange resin is selected from one or more of styrenic cation exchange resins, acrylic cation exchange resins, epoxy cation exchange resins and phenolic cation exchange resins.
According to some embodiments of the invention, the cation exchange resin in the hydrogen form is selected from one or more of the group consisting of D006 resin, D002 resin, Amberlyst-15 resin, Amberlyst-35 resin, Amberlyst-45 resin, and nkc-9 resin.
According to some embodiments of the invention, the molecular sieve catalyst is selected from one or more of mordenite, a Y-series molecular sieve, a ZSM-series molecular sieve, an MCM-series molecular sieve, a beta-series molecular sieve and a SAPO-series molecular sieve.
According to some embodiments of the invention, the molecular sieve catalyst is selected from one or more of ZSM-5, MCM-22, mordenite, MCM-41, SAPO-11, and SAPO-41.
According to some embodiments of the invention, the molecular sieve catalyst is synthesized using conventional methods, preferably the molecular sieve is prepared by a method comprising: mixing the molecular sieve powder with adhesive and acid in certain proportion, kneading, extruding, drying and roasting.
According to some embodiments of the invention, the binder is pseudoboehmite.
According to some embodiments of the invention, the acid is nitric acid.
According to some embodiments of the invention, the molecular sieve to binder weight ratio is from 8:2 to 5: 5.
According to some embodiments of the present invention, the drying temperature is 100-120 ℃, and the drying time is 2-6 h.
According to some embodiments of the present invention, the calcination temperature is 400-600 ℃, and the calcination time is 4-10 h.
According to some embodiments of the invention, the blended carbon four is selected from one or more of cracked carbon four, refinery carbon four, and FCC light carbon four.
In some preferred embodiments of the invention, the mixed C.sub.four is selected from any of the isobutene-containing C.sub.four, such as steam cracked C4, FCC light C4 or mixed C4, and coal chemical by-product C4.
According to some embodiments of the invention, the isobutylene content of the mixed C4 is 5-90% by mass.
According to some embodiments of the invention, the isobutene content of the mixed C4 is 10-80% by mass.
According to some embodiments of the invention, the carbon four blend is selected from the group consisting of cracking carbon four and/or refinery carbon four.
According to some embodiments of the invention, the mixed C.sub.D comprises 1 to 20 wt% alkanes and 20 to 90 wt% butenes.
According to some embodiments of the invention, the butenes include 1-butene, isobutene, trans-2-butene, and cis-2-butene.
According to some embodiments of the invention, the alkane comprises isobutane and/or n-butane.
According to some embodiments of the invention, the temperature of the first polymerization reaction is 15-70 ℃, such as 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃ and any value in between.
According to some embodiments of the invention, the temperature of the first polymerization reaction is between 25 and 50 ℃.
According to some embodiments of the invention, the pressure of the first folding reaction is between 0.4 and 1.5MPa, such as 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa and any value in between.
According to some embodiments of the invention, the pressure of the first polymerization reaction is between 0.5 and 1.0 MPa.
According to some embodiments of the invention, the first stacking reaction has a mixed C4 feed space velocity of 0.5h-1-5h-1E.g. 0.5h-1、1.0h-1、1.5h-1、2.0h-1、2.5h-1、3.0h-1、3.5h-1、4.0h-1、4.5h-1、5.0h-1And any value in between.
According to some embodiments of the invention, the feed space velocity of the mixed C4 is 1.5-4.0h-1。
According to some embodiments of the invention, the conversion of isobutylene in the first polymerization reaction is 70-95%, such as 70%, 72%, 74%, 75%, 76%, 78%, 80%, 82%, 84%, 74%, 85%, 86%, 87%, 88%, 90%, 92%, 94%, 95% and any value in between.
According to some embodiments of the invention, the conversion of isobutylene in the first polymerization reaction is 80-90%.
The invention can ensure a certain conversion of isobutene and reduce the conversion of 1-butene by controlling the reaction temperature of the first polymerization reaction and the conversion rate of isobutene in the first polymerization reaction.
According to some embodiments of the invention, the temperature of the second polymerization reaction is 50-150 ℃, such as 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 78 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃, 105 ℃, 110 ℃, 115 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃ and any value in between.
According to some embodiments of the invention, the temperature of the second polymerization reaction is 60-120 ℃.
According to some embodiments of the invention, the pressure of the second polymerization reaction is between 0.4 and 1.5MPa, such as 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa and any value in between.
According to some embodiments of the invention, the pressure of the second polymerization reaction is between 0.6 and 1.0 MPa.
According to some embodiments of the invention, the temperature of the separation process is 180-.
According to some embodiments of the invention, the temperature of the separation process is 190-210 ℃.
According to some embodiments of the invention, the pressure of the separation treatment is 0.4-1.5MPa, such as 0.4MPa, 0.5MPa, 0.6MPa, 0.7MPa, 0.8MPa, 0.9MPa, 1.0MPa, 1.1MPa, 1.2MPa, 1.3MPa, 1.4MPa, 1.5MPa and any value in between.
According to some embodiments of the invention, the pressure of the separation process is between 0.6 and 1.0 MPa.
According to some embodiments of the invention, the temperature of the second polymerization reaction is higher than the temperature of the first polymerization reaction.
In some preferred embodiments of the present invention, the temperature of the second polymerization reaction is 20 to 60 ℃ higher than that of the first polymerization reaction.
In some preferred embodiments of the invention, the method specifically comprises the steps of:
And 2, enabling the first polymerization reaction product to enter a separation tower, wherein a molecular sieve solid acid catalyst is arranged at the upper part of the separation tower, further performing polymerization reaction on unreacted isobutene under the catalytic action of the molecular sieve solid acid catalyst, obtaining residual carbon IV rich in 1-butene at the tower top, and obtaining a polymerization product at the tower bottom.
The inventor finds in research that during the reaction of the resin catalyst, the temperature is higher for obtaining higher isobutene conversion rate, but the 1-butene is converted at high temperature; in the reaction process of the molecular sieve catalyst, 1-butene basically does not react, but isobutene polymers are generated more, and the content of C8 in a superposed product is lower. According to the invention, by adopting the compatibility of the resin catalyst and the molecular sieve catalyst and combining the characteristics of the resin catalyst and the molecular sieve catalyst, 80-90% of isobutene is superposed on the low-temperature resin catalyst, about 10% of isobutene is superposed on the high-temperature molecular sieve, so that the dimerization selectivity of isobutene is ensured to be more than 80%, the 1-butene conversion rate is ensured to be less than 10%, meanwhile, the upper part of a second reaction separation tower in the reaction process of the molecular sieve catalyst is a reaction section, the lower part of the second reaction separation tower is a separation section, and the reaction and the separation are carried out simultaneously, so that the equilibrium conversion rate of isobutene is further improved, and the investment cost of the device is saved.
In a second aspect of the invention, the invention provides the use of the process of the first aspect in mixed C-C separations.
According to some embodiments of the present invention, there is provided the use of the process of the first aspect in the separation of 1-butene from isobutene.
In some preferred embodiments of the present invention, the process of the first aspect may be used for the separation of 1-butene in the etherification of C4 in the MTBE synthesis reaction.
According to a third aspect, the present invention provides a first polymerization reactor and a second reaction-separation column, the second reaction-separation column is provided with a separation section and a reaction section, and the first polymerization reactor is connected with the separation section of the second reaction-separation column.
According to some embodiments of the invention, the reaction section is disposed in an upper portion of the second reactive separation column and the separation section is disposed in a lower portion of the second reactive separation column.
According to some embodiments of the invention, the first polymerization reactor is used to subject mixed carbon four to a first polymerization reaction to obtain a first polymerization reactant.
According to some embodiments of the invention, the second reactive separation column is adapted to subject the first product of the first polymerization to a second polymerization reaction to obtain a second polymerization reactant.
In some preferred embodiments of the present invention, the separation section of the second reaction-separation column is used for separating the first polymerization reactant to obtain the gas phase material containing isobutene, and the reaction section of the second reaction-separation column is used for subjecting the gas phase material containing isobutene to a second polymerization reaction to obtain a second polymerization reactant.
The invention has the beneficial effects that: according to the invention, through the compatible use of the two catalysts, the deep conversion rate of isobutene in the mixed C4 can be increased to more than 97%, the conversion rate of 1-butene can be controlled to be less than 10%, so that the separation of isobutene and 1-butene is realized, and the obtained residual C4 meets the requirements of raw materials of a 1-butene separation device.
Drawings
FIG. 1 is a process flow diagram of the hybrid carbon-four stacking reaction of the present invention,
description of reference numerals: 1-mixed C4 raw material, 2-first superimposed reactor, 3-second reaction separation tower, 4-molecular sieve catalyst and 5-residual C6-superimposed product.
Detailed Description
The invention provides a mixed carbon four-polymerization reaction method, as shown in figure 1, mixed carbon four (5.51 percent of isobutane, 11.66 percent of n-butane, 7.53 percent of trans-2-butene, 29.6 percent of 1-butene, 41.33 percent of isobutene and 3.84 percent of cis-2-butene) enters a first fixed bed polymerization reactor 1 through a metering pump, a resin catalyst is filled in the reactor, the temperature is 25-50 ℃, the pressure is 0.5-1.0MPa, and the feeding airspeed is 1.5h-1～4.0h-1The polymerization reaction is carried out under the condition, and the conversion rate of the isobutene is controlled to be 85-90 percent. The superimposed product enters a separation tower from the middle lower part of the separation tower, the molecular sieve catalyst is arranged at the upper part of the separation tower, the reaction temperature is 60-120 ℃, the pressure is 0.6-1.0MPa, and the superimposed reaction is continuously carried out on the molecular sieve catalyst bed layer at the upper part of the separation tower. The total conversion rate of isobutene is more than 97%, and the total conversion rate of 1-butene is less than 10%. The residual carbon four rich in 1-butene is obtained at the top of the separation tower, and the superposed product is obtained at the bottom of the separation tower.
The present invention is further illustrated by the following examples, which are intended to be purely exemplary of the invention and are not to be construed as limiting the invention in any way.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1:
carbon four (5.51% isobutane, 11) was mixed.66 percent of normal butane, 7.53 percent of trans-2-butene, 29.6 percent of 1-butene, 41.33 percent of isobutene and 3.84 percent of cis-2-butene) enter a fixed bed polymerization reactor through a metering pump, 15g of NKC-9 resin catalyst is filled in the reactor, the temperature is 30 ℃, the pressure is 0.75MPa, and the feeding airspeed is 1.5h-1The polymerization reaction takes place under these conditions, with an isobutene conversion of 87% being controlled. The superimposed product enters a separation tower from the middle lower part of the separation tower, the upper part of the separation tower is filled with 30g of SAPO-11 molecular sieve catalyst (the mass ratio of the resin catalyst to the molecular sieve catalyst is 1:2), the reaction temperature is 70 ℃, the pressure is 0.6MPa, and the feeding airspeed is 0.5h-1. The temperature of the bottom of the separation tower is 193 ℃, and the pressure is 0.55MPa, under the condition, the superimposed product is separated from the unreacted C4. And (3) separating the superposed product from the bottom of the tower, allowing unreacted C4 to enter a molecular sieve catalyst bed layer on the upper part of the separation tower for continuous superposition reaction, allowing the product of the continuous reaction to enter the lower part of the separation tower for separation, and collecting the residual C4 from the top of the tower. Through the combined reaction, the total conversion rate of isobutene is 97.2 percent, and the total conversion rate of 1-butene is 6.5 percent. The top of the separation tower obtains 1-butene-rich residual carbon four, and the bottom of the separation tower obtains a superposed product, and the specific results and conditions are listed in table 1.
Example 2:
the same as example 1, except that Amberlyst-35 catalyst was used as the catalyst in the polymerization reactor. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 98.1%, the conversion rate of 1-butene is 7.5%, and specific results and conditions are listed in Table 1.
Example 3:
the same as example 1, except that the catalyst used in the polymerization reactor was Amberlyst-35 catalyst and the catalyst loaded in the upper part of the separation column was MCM-22 molecular sieve catalyst. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 98.5%, the conversion rate of 1-butene is 8.2%, and specific results and conditions are listed in Table 1.
Example 4
The same as example 1, except that the first polymerization reactor was charged with 10g of Amberlyst-35 resin catalyst and the second reactor was charged with 60g of MCM-22 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst was 1:6. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 99.5%, the conversion rate of 1-butene is 8.5%, and specific results and conditions are listed in Table 1.
Example 5
The same as example 1, except that the first polymerization reactor was packed with 15g of NKC-9 resin catalyst and the second reactor was packed with 60g of MCM-22 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst was 1:4. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 99.0%, the conversion rate of 1-butene is 8.2%, and specific results and conditions are listed in table 1.
Example 6
The same as example 1, except that the first polymerization reactor was packed with 10g of NKC-9 resin catalyst and the second reactor was packed with 50g of MCM-22 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst was 1:5. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 99.3%, the conversion rate of 1-butene is 7.5%, and specific results and conditions are listed in Table 1.
Example 7
The same as example 1 except that the first polymerization reactor was charged with 10g of Amberlyst-35 resin catalyst and the second reactor was charged with 50g of sappo 11 molecular sieve catalyst in a 1:5 mass ratio of resin catalyst to molecular sieve catalyst. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 98.6%, the conversion rate of 1-butene is 8.0%, and specific results and conditions are listed in table 1.
Example 8
The same as example 1, except that the first polymerization reactor was charged with 10g of NKC-9 resin catalyst and the second reactor was charged with 70g of SAPOP11 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst was 1:7. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 99.1%, the conversion rate of 1-butene is 7.7%, and specific results and conditions are listed in Table 1.
Example 9
The same as example 1, except that the first polymerization reactor was charged with 50g of NKC-9 resin catalyst and the second reactor was charged with 25g of SAPOP11 molecular sieve catalyst, the mass ratio of resin catalyst to molecular sieve catalyst was 1: 0.5. After the two catalysts are subjected to compatibility reaction, the total conversion rate of isobutene is 98.2%, the conversion rate of 1-butene is 14.3%, and specific results and conditions are listed in table 1.
Comparative example 1
The same as example 1 except that the first polymerization reactor was charged with 25g of NKC-9 resin catalyst and the second reactor was charged with 50g of NKC-9 resin catalyst, the total conversion of isobutylene was 92.5% and the conversion of 1-butene was 15.6% after the reaction, and the specific results and conditions are shown in Table 1.
Comparative example 2
The same as example 2, except that the first polymerization reactor was charged with 25g of Amberlyst-35 catalyst and the second reactor was charged with 50g of Amberlyst-35 catalyst, the total conversion of isobutylene was 95.1% and the conversion of 1-butene was 17.0% after the reaction, and the specific results and conditions are shown in Table 1.
TABLE 1
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A mixed carbon four-fold reaction method, comprising the following steps:
s1, carrying out a first polymerization reaction on the mixed C4 in a first reactor to obtain a first polymerization reactant, wherein the first reactor is provided with a first catalyst;
s2, introducing the first superposed reactant obtained in the step S1 into a second reaction separation tower, wherein the second reaction separation tower is provided with a separation section and a reaction section, the reaction section is provided with a second catalyst, the first superposed reactant is subjected to gas-liquid separation in the separation section, and a first gas phase obtained by the gas-liquid separation is subjected to a second superposed reaction in the reaction section to obtain a second superposed reactant;
wherein the first catalyst is selected from one or more of cation exchange resins in the hydrogen form and the second catalyst is selected from one or more of molecular sieve catalysts.
2. The process of claim 1 wherein said reaction section is disposed in an upper portion of said second reactive separation column and said separation section is disposed in a lower portion of said second reactive separation column.
3. The method according to claim 1 or 2, wherein the mass ratio of the first catalyst to the second catalyst is 1 (1-10), preferably 1 (2-7).
4. The process according to any one of claims 1 to 3, wherein the cation exchange resin in hydrogen form is selected from one or more of strong acid cation exchange resins, preferably from one or more of styrenic cation exchange resins, acrylic cation exchange resins, epoxy cation exchange resins and phenolic cation exchange resins, preferably from one or more of D006 resin, D002 resin, Amberlyst-15 resin, Amberlyst-35 resin, Amberlyst-45 resin and nkc-9 resin.
5. A process according to any one of claims 1 to 4, characterized in that the molecular sieve catalyst is selected from one or more of mordenite, Y-series molecular sieves, ZSM-series molecular sieves, MCM-series molecular sieves, beta-series molecular sieves and SAPO-series molecular sieves, preferably from one or more of ZSM-5, MCM-22, mordenite, MCM-41, SAPO-11 and SAPO-41.
6. The process according to any one of claims 1 to 5, wherein the mixed carbon four is selected from one or more of cracking carbon four, refinery carbon four and FCC light carbon four, preferably, the content of isobutene in the mixed carbon four is 5 to 90% by mass, more preferably 10 to 80% by mass.
7. The process according to any one of claims 1 to 6, wherein the temperature of the first polymerization reaction is 15 to 70 ℃, preferably 25 to 50 ℃;
and/or the pressure of the first polymerization reaction is 0.4-1.5MPa, preferably 0.5-1.0 MPa;
and/or the feeding space velocity of the mixed C4 is 0.5-5.0h-1Preferably 1.5-4.0h-1；
And/or the conversion of isobutene in the first polymerization reaction is from 70 to 95%, preferably from 80 to 90%.
8. The process according to any one of claims 1 to 6, wherein the temperature of the second polymerization reaction is 50 to 150 ℃, preferably 60 to 120 ℃;
and/or the pressure of the second polymerization reaction is 0.4-1.5MPa, preferably 0.6-1.0 MPa;
and/or the temperature of the separation treatment is 180-230 ℃, preferably 190-210 ℃;
and/or the pressure of the separation treatment is 0.4-1.5MPa, preferably 0.6-1.0 MPa;
preferably, the temperature of the second polymerization reaction is higher than that of the first polymerization reaction, and preferably, the temperature of the second polymerization reaction is 20-60 ℃ higher than that of the first polymerization reaction.
9. Use of the process of any one of claims 1 to 8 for mixed C-C separation, in particular for the separation of 1-butene from isobutene.
10. An apparatus for use in the process of any one of claims 1 to 8, comprising a first polymerization reactor and a second reaction-separation column, the second reaction-separation column being provided with a separation section and a reaction section, preferably the reaction section being provided in an upper portion of the second reaction-separation column, the separation section being provided in a lower portion of the second reaction-separation column; and the first polymerization reactor is connected with the separation section of the second reaction separation tower.
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