CN101973858A - Method for synthesizing tert-butylated hydroxyanisole through solid-liquid-phase reaction - Google Patents
Method for synthesizing tert-butylated hydroxyanisole through solid-liquid-phase reaction Download PDFInfo
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- CN101973858A CN101973858A CN2010105013048A CN201010501304A CN101973858A CN 101973858 A CN101973858 A CN 101973858A CN 2010105013048 A CN2010105013048 A CN 2010105013048A CN 201010501304 A CN201010501304 A CN 201010501304A CN 101973858 A CN101973858 A CN 101973858A
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- tertiary butyl
- methoxy phenol
- molecular sieve
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 22
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 239000007791 liquid phase Substances 0.000 title claims description 9
- 239000004255 Butylated hydroxyanisole Substances 0.000 title abstract description 11
- 229940043253 butylated hydroxyanisole Drugs 0.000 title abstract description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 6
- CZBZUDVBLSSABA-UHFFFAOYSA-N butylated hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1.COC1=CC=C(O)C=C1C(C)(C)C CZBZUDVBLSSABA-UHFFFAOYSA-N 0.000 claims description 18
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 230000009466 transformation Effects 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 abstract description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 abstract 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011973 solid acid Substances 0.000 description 5
- XRCRJFOGPCJKPF-UHFFFAOYSA-N 2-butylbenzene-1,4-diol Chemical compound CCCCC1=CC(O)=CC=C1O XRCRJFOGPCJKPF-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 4
- 230000002152 alkylating effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical class COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical group C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000006209 tert-butylation Effects 0.000 description 1
Classifications
-
- 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
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for synthesizing tert-butylated hydroxyanisole under the catalytic action of a hydrogen Y molecular sieve by using p-methoxy phenol and methyl tert-butyl ether as raw materials. In the method, the Y molecular sieve with a hydrogen Si/Al ratio of 2.6-7.6 is used, the reaction time is 15-180 min, the reaction temperature is 80-180 DEG C, the p-methoxy phenol conversion rate is 21-99 percent and the tert-butylated hydroxyanisole yield is 14-74 percent. The invention adopts a catalyst which has low cost and can be repeatedly used through simple solvent washing or roasting treatment, can solve the problems of unavailable catalyst recovery and great acidic wastewater discharge of a traditional tert-butylated hydroxyanisole production process through an F-C (Friedel-Crafts) reaction and has important industrial application prospects, and meanwhile, the catalyst and the reaction process, adopted in the method, benefits the improvement of the production efficiency.
Description
Technical field
The present invention relates to be a kind of be raw material with p methoxy phenol and methyl tertiary butyl ether, the method for synthetized oxidation preventive agent-butylhydroxy anisole under Hydrogen Y molecular sieve catalyst action.
Background technology
Butylhydroxy anisole (butylatedhydroxyanisole, claim tertiary butyl-4-hydroxy phenylmethylether, butyl hydroxy anisol again), comprise 3-tertiary butyl-4-hydroxy phenylmethylether (3-TBHA) and 2-tertiary butyl-4-hydroxy phenylmethylether (2-TBHA), be that a kind of white is to lurid waxy solid, have slight special smelly, fusing point 48-63 ℃, to thermally-stabilised.Under the weak base condition, be difficult for destroyed, not painted with the metal ion effect.
Butylhydroxy anisole is a kind of important oil-soluble inhibitor, is mainly used in food and oil prodution industry, also can be used for refining of petroleum and rubber etc.(reference: Zheng Yuguo, Wang Yuanshan etc. write, " production of antioxidant and application ", January in 2004 the 1st edition P404; Li Shuguo, Zhao Wenhua, Chen Hui, " edible grease antioxidant and safety research progress thereof ", grain and grease, 2006, the 5 phases: P.34-37; Yu Tao, Ye Jian, " high performance liquid chromatography is measured the research of BHA in the food, BHT, TBHQ method simultaneously ". Chinese sanitary inspection magazine, 2007.
17(12): p. 2136-2138)
The synthetic method about butylhydroxy anisole of bibliographical information is divided into following two big classes by the starting raw material difference at present:
(1) Resorcinol method.
Selecting phosphoric acid or sulfuric acid for use is catalyzer, with the Resorcinol and the trimethyl carbinol is raw material, carry out the normal pressure liquid phase reaction, 90 ℃ of temperature of reaction, reaction 1.5 ~ 2.5h, generate intermediate 2-Tert. Butyl Hydroquinone, obtain by product 2 simultaneously, the 5-di-tert-butyl hydroquinone, through operations such as neutralization, crystallizations, isolate the 2-Tert. Butyl Hydroquinone, again 2-Tert. Butyl Hydroquinone (TBHQ) and methyl-sulfate are carried out monomethylation reaction 1 ~ 2h under alkalescence, 40 ℃, make butylhydroxy anisole, this technology is had some improved method (reference: Li Jialin; Du Chenguang; Li Hua, a kind of technology that from the butylhydroxy anisole production process, reclaims Tert. Butyl Hydroquinone, CN101704727A, 2009)
(2) p-Methoxyphenol method.
Aforesaid method (1) and (2)
In need liquid acid as catalyzer, catalyst levels is big and be difficult to repeat reclaim and use, product postprocessing needs a large amount of water to wash, and can't avoid the discharging of a large amount of acid waste waters, method (2)
The middle solid acid catalyst that uses is avoided the problem of bringing with liquid acid catalyst preferably.But, in the method (2)
Though peak rate of conversion is very high, as alkylating reagent, the water that produces in the reaction process can influence catalyst activity with the trimethyl carbinol, and catalyzer mainly is a Zn – Al-MCM-41 molecular sieve, and preparation process complexity, cost are higher, comparatively speaking, and in the method (2)
Employed alkylating reagent methyl tertiary butyl ether, avoided the generation of reaction process water, known effective solid acid catalyst mainly is Filtrol-24 clay, K-10 montmorillonite clay at present, solvent is 1,4-dioxane(1, the 4-dioxan), perhaps catalyzer is the catalyzer such as the H of loaded by heteropoly acid type
3PW
12O
40/ Al
2O
3, but as a whole, the cost of these catalyst system is higher, and therefore, the present invention proposes the method for low, the effective catalysis synthesizing tertiary butyl BHA of a kind of cost.
Summary of the invention
The objective of the invention is to develop a kind of environment amenable, that the catalyzer low price is easy to get and reactive behavior is higher, prepare butylhydroxy anisole by p methoxy phenol and methyl tertiary butyl ether method, the present invention uses novel catalyzing technology, the problem of avoiding under the effect of traditional liquid acid synthetic a large amount of acid waste waters of discharging and catalyzer can't reclaim and regenerate and use, and can enhance productivity greatly.
Solution of the present invention is to be catalyzer with acid solid molecular sieves, realizes that in autoclave p methoxy phenol and methyl tertiary butyl ether are at the solid-liquid F-C reaction of condition mutually, the synthetic target product butylhydroxy anisole that obtains.
The invention provides a kind of method of solid-liquid phase reaction synthesizing tertiary butyl BHA, is raw material with p methoxy phenol and methyl tertiary butyl ether, and hexanaphthene is a solvent, with the Hydrogen Y molecular sieve is catalyzer, solid-liquid phase reaction synthesizing tertiary butyl BHA in autoclave, and reaction formula is as follows:
Synthesis step is as follows:
In autoclave, add a certain amount of Hydrogen Y molecular sieve catalyzer, and the mixed solution of p methoxy phenol, methyl tertiary butyl ether and solvent hexanaphthene, their mol ratio is 1:(1～6): (0～14.2), with high-purity N
2The air in the replacement reaction kettle repeatedly, feeding initial pressure at last is the N of 0～0.5MPa
2Make protection gas; under 80～180 ℃ of a certain steady temperatures, react 15～180min; reaction is cooled off reactor rapidly after finishing; suction filtration separating reaction liquid and catalyzer; with the content of p methoxy phenol and butylhydroxy anisole in the gas chromatographic analysis product, determine the yield of the transformation efficiency and the butylhydroxy anisole of p methoxy phenol.
Silicon/the aluminum ratio of Hydrogen Y molecular sieve catalyzer of the present invention is 2.6 ~ 7.6, sample roasting 4h in 300～600 ℃ of retort furnaces before using, the cooling back is standby, the weight ratio of Hydrogen Y molecular sieve catalyzer and p methoxy phenol is 1:(3～27), can be repeatedly used after described reacted Hydrogen Y molecular sieve catalyzer process solvent wash or the roasting.
Characteristics of the present invention are that catalyzer can't be reused the problem of amplification quantity acid waste water side by side in the F-C reaction production butylhydroxy anisole technology that can avoid traditional, employed catalyzer and reaction process have improved production efficiency simultaneously, have important prospects for commercial application.
Embodiment
Embodiment 1
In the autoclave of 20mL, add Hydrogen Y molecular sieve catalyzer (Si/Al mol ratio=3:1, through 500 ℃ of roasting 4h pre-treatment), the mixed solution of p methoxy phenol, methyl tertiary butyl ether and 10mL solvent hexanaphthene (three's mol ratio is 1:3:14.2) is with N
2Air in the replacement reaction kettle repeatedly feeds the N of 0.3MPa at last
2Make protection gas; keeping temperature is 160 ℃; reaction 180min; reaction is cooled off reactor rapidly after finishing, and suction filtration separating reaction liquid and catalyzer are with the content of p methoxy phenol and butylhydroxy anisole in the gas chromatographic analysis product; determine the yield of the transformation efficiency and the butylhydroxy anisole of p methoxy phenol; the transformation efficiency of p methoxy phenol is 97.9%, and the yield of butylhydroxy anisole (TBHA) is 45.8%, and related data is listed in the table 1.
Embodiment 2～6
Under the identical condition of other conditions and embodiment 1, change the reaction times (being respectively 15min, 30min, 60min, 90min, 120min), the result lists in table 1(2～6 respectively) in.
Embodiment 7～11
Under the identical condition of other conditions and embodiment 1, change temperature of reaction (being respectively 80 ℃, 100 ℃, 120 ℃, 140 ℃, 180 ℃), reaction result is listed in table 1(7～11 respectively) in.
Embodiment 12～14
Under the identical condition of other conditions and embodiment 1, change material molar ratio (being respectively 1:1,1:2,1:4), reaction result is listed in respectively in the table 1 (12～14).
Embodiment 15
Under the identical condition of other conditions and embodiment 1, the change material molar ratio is 1:6, no longer adds the solvent hexanaphthene in reaction system, and reaction result is listed in the table 1 (15).
Embodiment 16
Under the identical condition of other conditions and embodiment 1, the change material molar ratio is 1:1, and solvent hexanaphthene consumption is reduced to 5mL, and reaction result is listed in the table 1 (16).
Embodiment 17～19
Under the identical condition of other conditions and embodiment 1, change Hydrogen Y molecular sieve catalyst levels (being respectively 0.03g, 0.1g, 0.2g), reaction result is listed in respectively in the table 1 (17～19).
Embodiment 20～21
Under the identical condition of other conditions and embodiment 1, respectively with the H-Y molecular sieve of 300 ℃, 600 ℃ roastings as catalyzer, the result of reaction lists in table 1(20～21 respectively) in.
Embodiment 22
Under the identical condition of other conditions and embodiment 1, change N
2The initial pressure of protection gas, N
2Initial pressure changes 0MPa into, and reaction result is listed in table 1(22) in.
Embodiment 23
Under the identical condition of other conditions and embodiment 1, N
2The initial pressure of protection gas changes 0.5MPa into, and 1(23 is shown in the results are shown in of reaction) in.
Embodiment 24
Under the identical condition of other conditions and embodiment 1, the H-Y that uses Si/Al mol ratio=2.6 instead is a catalyzer, reaction the results are shown in table 1(24) in.
Embodiment 25
Under the identical condition of other conditions and embodiment 1, the H-Y that uses Si/Al mol ratio=7.6 instead is a catalyzer, and material molar ratio is 1:2, reaction the results are shown in table 1(25) in.
Table 1. utilizes the result of Hydrogen Y molecular sieve catalyzer p methoxy phenol and methyl tertiary butyl ether reaction under the differential responses condition
Embodiment 26
With embodiment 1 reacted catalyzer filtered and recycled, with drying behind the washing with acetone, catalyzer is roasting no longer again, reacts under the identical condition of other conditions and embodiment 1, and after being repeatedly used, the results are shown in Table 2 in reaction.
Table 2 catalyzer is reused reaction result
Embodiment 27
With the catalyzer 500 ℃ of roasting 4h in air after embodiment 26 last the uses, catalyzer after the roasting is reacted under the identical condition of embodiment 1, analytical results shows that the transformation efficiency of p methoxy phenol is 82.6%, and the yield of butylhydroxy anisole (TBHA) is 42.0%.
Claims (4)
1. the method for a solid-liquid phase reaction synthesizing tertiary butyl BHA, it is characterized in that: with p methoxy phenol and methyl tertiary butyl ether is raw material, and hexanaphthene is a solvent, is catalyzer with the Hydrogen Y molecular sieve, synthesizing tertiary butyl BHA in autoclave, reaction formula is as follows:
Synthesis step is as follows:
(1) a certain amount of Hydrogen Y molecular sieve catalyzer of in autoclave, packing into, and the mixed solution of p methoxy phenol, methyl tertiary butyl ether and solvent hexanaphthene, their mol ratio is 1:(1～6): (0～14.2), with N
2Air in the replacement reaction kettle repeatedly, feeding initial pressure at last is the N of 0～0.5MPa
2Make protection gas, at 80～180 ℃ of a certain steady temperature reaction 15～180min;
(2) reactor is cooled off rapidly, suction filtration separating reaction liquid and catalyzer with the content of p methoxy phenol and butylhydroxy anisole in the gas chromatographic analysis product, are determined the yield of the transformation efficiency and the butylhydroxy anisole of p methoxy phenol.
2. according to the method for right 1 described solid-liquid phase reaction synthesizing tertiary butyl BHA, the silicon/aluminum ratio that it is characterized in that described Hydrogen Y molecular sieve catalyzer is 2.6 ~ 7.6, sample roasting 4h in 300～600 ℃ of retort furnaces before using, and the cooling back is standby.
3. according to the method for right 1 described solid-liquid phase reaction synthesizing tertiary butyl BHA, the weight ratio that it is characterized in that described Hydrogen Y molecular sieve catalyzer and p methoxy phenol is 1:(3～27).
4. according to the method for right 1 described solid-liquid phase reaction synthesizing tertiary butyl BHA, it is characterized in that to be repeatedly used after described reacted catalyzer is through solvent wash or roasting.
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| CN2010105013048A CN101973858A (en) | 2010-10-11 | 2010-10-11 | Method for synthesizing tert-butylated hydroxyanisole through solid-liquid-phase reaction |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018214630A1 (en) * | 2017-05-24 | 2018-11-29 | 中国人民解放军军事医学科学院生物医学分析中心 | New method for preparing 2-tert-butyl-4-methoxyphenol and new crystal form thereof |
| CN112718005A (en) * | 2020-12-31 | 2021-04-30 | 兄弟科技股份有限公司 | Catalyst composition for synthesizing 3-tert-butyl-4-hydroxyanisole from p-hydroxyanisole and application thereof |
| CN115069294A (en) * | 2022-07-08 | 2022-09-20 | 北京石油化工学院 | Supported catalyst and application thereof in preparation of tert-butylhydroquinone |
-
2010
- 2010-10-11 CN CN2010105013048A patent/CN101973858A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| HUANGJU CAI,ET AL: "Alkylation of 4-methoxyphenol with MTBE catalyzed by 12-tungstophoric acid supported on neutral alumina", 《REACT KINET CATAL LETT》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018214630A1 (en) * | 2017-05-24 | 2018-11-29 | 中国人民解放军军事医学科学院生物医学分析中心 | New method for preparing 2-tert-butyl-4-methoxyphenol and new crystal form thereof |
| CN108929202A (en) * | 2017-05-24 | 2018-12-04 | 中国人民解放军军事医学科学院生物医学分析中心 | 2- tert-butyl -4- metoxyphenol novel preparation method and its novel crystal forms |
| US11655201B2 (en) | 2017-05-24 | 2023-05-23 | Biomedical Analysis Center, Academy Of Military Medical Sciences | Method for preparing 2-tert-butyl-4-methoxyphenol and new crystal form thereof |
| CN112718005A (en) * | 2020-12-31 | 2021-04-30 | 兄弟科技股份有限公司 | Catalyst composition for synthesizing 3-tert-butyl-4-hydroxyanisole from p-hydroxyanisole and application thereof |
| CN115069294A (en) * | 2022-07-08 | 2022-09-20 | 北京石油化工学院 | Supported catalyst and application thereof in preparation of tert-butylhydroquinone |
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