CN112225643A - Method for performing cresol alkylation reaction in microreactor by using acidic ionic liquid - Google Patents
Method for performing cresol alkylation reaction in microreactor by using acidic ionic liquid Download PDFInfo
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- CN112225643A CN112225643A CN202011278606.3A CN202011278606A CN112225643A CN 112225643 A CN112225643 A CN 112225643A CN 202011278606 A CN202011278606 A CN 202011278606A CN 112225643 A CN112225643 A CN 112225643A
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- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 38
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000011831 acidic ionic liquid Substances 0.000 title claims abstract description 28
- 229930003836 cresol Natural products 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 132
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000002608 ionic liquid Substances 0.000 claims abstract description 106
- 239000000203 mixture Substances 0.000 claims abstract description 91
- 239000003054 catalyst Substances 0.000 claims abstract description 57
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 claims abstract description 26
- QWQNFXDYOCUEER-UHFFFAOYSA-N 2,3-ditert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1C(C)(C)C QWQNFXDYOCUEER-UHFFFAOYSA-N 0.000 claims abstract description 24
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000002168 alkylating agent Substances 0.000 claims abstract description 14
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 7
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000005086 pumping Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 49
- 239000007810 chemical reaction solvent Substances 0.000 description 42
- 238000004817 gas chromatography Methods 0.000 description 42
- 230000032798 delamination Effects 0.000 description 21
- 238000004064 recycling Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 125000002883 imidazolyl group Chemical group 0.000 description 20
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- 230000029936 alkylation Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 4-tert-butyl-2-methylphenol Chemical compound CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0282—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aliphatic ring, e.g. morpholinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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Abstract
The invention discloses a method for carrying out cresol alkylation reaction in a microreactor by utilizing acidic ionic liquid, aiming at providing a method which has the advantages of small environmental pollution, high selection and low production cost and carries out cresol alkylation reaction in the microreactor by utilizing the acidic ionic liquid; the technical scheme is as follows: 1) weighing p-cresol, an alkylating agent and an ionic liquid catalyst according to a molar ratio of 1: 0.5-3.0: 0.02-0.08; 2) pressurizing and liquefying the alkylating agent weighed in the step 1), pumping a reaction substrate uniformly mixed with p-cresol, an ionic liquid catalyst and cyclohexane into a micro mixer in a micro reactor device at the speed of 200-3400mm/min, fully mixing, simultaneously conveying the mixture into a liquid-liquid phase microchannel reactor through a metering pump, heating to 313-373K, and reacting in the reactor for 1-200min under the medium pressure condition; 3) the mixture generated by the reaction is rectified to obtain 4-methyl-2-tert-butylphenol and methyl di-tert-butylphenol, and the ionic liquid catalyst is collected and reused after vacuum dehydration.
Description
Technical Field
The invention relates to the technical field of synthesis, in particular to a method for carrying out cresol alkylation reaction in a microreactor by using acidic ionic liquid.
Background
The phenol alkylation reaction is one of the currently important fine chemical reactions. The tert-butyl alkylated product obtained by the p-cresol alkylation reaction is an important raw material in the chemical industry at present, and particularly, the monoalkylated product 4-methyl-2-tert-butyl phenol (2-TBC) can be used as an intermediate synthetic body of an antioxidant, an ultraviolet absorbent and a surfactant. In addition, the alkylation products of p-cresol are still in market shortage.
According to the research of alkylation reaction technology, the purification and separation of cresol products are realized by using the boiling points of different alkylation products after the alkylation reaction in the industry at present. Since p-cresol belongs to aromatic compounds and has a plurality of reaction sites on benzene ring, the problem of regioselectivity of alkylated products needs to be solved, and the requirement and the dependence on the catalyst are increased. The acid catalyst adopted in industry generally has the problems of corrosion pollution, short service life of the catalyst, poor thermal stability and the like.
Chinese patent CN101863742A discloses a novel separation method of m-cresol and p-cresol, which utilizes strong acid catalyst to carry out alkylation reaction of m-cresol and p-cresol mixture with isobutene in a reaction kettle to generate 2-tert-butyl p-cresol and 6-tert-butyl m-cresol. Although the reaction time is greatly reduced within 1-2 h, the reaction kettle has the defects of small treatment capacity and discontinuous production, and isobutene is used as an alkylating agent instead, so that the price is high, and the cost is not limited. The strong acid catalyst used also causes the problems of equipment corrosion, much heat generation and unfavorable actual operation.
In order to solve the problems, the new functionalized ionic liquid becomes an effective legal instrument for solving the problems. Because the ionic liquid has the advantages of low pollution, low vapor pressure, manual adjustability and good thermal stability, the functionalized group of the ionic liquid has special performance, and thus the ionic liquid becomes a research hotspot in the field of acid catalysis.
Chinese patent CN201710169764.7 discloses a solid catalyst, a preparation method and application thereof, the invention uses an immobilized acidic ionic liquid as the catalyst to carry out alkylation reaction in a fixed bed to separate m-cresol and p-cresol, wherein the selectivity of methyl mono-tert-butylphenol is 60-70%. The alkylating agent used is isobutene, which is expensive and not beneficial to controlling the cost. Although the invention adopts the fixed bed reactor to enable the reaction to be continuously carried out, in order to solve the problem that the residence time of isobutene in the mixed m-cresol and p-cresol solution is too short due to insufficient contact of vapor and liquid phases, the reaction space velocity is further reduced, and the production efficiency is reduced.
Microchannel reactors have greater production advantages over conventional reactors. The mass transfer and heat transfer efficiency is high, the reaction which is easy to release heat is well controlled, and the production safety is improved; the research and development period is short, the finished small test results can be directly amplified for production without amplification effect, the research cost is saved, and the production benefit is increased; the continuous reaction replaces the traditional intermittent reaction, the reaction condition is easy to control, the reaction with more byproducts such as cresol alkylation and the like or other complex reactions can be better regulated and controlled, and the selectivity and the conversion rate of reactants and products are improved. Therefore, there is a rising trend to find alkylation processes that meet the green chemistry goals, reducing cost-effectiveness. In order to achieve the aim, the invention has important significance in exploring the method for continuously preparing the methyl mono-tert-butylphenol in the microchannel reactor by using the acidic ionic liquid.
Disclosure of Invention
Therefore, the invention aims to provide a method for carrying out the p-cresol alkylation reaction in a microreactor by utilizing acidic ionic liquid, which has the advantages of small environmental pollution, high selectivity and low production cost.
Therefore, the first technical scheme provided by the invention is as follows:
a method for carrying out cresol alkylation reaction by using acidic ionic liquid in a microreactor sequentially comprises the following steps:
1) weighing p-cresol, alkylating agent and ionic liquid catalyst according to the molar ratio of 1: 0.5-3.0: 0.02-0.08;
2) pressurizing and liquefying the alkylating agent weighed in the claim 1, pumping a reaction substrate uniformly mixed with p-cresol, an ionic liquid catalyst and cyclohexane into a micro mixer in a micro reactor device at 200-3400mm/min, fully mixing, simultaneously conveying the mixture into a liquid-liquid phase microchannel reactor through a metering pump, heating to 313-373K, and reacting in the reactor for 1-200min under medium pressure;
3) the mixture generated by the reaction is rectified to obtain 4-methyl-2-tert-butylphenol and methyl di-tert-butylphenol, and the ionic liquid catalyst is collected and reused after vacuum dehydration.
Further, in the method for performing a cresol alkylation reaction in the microreactor by using the acidic ionic liquid, the functionalized sulfonic acid ionic liquid is a morpholine-containing sulfonic acid functionalized acidic ionic liquid, a imidazole-containing monosulfonic acid ionic liquid, or a imidazole-containing disulfonic acid bisulfate ionic liquid.
Further, in the method for performing cresol alkylation reaction in the microreactor by using the acidic ionic liquid, the alkylating agent is isobutene or tert-butyl alcohol or methyl tert-butyl ether.
Further, in the method for performing the cresol alkylation reaction on the cresol in the microreactor by using the acidic ionic liquid, the molar ratio of the p-cresol to the alkylating agent to the ionic liquid is 1: 1.0 to 1.5: 0.05 to 0.07.
Further, in the method for carrying out cresol alkylation reaction in the microreactor by using the acidic ionic liquid, the liquefaction pressure of the alkylating agent is 0.5-3.0 MPa.
Further, in the method for carrying out the cresol alkylation reaction in the microreactor by using the acidic ionic liquid, the feeding pressure of the mixed material pumped into the microreactor device is 3.0-5.0 MPa.
Further, in the above method for performing cresol alkylation reaction by using acidic ionic liquid in a microreactor, the reaction temperature in step 2) is 340K to 355K.
Further, in the method for carrying out the cresol alkylation reaction by using the acidic ionic liquid in the microreactor, the retention time of a reaction substrate in the reactor is 30-90 min.
Further, the method for performing cresol alkylation reaction on the acidic ionic liquid in the microreactor is characterized in that the medium pressure is 6-10 MPa.
Further, in the method for carrying out cresol alkylation reaction by using the acidic ionic liquid in the microreactor, the flow speed in the reaction substrate microchannel is 700-2500 mm/min.
Compared with the prior art, the technical scheme provided by the invention has the advantages that the sulfonic acid functionalized ionic liquid is used as the catalyst, the paracresol alkylation reaction is continuously carried out in the microreactor, the methyl mono-tert-butylphenol is synthesized with high selectivity, the regioselectivity is high, the environmental pollution is small, the equipment is corroded, the catalyst can be repeatedly used after being treated, and the cost is saved. And a continuous production mode is adopted, so that the operation difficulty is reduced, and the production efficiency is improved.
Drawings
FIG. 1 is a schematic representation of the reaction scheme of the present invention;
FIG. 2 effect of reaction time on alkylation of p-cresol;
FIG. 3 effect of reaction temperature on cresol alkylation;
FIG. 4 effect of p-cresol to t-butanol ratio on cresol alkylation;
FIG. 5 Effect of p-cresol to ionic liquid catalyst ratio on cresol alkylation.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention in any way, and any limited number of modifications which can be made by anyone within the scope of the claims are still within the scope of the claims.
Example 1
Takes sulfonic acid functionalized acidic ionic liquid (IL-1) containing morpholinyl as a catalyst. 1.705g (6mmol) of IL-1 and 9.4ml (100mmol) of TBA were weighed, and 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 62.8% and the selectivity of 2-TBC was 53.5%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 2
Monosulfonic acid ionic liquid (IL-2) containing imidazolyl is used as a catalyst. 1.975g (6mmol) of IL-2 and 9.4ml (100mmol) of TBA were weighed, and 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 68.1% and the selectivity of 2-TBC was 63.2%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 3
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper layer product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 89.7% and the selectivity of 2-TBC was 97.3%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 4
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 30min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper layer product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 77.9% and the selectivity of 2-TBC was 89.2%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 5
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 90min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 77.3% and the selectivity of 2-TBC was 90.6%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 6
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 120min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 72.9% and the selectivity of 2-TBC was 71.1%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 7
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 150min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper layer product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 74.9% and the selectivity of 2-TBC was 83.9%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 8
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 180min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 73.3% and the selectivity of 2-TBC was 86.5%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 9
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 323K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 59.9% and the selectivity of 2-TBC was 53.4%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 10
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 333K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 78.2% and the selectivity of 2-TBC was 67.1%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 11
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 353K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 81.2% and the selectivity of 2-TBC was 92.3%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 12
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 4.7ml (50mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 65.4% and the selectivity of 2-TBC was 79.5%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 13
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 14.1ml (150mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 93.2% and the selectivity of 2-TBC was 84.6%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 14
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 18.8ml (200mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 76.8% and the selectivity of 2-TBC was 80.1%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 15
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.136g (6mmol) of IL-3 and 23.5ml (250mmol) of TBA were weighed out, 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 74.1% and the selectivity of 2-TBC was 72.9%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 16
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 0.712g (2mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, and 10.80g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 73.4% and the selectivity of 2-TBC was 87.1%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa) and 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 17
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 1.068g (3mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed, and 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 76.6% and the selectivity of 2-TBC was 85.3%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 18
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 1.424g (4mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, and 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 78.9% and the selectivity of 2-TBC was 86.2%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 19
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 1.602g (4.5mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, and 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 84.5% and the selectivity of 2-TBC was 92.6%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 20
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 1.78g (5mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, and 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 86.9% and the selectivity of 2-TBC was 95.6%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
Example 21
The bisulfate disulfonate ionic liquid (IL-3) containing imidazolyl is used as a catalyst. 2.492g (7mmol) of IL-3 and 9.4ml (100mmol) of TBA were weighed out, and 10.8g (0.1mol) of p-cresol and 60ml of cyclohexane were weighed out. Inputting the mixture into a micro mixer through a metering pump, mixing, and simultaneously conveying the mixture into a micro-channel reactor with the inner diameter of 1.0mm, wherein the reaction residence time is controlled to be 60min, and the reaction temperature is 343K. After the reaction was completed, the mixture was cooled to room temperature and allowed to stand for delamination. The upper product was removed and analyzed by Gas Chromatography (GC) to find that the conversion of p-cresol was 84.3% and the selectivity of 2-TBC was 96.2%.
After reaction, the ionic liquid catalyst is filtered, washed and dried under the conditions of 60 ℃ and vacuum degree of-0.85 Bar, and then collected and reused. And distilling the upper-layer product at normal pressure to remove the reaction solvent (80-84 ℃) and the generated water (100 ℃), and recycling the reaction solvent for reuse. The residual mixture enters the middle section of the rectifying tower after being decompressed (reduced to 2.67kPa), 4-methyl-2-tert-butylphenol (about 115 ℃) is extracted from the top of the rectifying tower, and methyl di-tert-butylphenol (about 145 ℃) is extracted from the bottom of the rectifying tower.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for carrying out cresol alkylation reaction by using acidic ionic liquid in a microreactor is characterized by sequentially comprising the following steps:
1) weighing p-cresol, an alkylating agent and an ionic liquid catalyst according to a molar ratio of 1: 0.5-3.0: 0.02-0.08;
2) pressurizing and liquefying the alkylating agent weighed in the claim 1, pumping a reaction substrate uniformly mixed with p-cresol, an ionic liquid catalyst and cyclohexane into a micro mixer in a micro reactor device at 200-3400mm/min, fully mixing, simultaneously conveying the mixture into a liquid-liquid phase microchannel reactor through a metering pump, heating to 313-373K, and reacting in the reactor for 1-200min under a medium pressure condition;
3) the mixture generated by the reaction is rectified to obtain 4-methyl-2-tert-butylphenol and methyl di-tert-butylphenol, and the ionic liquid catalyst is collected and reused after vacuum dehydration.
2. The method for carrying out cresol alkylation reaction on a microreactor by using acidic ionic liquid according to claim 1, wherein the functionalized sulfonic acid ionic liquid is a morpholine-containing sulfonic acid functionalized acidic ionic liquid, an imidazole-containing monosulfonic acid ionic liquid or an imidazole-containing bisulfate ionic liquid.
3. The method of claim 1, wherein the alkylating agent is isobutylene, tert-butyl alcohol or methyl tert-butyl ether.
4. The method of claim 1, wherein the molar ratio of p-cresol to alkylating agent to ionic liquid in the microreactor is 1: 1.0 to 1.5: 0.05 to 0.07.
5. The method for carrying out cresol alkylation reaction by using acidic ionic liquid in the microreactor as claimed in claim 1, wherein the liquefaction pressure of the alkylating agent is 0.5-3.0 MPa.
6. The method for carrying out cresol alkylation reaction on a microreactor by using acidic ionic liquid as claimed in claim 1, wherein the feeding pressure of the mixed material when being pumped into the microreactor device is 3.0-5.0 MPa.
7. The method for carrying out cresol alkylation reaction by using acidic ionic liquid in the microreactor as claimed in claim 1, wherein the reaction temperature in step 2) is 340K-355K.
8. The method of claim 1, wherein the residence time of the reaction substrate in the reactor is 30-90 min.
9. The method for carrying out cresol alkylation reaction by using acidic ionic liquid in the microreactor according to claim 1, wherein the medium pressure is 6-10 MPa.
10. The method for carrying out cresol alkylation reaction by using acidic ionic liquid in the microreactor as claimed in claim 1, wherein the flow rate in the reaction substrate microchannel is 700-2500 mm/min.
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| CN (1) | CN112225643A (en) |
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