CN103044209A - Preparation method for co-production of TBHQ (tertiary butylhydroquinone) and butylated hydroxyanisole - Google Patents
Preparation method for co-production of TBHQ (tertiary butylhydroquinone) and butylated hydroxyanisole Download PDFInfo
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Abstract
The invention discloses a preparation method for co-production of TBHQ and butylated hydroxyanisole. The method takes hydroquinone as the raw material and includes dissolving hydroquinone in a mixed methanol solvent first; adding a catalyst; heating quickly to a target reaction temperature, and then adding isobutene until charging is over; performing a thermal insulation reaction until the reaction is over; and finally performing purification treatment to obtain the final products TBHQ and butylated hydroxyanisole. Compared with the prior art, the preparation method has the following advantages: (1) the raw material utilization rate is high, and phenols by-products are few; (2) the main product TBHQ is low in cost and good in quality; (3) the proportion of 2-BHA (butylated hydroxyanisole) to 3-BHA in the secondary product BHA is about 98.5:1.5; (4) the catalyst can be reused, and the recovering method is simple; and (5) the whole technique achieves environmental-friendliness truly, and harmful waste is not discharged.
Description
Technical field
The present invention relates to the method for a kind of 2-of preparation Tert. Butyl Hydroquinone and coproduction butylhydroxy anisole.
Background technology
Tert. Butyl Hydroquinone chemical name: 2-Tert. Butyl Hydroquinone (TBHQ)
English name: 2-t-butyl-1,4-dihydroxybenzene
Butylhydroxy anisole chemical name: 2-tertiary butyl-4-hydroxy phenylmethylether or 3-tertiary butyl-4-hydroxy phenylmethylether (BHA)
English name: Butylated hydroxyanisole
Resorcinol chemical name Isosorbide-5-Nitrae-dihydroxy-benzene (HQ)
English name hydroquinone
Tert. Butyl Hydroquinone (TBHQ) is a kind of food antioxidant commonly used, and it can be widely used in each field such as food, feed.Its antioxygen property is better than other like product (BHA, BHT), and especially the antioxidant effect in grease and goods thereof is best, and antioxidant effect has significantly and improves when with the BHA coupling.BHA belongs to a kind of Xing biology of TBHQ, also is a kind of very good food antioxidant, more is usually used in the based foods such as animal grease and goods thereof.
The production technique of TBHQ, all adopting Resorcinol is raw material, reacts under the effect of catalyzer with iso-butylene or the trimethyl carbinol to generate TBHQ.Adopt acid as catalyst at this reacting middle catalyst, the research of useful Louis's acid as catalyst there is not industrial value because its activity is hanged down more.Available strong acid is made catalyzer, such as sulfuric acid, and phosphoric acid.The transformation efficiency of making the catalyzer raw material with strong acid can reach 90%, and selectivity but is difficult to improve, and has by product many, the high relevant unfavorable factor of production cost, and it is not high to add that the phenols by-product utilized is worth, easily to environment.Such as GB761613, GB1359290A, JP8176042A, the Patents such as US4323713A all disclose the method for preparing the 2-Tert. Butyl Hydroquinone with sulfuric acid or phosphoric acid does catalyst, because the Resorcinol activity is higher, symmetrical configuration is very easily introduced dual-tert-butyl and is generated 2,5 di tert butyl hydroquinone (DT) by product.The selectivity that someone attempts to improve single tertiary butyl substitution reaction adds a certain proportion of alkanones such as US4323713 to reduce the generation of by product in reaction solution, the Patents such as JP62081338 are disclosed, but effect and not obvious.Use solid strong acid except doing to have the catalyzer people to study with strong acid etc., strongly acidic cation-exchange and MCM-49 etc. is made catalyzer, but yield is all undesirable.
BHA also is a kind of good food antioxidant, and it is that raw material prepares BHA with the methylating reagent monoether that its industrial process generally adopts TBHQ, and when the river rises the boat goes up with the cost of TBHQ for its production cost.
Sulfonic acid type polystyrene macroporous resin has the alkylation catalytic activity of strong acid, also is a kind of good catalyst for etherification, but uses separately strong its etherification activity of acidity higher.The part transition metal ion also has very high alkylation catalytic activity, and with the H ion of active metallic ion substituted sulfonic acid type polystyrene macroporous resin, the oxidisability that has not only reduced the strong acid of resin itself has also improved the alkylation catalytic activity of catalyzer.Add that sulfonic acid type polystyrene macroporous resin aperture is moderate, the larger high adsorption capacity of specific surface area, the advantage such as high temperature resistant wear-resistant broken ability is strong, M
X+-Amberlyst catalyzer has good industrial applications and is worth.
Mixed solvent can separate back for 3～5 times afterwards in use, and is reusable.Just can be all or part of before reaction finishes cooling the mode of lower boiling methyl alcohol by common distillation be reclaimed because the boiling point of two kinds of mixed solvents differs larger, separated very simple.
Summary of the invention
The purpose of this invention is to provide that a kind of raw material availability is high, reaction conditions is gentle, environmental friendliness and the high method for preparing 2-Tert. Butyl Hydroquinone and coproduction butylhydroxy anisole of productive rate.
A kind of method for preparing 2-Tert. Butyl Hydroquinone and coproduction butylhydroxy anisole provided by the invention, it is characterized in that: take Resorcinol as raw material, it is dissolved in the methanol mixed solvent first, add catalyzer, and be heated to rapidly the goal response temperature, then adding iso-butylene finishes to carry out insulation reaction to carry out at last purification processes and obtain the finished product 2-Tert. Butyl Hydroquinone and butylhydroxy anisole until reaction finishes to reinforced.Its concrete condition is:
The envelope-bulk to weight ratio of described methanol mixed solvent and Resorcinol is 5: 1～8: 1.
Described methanol mixed solvent refers to the mixed solvent that methyl alcohol and solvent X are mixed in proportion, and wherein solvent X is one or both the mixture in acetonitrile, methyl iso-butyl ketone (MIBK), Isosorbide-5-Nitrae-dioxane and the toluene.
The blending ratio of described methanol mixed solvent is methyl alcohol: solvent X=9: 1～6: 4.
Be 10～50 minutes described heat-up time, preferred 15～30 minutes.Temperature-rise period will be lacked as far as possible, and general control was warming up to target temperature in 15～30 minutes, or more short better.
Described goal response temperature is 95～125 ℃, preferred 98～118 ℃.Temperature of reaction should not be crossed low or too high, is controlled at 98～118 ℃ of comparatively ideals.
Described catalyzer is the sulfonic acid type polystyrene macroporous ion exchange resin of processing through active metallic ion, such as ROHM AND HAAS resin series Amberlyst15, and Amberlyst36, or self-control sulfonic acid type catalyzer.Described active metallic ion is Bivalent Tin, trivalent cerium, quadrivalent cerium, trivalent lanthanum, ferric iron or trivalent neodymium.The general formula of catalyzer can be used M
X+-Amberlyst15, or M
X+-Amberlyst36 represents, wherein M
X+Be Sn
2+, Ce
3+, Ce
4+, La
3+, Fe
3+, Nd
3+
The consumption of described catalyzer is 18～25% of Resorcinol quality, or the active metallic ion that adsorbs of catalyzer and the mass ratio of Resorcinol are 1: 100～1: 40.
The joining day of described iso-butylene is 1.5～2.5 hours.Reaction solution begins to add after being warmed up to target temperature, and the joining day is controlled in 1.5～2.5 hours and is advisable, and adding too fast exothermic heat of reaction and iso-butylene can raise by reacting kettle inner pressure, and temperature of reaction system also can surpass the target setting temperature.The pressure of anti-still floats for the steaming almost of solvent system under the target temperature condition presses lower 60Kpa scope.
Compared with prior art, the present invention has following advantage:
(1) raw material availability is high, and the phenols by product is few.
(2) main products TBHQ cost is lower, quality better.
(3) about 98.5: 1.5 of the ratio of 2-BHA and 3-BHA among the secondary product BHA.
(4) catalyzer can be reused, and recovery method is simple.
(5) whole technique really realizes environmental friendliness, does not have the bazardous waste discharging.
Embodiment
Below by specific embodiment the present invention is set forth, but protection scope of the present invention is not limited to this.The person of an ordinary skill in the technical field all can realize purpose of the present invention according to above content disclosed by the invention.
Embodiment 1
Get 100g Amberlyst36 type resin, add 500ml methyl alcohol and soaked 24 hours, separation of methanol use the washed with methanol resin with the resin ion exchange column of packing into, and flow rate control is 50～80ml/h, until outflow methyl alcohol is again without color or other impurity.Ce with 15% mass concentration for preparing in advance
2(SO
4)
3Solution flushing resin, flow rate control is 15～30ml/h, goes out until the H ion in the resin is fully exchanged, its terminal point can be judged according to the acid-basicity of exchange liquid, then use the deionized water rinsing resin, directly without SO
4 2-Detect, with the resin dry for standby.
Add 2500mL9 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 1-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst36 catalyzer is warming up to 118 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 1.5 hours, and whole reaction process keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ4.3%, TBHQ content 80.9%, BHA10.7%, DTBHQ2.3%, other composition 1.8%.Filtering recovering catalyst, and Distillation recovery methyl alcohol, the reconcentration cooling crystallization, crystal can be divided out DTBHQ and BHA with suitable hot water dissolving's heat filtering, filter cake is DTBHQ and BHA, be TBHQ and unreacted raw material HQ in the filtrate, the filtrate cooling crystallization filters to get TBHQ, but HQ reaches the finite concentration concentration and recovery in water handy again; Filter cake can obtain the finished product TBHQ606 gram and BHA83 gram with the separable by product DTBHQ that discards of sherwood oil recrystallization through further purifying technique, and DTBHQ and a small amount of other impurity recycling or residue production focus on.
Embodiment 2
Fe
3+-Amberlyst36 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL9 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 1-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Fe
3+-Amberlyst36 catalyzer is warming up to 118 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 1.5 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ6.3%, TBHQ content 63.8%, BHA20.9%, DTBHQ3.7%, other composition 5.3%.Post-treating method finally obtains product TBHQ476.3 gram and BHA166.8 gram with embodiment 1.
Embodiment 3
Ce
3+-Amberlyst36 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL9 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 1-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst36 catalyzer is warming up to 110 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 1.5 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ4.5%, TBHQ content 86.0%, BHA6.7%, DTBHQ1.7%, other composition 1.1%.Aftertreatment technology is identical with embodiment 1, obtains the finished product TBHQ643.2 gram and BHA51.5 gram.
Embodiment 4
Ce
3+-Amberlyst36 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL9 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 1-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst36 catalyzer is warming up to 102 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 1.5 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ5.5%, TBHQ content 77.1, BHA12.7%, DTBHQ1.6%, other composition 3.1%.Aftertreatment technology is identical with embodiment 1, obtains the finished product TBHQ577 gram and BHA100.3 gram.
Embodiment 5
Ce
3+-Amberlyst36 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL8 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 2-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst36 catalyzer is warming up to 110 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 1.5 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ7.9%, TBHQ content 81.5%, BHA7.1%, DTBHQ2.2%, other composition 1.3%.Aftertreatment technology is identical with embodiment 1, obtains the finished product TBHQ610.7 gram and BHA55.0 gram.
Embodiment 6
Ce
3+-Amberlyst36 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL9 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 1-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst36 catalyzer is warming up to 110 ℃ in 30 minutes, begin to add iso-butylene 255 grams, adds in 1.5 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ4.3%, TBHQ content 81.5%, BHA9.7%, DTBHQ1.6%, other composition 2.9%.Aftertreatment technology is identical with embodiment 1, obtains the finished product TBHQ612.2 gram and BHA75.1 gram.
Embodiment 7
Ce
3+-Amberlyst36 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL9 in the 5000mL reactor: 1 methanol/toluene is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst36 catalyzer is warming up to 110 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 2.0 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ3.8%, TBHQ content 84.4%, BHA8.7%, DTBHQ1.8%, other composition 1.3%.Aftertreatment technology is identical with embodiment 1, obtains the finished product TBHQ631.8 gram and BHA67.0 gram.
Embodiment 8
Ce
3+-Amberlyst15 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL9 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 1-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst15 catalyzer is warming up to 110 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 1.5 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ6.5%, TBHQ content 84.6%, BHA5.3%, DTBHQ2.2%, other composition 1.4%.Aftertreatment technology is identical with embodiment 1, obtains the finished product TBHQ632.6 gram and BHA37.6 gram.
Embodiment 9
Ce
3+-Amberlyst15 active metallic ion CatalystT treatment process is with reference to embodiment 1.
Add 2500mL8 in the 5000mL reactor: methyl alcohol/Isosorbide-5-Nitrae of 2-dioxane is made solvent, and 500g Resorcinol and stirring and dissolving add 100 gram Ce
3+-Amberlyst15 catalyzer is warming up to 118 ℃ in 15 minutes, begin to add iso-butylene 255 grams, adds in 2.5 hours, and whole kind of the reaction process of crossing keeps constant temperature.Iso-butylene passes into complete rear insulation reaction 30 minutes, and negate is used its result of gas chromatographic analysis and shown, raw material residue HQ4.9%, TBHQ content 81.4%, BHA8.4%, DTBHQ3.1%, other composition 2.2%.Aftertreatment technology is identical with embodiment 1, obtains the finished product TBHQ608.1 gram and BHA61.5 gram.
Claims (10)
1. method for preparing 2-Tert. Butyl Hydroquinone and coproduction butylhydroxy anisole, it is characterized in that: take Resorcinol as raw material, it is dissolved in the methanol mixed solvent first, add catalyzer, and be heated to rapidly the goal response temperature, then adding iso-butylene finishes to carry out insulation reaction to carry out at last purification processes and obtain the finished product 2-Tert. Butyl Hydroquinone and butylhydroxy anisole until reaction finishes to reinforced.
2. method according to claim 1, it is characterized in that: the envelope-bulk to weight ratio of described methanol mixed solvent and Resorcinol is 5: 1～8: 1.
3. method according to claim 1 and 2, it is characterized in that: described methanol mixed solvent refers to the mixed solvent that methyl alcohol and solvent X are mixed in proportion, wherein solvent X is one or both the mixture in acetonitrile, methyl iso-butyl ketone (MIBK), Isosorbide-5-Nitrae-dioxane and the toluene.
4. method according to claim 3, it is characterized in that: the blending ratio of described methanol mixed solvent is methyl alcohol: solvent X=9: 1～6: 4.
5. method according to claim 1, it is characterized in that: be 10～50 minutes described heat-up time.
6. method according to claim 1, it is characterized in that: described goal response temperature is 95～125 ℃.
7. method according to claim 1, it is characterized in that: described catalyzer is the sulfonic acid type polystyrene macroporous ion exchange resin of processing through active metallic ion.
8. method according to claim 7, it is characterized in that: described active metallic ion is Bivalent Tin, trivalent cerium, quadrivalent cerium, trivalent lanthanum, ferric iron or trivalent neodymium.
9. according to claim 7 or 8 described methods, it is characterized in that: the consumption of described catalyzer is 18～25% of Resorcinol quality, or the active metallic ion that adsorbs of catalyzer and the mass ratio of Resorcinol are 1: 100～1: 40.
10. method according to claim 1, it is characterized in that: the joining day of described iso-butylene is 1.5～2.5 hours.
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Cited By (4)
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| CN103709302A (en) * | 2013-12-26 | 2014-04-09 | 王金明 | Preparation method of catalyst used in production of tertiary butyl hydroquinone |
| CN108314609A (en) * | 2018-01-03 | 2018-07-24 | 兄弟科技股份有限公司 | A kind of synthetic method of butylated hydroxy anisole |
| CN112441882A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Stabilizer for refining ethylene glycol and preparation method thereof |
| CN114149308A (en) * | 2021-12-13 | 2022-03-08 | 杭州可菲克化学有限公司 | Method for preparing beta-naphthyl methyl ether |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709302A (en) * | 2013-12-26 | 2014-04-09 | 王金明 | Preparation method of catalyst used in production of tertiary butyl hydroquinone |
| CN103709302B (en) * | 2013-12-26 | 2016-02-03 | 王金明 | A kind of preparation method for the production of Tert. Butyl Hydroquinone catalyzer |
| CN108314609A (en) * | 2018-01-03 | 2018-07-24 | 兄弟科技股份有限公司 | A kind of synthetic method of butylated hydroxy anisole |
| CN112441882A (en) * | 2019-09-02 | 2021-03-05 | 中国石油化工股份有限公司 | Stabilizer for refining ethylene glycol and preparation method thereof |
| CN112441882B (en) * | 2019-09-02 | 2023-04-07 | 中国石油化工股份有限公司 | Stabilizer for refining ethylene glycol and preparation method thereof |
| CN114149308A (en) * | 2021-12-13 | 2022-03-08 | 杭州可菲克化学有限公司 | Method for preparing beta-naphthyl methyl ether |
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