CN111099966B - Method for preparing tert-butyl phenol - Google Patents
Method for preparing tert-butyl phenol Download PDFInfo
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- CN111099966B CN111099966B CN201811262161.2A CN201811262161A CN111099966B CN 111099966 B CN111099966 B CN 111099966B CN 201811262161 A CN201811262161 A CN 201811262161A CN 111099966 B CN111099966 B CN 111099966B
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- 238000000034 method Methods 0.000 title claims abstract description 61
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 87
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000006243 chemical reaction Methods 0.000 claims abstract description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000011049 filling Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 45
- 239000007787 solid Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000005192 partition Methods 0.000 claims description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 22
- 230000002378 acidificating effect Effects 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 17
- 239000006004 Quartz sand Substances 0.000 claims description 14
- DDTCPFLJOHVHIM-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ag+] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ag+] DDTCPFLJOHVHIM-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- QQPGSKVIALIXNV-UHFFFAOYSA-N S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] Chemical compound S(O)(O)(=O)=O.[N+](=O)([O-])[O-].[Ni+2].[N+](=O)([O-])[O-] QQPGSKVIALIXNV-UHFFFAOYSA-N 0.000 claims description 12
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 230000006837 decompression Effects 0.000 claims description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 208000012839 conversion disease Diseases 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 44
- 238000007598 dipping method Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000001291 vacuum drying Methods 0.000 description 9
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 8
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 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 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 238000006683 Mannich reaction Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000003930 superacid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/0015—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor
- B01J8/0025—Feeding of the particles in the reactor; Evacuation of the particles out of the reactor by an ascending fluid
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/008—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction
- B01J8/0085—Details of the reactor or of the particulate material; Processes to increase or to retard the rate of reaction promoting uninterrupted fluid flow, e.g. by filtering out particles in front of the catalyst layer
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for preparing tert-butyl phenol adopts a fixed bed tubular reactor, the middle part is a catalyst bed layer, the upper part is provided with a clapboard along the axial direction, the lower end of the clapboard extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts, the two sides of the clapboard are an upper feeding section and a discharging section, and the lower feeding section is arranged below a catalyst filling layer; MTBE and p-methyl phenol enter from a raw material inlet of an upper feeding section as a feeding I, MTBE and nitrogen enter from a raw material inlet of a lower feeding section as a feeding II, the feeding I reacts on a catalyst bed layer, the reacted material is mixed with the feeding II from bottom to top for further reaction, and a product is discharged from a discharge hole of a discharging section. The reaction mode of the method enables the materials to react more fully, improves the reaction conversion rate, enables the feeding at the upper end to pass through the catalyst bed layer repeatedly, reacts more fully, and improves the conversion rate of MTBE.
Description
Technical Field
The invention relates to a method for preparing tert-butyl phenol, in particular to a method for preparing 2, 6-di-tert-butyl 4-methylphenol by using MTBE (methyl tert-butyl ether) and p-methylphenol as raw materials.
Background
2, 6-di-tert-butyl-4-methylphenol is white or light yellow crystal, and the molecular formula is C 15 H 24 And O. It is easily soluble in toluene, soluble in organic solution such as acetone, ethanol, benzene, diethyl ether, isopropanol, methanol, 2-butanone, ethylene glycol ethyl ether, petroleum ether, etc., and insoluble in water and alkali solution. 2, 6-tert-butyl 4-methyl phenol is a general antioxidant, mainly used as antioxidant additive of various petroleum products, antioxidant and stabilizer of some high molecular materials, antioxidant of food processing industry, phenol antioxidant for rubber, widely used in natural rubber, various synthetic rubbers and latex thereof, and stabilizer for synthetic rubber and post-treatment and storage, such as styrene-butadiene rubber,Butadiene rubber, chloroprene rubber, ethylene propylene rubber and the like.
The synthesis method of 2, 6-di-tert-butyl-4-methylphenol mainly comprises the following steps:
the p-cresol process. The paracresol and the alkylating agent are subjected to Friedel-crafts reaction and then purified. The method is widely adopted in China.
The mixed phenol method. The mixed phenol and the alkylating agent are subjected to Friedel-crafts reaction, then are rectified and separated, and finally are crystallized. The process requirement is higher, and the method is more suitable for German factories at present.
The scherdam method. The product can be directly obtained by catalytic hydrogenation after the mannich reaction of phenol. The cost is low because phenol is used as a main raw material, but the product quality is the most unstable of the three processes, and the Russian factory mostly adopts the method.
In recent years, MTBE has been favored by regulators as a high octane additive and antiknock agent for gasoline. However, with the development of substitutes such as alkylate and ethanol gasoline, the market demand of MTBE is greatly influenced. In addition, there are studies that indicate that MTBE has potential threats to the environment and human health. After the environmental protection agency of the united states lists MTBE as a carcinogen, several countries in north america and europe have developed a series of policies that prohibit or limit the use of MTBE in gasoline. China will gradually limit the application of MTBE in gasoline, and the MTBE capacity will be surplus, so the utilization of MTBE isobutene will become a future development trend. MTBE is used as a raw material, and the MTBE and p-methylphenol are synthesized into 2, 6-di-tert-butyl-4-methylphenol, which can be used as one of effective ways for utilizing the MTBE.
Patent CN106631705A discloses a production process for alkylating 2, 6-di-tert-butyl-4-methylphenol antioxidant, which takes isobutene and p-methylphenol as raw materials, adopts three alkylation reaction kettles to carry out continuous, intermittent and continuous operation modes respectively for reaction, and has longer process flow and more complex operation. According to the report of the literature, isobutene and p-methyl phenol are used as raw materials, concentrated sulfuric acid is used as a catalyst, the reaction is carried out in an autoclave, the problems of discontinuous reaction, serious corrosion of equipment and environmental pollution exist, and the reaction conversion rate and the selectivity are low.
Disclosure of Invention
Aiming at the problems of strong catalyst corrosivity, environmental pollution, low reaction conversion rate, poor selectivity, complex flow and operation and the like in the method for preparing 2, 6-tert-butyl 4-methylphenol by using MTBE and p-methylphenol as raw materials in the prior art, the invention provides the method for preparing tert-butylphenol. The method takes MTBE and p-methylphenol as raw materials to prepare 2, 6-di-tert-butyl 4-methylphenol, a fixed bed tubular reactor with a partition plate in the middle is adopted in the reactor, the reaction is carried out under the action of a metal-doped solid super acidic catalyst, and the feeding mode adopts a mode of feeding materials simultaneously from top to bottom. The method can effectively improve the conversion rate of MTBE, and has the advantages of simple process, high efficiency, no pollution, mild conditions, stable catalyst activity and long-period operation.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method for preparing tert-butyl phenol adopts a fixed bed tubular reactor, wherein a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, a partition plate is arranged on the upper part of the fixed bed tubular reactor along the axial direction, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; MTBE and p-methylphenol enter the reactor from the raw material inlet of the upper feeding section as feeding I, MTBE and nitrogen enter the reactor from the raw material inlet of the lower feeding section as feeding II, the feeding I reacts on the catalyst bed layer in the middle of the reactor, the reacted materials are mixed with the feeding II from bottom to top for further reaction, and the reaction product is discharged from the discharge hole of the discharge section.
In the method, the length of the partition plate is 1/2-2/3 of the length of the reactor, and the top of the partition plate and two side edges of the partition plate are hermetically connected with the wall of the reactor.
In the method, the molar ratio of MTBE to p-methyl phenol in the feed I is 1: 1-5: 1, preferably 3: 1-4: 1, the total liquid hourly space velocity is 0.5-5 h -1 Preferably 1 to 2 hours -1 。
In the process of the invention, the feedThe liquid hourly space velocity of MTBE in II on the catalyst is 0.5-1 h -1 Preferably 0.6 to 0.8h -1 The molar ratio of nitrogen to p-methylphenol is 100-200: 1.
in the method of the invention, the total liquid hourly space velocity of the feed I is greater than that of the feed II
According to the method, quartz sand is filled at two ends of a reactor, and a mixture of the catalyst and the quartz sand is filled in a catalyst bed section, wherein the granularity range of the quartz sand is 1.5-2.0 mm, and the catalyst accounts for 60-70 v% of the total filling amount.
In the method of the invention, the reaction conditions are as follows: the reaction temperature is 80-140 ℃, and preferably 110-130 ℃; the reaction pressure is 0.01 to 0.1MPa, preferably 0.04 to 0.06 MPa.
In the process of the present invention, the catalyst used for the reaction is preferably a metal-doped solid superacid catalyst. In the method of the invention, the catalyst is prepared by the following method:
(1) ZrOCl 2 Dissolving in ethanol to obtain ZrOCl 2 Titrating with ammonia water until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, molding, drying, and roasting to obtain white solid particles;
(2) and (2) respectively soaking the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, drying and roasting after each step of soaking, and finally obtaining the metal-doped solid super acidic catalyst.
In the preparation method of the catalyst, the ZrOCl in the step (1) 2 The mass concentration of the ethanol solution is 30-50%.
The drying temperature in the step (1) is 70-90 ℃, the drying time is 4-6 hours, the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
The white solid particles obtained in the step (1) are cylindrical particles with the particle size of 1.0-1.5 mm.
The preparation process of the nitrate sulfuric acid solution in the step (2) is as follows: dissolving nitrate in dilute sulfuric acid to obtain a nitrate sulfuric acid solution; wherein the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the nickel nitrate sulfuric acid solution is 5-10 mol/L, and the concentration of the palladium nitrate sulfuric acid solution is 0.1-0.3 mol/L.
The impregnation process of the step (2) is carried out under the conditions of decompression and ultrasound; the decompression is carried out at the vacuum degree of 15000-20000 Pa; the ultrasonic wave has the vibration frequency of 50-60 kHz. The dipping temperature is 55-60 ℃, and the dipping time is 4-6 h.
The drying conditions in the step (2) are as follows: the drying temperature is 80-100 ℃, and the drying time is 6-8 hours; the roasting conditions are as follows: the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
Compared with the prior art, the invention has the following advantages:
(1) the reaction is carried out on a fixed bed continuous reactor with a partition plate, the materials are fed in an upper and lower simultaneous feeding mode, the reaction materials fed in the upper mode enter the reactor and pass through a catalyst bed layer under a certain airspeed condition, part of reactants firstly react to a certain degree and move downwards, the reaction materials fed in the lower mode enter the reactor under a certain airspeed condition, are mixed with the materials moving downwards, pass through the catalyst bed layer and move upwards, the reaction is further carried out after the materials are mixed, and the reaction conversion rate is improved.
(2) The upper feeding and the lower feeding have an airspeed difference (the upper feeding airspeed is greater than the lower feeding airspeed), so that the feeding at the upper end of the reactor passes through the catalyst bed layer in a reciprocating manner, the reaction is more sufficient, and the conversion rate of the MTBE is improved.
(3) The catalyst filling section is filled by mixing with quartz sand, the lower feeding section is filled by mixing p-methyl phenol with nitrogen, and the catalyst is continuously boiled in a gap formed by the quartz sand under the driving action of the nitrogen with certain air flow and air speed, so that the contact probability and mass transfer efficiency of reaction materials and catalyst active centers are increased, and the reaction efficiency and the conversion rate are improved.
(4) The axial partition plate is added in the reactor, so that the moving path of the feeding material at the inlet I is limited, the process that the feeding material at the inlet I is partially reacted firstly and then is further reacted with the feeding material at the inlet II is realized, the reaction is more sufficient, and the conversion rate of MTBE is higher.
(5) In the preparation process of the solid super acidic catalyst, different metal solutions are adopted to be respectively impregnated according to a certain sequence, the impregnation is carried out under the conditions of reduced pressure, ultrasonic vibration and a certain impregnation temperature, and the impregnation solution is continuously boiled, SO that the catalyst has uniform particle size and SO 4 2- The coordination with the metal ions on the surface of the oxide is rapid and uniform, so that the catalyst has stronger acidity. Ag + Is pre-doped to ZrO 2 The crystal grains tend to exist in a monoclinic type (M), and the monoclinic type (M) is a relatively stable crystal phase structure, so that the catalyst has higher activity and better stability.
Drawings
FIG. 1 is a schematic diagram of the process for preparing 2, 6-di-tert-butyl-4-methylphenol according to the present invention.
Wherein: 1-an upper feeding section; 2-a lower feeding section; 3-discharging section; 4-a separator; 5-catalyst bed layer.
Detailed Description
The preparation process of the solid super acidic catalyst of the present invention is specifically described as follows: firstly, 50-100 g ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with the mass concentration of 30-50% 2 And (2) titrating the ethanol solution with 20-25% ammonia water until no white precipitate exists, washing the solution with deionized water for several times, wherein the washing time is 5-10 minutes each time, the washing temperature is 40-50 ℃, washing the solution until no chloride ion exists, drying the solution in a vacuum drying oven for 4-6 hours at the temperature of 80-90 ℃, extruding the solution into strips, and roasting the strips for 8 hours at the temperature of 500 ℃ to obtain white solid particles for later use. Secondly, dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2-4 mol/L, wherein the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h; the decompression vacuum degree is 15000-20000 Pa; and (3) the ultrasonic vibration frequency is 50-60 kHz, then the solid particles are placed in a vacuum drying oven to be dried for 4-6 hours at the temperature of 80-90 ℃, and then the solid particles are roasted for 8 hours at the temperature of 500 ℃ to obtain particles I. Thirdly, repeating the impregnation process of the second step by using a nickel nitrate sulfuric acid solution to obtain particles II. Fourthly, repeating the steps by using a palladium nitrate sulfuric acid solutionAnd secondly, obtaining the metal-doped solid super acidic catalyst.
The following examples are provided to illustrate specific embodiments of the present invention. In the following examples and comparative examples,% represents mass unless otherwise specified. The ultrasonic vibrator used in the preparation of the solid super acidic catalyst is KQ-550B, the circulating water type multipurpose vacuum pump is SHB-B95T, and the product is purchased from Zhengzhou great wall Korsao Co.
The preparation of 2, 6-di-tert-butyl 4-methylphenol in the invention is carried out according to the process flow diagram shown in figure 1: the method comprises the steps of carrying out reaction on a fixed bed continuous reactor with a partition plate, wherein a catalyst bed layer 5 is arranged in the middle of the fixed bed continuous reactor, a partition plate 4 is arranged on the upper portion of the fixed bed continuous reactor along the axial direction, the length of the partition plate is 1/2 of the length of the reactor, the lower end of the partition plate 4 extends into the catalyst bed layer 5 and does not completely penetrate through the catalyst bed layer 5, the reactor is divided into three parts by the partition plate 4 and the catalyst bed layer 5, an upper feeding section 1 and a discharging section 3 are arranged on two sides of the partition plate, and a lower feeding section 2 is arranged below the catalyst bed layer 5; the mixed solution of MTBE and p-methyl phenol is used as a feed I and is pumped into the reactor from a raw material inlet of an upper feeding section 1 by a Rewa micro-metering pump, the MTBE is used as a feed II and is pumped into the reactor from a raw material inlet of a lower feeding section 2 by a high-pressure plunger pump, the feed I is reacted on a catalyst bed layer 5 in the middle of the reactor, the reacted material is mixed with the feed II from bottom to top and is further reacted, and the reaction product is discharged from a discharge hole of a discharge section 3.
Example 1
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 30% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 15000 Pa; the ultrasonic vibration frequency was 55kHz,the solid particles were then dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a palladium nitrate sulfuric acid solution with the concentration of 0.1mol/L to obtain the metal-doped solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 110 ℃, the reaction pressure is 0.05MPa, and the upper feeding total liquid hourly space velocity is 1h -1 And the molar ratio of MTBE to p-methylphenol is 3: 1; the liquid hourly space velocity of MTBE to the catalyst in the lower feed is 0.6 h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 2
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 35% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 3mol/L, wherein the dipping temperature is 58 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 16000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a palladium nitrate sulfuric acid solution with the concentration of 0.1mol/L to obtain the metal-doped solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 110 ℃, the reaction pressure is 0.05MPa, and the upper feeding total liquid hourly space velocity is 1.5h -1 And the molar ratio of MTBE to p-methylphenol is 3: 1; the liquid hourly space velocity on the MTBE to the catalyst in the lower feed was 0.7 h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 3
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 35% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 57 ℃, and the dipping time is 6 hours; the vacuum degree is 18000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 8mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a palladium nitrate sulfuric acid solution with the concentration of 0.2mol/L to obtain the metal-doped solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 120 ℃, the reaction pressure is 0.06MPa, and the upper feeding total liquid hourly space velocity is 1h -1 And the molar ratio of MTBE to p-methylphenol is 4: 1; the liquid hourly space velocity of MTBE on the catalyst in the lower feed was 0.7 -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 4
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 40% 2 Titrating with 20% ammonia water to remove white precipitate, washing with deionized water for 5 times (10 min each time at 40 deg.C) until no chloride ion is formed, and vacuum drying at 90 deg.C in a vacuum drying ovenDrying for 6 hours, extruding and molding, and roasting for 8 hours at 500 ℃ to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 3mol/L, wherein the dipping temperature is 60 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 17000 Pa; the ultrasonic vibration frequency was 58kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 8mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a palladium nitrate sulfuric acid solution with the concentration of 0.3mol/L to obtain the metal-doped solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 130 ℃, the reaction pressure is 0.06MPa, and the upper feeding total liquid hourly space velocity is 1h -1 And the molar ratio of MTBE to p-methylphenol is 4: 1; the liquid hourly space velocity of MTBE to the catalyst in the lower feed is 0.6 h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in table 1.
Example 5
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 40% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 4mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 16000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: repeating the process of the second step by using a palladium nitrate sulfuric acid solution with the concentration of 0.2mol/L to obtain goldBelongs to a doped solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 130 ℃, the reaction pressure is 0.05MPa, and the upper feeding total liquid hourly space velocity is 1.5h -1 And the molar ratio of MTBE to p-methylphenol is 4: 1; the liquid hourly space velocity of MTBE in the lower feed to the catalyst was 0.6 h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 6
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 30% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 15000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a nickel nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a palladium nitrate sulfuric acid solution with the concentration of 0.3mol/L to obtain the metal-doped solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 110 ℃, the reaction pressure is 0.05MPa, and the upper feeding total liquid hourly space velocity is 1h -1 And the molar ratio of MTBE to p-methylphenol is 3: 1; the liquid hourly space velocity of MTBE to the catalyst in the lower feed is 0.6 h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in table 1.
Example 7
During the reaction, only the feeding mode is adopted, other conditions are the same as example 4, and the reaction results are shown in table 1.
Example 8
In the reaction process, the fixed bed reactor has no partition plate in the middle, other conditions are the same as example 4, and the reaction results are shown in Table 1.
Example 9
During the reaction, only MTBE was fed into the lower feed without nitrogen, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
Example 10
The preparation process of the used catalyst has no ultrasonic vibration and decompression process, only adopts the conventional supersaturated impregnation method to modify the catalyst, and the impregnation sequence is that the sulfuric acid solution of silver nitrate is put at the end, other conditions are the same as the example 4, and the reaction result is shown in the table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Claims (11)
1. A method for preparing tert-butyl phenol adopts a fixed bed tubular reactor, and is characterized in that a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, a partition plate is axially arranged on the upper part of the fixed bed tubular reactor, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; MTBE and p-methylphenol enter the reactor from a raw material inlet of an upper feeding section as a feeding material I, MTBE and nitrogen enter the reactor from a raw material inlet of a lower feeding section as a feeding material II, the feeding material I reacts on a catalyst bed layer in the middle of the reactor, the reacted material is mixed with the feeding material II from bottom to top for further reaction, and a reaction product is discharged from a discharge hole of a discharging section;
the reaction conditions were as follows: the reaction temperature is 80-140 ℃, and the reaction pressure is 0.01-0.1 Mpa;
the catalyst used in the reaction is a metal-doped solid super acidic catalyst, and the preparation method of the solid super acidic catalyst comprises the following steps:
(1) ZrOCl 2 Dissolving in ethanol to obtain ZrOCl 2 Titrating with ammonia water until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, molding, drying, and roasting to obtain white solid particles;
(2) and (2) respectively soaking the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, drying and roasting after each step of soaking, and finally obtaining the metal-doped solid super acidic catalyst.
2. The method of claim 1, wherein the length of the partition is 1/2-2/3 of the length of the reactor, and the top of the partition and the two sides of the partition are hermetically connected with the wall of the reactor.
3. The process according to claim 1, wherein the molar ratio of MTBE to p-methylphenol in the feed I is 1: 1-5: 1.
4. the process according to claim 3, wherein the total liquid hourly space velocity of the feed I is 0.5 to 5h -1 。
5. The process of claim 1, wherein the liquid hourly space velocity of MTBE in feed II on the catalyst is 0.5 to 1h -1 。
6. The process of any one of claims 1 to 5, wherein the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II.
7. The process according to claim 5, wherein the molar ratio of nitrogen to MTBE in feed II is from 100 to 200: 1.
8. the method as claimed in claim 1, wherein the catalyst is loaded by filling quartz sand at both ends of the reactor, and the catalyst bed section is filled with a mixture of the catalyst and the quartz sand, wherein the particle size of the quartz sand is 1.5-2.0 mm, and the catalyst accounts for 60-70 v% of the total loading amount of the catalyst bed.
9. The method of claim 1, wherein said ZrOCl of step (1) 2 The mass concentration of the ethanol solution is 30-50%.
10. The method as claimed in claim 1, wherein the silver nitrate sulfuric acid solution in the step (2) is prepared by: dissolving silver nitrate in dilute sulfuric acid to obtain a silver nitrate sulfuric acid solution; the preparation processes of the nickel nitrate sulfuric acid solution and the palladium nitrate sulfuric acid solution are the same as those of the silver nitrate sulfuric acid solution; wherein the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the nickel nitrate sulfuric acid solution is 5-10 mol/L, and the concentration of the palladium nitrate sulfuric acid solution is 0.1-0.3 mol/L.
11. The method according to claim 1, wherein the impregnation process of step (2) is performed under reduced pressure and ultrasonic conditions; the decompression is carried out at the vacuum degree of 15000-20000 Pa; the ultrasonic wave has the vibration frequency of 50-60 kHz.
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| JP2001072633A (en) * | 1999-09-06 | 2001-03-21 | Sumitomo Chem Co Ltd | PRODUCTION OF t-BUTYLCRESOLS |
| CN1572760A (en) * | 2002-07-17 | 2005-02-02 | 中国石油天然气集团公司 | Tertiary butyl phenol synthesis method by methyl tertiary butyl ether alkylation reaction |
| CN1733672A (en) * | 2005-07-29 | 2006-02-15 | 华东师范大学 | 2-tertiary-butyl-4-methyl phenol preparation method |
| CN106866380A (en) * | 2017-02-20 | 2017-06-20 | 河北工业大学 | A kind of micro- reactive distillation plate prepares the method and its equipment of 2,6 BHTs |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001072633A (en) * | 1999-09-06 | 2001-03-21 | Sumitomo Chem Co Ltd | PRODUCTION OF t-BUTYLCRESOLS |
| CN1572760A (en) * | 2002-07-17 | 2005-02-02 | 中国石油天然气集团公司 | Tertiary butyl phenol synthesis method by methyl tertiary butyl ether alkylation reaction |
| CN1733672A (en) * | 2005-07-29 | 2006-02-15 | 华东师范大学 | 2-tertiary-butyl-4-methyl phenol preparation method |
| CN106866380A (en) * | 2017-02-20 | 2017-06-20 | 河北工业大学 | A kind of micro- reactive distillation plate prepares the method and its equipment of 2,6 BHTs |
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