CN111377788B - Method for oligomerization of isobutene - Google Patents
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- CN111377788B CN111377788B CN201811622909.5A CN201811622909A CN111377788B CN 111377788 B CN111377788 B CN 111377788B CN 201811622909 A CN201811622909 A CN 201811622909A CN 111377788 B CN111377788 B CN 111377788B
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- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 150000003457 sulfones Chemical class 0.000 claims abstract description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 15
- 239000000539 dimer Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims description 23
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 7
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 2
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 claims description 2
- JEXYCADTAFPULN-UHFFFAOYSA-N 1-propylsulfonylpropane Chemical compound CCCS(=O)(=O)CCC JEXYCADTAFPULN-UHFFFAOYSA-N 0.000 claims description 2
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 claims description 2
- JEIQEQBAZNCTKR-UHFFFAOYSA-N 3-butylthiolane 1,1-dioxide Chemical compound CCCCC1CCS(=O)(=O)C1 JEIQEQBAZNCTKR-UHFFFAOYSA-N 0.000 claims description 2
- XWVQGSWWPONKGD-UHFFFAOYSA-N 3-propylthiolane 1,1-dioxide Chemical compound CCCC1CCS(=O)(=O)C1 XWVQGSWWPONKGD-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- -1 carbonium ions Chemical class 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 4
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000006004 Quartz sand Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- RGYAVZGBAJFMIZ-UHFFFAOYSA-N 2,3-dimethylhex-2-ene Chemical compound CCCC(C)=C(C)C RGYAVZGBAJFMIZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007337 electrophilic addition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- 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
- C07C2/06—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 of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/28—Catalytic processes with hydrides or organic compounds with ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- C07C2531/08—Ion-exchange resins
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The oligomerization reaction of isobutene in reactor with resin catalyst is carried out by passing the mixture of isobutene and sulfone reagent through reactor to obtain dimer. The weight of the sulfone reagent in the mixture of the isobutene and the sulfone reagent is 0.05-10% of that of the isobutene. The adopted catalyst is strong acid cation exchange resin, and toluene and methyl isobutyl ketone are preferably used for modification and then catalytic oligomerization reaction is carried out. Due to the existence of sulfones, the adsorption capacity of isobutene on the surface of the catalyst is reduced, the reaction speed of isobutene forming two carbonium ions to polymerize to form dimers under the action of an acid center of the catalyst is increased, the reaction speed of three carbonium ions or a plurality of carbonium ions to further polymerize to form polymers is simulated, the selectivity of isobutene dimers is increased, and meanwhile, the higher isobutene conversion rate can be kept.
Description
Technical Field
The invention relates to a method for oligomerization of isobutene, in particular to a process method for effectively improving isobutene conversion rate and dimer selectivity.
Background
At present, isobutene is mostly used for synthesizing methyl tert-butyl ether (MTBE) and is used as a blending component of high-octane motor gasoline. However, this method using isobutylene has become unreasonable due to the serious pollution effect of methyl t-butyl ether on groundwater. Thus, is C 4 The isobutene in the fraction has very important practical significance for seeking a more reasonable utilization way.
The oligomerization of low-carbon olefin is one of the important chemical processes in the oil refining and organic chemical industry, wherein the oligomerization product of butylene is an important chemical intermediate, can be used for producing oligomerization gasoline and diesel oil, and can also be used as an important intermediate for producing detergents, plasticizers, additives and pesticides.
The oligomerization of isobutene is a typical acid-catalyzed reaction, and the catalyst mainly comprises a liquid acid catalyst and a solid acid catalyst. When liquid acid catalysts (sulfuric acid, methyl benzenesulfonic acid and the like) are adopted in the early stage, the reaction selectivity is poor, the purity of the product isobutene dimer is low, the catalysts are not easy to separate, the equipment is corroded, and the production process continuity is difficult to realize. In recent years, solid acid catalysts have gradually become hot spots for research on oligomerization of isobutene, and mainly include solid phosphoric acid catalysts, oxides and composite oxide catalysts, molecular sieve catalysts, ion exchange resin catalysts, supported sulfate catalysts, solid super acidic catalysts and the like.
At present, ion exchange resin is generally used as a catalyst for isobutene oligomerization, and in order to improve the selectivity of isobutene dimer, a solvent is added into a reaction system to reduce the generation of isobutene dimer.
Petrochemical 2007, volume 36, phase 3 reports that strong-acid cation exchange resin in tertiary butanol catalyzes oligomerization kinetics of isobutylene, and oligomerization kinetics of isobutylene (m) in a system of strong-acid cation exchange resin (catalyst) and tertiary butanol is studied. The result shows that isobutene oligomerization has the characteristic of first-order series irreversible reaction, and the addition of tertiary butanol in a reaction system can reduce the acidity of the catalyst, but improve the adsorption capacity of isobutene on the surface of the catalyst, and obviously improve the selectivity of a dimer (trimethylpentene) of isobutene, but reduce the conversion rate.
Disclosure of Invention
Aiming at the problems of low conversion rate or low dimer selectivity in an isobutene oligomerization reaction system in the prior art, the invention provides the isobutene oligomerization reaction method, so that the selectivity of the dimer can be obviously improved on the basis of keeping higher isobutene conversion rate of the reaction, and the subsequent products are easier to separate and the energy consumption is lower.
The oligomerization reaction of isobutylene is carried out by passing mixture of isobutylene and sulfone reagent into reactor with resin catalyst, and oligomerizing isobutylene to obtain dimer.
In the method, the weight of the sulfone reagent in the mixture of the isobutene and the sulfone reagent is 0.05-10 percent of that of the isobutene, and preferably 0.5-2.0 percent.
In the above method, the sulfone reagent is at least one selected from the group consisting of sulfolane, 2-methylsulfolane, 3-propylsulfolane, 3-butylsulfolane, dimethylsulfone, diethylsulfone, methylethylsulfone, and dipropylsulfone, and preferably at least one selected from the group consisting of sulfolane and dimethylsulfone.
In the above method, the specific operating conditions of the isobutylene oligomerization reaction are as follows: the liquid hourly space velocity of isobutene is 1.0h -1 ～18.0h -1 The reaction temperature is 100-200 ℃, and the reaction pressure is 1.0-5.0 MPa. Further, it is preferable that: the liquid hourly space velocity of isobutene is 2.0h -1 ～6.0h -1 The reaction temperature is 120-160 ℃, and the reaction pressure is 2.0-3.0 MPa.
In the above process, the catalyst used is a resin catalyst which is disclosed in the prior art and can be used for oligomerization of isobutylene, specifically a strong acid cation exchange resin, more preferably a temperature-resistant strong acid cation exchange resin, and a commercially available product can be used or the catalyst can be prepared by the prior art, specifically a DNW-i type strong acid cation exchange resin catalyst manufactured by dandong pearl special resin limited.
In the above method, as a further preferred method, the strong acid cation exchange resin catalyst is modified by the following method and then catalyzed by oligomerization: (1) soaking in toluene at 50-130 ℃ for 8-24h; (2) soaking for 4 to 24h at the temperature of 50-120 ℃ by using methyl isobutyl ketone; (3) soaking the mixture in distilled water with oxygen content less than or equal to 10mg/L, and introducing inert gas or nitrogen gas, wherein the soaking is carried out in three stages: the first stage treatment conditions are that the pressure is 0.5MPa to 1.0MPa, the temperature is 65 ℃ to 80 ℃, the soaking is carried out for 8h to 12h, and inert gas is introduced; the second stage treatment conditions are that the pressure is 0.9MPa to 1.0MPa, and the temperature is 85 ℃ to 100 ℃ for soaking for 12h to 24h; the third stage treatment conditions are that the pressure is 1.0MPa to 1.5MPa, and the temperature is 120 ℃ to 140 ℃ for soaking for 12h to 24h; and washing and drying to obtain the modified strong-acid cation exchange resin catalyst.
In the above method, further, when the catalyst is modified, the volume ratio of toluene or methyl isobutyl ketone to the resin catalyst in (1) and (2) is 5 to 10:1; preferably 5~8:1, and most preferably 5 to 6.
In the method, when the catalyst is modified, the soaking temperature in the step (1) is preferably 80-120 ℃, and the soaking time is preferably 10-10h.
In the above method, when the catalyst is modified, the soaking temperature in (2) is preferably 60 ℃ to 80 ℃, and the soaking time is preferably 6h to 12h.
In the above method, further, when the catalyst is modified, the flow rate of the inert gas or nitrogen gas introduced during the soaking in the first stage in (3) is 20m 3 /h～50m 3 H, the flow rate of the inert gas or the nitrogen introduced in the soaking process of the second stage is 10m 3 /h～25m 3 The flow rate of the inert gas or the nitrogen introduced in the soaking process of the third stage is 5m 3 /h～10m 3 /h。
In the above method, further, when the catalyst is modified, the oxygen content of the distilled water in (3) is preferably not more than 5mg/L, most preferably not more than 3mg/L, as a preferable embodiment, in the condition of 25 ℃ and 100 kPa.
The mechanism of oligomerization of isobutene over acidic catalysts is as follows: isobutene is firstly adsorbed on the surface of a catalyst, then carbonium ions are formed under the action of an acid center of the catalyst, two carbonium ions are polymerized to generate dimers, or three carbonium ions are polymerized to generate trimers, a plurality of carbonium ions are polymerized to generate polymers, and the reaction of isobutene oligomerization to generate dimers, trimers and polymers belongs to electrophilic addition reaction. The sulfone reagent is added into the reaction system, under the condition of isobutene oligomerization reaction, due to the existence of sulfones, the adsorption capacity of isobutene on the surface of the catalyst is reduced, the reaction speed of isobutene forming two carbonium ions to polymerize into a dimer under the action of an acid center of the catalyst is increased, and the reaction speed of three carbonium ions or a plurality of carbonium ions to further polymerize into a polymer is simulated, so that the selectivity of isobutene dimer is increased, and the high isobutene conversion rate can be maintained.
Detailed Description
The invention is further described below by means of specific examples. The conversion of isobutylene and the selectivity for dimer alcohol in examples and comparative examples were calculated by the following formulas.
In examples 1 to 10, the oligomerization of isobutylene was catalyzed by using DNW-I type temperature resistant strong acid cation exchange resin catalyst (manufacturer: special resin of Dandeng Mingzhu Co., ltd.):
examples 1 to 5
The oligomerization reaction adopts a fixed bed reactor, the size of the fixed bed reactor is phi 20mm multiplied by 1000mm, and the material is a stainless steel single tube. The reactor is divided into three sections and filled, a certain amount of quartz sand is filled at the bottom, 30mL of DNW-I type temperature-resistant strong acid cation exchange resin catalyst (manufacturer: special resin Co., ltd. Of Dandongming pearl) is filled at the middle section, the properties of the catalyst are shown in Table 1, and the quartz sand is filled at the top until the catalyst is filled. Replacing air in the fixed bed reactor with nitrogen, sending isobutene and sulfolane into a preheater by using a metering pump according to a required ratio after the air tightness is qualified, preheating reaction materials, sending the preheated reaction materials into the fixed bed reactor for reaction, keeping the reaction temperature at 120 ℃ and the reaction pressure at 3.0MPa, and recycling unreacted materials. The mixing ratio of isobutylene and sulfolane, the volumetric space velocity of isobutylene and the like during the reaction are shown in Table 2, and the reaction results of the conversion of isobutylene and the selectivity of dimer are also shown in Table 2.
Examples 6 to 10
The experimental setup was as above, changing sulfolane to dimethylsulfone, the reaction conditions such as the mixing ratio of isobutylene and dimethylsulfone, the volumetric space velocity of isobutylene and the like during the reaction are shown in Table 3, and the reaction results of isobutylene conversion and dimer selectivity are also shown in Table 3.
In examples 11 to 20, the oligomerization of isobutylene was catalyzed by using DNW-I type temperature resistant strong acid cation exchange resin catalyst (manufacturer: special resin of Dandeng pearl Co., ltd.) modified with toluene and methyl isobutyl ketone:
examples 11 to 20
DNW-I type temperature-resistant strong acid cation exchange resin catalyst (manufacturer: special Dandong Mingzhu)Resin limited) is firstly soaked in toluene at 80 ℃ for 16h, then soaked in methyl isobutyl ketone at 60 ℃ for 12h after filtration, washed and dried after filtration, and the volume ratio of the toluene or the methyl isobutyl ketone to the resin catalyst is 10:1. placing the catalyst in deoxygenated water with oxygen content of 3mg/L at 20 m/hr 3 Introducing nitrogen at a flow rate, and soaking for 16h at a pressure of 0.6MPa and a temperature of 65 ℃; the nitrogen flow rate was then adjusted to 15m 3 Soaking for 18 hours at 90 ℃ under the pressure of 1.0 MPa; the nitrogen flow rate was adjusted to 5m 3 And/h, soaking for 24h under the conditions that the pressure is increased to 1.5MPa and the temperature is increased to 140 ℃, and obtaining the modified resin catalyst after the treatment is finished.
The operation method of the modified catalyst used for the oligomerization of isobutylene is the same as that of example 1, and the types of sulfone reagents used and other specific reaction conditions and results are shown in Table 4.
Comparative examples 1 to 2
The procedure of example 1 was followed, with only isobutene being fed in, and the other specific reaction conditions are shown in Table 5. The results are shown in Table 5.
Comparative examples 3 to 4
Isobutylene and t-butanol, an organic solvent, were added to the feed in accordance with the procedure of example 1, and other specific reaction conditions are shown in Table 5. The results are shown in Table 5.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
TABLE 5
Claims (6)
1. The method for oligomerization reaction of isobutene is characterized in that isobutene is subjected to oligomerization reaction to obtain a dimer in a mixture consisting of isobutene and sulfone reagents in a reactor filled with a strong-acid cation exchange resin catalyst; the sulfone reagent in the mixture of the isobutene and the sulfone reagent accounts for 0.05-10% of the weight of the isobutene; the sulfone reagent is at least one selected from sulfolane, 2-methyl sulfolane, 3-propyl sulfolane, 3-butyl sulfolane, dimethyl sulfone, diethyl sulfone, methyl ethyl sulfone and dipropyl sulfone; the specific operating conditions of the isobutene oligomerization reaction are as follows: the liquid hourly space velocity of isobutene is 1.0h -1 ～18.0h -1 The reaction temperature is 100-200 ℃, and the reaction pressure is 1.0-5.0 MPa.
2. The method according to claim 1, wherein the weight of the sulfone reagent in the mixture of isobutylene and the sulfone reagent is 0.5-2.0% of the weight of isobutylene.
3. The method of claim 1, wherein the sulfone reagent is selected from at least one of sulfolane and dimethylsulfone.
4. The process as claimed in claim 1, wherein the liquid hourly space velocity of isobutene is 2.0h -1 ～6.0h -1 The reaction temperature is 120-160 ℃, and the reaction pressure is 2.0-3.0 MPa.
5. The method of claim 1, wherein the strong acid cation exchange resin catalyst is modified by the following method prior to catalyzing oligomerization: (1) soaking the raw materials in toluene at 50-130 ℃ for 8-24h; (2) soaking for 4 to 24h at the temperature of 50-120 ℃ by using methyl isobutyl ketone; (3) then soaking the substrate by distilled water with the oxygen content less than or equal to 10mg/L, and simultaneously introducing inert gas, wherein the soaking is carried out in three stages: the first stage treatment conditions are that the pressure is 0.5MPa to 1.0MPa, the temperature is 65 ℃ to 80 ℃, the soaking is carried out for 8h to 12h, and inert gas is introduced; the second stage treatment conditions are that the pressure is 0.9MPa to 1.0MPa, and the temperature is 85 ℃ to 100 ℃ for soaking for 12h to 24h; the third stage treatment condition is that the mixture is soaked for 12 to 24 hours at the pressure of 1.0 to 1.5MPa and the temperature of 120 to 140 ℃; and washing and drying to obtain the modified strong-acid cation exchange resin catalyst.
6. The method according to claim 5, wherein the volume ratio of toluene or methyl isobutyl ketone to the resin catalyst in (1) and (2) is 5 to 10:1.
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| CN114436853B (en) * | 2020-10-31 | 2024-07-05 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine by amination of isobutene |
| CN114436855B (en) * | 2020-10-31 | 2024-07-02 | 中国石油化工股份有限公司 | Method for preparing tert-butylamine from isobutene |
| CN113527025B (en) * | 2021-06-24 | 2024-10-18 | 丹东明珠特种树脂有限公司 | Preparation method for synthesizing pure isobutene and catalyst for synthesizing pure isobutene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4100220A (en) * | 1977-06-27 | 1978-07-11 | Petro-Tex Chemical Corporation | Dimerization of isobutene |
| CN1835902A (en) * | 2003-08-21 | 2006-09-20 | 三菱丽阳株式会社 | Method for producing tertiary butyl alcohol |
| CN107537568A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of method of modifying of cationic ion-exchange resin and the method for preparing tert amyl methyl ether(TAME) |
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| US4100220A (en) * | 1977-06-27 | 1978-07-11 | Petro-Tex Chemical Corporation | Dimerization of isobutene |
| CN1835902A (en) * | 2003-08-21 | 2006-09-20 | 三菱丽阳株式会社 | Method for producing tertiary butyl alcohol |
| CN107537568A (en) * | 2016-06-23 | 2018-01-05 | 中国石油化工股份有限公司 | A kind of method of modifying of cationic ion-exchange resin and the method for preparing tert amyl methyl ether(TAME) |
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