CN110937982B - Method for preparing p-tert-butylphenol - Google Patents
Method for preparing p-tert-butylphenol Download PDFInfo
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- CN110937982B CN110937982B CN201811114255.5A CN201811114255A CN110937982B CN 110937982 B CN110937982 B CN 110937982B CN 201811114255 A CN201811114255 A CN 201811114255A CN 110937982 B CN110937982 B CN 110937982B
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- 238000000034 method Methods 0.000 title claims abstract description 49
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- 239000007787 solid Substances 0.000 claims abstract description 51
- 230000002378 acidificating effect Effects 0.000 claims abstract description 26
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000007921 spray Substances 0.000 claims abstract description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 76
- 239000002245 particle Substances 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 36
- 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 29
- 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 25
- 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 22
- 238000007598 dipping method Methods 0.000 claims description 19
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 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
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 238000005470 impregnation Methods 0.000 claims description 6
- 230000006837 decompression Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000007796 conventional method Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008187 granular material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 4
- 239000003930 superacid Substances 0.000 description 4
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002168 alkylating agent Substances 0.000 description 2
- 229940100198 alkylating agent Drugs 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000000889 atomisation Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000575 pesticide Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- GAZYKNYEOMWYSH-UHFFFAOYSA-N 2-methylprop-1-ene;phenol Chemical group CC(C)=C.OC1=CC=CC=C1 GAZYKNYEOMWYSH-UHFFFAOYSA-N 0.000 description 1
- HUXINJXECPLJSS-UHFFFAOYSA-N 2-methylprop-1-ene;phenol Chemical group CC(C)=C.CC(C)=C.OC1=CC=CC=C1 HUXINJXECPLJSS-UHFFFAOYSA-N 0.000 description 1
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- NXQFOOPVHVMQMF-UHFFFAOYSA-N CC(C)(O)C.OC1=CC=CC=C1 Chemical compound CC(C)(O)C.OC1=CC=CC=C1 NXQFOOPVHVMQMF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- YDCAYRSIYGQPLP-UHFFFAOYSA-N [Ti].[Mo]=O Chemical compound [Ti].[Mo]=O YDCAYRSIYGQPLP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000000895 acaricidal effect Effects 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000001079 digestive effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil 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
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- ZYHMJXZULPZUED-UHFFFAOYSA-N propargite Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1C(OS(=O)OCC#C)CCCC1 ZYHMJXZULPZUED-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- -1 tert-butyl phenolic resin Chemical compound 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
- 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
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing p-tert-butylphenol, which comprises the following steps: under the alkylation reaction condition, isobutene and phenol are used as a feed I to enter from the top of the reactor in a spray mode, pass through a plurality of layers of catalyst bed layers which are horizontally staggered from top to bottom, react layer by layer, isobutene is used as a feed II to enter from the lower part of the reactor, are quickly gasified, ascend layer by layer from bottom to top, further react with material flows from top to bottom, and reaction products are discharged from the bottom of the reactor; wherein the catalyst bed layer comprises a bed plate with air holes and a catalyst on the bed plate. The method has the advantages that the conversion rate of the reaction can be effectively improved by the tubular reactor which is fed up and down simultaneously and the metal-doped solid super acidic catalyst, the process is simple, no pollution is caused, the condition is mild, and the reactor can stably run for a long period.
Description
Technical Field
The invention relates to a method for preparing p-tert-butylphenol, in particular to a method for preparing p-tert-butylphenol by using isobutene and phenol as raw materials.
Background
P-tert-butylphenol is also known as 4-tert-butylphenol and is abbreviated as PTBP. P-tert-butylphenol is a white or essentially white flaky solid at room temperature and has a specific alkylphenol odor. Is easily soluble in organic solvents such as alcohols, esters, alkanes, aromatic hydrocarbons, etc., such as ethanol, acetone, butyl acetate, gasoline, toluene, etc. Slightly soluble in water and soluble in strong alkaline solutions. P-tert-butylphenol has antioxidant properties and can be used as a stabilizer for rubber, soap, chlorinated hydrocarbons and digestive fibers. Ultraviolet absorbent, and cracking-preventing agent such as pesticide, rubber, and paint. The stabilizer is used for polycarbonate resin, tert-butyl phenolic resin, epoxy resin, polyvinyl chloride and styrene. In addition, the product can also be used as raw material for preparing medicinal insect repellent, pesticide acaricide propargite, perfume and plant protectant. It can also be used as softener, solvent, dye and paint additive, antioxidant of lubricating oil, oil field demulsifier and additive of vehicle fuel.
The common preparation methods of p-tert-butylphenol mainly comprise: (1) phenol isobutylene Process: taking phenol and isobutene as raw materials, taking cation exchange resin as a catalyst, carrying out alkylation reaction at the normal pressure and the temperature of 110 ℃, and carrying out reduced pressure distillation on the product to obtain a product; (2) phenol diisobutylene Process: adopting a silicon-aluminum catalyst, carrying out the reaction under a liquid phase condition to obtain p-octyl phenol and o-tert-butyl phenol besides the p-tert-butyl phenol, and separating the reaction product to obtain the p-tert-butyl phenol; (3) carbon four-cut method: the cracking carbon four fraction and phenol are taken as raw materials, titanium-molybdenum oxide is taken as a catalyst, a mixture of phenol alkylation reaction mainly comprising p-tert-butylphenol is obtained through reaction, and a product is obtained through separation; (4) phenol tert-butanol method: the product is prepared by using phenol and tert-butyl alcohol as raw materials and through water washing, crystallization and separation.
MTBE is recently gaining favor as a high octane additive and an 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, so the MTBE capacity is necessary to be surplus, the production of MTBE is limited, and a large amount of isobutene is left, so that the utilization of isobutene becomes a future development trend. Isobutene is used as an alkylating agent, and the isobutene and phenol are synthesized into p-tert-butylphenol which can be used as one of ways of isobutene utilization.
According to the reports of the literature, sulfuric acid or phosphoric acid is mostly used as a catalyst in the production process of the p-tert-butylphenol, and the problems of serious corrosion of equipment, environmental pollution, difficult separation and recovery of products and the like exist. Domestic literature reports that solid superacid, temperature-resistant resin and the like are used as catalysts, isobutene is used as an alkylating agent to synthesize p-tert-butylphenol, but the reaction is a kettle type reaction, the reaction process is discontinuous, the temperature is high, and the conversion rate of phenol and the product selectivity are low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing p-tert-butylphenol. The method has the advantages that the conversion rate of the reaction can be effectively improved by the tubular reactor which is fed up and down simultaneously and the metal-doped solid super acidic catalyst, the process is simple, no pollution is caused, the condition is mild, and the reactor can stably run for a long period.
The method for preparing the p-tert-butylphenol comprises the following steps: under the condition of alkylation reaction, isobutene and phenol enter from the top of a reactor in a spray mode as a feed I, penetrate through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom, react layer by layer, isobutene enters from the lower part of the reactor as a feed II, is rapidly gasified, ascends layer by layer from bottom to top, further reacts with material flows from top to bottom, and reaction products are discharged from the bottom of the reactor; wherein the catalyst bed layer comprises a bed plate with air holes and a catalyst on the bed plate.
In the method of the invention, the alkylation reaction conditions are as follows: the reaction temperature is 80-120 ℃, and the preferable temperature is 90-110 ℃; the reaction pressure is 2 to 5MPa, preferably 3 to 4MPa.
In the process of the present invention, the molar ratio of isobutylene to phenol in feed I is 1:1 to 5:1, preferably 3:1 to 4:1, the total volume airspeed is 1-4 h -1 Preferably 2 to 3 hours -1 。
In the method, the spray type feeding adopts a conventional atomizing nozzle for spray feeding.
In the method, the volume space velocity of the feed II (isobutene) is 1-2 h -1 Preferably 1 to 1.5h -1 。
The method of the invention also provides an alkylation reactor, wherein a plurality of layers of horizontally staggered bed plates are arranged along the axial direction of the reactor, one end of each bed plate is hermetically connected with the wall of the reactor, the other end of each bed plate is at a certain distance from the wall of the reactor and is provided with a baffle plate, and a plurality of air holes are formed in each bed plate; the top of the reactor is provided with an upper feed inlet, the upper feed inlet is provided with an atomizing nozzle, the lower part of the reactor is provided with a lower feed inlet, and the bottom of the reactor is provided with a feed inlet.
The length of the bed plate is 2/3-3/4 of the diameter of the reactor, and the edge of the bed plate is hermetically connected with the tube wall of the reactor.
The aperture of the air holes is 0.5-1 mm, and the air holes are uniformly distributed on the bed plate; the height of the baffle at the end of the bed board is 0.3-0.5 cm.
In the method of the present invention, the catalyst may be solid super acid or high temperature resistant resin, etc. well known in the art.
The invention also provides a preparation method of the solid super acidic catalyst, which 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 by a conventional method, drying, and roasting to obtain white solid particles for later use;
(2) Respectively preparing a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, impregnating the white solid particles obtained in the step (1) with the silver nitrate sulfuric acid solution, drying and roasting to obtain particles I, impregnating the particles I with the nickel nitrate sulfuric acid solution, drying and roasting to obtain particles II, impregnating the particles II with the palladium nitrate sulfuric acid solution, drying and roasting to obtain a metal-doped solid super acidic catalyst; the impregnation process is carried out under reduced pressure and ultrasonic vibration.
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 step (2) is that the preparation process of the silver nitrate sulfuric acid solution comprises the following steps: 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.
The decompression condition in the step (2) is 15000 to 20000Pa; the ultrasonic condition is that the vibration frequency is 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 to 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 alkylation reaction is carried out on a tubular reactor with a bed plate, the material is fed in an upper and lower simultaneous feeding mode, the reaction material fed in the upper mode enters the reactor through an atomizing nozzle under a certain airspeed condition, the material passing through the atomizing nozzle exists in a mixing state of mist small liquid drops under the reaction condition, the mixture and the distribution are more uniform, the material is in contact with and reacts with a catalyst on the bed plate, a reactant flows to a next bed plate step by step through air holes on the catalyst bed plate and reacts, the reaction material fed in the lower mode enters the reactor under a certain airspeed condition, the reaction material is gasified rapidly under the reaction condition, the air holes on the bed plate rise step by step and diffuse in the space of the reactor through gaps between the catalyst bed plates, the concentration and the flow rate of the gas fed in the reactor are improved, the reaction material is mixed with the reactant fed in the upper mode and then reacts on the catalyst bed plate, and the reaction process has the advantages of a trickle bed and catalytic rectification simultaneously through the reactor and the feeding mode, and the reaction conversion rate is improved.
(2) 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 grains tend to exist in a monoclinic type (M),the monoclinic type (M) has a 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 p-tert-butylphenol according to the invention.
Wherein: 1-an upper feeding port; 2-lower feed inlet; 3-discharging port; 4-a catalyst; 5-a baffle plate; 6-bed board; 7-atomizing nozzle.
The alkylation reactor of the present invention works as follows: the feeding I enters the reactor from the upper feeding port 1, is atomized by the atomizing nozzle 7 to form a mist mixture, falls on the catalyst bed plate 6, reacts under certain reaction conditions and under the action of the catalyst 4, reactants flow to the next bed plate step by step through the air holes on the catalyst bed plate 6 and react, the feeding II enters the reactor from the lower feeding port 2, is rapidly gasified under the reaction conditions, rises step by step through the air holes on the bed plate, and permeates through the space between the catalyst bed plates to permeate into the space of the reactor, further reacts on the catalyst bed plate after being mixed with the reactants fed at the upper part, and finally the reaction product is discharged from the discharging port 3.
Detailed Description
The preparation process of the solid super acidic catalyst of the present invention is specifically described as follows: 1. reacting ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with a mass concentration of 30-50% 2 The ethanol solution is titrated by ammonia water until no white precipitate is generated, is washed by deionized water and is filtered until no chloride ion is generated, the drying time is 4 to 6 hours under the condition of 70 to 90 ℃ to obtain white powder, the white powder is extruded by a conventional method, is dried for 4 to 6 hours under the condition of 70 to 90 ℃ after being molded, and is roasted for 4 to 6 hours under the condition of 450 to 550 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.3-0.6 mol/L to prepare silver nitrate sulfuric acid solution with the molar concentration of 2-4 mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.3-0.6 mol/L to prepare nickel nitrate sulfuric acid solution with the molar concentration of 5-10 mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.3-0.6 mol/L to prepare palladium nitrate sulfuric acid solution with the molar concentration of 0.1-0.3 mol/L. 3. Impregnating the solution in the first step with silver nitrate sulfuric acid solution to obtainWhite solid particles of (2) under the vacuum degree of 15000-20000 Pa; the ultrasonic vibration frequency is 50-60 kHz; the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h; filtering, drying at the drying temperature of 80-100 ℃ for 6~8 hours, and roasting at the roasting temperature of 450-550 ℃ for 4~6 hours to obtain the particles I. 4. And (3) treating the particles I with a nickel nitrate sulfuric acid solution according to the method and conditions of the step three to obtain particles II, and treating the particles II with a palladium nitrate sulfuric acid solution according to the method and conditions of the step three to obtain the metal-doped solid super acidic catalyst.
The specific embodiment of the invention is as follows: the method comprises the steps of carrying out reaction on a fixed bed continuous reactor with a catalyst bed plate, pumping isobutene and phenol serving as a feed I into the reactor by a lining micro-dosage pump under the alkylation reaction condition, spraying the isobutene and the phenol from the top of the reactor, penetrating through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom, reacting layer by layer, pumping the isobutene serving as a feed II into the reactor by a high-pressure plunger pump, quickly gasifying the isobutene, ascending layer by layer from bottom to top, further reacting with material flow from top to bottom, and discharging a reaction product from the bottom of the reactor; wherein the catalyst bed layer comprises a bed plate with air holes and a catalyst on the bed plate.
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 model of an ultrasonic vibrator used in the preparation of the metal-doped solid super acidic catalyst is KQ-550B, and the model of an upper feeding atomization nozzle is JLN-G type high-pressure fine atomization nozzle, which is purchased from Jining Jun spray equipments, inc. The alkylation reactor has an internal diameter of 25mm and a height of 160cm. The length of the bed plate is 2/3-3/4 of the diameter of the reactor, and the edge of the bed plate is hermetically connected with the tube wall of the reactor. The aperture of the air holes is 0.5-1 mm, and the air holes are uniformly distributed on the bed plate; the height of the baffle at the end of the bed board is 0.3-0.5 cm.
Example 1
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanolZrOCl with mass concentration of 30% 2 And (2) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chloride ion is generated, drying for 4 hours at the temperature of 70 ℃ to obtain white powder, extruding the white powder into strips by using a conventional method, drying for 4 hours at the temperature of 70 ℃, and roasting for 4 hours at the temperature of 450 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 2mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 5mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.1 mol/L. 3. Dipping the white solid particles obtained in the first step by using silver nitrate sulfuric acid solution, and keeping the vacuum degree at 15000Pa; the ultrasonic vibration frequency is 50kHz; dipping at 55 ℃ for 4 h; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 450 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 90 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 3:1, total volume space velocity of 2h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 2
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with mass concentration of 35% 2 Titrating with ammonia water to remove white precipitate, washing with deionized water, filtering to remove chloride ion, drying at 80 deg.C for 5 hr to obtain white powder, squeezing with conventional methodThe strands were dried at 80 ℃ for 4 hours after molding and then calcined at 450 ℃ for 4 hours to give white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 3mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 7mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.2 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, and keeping the vacuum degree at 17000Pa; the ultrasonic vibration frequency is 55kHz; the dipping temperature is 60 ℃, and the dipping time is 4 hours; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 450 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 100 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 4:1, total volume space velocity of 2h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 3
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with the mass concentration of 40 percent 2 And (3) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chloride ion is generated, drying for 4 hours at 80 ℃ to obtain white powder, extruding and molding by using a conventional method, drying for 6 hours at 90 ℃, and roasting for 4 hours at 550 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare silver nitrate sulfuric acid solution with the molar concentration of 3mol/L,dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare nickel nitrate sulfuric acid solution with the molar concentration of 8mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare palladium nitrate sulfuric acid solution with the molar concentration of 0.2 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, and keeping the vacuum degree at 18000Pa; the ultrasonic vibration frequency is 56kHz; dipping at 55 ℃ for 4 h; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 450 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and conditions in the step three to obtain white particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and conditions in the step three to obtain the metal-doped solid super acid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 100 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 3:1, total volume space velocity of 2h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 4
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with the mass concentration of 45% 2 And (2) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chlorine ion is generated, drying for 4 hours at 90 ℃ to obtain white powder, extruding the white powder into strips by using a conventional method, drying for 4 hours at 80 ℃, and roasting for 4 hours at 500 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 4mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 8mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.3mol/L. 3. With silver nitrateDipping the white solid particles obtained in the first step by using a sulfuric acid solution under the vacuum degree of 18000Pa; the ultrasonic vibration frequency is 59kHz; the dipping temperature is 60 ℃, and the dipping time is 4 h; after filtration, the mixture was dried at 90 ℃ for 6 hours and then calcined at 500 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 110 ℃, the reaction pressure is 4.0MPa, and the molar ratio of isobutene to phenol in the feed I is 4:1, the total volume space velocity is 2.5h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 5
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with mass concentration of 50% 2 And (3) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chloride ion is generated, drying for 4 hours at 90 ℃ to obtain white powder, extruding the white powder into strips by using a conventional method, drying for 6 hours at 90 ℃, and roasting for 6 hours at 450 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 2mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 5mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.1 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, wherein the vacuum degree is 16000Pa; the ultrasonic vibration frequency is 50kHz; dipping at 55 ℃ for 4 h; filtering, drying at 80 deg.C for 6 hr, and drying at 500 deg.CCalcining for 4 hours under the condition to obtain the particles I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 110 ℃, the reaction pressure is 4.0MPa, and the molar ratio of isobutene to phenol in the feed I is 4:1, the total volume space velocity is 2.5h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 6
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with mass concentration of 40% 2 Titrating the ethanol solution by ammonia water until no white precipitate is generated, washing by deionized water, filtering until no chloride ion is generated, drying for 4 hours at 80 ℃ to obtain white powder, extruding the white powder by a conventional method, drying for 5 hours at 70 ℃, and roasting for 5 hours at 450 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 2mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 5mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.1 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, and keeping the vacuum degree at 17000Pa; the ultrasonic vibration frequency is 55kHz; dipping at 55 ℃ for 4 h; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 550 ℃ for 4 hours to obtain granules I. 4. Treating the particles I with the nickel nitrate sulfuric acid solution prepared in the second step according to the method and conditions of the third step to obtain particles II, and treating with the palladium nitrate sulfuric acid solution prepared in the second step according to the method and conditions of the third stepThe particles II give the metal-doped solid superacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 100 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 3:1, total volume space velocity of 2h -1 A step of,; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Comparative example 1
The catalyst used in the reaction was D005 II type resin catalyst, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
Comparative example 2
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.
Comparative example 3
In the reaction process, the fixed bed reactor has no bed plate in the middle, other conditions are the same as example 4, and the reaction results are shown in Table 1.
Comparative example 4
The preparation process of the catalyst used has no ultrasonic vibration and pressurization operation process, the modified solution is not impregnated according to the specified sequence, only the catalyst is modified by adopting the conventional impregnation method, the other conditions are the same as the example 4, and the reaction results are shown in the table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Claims (9)
1. The method for preparing the p-tert-butyl phenol is characterized by comprising the following steps: under the condition of alkylation reaction, isobutene and phenol as a feed I enter from the top of the reactor in a spray mode, pass through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom to react layer by layer, and isobutene as a feed II passes through the reactorThe lower part enters and is rapidly gasified, the materials ascend layer by layer from bottom to top and further react with material flows from top to bottom, and reaction products are discharged from the bottom of the reactor; wherein the catalyst bed layer comprises a bed plate with air holes and a catalyst on the bed plate; the catalyst is a solid super acidic catalyst, and the preparation method of the solid super acidic catalyst comprises the following steps: (1) Reacting 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, drying, and roasting to obtain white solid particles for later use; (2) Respectively preparing a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, impregnating the white solid particles obtained in the step (1) with the silver nitrate sulfuric acid solution, drying and roasting to obtain particles I, impregnating the particles I with the nickel nitrate sulfuric acid solution, drying and roasting to obtain particles II, impregnating the particles II with the palladium nitrate sulfuric acid solution, drying and roasting to obtain a metal-doped solid super acidic catalyst; the impregnation process is carried out under reduced pressure and ultrasonic vibration.
2. The method of claim 1, wherein: the alkylation reaction conditions are as follows: the reaction temperature is 80-120 ℃; the reaction pressure is 2-5 MPa.
3. The method of claim 1, wherein: the isobutylene to phenol mole ratio in feed I was 1:1 to 5:1, the total volume airspeed is 1-4 h -1 。
4. The method of claim 1, wherein: the volume space velocity of the feed II is 1 to 2h -1 。
5. The method of claim 1, wherein: in the preparation method of the solid super acidic catalyst, the ZrOCl in the step (1) 2 The mass concentration of the ethanol solution is 30-50%.
6. The method of claim 1, wherein: in the preparation method of the solid super acidic catalyst, the drying temperature in the step (1) is 70-90 ℃, and the drying time is 4-6 hours.
7. The method of claim 1, wherein: in the preparation method of the solid super acidic catalyst, the step (2) is that the preparation process of the silver nitrate sulfuric acid solution is as follows: dissolving silver nitrate in dilute sulfuric acid to obtain a silver nitrate sulfuric acid solution; the preparation process of the nickel nitrate sulfuric acid solution and the palladium nitrate sulfuric acid solution is the same as that 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.
8. The method of claim 1, wherein: in the preparation method of the solid super acidic catalyst, the decompression condition in the step (2) is 15000 to 20000Pa; the ultrasonic condition is that the vibration frequency is 50-60 kHz; the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h.
9. The method of claim 1, wherein: in the preparation method of the solid super acidic catalyst, the drying conditions in the step (2) are as follows: the drying temperature is 80 to 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.
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