CN102451678B - Catalyst for synthesizing phenylacetate and application thereof - Google Patents
Catalyst for synthesizing phenylacetate and application thereof Download PDFInfo
- Publication number
- CN102451678B CN102451678B CN 201010510529 CN201010510529A CN102451678B CN 102451678 B CN102451678 B CN 102451678B CN 201010510529 CN201010510529 CN 201010510529 CN 201010510529 A CN201010510529 A CN 201010510529A CN 102451678 B CN102451678 B CN 102451678B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- aceticanhydride
- phenyl ester
- acetic acid
- phenol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 title abstract description 29
- 229940049953 phenylacetate Drugs 0.000 title abstract description 25
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 title abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 141
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 93
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 36
- -1 phenyl ester Chemical class 0.000 claims description 34
- 229920002472 Starch Polymers 0.000 claims description 30
- 235000019698 starch Nutrition 0.000 claims description 30
- 239000008107 starch Substances 0.000 claims description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 150000002751 molybdenum Chemical class 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 54
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 238000000926 separation method Methods 0.000 abstract description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 27
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000499 gel Substances 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000011973 solid acid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- JECYUBVRTQDVAT-UHFFFAOYSA-N 2-acetylphenol Chemical compound CC(=O)C1=CC=CC=C1O JECYUBVRTQDVAT-UHFFFAOYSA-N 0.000 description 2
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 description 1
- YVWNBNDYTKPZFP-UHFFFAOYSA-N 2-oxo-2-phenoxyacetic acid Chemical compound OC(=O)C(=O)OC1=CC=CC=C1 YVWNBNDYTKPZFP-UHFFFAOYSA-N 0.000 description 1
- TXFPEBPIARQUIG-UHFFFAOYSA-N 4'-hydroxyacetophenone Chemical compound CC(=O)C1=CC=C(O)C=C1 TXFPEBPIARQUIG-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- NDAUXUAQIAJITI-UHFFFAOYSA-N albuterol Chemical compound CC(C)(C)NCC(O)C1=CC=C(O)C(CO)=C1 NDAUXUAQIAJITI-UHFFFAOYSA-N 0.000 description 1
- 230000003288 anthiarrhythmic effect Effects 0.000 description 1
- 230000001088 anti-asthma Effects 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 230000001741 anti-phlogistic effect Effects 0.000 description 1
- 239000000924 antiasthmatic agent Substances 0.000 description 1
- MXJWRABVEGLYDG-UHFFFAOYSA-N bufexamac Chemical compound CCCCOC1=CC=C(CC(=O)NO)C=C1 MXJWRABVEGLYDG-UHFFFAOYSA-N 0.000 description 1
- 229960000962 bufexamac Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229960002443 propafenone hydrochloride Drugs 0.000 description 1
- XWIHRGFIPXWGEF-UHFFFAOYSA-N propafenone hydrochloride Chemical compound Cl.CCCNCC(O)COC1=CC=CC=C1C(=O)CCC1=CC=CC=C1 XWIHRGFIPXWGEF-UHFFFAOYSA-N 0.000 description 1
- 229960002052 salbutamol Drugs 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a catalyst for a phenylacetate synthesis reaction by acetic anhydride and phenol. The catalyst comprises ingredients of, with a total weight as reference, 27-73 wt% of Mo calculated by MoO3, 25-70 wt% of Si calculated by SiO2, and 0.1-3 wt% of S calculated by SO3 or P calculated by P2O5. Meanwhile, the invention also provides a sol-gel preparation method of the catalyst. The obtained catalyst has advantages of mild reaction conditions, high phenylacetate yield higher than 99%, fast reaction speed and easy separation, etc.
Description
Technical field
The present invention relates to a kind of catalyst and application thereof, relate in particular to catalyst and the application thereof of a kind of aceticanhydride and the acetic acid synthesized phenyl ester of phenol.
Background technology
Phenylacetate is important organic synthesis intermediate, particularly resets through Fries under acid catalysis, can generate hydroxy acetophenone, for the synthesis of catechol and guaiacol etc.In pharmaceuticals industry, orthohydroxy-acetophenone can be used for synthetic LA class antiarrhymic propafenone hydrochloride, and the monohydroxy acetophenone be can be used for making antiasthmatic salbutamol and antiphlogistic bufexamac.In addition, but phenylacetate and dimethyl carbonate effect diphenyl carbonate synthesis (DPC), and DPC is the raw material of the synthetic a kind of important engineering plastics Merlon of fusion method ester exchange.
At present, the synthetic method of phenylacetate mainly contains: (1) generates sodium phenate by phenol and the reaction of certain density NaOH, and then dropping acetic anhydride, through steps such as washing, neutralization, drying and rectifying, product yield reaches 77%, and there are shortcomings such as the serious and utilization rate of equipment and installations of equipment corrosion is low in this method; (2) be raw material synthesis of acetic acid phenyl ester with phenol and chloroacetic chloride, product yield reaches 95.55%, though the yield of the method phenylacetate is higher, and the seriously corroded of byproduct hydrogen chloride; (3) the direct esterification synthesis of acetic acid phenyl ester under phosphoric acid catalyzed by phenol and aceticanhydride, product yield 83%, when this method was catalyst with phosphoric acid, catalytic activity was low, and separation difficulty generates the black jelly and is bonded in Polycondensation Reactor and Esterification Reactor during rectifying, be difficult to remove.The researcher addresses the above problem by using solid acid catalyst.Solid acid catalyst has in many acid catalyzed reactions that high catalytic activity, product are easy to separate with catalyst, advantage such as etching apparatus, free from environmental pollution and reusability not, more and more receives publicity.
Sichuan University uses TiO
2Prepare superpower solid acid, in aceticanhydride and the acetic acid synthesized phenyl ester of phenol, obtain higher yields, but reaction temperature higher (Industrial Catalysis, 2009,17,62).In patent CNl072203, use the solid acid catalyst that contains ZSM-5, REY and three kinds of zeolites of high silicon Y that petroleum distillate, residual oil or crude oil are converted into fecund and be rich in C
3 -, C
4 -Liquefied gas and the hydro carbons of high-knock rating gasoline.In patent CNll21441, use solid acid catalyst vapor phase catalytic oxidation methacrylaldehyde to produce acrylic acid.In patent CN 1583254A, adopt slurry attitude immersion process for preparing MoO
3Catalyst is applied in the synthesis of oxalic acid phenyl ester.Adopt the synthetic MoO of sol-gel process in this patent
3Catalyst is applied in phenylacetate synthetic.
Summary of the invention
The purpose of this invention is to provide the acetic acid synthesized phenyl ester catalyst of a kind of aceticanhydride and phenol, adopt the yield height of this Preparation of Catalyst phenylacetate, reaction temperature is lower.
The object of the present invention is achieved like this, uses solid acid Mo series catalysts to improve the yield of phenylacetate.
One aspect of the present invention provides the catalyst of a kind of aceticanhydride and the acetic acid synthesized phenyl ester of phenol reactant, it is characterized in that, and be benchmark in the gross weight of catalyst, comprise following weight percentage component by oxide:
Mo is with MoO
3Meter 27-73%; Be preferably 63～73%;
Si is with SiO
2Meter 25-70%; Be preferably 25-35%;
S is with SO
3Meter or P are with P
2O
5Meter 0.1-3%.
In the above-mentioned catalyst: MoO
3Be major catalyst, SiO
2Be dispersant, SO
3Or P
2O
5Be auxiliary agent, the adding of auxiliary agent can improve the yield of phenylacetate.
Preferably, be benchmark in the gross weight of catalyst, S is with SO
3The weight percentage of meter is 0.5-2%.
The present invention provides above-mentioned Preparation of catalysts method on the other hand, comprises the steps:
A) in the aqueous solution with soluble molybdenum salt vitriolization or phosphoric acid, add the predecessor of Si element then, make the gained mixture form gel; Wherein, the mol ratio of contained Mo element and Si element is 0.22-1.25 in the predecessor of described soluble molybdenum salt and Si element: 1;
B) with the gained gel drying, in 480-520 ℃ of following roasting 3-5 hour, make required catalyst again.
Preferably, the mol ratio of contained Mo element and Si element is 0.75-1.25 in the predecessor of described soluble molybdenum salt and Si element: 1.
Preferable, described soluble molybdenum salt is ammonium molybdate, is preferably ammonium paramolybdate.
Preferable, the predecessor of described Si element is ethyl orthosilicate or Ludox.SiO in the described Ludox
2Content be 10-30wt%, its pH value is 8-10.
Preferable, the aqueous solution of described sulfuric acid or phosphoric acid and the envelope-bulk to weight ratio of described soluble molybdenum salt are (10-100) ml: 1g.The mass concentration of the aqueous solution of described sulfuric acid or phosphoric acid is 0.02-5%.
Preferable, for dispersed catalyst better, in step a), add starch, the addition of starch is the 5-20% of the aqueous solution weight of described sulfuric acid or phosphoric acid; Starch is heated to and makes starch dissolution, and constantly be stirred to the formation gel after adding.
In the step b), described purpose with gel drying is the moisture of removing wherein, as the water that can remove wherein in dry 5-20 hour down at 100 ℃.
Originally return the purposes that above-mentioned catalyst is provided, namely this catalyst is used in aceticanhydride and the acetic acid synthesized phenyl ester of phenol.
The process conditions of described aceticanhydride and the acetic acid synthesized phenyl ester of phenol are: pressure is normal pressure, and temperature is 110 ℃, and the mol ratio of raw material aceticanhydride and phenol is 1.0-1.2.
The present invention is by the synthetic Mo series catalysts of sol-gel process, as the catalyst of aceticanhydride and the acetic acid synthesized phenyl ester of phenol.Catalyst of the present invention is used for aceticanhydride and the acetic acid synthesized phenyl ester technology of phenol, can improves the phenylacetate yield.Compared with prior art have following advantage:
1, reaction condition is more gentle;
2, the phenylacetate yield can be higher than 99wt%;
3, because reaction temperature is low, can prevent the generation of some side reactions, as: the decomposition of aceticanhydride, the phenyl ring of reactant and product react etc.
The specific embodiment
Embodiment 1
Presoma ammonium paramolybdate 7.08g with the Mo element, being dissolved in concentration is among the aqueous sulfuric acid 70ml of 1wt%, add ethyl orthosilicate 8.43g and starch (addition of starch be aqueous sulfuric acid weight 5%) then, be heated to 90-100 ℃, and stir the formation gel, after under 110 ℃ dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, its quality is 7.55g, be broken for 20～40 orders after, namely get required catalyst.
In oxide, the gained catalytic component is: MoO
3: 70wt%, SiO
2: 29.5wt%, SO
3: 0.5wt%.
The gained catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.1: 1, and reaction temperature is 110 ℃, and catalyst amount is 5% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 99.3% after testing.
The preparation of comparative catalyst: with the presoma ammonium paramolybdate 7.08g of Mo element, be dissolved in the 70ml water, add ethyl orthosilicate 8.43g and starch (addition of starch be water weight 5%) then, be heated to 90-100 ℃, and stir the formation gel, after under 110 ℃ dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, its quality is 7.51g, be broken for 20～40 orders after, namely get comparative catalyst.Because the difference of two kinds of catalyst in preparation process only is whether used sulfuric acid, and the weight of end product has differed 0.04g, can infer thus the SO that contains 0.5wt% in the prepared catalyst of present embodiment
3
The gained comparative catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.1: 1, and reaction temperature is 110 ℃, and catalyst amount is 5% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 88% after testing.
Embodiment 2
The presoma ammonium paramolybdate 7.10g of Mo element, being dissolved in concentration is among the phosphate aqueous solution 150ml of 0.02wt%, and (the pH value is 8, SiO to add Ludox 36.66g then
2Content be 10wt%) and starch (addition of starch be phosphate aqueous solution weight 10%), be heated to 80-90 ℃, and stirring forms gel, after under 110 ℃ dry 20 hours, roasting 4 hours under 480 ℃ of air atmospheres again, its quality is 8.87g, be broken for 20～40 orders after, namely get required catalyst.
In oxide, catalytic component is: MoO
3: 60wt%, SiO
2: 38wt%, P
2O
5: 2wt%.
The gained catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 6% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 95% after testing.
The preparation of comparative catalyst: the presoma ammonium paramolybdate 7.10g with the Mo element, be dissolved in the 150ml water, (the pH value is 8, SiO to add Ludox 36.67g then
2Content be 10wt%) with starch (addition of starch be water weight 10%), be heated to 90-100 ℃, and stir and form gel, at 110 ℃ down after dry 20 hours, roasting 4 hours under 480 ℃ of air atmospheres again, its quality is 8.68g, after being broken for 20～40 orders, namely get comparative catalyst.Because the difference of two kinds of catalyst in preparation process only is whether used phosphoric acid, and the weight of end product has differed 0.19g, can infer thus the P that contains 2wt% in the prepared catalyst of present embodiment
2O
5
The gained comparative catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 6% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 87% after testing.
Embodiment 3
The presoma ammonium paramolybdate 7.06g of Mo element, being dissolved in concentration is among the phosphate aqueous solution 70ml of 5wt%, and (the pH value is 10, SiO to add Ludox 46.33g then
2Content be 30wt%) and starch (addition of starch be phosphate aqueous solution weight 20%), be heated to 90-100 ℃, and stirring forms gel, after under 110 ℃ dry 5 hours, roasting 6 hours under 500 ℃ of air atmospheres again, its quality is 19.05g, be broken for 20～40 orders after, namely get required catalyst.
In oxide, catalytic component is: MoO
3: 29wt%, SiO
2: 70wt%, P
2O
5: 1wt%.
The gained catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 5% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 93% after testing.
The preparation of comparative catalyst: the presoma ammonium paramolybdate 7.10g with the Mo element, be dissolved in the 70ml water, (the pH value is 10, SiO to add Ludox 46.33g then
2Content be 30wt%) with starch (addition of starch be water weight 20%), be heated to 90-100 ℃, and stir and form gel, at 110 ℃ down after dry 5 hours, roasting 6 hours under 500 ℃ of air atmospheres again, its quality is 18.85g, after being broken for 20～40 orders, namely get comparative catalyst.Because the difference of two kinds of catalyst in preparation process only is whether used phosphoric acid, and the weight of end product has differed 0.2g, can infer thus the P that contains 1wt% in the prepared catalyst of present embodiment
2O
5
The gained comparative catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 5% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 89% after testing.
Embodiment 4
The presoma ammonium paramolybdate 0.94g of Mo element, being dissolved in concentration is among the aqueous sulfuric acid 94ml of 0.1wt%, add ethyl orthosilicate 0.91g and starch (addition of starch be aqueous sulfuric acid weight 10%) then, be heated to 90-100 ℃, and stir the formation gel, after under 110 ℃ dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, quality is 0.89g, be broken for 20～40 orders after, namely get required catalyst.
In oxide, catalytic component is: MoO
3: 73wt%, SiO
2: 25wt%, SO
3: 2wt%.
The gained catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 7% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 99% after testing.
The preparation of comparative catalyst: with the presoma ammonium paramolybdate 0.94g of Mo element, be dissolved in the 94ml water, add ethyl orthosilicate 0.91g and starch (addition of starch be water weight 10%) then, be heated to 90-100 ℃, and stir the formation gel, after under 110 ℃ dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, its quality is 0.87, be broken for 20～40 orders after, namely get comparative catalyst.Because the difference of two kinds of catalyst in preparation process only is whether used sulfuric acid, and the weight of end product has differed 0.02g, can infer thus the S0 that contains 2wt% in the prepared catalyst of present embodiment
3
The gained comparative catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 4% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 90% after testing.
Embodiment 5
The presoma ammonium paramolybdate 3.54g of Mo element, being dissolved in concentration is among the aqueous sulfuric acid 160ml of 5wt%, and (the pH value is 10, SiO to add Ludox 5.34g then
2Content be 30wt%) with starch (addition of starch be aqueous sulfuric acid weight 20%), be heated to 90-100 ℃, and stirring forms gel, after under 110 ℃ dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, quality is 3.80g, be broken for 20～40 orders after, namely get required catalyst.
In oxide, catalytic component is: MoO
3: 63wt%, SiO
2: 35wt%, SO
3: 2wt%.
The gained catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 7% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 93% after testing.
The preparation of comparative catalyst: the presoma ammonium paramolybdate 3.54g with the Mo element, be dissolved in the 160ml water, (the pH value is 10, SiO to add Ludox 5.34g then
2Content be 30wt%) with starch (addition of starch be water weight 20%), be heated to 90-100 ℃, and stir and form gel, at 110 ℃ down after dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, its quality is 3.72, after being broken for 20～40 orders, namely get comparative catalyst.Because the difference of two kinds of catalyst in preparation process only is whether used sulfuric acid, and the weight of end product has differed 0.08g, can infer thus the SO that contains 2wt% in the prepared catalyst of present embodiment
3
The gained comparative catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 7% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 89% after testing.
Embodiment 6
The presoma ammonium paramolybdate 3.56g of Mo element, being dissolved in concentration is among the aqueous sulfuric acid 210ml of 5wt%, add ethyl orthosilicate 26.11g and starch (addition of starch be aqueous sulfuric acid weight 20%) then, be heated to 90-100 ℃, and stir the formation gel, after under 110 ℃ dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, its quality is 9.88g, be broken for 20～40 orders after, namely get required catalyst.
In oxide, catalytic component is: MoO
3: 27wt%, SiO
2: 70wt%, SO
3: 3wt%.
The gained catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 7% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 94% after testing.
The preparation of comparative catalyst: with the presoma ammonium paramolybdate 3.57g of Mo element, be dissolved in the 210ml water, add ethyl orthosilicate 26.13g and starch (addition of starch be water weight 20%) then, be heated to 90-100 ℃, and stir the formation gel, after under 110 ℃ dry 10 hours, roasting 5 hours under 520 ℃ of air atmospheres again, its quality is 9.58g, be broken for 20～40 orders after, namely get comparative catalyst.Because the difference of two kinds of catalyst in preparation process only is whether used sulfuric acid, and the weight of end product has differed 0.3g, can infer thus the SO that contains 3wt% in the prepared catalyst of present embodiment
3
The gained comparative catalyst is applied in the reaction of aceticanhydride and the acetic acid synthesized phenyl ester of phenol: experiment is carried out in four-hole boiling flask, and the mol ratio of raw material aceticanhydride and phenol is 1.2: 1, and reaction temperature is 110 ℃, and catalyst amount is 7% of reaction raw materials gross weight.After reaction was finished, the yield of phenylacetate was 83% after testing.
Claims (10)
1. the catalyst of an aceticanhydride and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, is benchmark in the gross weight of catalyst,
Comprise following weight percentage component:
Mo is with MoO
3Meter 27-73%;
Si is with SiO
2Meter 25-70%;
S is with SO
3Meter or P are with P
2O
5Meter 0.1-3%;
Described catalyst is made by the preparation method who may further comprise the steps:
A) in the aqueous solution with soluble molybdenum salt vitriolization or phosphoric acid, add the predecessor of Si element then, make the gained mixture form gel; Wherein, the mol ratio of contained Mo element and Si element is 0.22-1.25:1 in the predecessor of described soluble molybdenum salt and Si element;
B) with the gained gel drying, in 480-520 ℃ of following roasting 3-5 hour, make required catalyst again.
2. the catalyst of aceticanhydride as claimed in claim 1 and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, is benchmark in the gross weight of catalyst, and S is with SO
3The weight percentage of meter is 0.5-2%.
3. the Preparation of catalysts method of aceticanhydride as claimed in claim 1 or 2 and the acetic acid synthesized phenyl ester of phenol reactant comprises the following steps:
A) in the aqueous solution with soluble molybdenum salt vitriolization or phosphoric acid, add the predecessor of Si element then, make the gained mixture form gel; Wherein, the mol ratio of contained Mo element and Si element is 0.22-1.25:1 in the predecessor of described soluble molybdenum salt and Si element;
B) with the gained gel drying, in 480-520 ℃ of following roasting 3-5 hour, make required catalyst again.
4. the Preparation of catalysts method of aceticanhydride as claimed in claim 3 and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, the mol ratio of contained Mo element and Si element is 0.75-1.25:1 in the predecessor of described soluble molybdenum salt and Si element.
5. the Preparation of catalysts method of aceticanhydride as claimed in claim 3 and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, described soluble molybdenum salt is ammonium molybdate.
6. the Preparation of catalysts method of aceticanhydride as claimed in claim 3 and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, the predecessor of described Si element is ethyl orthosilicate or Ludox.
7. the Preparation of catalysts method of aceticanhydride as claimed in claim 3 and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, the aqueous solution of described sulfuric acid or phosphoric acid and the envelope-bulk to weight ratio of described soluble molybdenum salt are (10-100) ml:1g.
8. the Preparation of catalysts method of aceticanhydride as claimed in claim 3 and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, the mass concentration of the aqueous solution of described sulfuric acid or phosphoric acid is 0.02-5%.
9. the Preparation of catalysts method of aceticanhydride as claimed in claim 3 and the acetic acid synthesized phenyl ester of phenol reactant is characterized in that, adds starch in step a), and the addition of starch is the 5-20% of the aqueous solution weight of described sulfuric acid or phosphoric acid.
10. the application of catalyst as claimed in claim 1 or 2 in aceticanhydride and the acetic acid synthesized phenyl ester technology of phenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010510529 CN102451678B (en) | 2010-10-18 | 2010-10-18 | Catalyst for synthesizing phenylacetate and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010510529 CN102451678B (en) | 2010-10-18 | 2010-10-18 | Catalyst for synthesizing phenylacetate and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102451678A CN102451678A (en) | 2012-05-16 |
| CN102451678B true CN102451678B (en) | 2013-09-11 |
Family
ID=46035606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010510529 Active CN102451678B (en) | 2010-10-18 | 2010-10-18 | Catalyst for synthesizing phenylacetate and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102451678B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583254A (en) * | 2004-05-25 | 2005-02-23 | 天津大学 | Preparation of loaded molybdenum oxide catalyst for synthesis of phenyloxalate by ester interchange process |
| CN1687003A (en) * | 2005-04-05 | 2005-10-26 | 天津大学 | Method for synthesizing phenyloxalate from dicthyl oxalate and phenol |
| CN101774911A (en) * | 2009-01-14 | 2010-07-14 | 常州化学研究所 | Catalyzing method of synthesizing diphenyl carbonate through ester exchange reaction |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4517594B2 (en) * | 2003-06-19 | 2010-08-04 | 東ソー株式会社 | Method for producing phenyl ester |
-
2010
- 2010-10-18 CN CN 201010510529 patent/CN102451678B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583254A (en) * | 2004-05-25 | 2005-02-23 | 天津大学 | Preparation of loaded molybdenum oxide catalyst for synthesis of phenyloxalate by ester interchange process |
| CN1687003A (en) * | 2005-04-05 | 2005-10-26 | 天津大学 | Method for synthesizing phenyloxalate from dicthyl oxalate and phenol |
| CN101774911A (en) * | 2009-01-14 | 2010-07-14 | 常州化学研究所 | Catalyzing method of synthesizing diphenyl carbonate through ester exchange reaction |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2005-8561A 2005.01.13 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102451678A (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | C 60 fullerenol as an active and stable catalyst for the synthesis of cyclic carbonates from CO 2 and epoxides | |
| Zhao et al. | Conversion of highly concentrated fructose into 5-hydroxymethylfurfural by acid–base bifunctional HPA nanocatalysts induced by choline chloride | |
| CN109715596A (en) | The method for producing hydroxyacetic acid | |
| CN111187148B (en) | Method for simultaneously preparing o-hydroxy phenetole and 1, 3-benzodioxole-2-one | |
| CN109796335A (en) | A kind of method of high efficiency joint production of propylene glycol methyl ether and propylene glycol methyl ether acetate | |
| CN108947776B (en) | Method for catalyzing oxidative cracking of lignin model aryl ether | |
| JP5800554B2 (en) | Method for producing C1-C4 alkyl nitrite | |
| CN102451678B (en) | Catalyst for synthesizing phenylacetate and application thereof | |
| JP2011068760A5 (en) | ||
| CN101817733A (en) | Method for preparing cyclohexanone by oxidizing cyclohexane | |
| CN105498828B (en) | The method of furfuran compound aromatisation light aromatic hydrocarbons | |
| CN103980307A (en) | Preparation method of 2,4,6-trimethyl benzoyl phenyl ethyl phosphinate | |
| CN105237453B (en) | Method for preparing methyl ethyl ketone peroxide by using acidic ion exchange resin as catalyst | |
| CN101628860A (en) | Method for preparing methylal | |
| CN103041863A (en) | Method for preparing ethyl acetate by metal-organic framework-loading phosphotungstic acid catalyst | |
| CN1232497C (en) | Catalytic alcohol acid esterizing method | |
| CN104248978B (en) | A kind of preparation method of phosphomolybdate crystal catalyst | |
| JP2009298734A (en) | Method for producing propylene glycol | |
| CN106631731A (en) | Method for preparing benzaldehyde by catalytic oxidation of benzyl alcohol through dicaryon morpholine phosphotungstate | |
| CN101792372B (en) | Method for preparing phenol and diphenol by direct hydroxylation of benzene and hydrogen peroxide | |
| CN101070282B (en) | Process for room-temperature ion liquid-catalytic preparation of ethyl linoleate | |
| Mei et al. | Effective and recoverable homogeneous catalysts for the transesterification of dimethyl carbonate with ethanol: lanthanide triflates | |
| CN101921178A (en) | A kind of method that is prepared methylphenol by one-step hydroxylation of toluene | |
| Jie et al. | ZrOCl2· 8H2O: An efficient and cheap catalyst for esterification of free fatty acids to methyl esters | |
| CN108025284B (en) | Catalyst for dehydration of glycerin, method for preparing the same, and method for producing acrolein using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: SHANGHAI HUAYI ENERGY + CHEMICAL INDUSTRY CO., LTD Free format text: FORMER NAME: SHANGHAI COKING CO., LTD. |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee after: Shanghai Hua Yi derived energy chemical Co., Ltd Address before: 200241 Minhang District, Wu Long Road, No. 4280, Shanghai Patentee before: Shanghai Coking Co., Ltd. |