CN103990475B - A kind of composite solid-acid catalyst and its preparation method and application - Google Patents
A kind of composite solid-acid catalyst and its preparation method and application Download PDFInfo
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- 239000011973 solid acid Substances 0.000 title claims abstract description 48
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000000741 silica gel Substances 0.000 claims abstract description 44
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000004913 activation Effects 0.000 claims abstract description 17
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 12
- 235000009754 Vitis X bourquina Nutrition 0.000 claims abstract description 7
- 235000012333 Vitis X labruscana Nutrition 0.000 claims abstract description 7
- 235000014787 Vitis vinifera Nutrition 0.000 claims abstract description 7
- 235000021028 berry Nutrition 0.000 claims abstract description 7
- 239000011592 zinc chloride Substances 0.000 claims abstract description 6
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 6
- 240000006365 Vitis vinifera Species 0.000 claims abstract 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 36
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 4
- -1 30 parts Chemical compound 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002168 alkylating agent Substances 0.000 claims description 3
- 229940100198 alkylating agent Drugs 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
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- 238000006424 Flood reaction Methods 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 16
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 15
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 14
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
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- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical class CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to technical field of organic synthesis, provide a kind of composite solid-acid catalyst, composite solid-acid catalyst is (SO
4 2-+ ZnCl
2)/silica gel, is composited by zinc chloride, sulfuric acid and silica gel, and its preparation method: by silica gel after Grape berry is placed in liquor zinci chloridi and floods, then dries, and then joins steeped overnight in sulfuric acid solution, after oven dry, and activation, obtained (SO
4 2-+ ZnCl
2)/silica gel composite solid-acid catalyst.Composite solid-acid catalyst provided by the invention has acid strong, active good, selective height, can be recycled and eco-friendly feature; Use composite solid-acid catalyst for the synthesis of 2,6-di-tert-butyl-4-methy phenol, have easy and simple to handle, reaction temperature is low, normal pressure, do not use that any organic solvent, conversion ratio are high, the reaction time is short, selective height, eco-friendly feature, meet friendly process requirement, be very suitable for suitability for industrialized production.
Description
Technical field
The invention belongs to technical field of organic synthesis, particularly a kind of composite solid-acid catalyst and preparation method thereof and the application of this catalyst in synthesis 2,6-di-tert-butyl-4-methy phenol.
Background technology
The chemical name of BHT (ButylatedHydroxytoluene) is 2,6-di-tert-butyl-4-methy phenol, (China's rubber industry custom claims age resistor to be commonly called as antioxidant 264, synthetic resin and plastic industry are then accustomed to claiming antioxidant, also to have and claim stabilizing agent), also known as T501.It is a kind of universal phenolic antioxidant of of many uses, large usage quantity.Can be used for the field such as synthetic rubber, synthetic resin and plastics, oil product (lubricating oil, lubricating grease, paraffin etc.), food and feed.
BHT, since nineteen thirty-seven industrialization, has had longer developing history.Although it is an old kind in phenol antiager, because its anti ageing property is good, cheap, safe and convenient to use, stable, so lasting.More than ten, existing China, the U.S., Britain, Russia, France, Japan, Germany, Canada and Czech etc. are national at production BHT product in the world now.Domestic BHT market application structure is: what the application market of BHT antioxidant held pride of place is oil product.Another main application of BHT is used as natural rubber and elastomeric antiaging agent in rubber.BHT, in the production and modification of synthetic resin and plastics, once must be for primary antioxidant and apply more widely.Antioxidant and the heat stabilizer of polyolefin, polyester, polystyrene, cellulose-based resin, PVC etc. is used as in plastics.Also can be used as the antioxidant of food.Synthetic material for food, medicine, cosmetic package also makes antioxidant with food-grade BHT.
Because BHT has purposes so widely, therefore, improve its production technology, to seek efficient, cheap, eco-friendly catalyst and production technology be very important and highly significant.
The raw material route of synthesis BHT is a lot, such as, can from paracresol, to and the raw material such as a position mixture cresol, phenol, 2,6-DI-tert-butylphenol compounds start to synthesize BHT.
At present, the technique of domestic and international production and preparation antioxidant BHT, isobutene is mostly adopted to make alkylating agent, catalyst is made with the concentrated sulfuric acid or aryl sulfonic acid, to depress and react and prepare (such as, the patent CN1215042A that Zhang Yue attains etc., 1999-04-28 at normal pressure or add with paracresol, " process for pressing preparation of 2,6-di-tert-butyl-p-cresol ").Do by traditional liquid acid (the such as concentrated sulfuric acid or hydrofluoric acid) in the process of catalyst synthesis BHT, there is selective low, the drawback such as post processing is complicated, product separation is difficult, produce a large amount of waste water, severe corrosion equipment and pipeline, catalyst can not reclaim and reuse and product cost is high of reaction.Simultaneously contaminated environment, be difficult to the environmental requirement that adapts to day by day improve.Therefore, prior art cannot realize that yield is high, cost is low, eco-friendly target simultaneously.So, the research of alkylation solid acid catalyst is caused day by day to concern and the attention of people.
Substitute with solid acid catalyst the development trend that liquid acid become undisputed in world wide in organic synthesis.The alkylated reaction using solid acid to be catalyst paracresol and isobutene, research and develop novel paracresol and isobutene alkylation catalyst and environment-protective process thereof, breeds in this context just and be born.Therefore, develop a kind of with simple to operate, active high, selective good and clean environment friendly catalyst replaces traditional catalyst, be applied to organic synthesis field, to meet the needs of practical application.
Summary of the invention
The object of this invention is to provide a kind of composite solid-acid catalyst, to overcome the defect that in prior art, catalyst activity is not high, and the application of this catalyst in synthesis 2,6-di-tert-butyl-4-methy phenol.
For achieving the above object, the invention provides a kind of composite solid-acid catalyst, composite solid-acid catalyst is (SO
4 2-+ ZnCl
2)/silica gel, is composited by zinc chloride, sulfuric acid and silica gel; Described silica gel available alumina is replaced, but the catalytic performance of catalyst is not as using silica gel effective.
Preferably, described (SO
4 2-+ ZnCl
2)/silica gel by weight, is prepared from by the raw material comprising following component: zinc chloride 1 ~ 7 part, 3 ~ 7 parts, sulfuric acid, 30 parts, silica gel.Wherein, sulfuric acid and zinc chloride can be buied in market.
The present invention also provides a kind of preparation method of above-mentioned catalyst, by silica gel after Grape berry, is placed in liquor zinci chloridi and floods, then dry, then join steeped overnight in sulfuric acid solution, after oven dry, and activation, obtained (SO
4 2-+ ZnCl
2)/silica gel composite solid-acid catalyst.
Preferably, the concentration of described liquor zinci chloridi is 0.3 ~ 1.5mol/L, and the concentration of described sulfuric acid solution is 1mol/L, and the solvent of described liquor zinci chloridi is water or absolute ethyl alcohol, and the solvent of described liquor zinci chloridi is that water is best.
Preferably, the temperature of described activation is 200 ~ 500 DEG C, and further, the temperature of described activation is 200 ~ 250 DEG C.
Preferably, the time of described activation is 0.25 ~ 3h.
The present invention also provides the application of a kind of above-mentioned catalyst in preparation 2,6-di-tert-butyl-4-methy phenol.
Preferably, 60 ~ 90 DEG C, under condition of normal pressure, under the effect of described composite solid-acid catalyst, paracresol and isobutene carry out alkylated reaction to synthesize 2,6-di-tert-butyl-4-methy phenol.
Preferably, the mol ratio of paracresol and alkylating agent is 1:1 ~ 3; The mass ratio of paracresol and composite solid-acid catalyst is 1:0.01 ~ 0.08, and further, the mass ratio of paracresol and composite solid-acid catalyst is 1:0.03 ~ 0.05.
Preferably, the time of described alkylated reaction is 1 ~ 10h, and further, the time of described alkylated reaction is 4 ~ 8h.
The present invention compared with prior art, has the following advantages:
1, composite solid-acid catalyst provided by the invention has acid strong, active good, selective height, can be recycled and eco-friendly feature;
2, the present invention uses composite solid-acid catalyst for the synthesis of 2,6-di-tert-butyl-4-methy phenol, have easy and simple to handle, reaction temperature is low, normal pressure, do not use that any organic solvent, conversion ratio are high, the reaction time is short, selective height, eco-friendly feature, meet friendly process requirement, be very suitable for suitability for industrialized production.
Detailed description of the invention
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.ZnCl
2and H
2sO
4can buy in market.
Embodiment 1
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
Making carrier with silica gel, take water as solvent, with the paracresol of question response for benchmark, according to paracresol: carrier (silica gel)=1:0.03 (mass ratio), paracresol: ZnCl
2=1:0.33% (mass ratio), paracresol: H
2sO
4=1:0.66% (mass ratio) prepares composite solid-acid catalyst.
By silica gel after Grape berry, be placed in the ZnCl of 0.7mol/L
2steeped overnight in the aqueous solution, then dry.Then the H of 1mol/L is added
2sO
4aqueous impregnation spends the night, after oven dry, at 200 DEG C of activation 3h.
2, the preparation of 2,6-di-tert-butyl-4-methy phenols
In a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe, add 7.5g paracresol and by the compound solid-acid [(SO obtained by step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, a balloon is fixed on condenser pipe top, plays sealing and safety effect.Reactant is warmed up to 80 DEG C, stirs simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.After duration of ventilation 4h, stop ventilation, be incubated 0.5h at this temperature.Solid catalyst participate under, the alkylated reaction of paracresol and isobutene be carry out at ambient pressure gas-solid-liquid phase reaction, reaction time 4h.
3, the analysis of 2,6-di-tert-butyl-4-methy phenol crude products
Sample from 2, the 6-di-tert-butyl-4-methy phenol crude products that step 2 obtains, isolate clear liquid, carry out quantitative analysis with GC (gas chromatography), as shown in table 1.
Table 1 quantitative analysis results
As known from Table 1, by two composite solid-acid catalyst [(SO that identical conditions and method are prepared at different times
4 2-+ ZnCl
2)/silica gel] sample, give very close experimental result.Reappearance is satisfactory.
Embodiment 2
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
Making carrier with silica gel, take water as solvent, with the paracresol of question response for benchmark, according to paracresol: carrier (silica gel)=1:0.03 (mass ratio), paracresol: ZnCl
2=1:0.66% (mass ratio), paracresol: H
2sO
4=1:0.66% (mass ratio) prepares composite solid-acid catalyst.
By silica gel after Grape berry, be placed in ZnCl
2the aqueous solution in steeped overnight, then to dry.Then the H of 1mol/L is added
2sO
4aqueous impregnation spends the night, and after oven dry, activation 3h, activation temperature does contrast test with 250 DEG C, 200 DEG C and 150 DEG C respectively.
2, the preparation of 2,6-di-tert-butyl-4-methy phenols
In a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe, add 7.5g paracresol and by the compound solid-acid [(SO prepared by step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, a balloon is fixed on condenser pipe top, plays sealing and safety effect.Reactant is warmed up to 80 DEG C, stirs simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.After duration of ventilation reaches 4h, stop ventilation (namely reaction temperature is 80 DEG C, and the reaction time is 4h).
3, the analysis of 2,6-di-tert-butyl-4-methy phenol crude products
Sample from 2, the 6-di-tert-butyl-4-methy phenol crude products that step 2 obtains, isolate clear liquid, carry out quantitative analysis with GC.Catalyst activation temperature changes the impact on reaction result, as shown in table 2.
The catalytic performance of institute's controlling catalyst under the different activation temperature of table 2
As shown in Table 2,200 DEG C is compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] the more suitably activation temperature of catalyst.
Embodiment 3
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
The preparation method of catalyst is with embodiment 2, but activation temperature is 200 DEG C.
2, the preparation of 2,6-di-tert-butyl-4-methy phenols
By 7.5g paracresol and by embodiment 2 step 1 Raw proportioning prepared by compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] catalyst, join in a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe.One balloon is fixed on condenser pipe top, plays sealing and safety effect.Reactant is warmed up to 80 DEG C, stirs simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.Ventilation is respectively 4h and 8h and is contrast experiment, stops ventilation.
3, the analysis of 2,6-di-tert-butyl-4-methy phenol crude products
Sample from 2, the 6-di-tert-butyl-4-methy phenol crude products that step 2 obtains, isolate clear liquid, carry out quantitative analysis with GC.The alkylation differential responses time is on the impact of reaction result, as shown in table 3.
The crude assay result of differential responses time in table 3 alkylated reaction
As seen from Table 3, along with the prolongation in reaction time, the yield of 2,6-di-tert-butyl-4-methy phenol improves, but extends 4h, and yield only improves 8%.Consider, the alkylated reaction time is advisable with 4h.
Embodiment 4
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
With the paracresol of question response for benchmark, paracresol: carrier (silica gel)=1:0.03 (mass ratio), respectively with water and absolute ethyl alcohol for solvent makes ZnCl
2contrast experiment is in dissolving, according to paracresol: ZnCl
2=1:0.33% (mass ratio), paracresol: H
2sO
4=1:0.33% (mass ratio) prepares composite solid-acid catalyst, by silica gel after Grape berry, is placed in ZnCl
2steeped overnight in solution, then dry.Then the H of 1mol/L is added
2sO
4aqueous impregnation spends the night, after oven dry, at 200 DEG C of activation 3h.
2, the preparation of 2,6-di-tert-butyl-4-methy phenols
In a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe, add 7.5g paracresol and by the compound solid-acid [(SO prepared by step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst.A balloon is fixed on condenser pipe top, plays sealing and safety effect.Make reactant be warmed up to 80 DEG C, stir simultaneously; Slowly pass into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.Ventilation, to 4h, stops ventilation (namely reaction temperature is 80 DEG C, and the reaction time is 4h).
3, the analysis of 2,6-di-tert-butyl-4-methy phenol crude products
Sample from 2, the 6-di-tert-butyl-4-methy phenol crude products that step 2 obtains, isolate clear liquid, carry out quantitative analysis with GC.ZnCl is dissolved with different solvents
2on the impact of reaction result, as shown in table 4.
The analysis result of table 4 different solvents
As shown in Table 4, very clear, the difference of solvent is for obtained composite solid-acid catalyst [(SO
4 2-+ ZnCl
2)/silica gel] catalytic performance almost do not have anything to affect.Obviously, with use the inexpensive and water be easy to get for solvent preferably.
Embodiment 5
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
With the paracresol of question response for benchmark, paracresol: carrier (silica gel)=1:0.03 (mass ratio), active component (ZnCl used when will prepare composite solid-acid catalyst
2and H
2sO
4) composition change be contrast experiment, be that solvent makes ZnCl with water
2dissolve.By silica gel after Grape berry, be placed in ZnCl
2the aqueous solution in steeped overnight, then to dry.Then the H of 1mol/L is added
2sO
4aqueous impregnation spends the night, after oven dry, at 200 DEG C of activation 3h.
2, the preparation of 2,6-di-tert-butyl-4-methy phenols
By 7.5g paracresol with by the compound solid-acid [(SO prepared by step 1 and table 5 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, add in a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe.One balloon is fixed on condenser pipe top, plays sealing and safety effect.Under agitation reactant is warming up to 80 DEG C, then passes into high-purity isobutene gas lentamente, regulate and pass into speed, guarantee without gas overflowing reaction bulb.After ventilation 4h, stop ventilation (namely reaction temperature is 80 DEG C, and the reaction time is 4h).
3, the analysis of 2,6-di-tert-butyl-4-methy phenol crude products
Sample from 2, the 6-di-tert-butyl-4-methy phenol crude products that step 2 obtains, isolate clear liquid, carry out quantitative analysis with GC.Prepare the impact of composition change on reaction result of active component used during composite solid-acid catalyst, as shown in table 5.
The composition of table 5 different activities component is on the impact of reaction result
A is paracresol: ZnCl
2; B is paracresol: H
2sO
4.
As can be seen from Table 5, as the component composition preparing composite solid-acid catalyst be more suitably: paracresol: ZnCl
2=1:0.33% (mass ratio), paracresol: H
2sO
4=1:0.66% (mass ratio).
Embodiment 6
1, compound solid-acid [(SO
4 2-+ ZnCl
2)/silica gel] preparation of catalyst
The preparation method of catalyst is with embodiment 2, but only soak time is respectively 0.25h, 0.5h, 1h, 2h and 3h.
2, the preparation of 2,6-di-tert-butyl-4-methy phenols
By 7.5g paracresol with by the compound solid-acid [(SO prepared by embodiment 1 step 1 Raw proportioning
4 2-+ ZnCl
2)/silica gel] catalyst, join in a 100mL round-bottomed flask with magnetic stirring apparatus, condenser pipe, thermometer and isobutene ingress pipe.One balloon is fixed on condenser pipe top, plays sealing and safety effect.Under stirring, reactant is warmed up to 80 DEG C, slowly passes into high-purity isobutene gas, regulate and pass into speed, guarantee without gas overflowing reaction unit.Duration of ventilation 4h, stops ventilation (namely reaction temperature is 80 DEG C, and the reaction time is 4h).
3, the analysis of 2,6-di-tert-butyl-4-methy phenol crude products
Sample from 2, the 6-di-tert-butyl-4-methy phenol crude products that step 2 obtains, isolate clear liquid, carry out quantitative analysis with GC.The difference of catalyst soak time is on the impact of reaction result, as shown in table 6.
Table 6 soak time is to composite solid-acid catalyst [(SO
4 2-+ ZnCl
2)/silica gel] impact of catalytic performance
As can be seen from Table 6, be 1h as the more suitably soak time preparing composite solid-acid catalyst.
Although above with general explanation, detailed description of the invention and test, the present invention is described in detail, and on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (9)
1. a composite solid-acid catalyst, is characterized in that, composite solid-acid catalyst is (SO
4 2-+ ZnCl
2)/silica gel, is composited by zinc chloride, sulfuric acid and silica gel;
Described (SO
4 2-+ ZnCl
2)/silica gel by weight, is prepared from by the raw material comprising following component: zinc chloride 1 ~ 7 part, 3 ~ 7 parts, sulfuric acid, 30 parts, silica gel.
2. a preparation method for catalyst as claimed in claim 1, is characterized in that, by silica gel after Grape berry, be placed in liquor zinci chloridi and flood, then dry, then join steeped overnight in sulfuric acid solution, after oven dry, and activation, obtained (SO
4 2-+ ZnCl
2)/silica gel composite solid-acid catalyst.
3. preparation method according to claim 2, is characterized in that, the concentration of described liquor zinci chloridi is 0.3 ~ 1.5mol/L, and the concentration of described sulfuric acid solution is 1mol/L, and the solvent of described liquor zinci chloridi is water or absolute ethyl alcohol.
4. preparation method according to claim 3, is characterized in that, the temperature of described activation is 200 ~ 500 DEG C.
5. preparation method according to claim 4, is characterized in that, the time of described activation is 0.25 ~ 3h.
6. the application of catalyst in preparation 2,6-di-tert-butyl-4-methy phenol as claimed in claim 1.
7. application according to claim 6, is characterized in that, 60 ~ 90 DEG C, under condition of normal pressure, under the effect of described composite solid-acid catalyst, paracresol and isobutene carry out alkylated reaction to synthesize 2,6-di-tert-butyl-4-methy phenol.
8. application according to claim 7, is characterized in that, the mol ratio of paracresol and alkylating agent is 1:1 ~ 3; The mass ratio of paracresol and composite solid-acid catalyst is 1:0.01 ~ 0.08.
9. the application according to claim 7 or 8, is characterized in that, the time of described alkylated reaction is 1 ~ 10h.
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| CN106631706B (en) * | 2016-10-28 | 2020-06-09 | 江苏迈达新材料股份有限公司 | Method for preparing 2, 6-di-tert-butyl-4-methylphenol by using silica gel as catalyst |
| CN107649170B (en) * | 2017-09-30 | 2020-02-21 | 宝鸡文理学院 | Supported molecular sieve catalyst for synthesizing 4-methyl-2, 6-di-tert-butylphenol and application thereof |
| CN108285406A (en) * | 2018-02-07 | 2018-07-17 | 常州大学 | A kind of preparation method of antioxidant BHT |
| CN108654687A (en) * | 2018-05-03 | 2018-10-16 | 哈尔滨理工大学 | A kind of mesoporous silica gel load alkyl sulfonic acid catalyst and preparation method thereof |
| CN109704924A (en) * | 2018-12-27 | 2019-05-03 | 江苏迈达新材料股份有限公司 | A method of using solid acid as catalyst preparation DBPC 2,6 ditertiary butyl p cresol |
| CN112007665B (en) * | 2019-11-22 | 2023-08-04 | 南京林业大学 | High-activity sulfuric acid-promoted solid super-strong composite acid and preparation method thereof |
| CN111871432A (en) * | 2020-06-16 | 2020-11-03 | 南京晶典抗氧化技术研究院有限公司 | Preparation method of mesoporous solid acid catalyst and application of mesoporous solid acid catalyst in antioxidant BHT synthesis |
| CN112694389A (en) * | 2020-12-25 | 2021-04-23 | 南京晶典抗氧化技术研究院有限公司 | Synthesis method for synthesizing 2,6 di-tert-butyltoluene through heterogeneous catalysis |
| CN113952965A (en) * | 2021-10-15 | 2022-01-21 | 南京工业大学 | Stable double-active-component solid acid catalyst, preparation method and application thereof |
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