CN110642697A - Production method for preparing sorbic acid by acidolysis of sorbic acid polyester with macroporous solid acid catalyst - Google Patents
Production method for preparing sorbic acid by acidolysis of sorbic acid polyester with macroporous solid acid catalyst Download PDFInfo
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- 235000010199 sorbic acid Nutrition 0.000 title claims abstract description 67
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229940075582 sorbic acid Drugs 0.000 title claims abstract description 63
- 239000004334 sorbic acid Substances 0.000 title claims abstract description 63
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 239000011973 solid acid Substances 0.000 title claims abstract description 47
- 229920000728 polyester Polymers 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 10
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 8
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 35
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- 229910052681 coesite Inorganic materials 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 8
- 229910052906 cristobalite Inorganic materials 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 229910052682 stishovite Inorganic materials 0.000 claims description 8
- 229910052905 tridymite Inorganic materials 0.000 claims description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 5
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical group [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 6
- 238000012824 chemical production Methods 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- WSWCOQWTEOXDQX-UHFFFAOYSA-N 2,4-Hexadienoic acid Chemical compound CC=CC=CC(O)=O WSWCOQWTEOXDQX-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- CHHHXKFHOYLYRE-UHFFFAOYSA-M 2,4-Hexadienoic acid, potassium salt (1:1), (2E,4E)- Chemical compound [K+].CC=CC=CC([O-])=O CHHHXKFHOYLYRE-UHFFFAOYSA-M 0.000 description 5
- 235000010241 potassium sorbate Nutrition 0.000 description 5
- 239000004302 potassium sorbate Substances 0.000 description 5
- 229940069338 potassium sorbate Drugs 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- -1 unsaturated fatty acid salt Chemical class 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 244000061176 Nicotiana tabacum Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 241001148470 aerobic bacillus Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- CHHHXKFHOYLYRE-STWYSWDKSA-M potassium sorbate Chemical compound [K+].C\C=C\C=C\C([O-])=O CHHHXKFHOYLYRE-STWYSWDKSA-M 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of chemical production, and particularly relates to a production method for preparing sorbic acid by carrying out acidolysis on sorbic acid polyester by using a macroporous solid acid catalyst. The method comprises the following steps: (1) putting 150-200 parts of sorbic acid polyester into a reaction kettle, adding deionized water, putting 1-5 parts of solid acid catalyst, opening a stirring and steam valve, and heating for acidolysis; (2) Filtering while the solution is hot; (3) cooling, crystallizing, washing and drying to obtain sorbic acid; wherein the pore diameter of the solid acid catalyst is 8-50nm, and the specific surface area is 180-350m2The preparation method comprises the following steps: 1) aging to form aluminosilicate gel by taking sodium metaaluminate as an aluminum source, silica sol as a silicon source, quaternary ammonium salt as a template agent and sodium bicarbonate as a pore-expanding agent, and hydrothermally synthesizing a catalyst carrier; 2) zirconia is loaded with strong acid. The invention can improve the permeability of the sorbic acid polyester, increase the yield of sorbic acid, reduce the amount of tar byproduct, avoid the generation of three wastes and is environment-friendly.
Description
Technical Field
The invention belongs to the technical field of chemical production, and particularly relates to a production method for preparing sorbic acid by carrying out acidolysis on sorbic acid polyester by using a macroporous solid acid catalyst.
Background
Potassium sorbate, 2, 4-hexadienoic acid potassium, is a white flaky crystal, odorless or slightly odorous; the molecular formula is as follows: c6H7O2K, molecular weight: 150.22, is easily soluble in water, and is soluble in ethanol and propylene glycol. Potassium sorbate is an internationally recognized low-toxicity and high-efficiency acid type preservative, and has the same preservative effect as sorbic acid.
The potassium sorbate is an unsaturated fatty acid salt with conjugated diene, can effectively inhibit the activity of mould, yeast and aerobic bacteria, has stronger inhibiting effect on the development and propagation of harmful microorganisms than sterilizing effect, and is a preservative recommended to all countries in the world by food organization of United nations. Potassium sorbate is widely applied to the corrosion prevention and preservation of various industries such as food, vegetables, fruits, medicines, rubber, paper, animal feed, cosmetics, paint, tobacco, beverage and the like.
At present, the production process commonly used in industry is as follows: hydrolyzing sorbic acid polyester in the presence of concentrated hydrochloric acid or concentrated sulfuric acid to obtain a crude product of 2, 4-hexadienoic acid, performing alkali dissolution, decoloring, filtering to remove tar, neutralizing and acid-separating with hydrochloric acid, filtering, washing with water, drying to obtain a finished product of the 2, 4-hexadienoic acid, salifying with potassium hydroxide or potassium carbonate, and drying to obtain the product. The process has the following disadvantages: the sorbic acid polyester is not depolymerized completely in the presence of concentrated hydrochloric acid or concentrated sulfuric acid, the sorbic acid yield is low, the amount of byproduct tar is large, and the amount of waste water is large.
Chinese patent CN103570527A discloses a method for preparing potassium sorbate, wherein, 2, 4-hexadienoic acid polyester is depolymerized under the catalysis of a composite solid acid catalyst to obtain a crude product of 2, 4-hexadienoic acid. Although the yield of sorbic acid is improved to a certain extent, the yield is still not very high, and the amount of tar byproduct is still very large.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a production method for preparing sorbic acid by carrying out acidolysis on sorbic acid polyester by using a macroporous solid acid catalyst.
The production method for preparing sorbic acid by acidolysis of sorbic acid polyester by using the macroporous solid acid catalyst comprises the following steps:
(1) putting 150 plus 200 parts of sorbic acid polyester into a reaction kettle, adding deionized water, putting 1-5 parts of solid acid catalyst, opening a stirring and steam valve, heating to the acidolysis temperature of 80-100 ℃, and carrying out acidolysis for 30-120 min;
(2) filtering while the solution is hot to obtain a sorbic acid aqueous solution;
(3) cooling, crystallizing, washing and drying to obtain sorbic acid;
wherein, the aperture of the solid acid catalyst in the step (1) is 8-50nm, and the specific surface area is 180-350m2The preparation method comprises the following steps:
1) preparation of macroporous support
Aging to form aluminosilicate gel by taking sodium metaaluminate as an aluminum source, silica sol as a silicon source, quaternary ammonium salt as a template agent and sodium bicarbonate as a pore-expanding agent, and hydrothermally synthesizing a catalyst carrier;
2) zirconia strong acid loading
Preparing 20-60% zirconium oxychloride solution, vacuum equivoluminal dipping for 10-24h, drying, and roasting to obtain the solid acid catalyst.
Wherein:
the step 1) comprises the following specific operation steps:
preparing an aluminum source solution: putting sodium metaaluminate into the prepared sulfuric acid solution, and stirring and dissolving;
preparing a silicon source solution: adding silica sol, quaternary ammonium salt and sodium bicarbonate into deionized water, and uniformly stirring;
dropwise adding an aluminum source solution into a silicon source solution, stirring for 1-5h, and aging for 2-20h to obtain aluminosilicate gel;
putting the aluminosilicate gel into a hydrothermal synthesis kettle, and reacting at the temperature of 100 ℃ and 180 ℃ for 10-36 h;
filtering, drying at 150 ℃ under 100-;
the raw material feeding molar ratio is as follows:
Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：45-230：2-6：0.01-1：0.5-1：300-650。
The quaternary ammonium salt in the above step is tetrapropylammonium bromide.
In the step 2), the drying temperature is 100-150 ℃, preferably 120 ℃, and the drying time is 2-4 hours, preferably 3 hours.
In the step 2), the roasting temperature is 550-650 ℃, and the roasting time is 3-5 h.
The invention has the following beneficial effects:
1. the aperture of the solid acid catalyst is 8-50nm, the molecular diameter of the sorbic acid polyester is 5-10nm, the permeability of the sorbic acid polyester in the aperture is more than 95 percent, the effective catalytic area can be increased, the yield of the sorbic acid can be increased to 92.5 percent, and the tar content is less than 5 percent.
2. In the production process, the method has the advantages of no generation of three wastes, environmental protection, capability of recycling the solid acid catalyst for multiple times and strong regeneration capability.
Detailed Description
The present invention is further described below with reference to examples.
The raw materials used in the examples were all commercially available raw materials except for those specifically mentioned.
Example 1
The preparation method of the solid acid catalyst comprises the following steps:
(1) preparation of macroporous support
1. Preparing an aluminum source solution: putting sodium metaaluminate into the prepared sulfuric acid solution, and stirring and dissolving;
2. preparing a silicon source solution: adding silica sol, quaternary ammonium salt (tetrapropyl ammonium bromide) and pore-expanding agent sodium bicarbonate into deionized water, and uniformly stirring;
3. dropwise adding an aluminum source solution into a silicon source solution, stirring for 3 hours, and aging for 12 hours to obtain aluminosilicate gel; wherein, the feeding proportion (mol ratio) of Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：55：2.3：0.01：0.5：300。
4. Putting the gel into a hydro-thermal synthesis kettle, and reacting at 150 ℃ for 22 hours;
5. filtering, drying at 120 deg.C, and calcining at 400 deg.C.
(2) Zirconia strong acid loading
Preparing 40% zirconium oxychloride solution, vacuum isovolumetric impregnating on the prepared macroporous carrier, impregnating for 16h, drying at 120 deg.C for 3h, and roasting at 600 deg.C for 4 h.
The pore diameter of the prepared solid acid catalyst is 17.8 nm.
The preparation method for acidolyzing the sorbic acid polyester by using the solid acid catalyst comprises the following steps:
(1) putting 200g of sorbic acid polyester into a reaction kettle, adding 250g of deionized water, putting 5g of solid acid catalyst, opening a stirring and steam valve, heating to an acidolysis temperature of 90 ℃, and carrying out acidolysis for 80 min;
(2) filtering while the solution is hot to obtain a sorbic acid aqueous solution;
(3) the mixture was cooled, crystallized, washed and dried to obtain 183.4g of sorbic acid, the yield was 91.7%, the purity was 99.2%, and 14.8g of tar was produced as a by-product.
After the solid acid catalyst is recycled for 20 times, the yield of sorbic acid prepared by acidolysis is 91.1%, the purity is 99.0%, and the byproduct tar is 15.3g under the same process conditions.
Example 2
The preparation method of the solid acid catalyst comprises the following steps:
(1) preparation of macroporous support
1. Preparing an aluminum source solution: putting sodium metaaluminate into the prepared sulfuric acid solution, and stirring and dissolving;
2. preparing a silicon source solution: adding silica sol, quaternary ammonium salt (tetrapropyl ammonium bromide) and pore-expanding agent sodium bicarbonate into deionized water, and uniformly stirring;
3. dropwise adding an aluminum source solution into a silicon source solution, stirring for 1h, and aging for 20h to obtain aluminosilicate gel; wherein, the feeding proportion (mol ratio) of Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：55：2.3：0.01：0.8：300。
4. Putting the gel into a hydro-thermal synthesis kettle, and reacting at 100 ℃ for 36 hours;
5. filtering, drying at 100 deg.C, and roasting at 400 deg.C for use.
(2) Zirconia strong acid loading
Preparing 20% zirconium oxychloride solution, vacuum isovolumetric impregnating on the prepared macroporous carrier, impregnating for 24h, drying at 120 ℃ for 3h, and roasting at 550 ℃ for 5 h.
The pore diameter of the prepared solid acid catalyst is 29.3 nm.
The preparation method for acidolyzing the sorbic acid polyester by using the solid acid catalyst comprises the following steps:
(1) putting 200g of sorbic acid polyester into a reaction kettle, adding 250g of deionized water, putting 5g of solid acid catalyst, opening a stirring and steam valve, heating to the acidolysis temperature of 100 ℃, and carrying out acidolysis for 30 min;
(2) filtering while the solution is hot to obtain a sorbic acid aqueous solution;
(3) cooling, crystallizing, washing and drying to obtain 185g of sorbic acid, the yield is 92.5%, the purity is 99.3%, and 9.8g of tar as a byproduct.
After the solid acid catalyst is recycled for 20 times, the yield of sorbic acid prepared by acidolysis is 91.9%, the purity is 99.1%, and the byproduct tar is 10.5g under the same process conditions.
Example 3
The preparation method of the solid acid catalyst comprises the following steps:
(1) preparation of macroporous support
1. Preparing an aluminum source solution: putting sodium metaaluminate into the prepared sulfuric acid solution, and stirring and dissolving;
2. preparing a silicon source solution: adding silica sol, quaternary ammonium salt (tetrapropyl ammonium bromide) and pore-expanding agent sodium bicarbonate into deionized water, and uniformly stirring;
3. dropwise adding an aluminum source solution into a silicon source solution, stirring for 5 hours, and aging for 10 hours to obtain aluminosilicate gel; wherein, the feeding proportion (mol ratio) of Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：55：2.3：0.01：1.0：300。
4. Putting the gel into a hydro-thermal synthesis kettle, and reacting at 180 ℃ for 10 hours;
5. filtering, drying at 150 deg.C, and roasting at 400 deg.C for use.
(2) Zirconia strong acid loading
Preparing a 60% zirconium oxychloride solution, impregnating the prepared macroporous carrier in vacuum with the same volume, wherein the impregnation time is 10 hours, the drying is carried out at 120 ℃ for 3 hours, and the roasting is carried out at 650 ℃ for 3 hours.
The pore diameter of the prepared solid acid catalyst is 26.7 nm.
The preparation method for acidolyzing the sorbic acid polyester by using the solid acid catalyst comprises the following steps:
(1) putting 200g of sorbic acid polyester into a reaction kettle, adding 250g of deionized water, putting 5g of solid acid catalyst, opening a stirring and steam valve, heating to an acidolysis temperature of 90 ℃, and carrying out acidolysis for 80 min;
(2) filtering while the solution is hot to obtain a sorbic acid aqueous solution;
(3) cooling, crystallizing, washing and drying to obtain 182g of sorbic acid, the yield is 91.0%, the purity is 99.2%, and 13.8g of tar as a byproduct.
After the solid acid catalyst is recycled for 20 times, the yield of sorbic acid prepared by acidolysis is 90.5 percent, the purity is 99.1 percent, and the byproduct tar is 14.7g under the same process conditions.
Comparative example 1
The procedure for preparing a solid acid catalyst of comparative example 1 is the same as in example 1 except that:
charge ratio (molar ratio) of Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：55：2.3：0.01：0：300。
The pore diameter of the prepared solid acid catalyst is 3.5 nm.
The same procedure as in example 1 was used to prepare a sorbic acid polyester by acid hydrolysis using the solid acid catalyst described above.
170g of sorbic acid is prepared, the yield is 85.0%, the purity is 99.2%, and 26g of tar is a byproduct.
Comparative example 2
The procedure for preparing a solid acid catalyst of comparative example 2 is the same as in example 1 except that:
charge ratio (molar ratio) of Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：55：2.3：0.01：0.05：300。
The aperture of the prepared solid acid catalyst is 8.0 nm.
The same procedure as in example 1 was used to prepare a sorbic acid polyester by acid hydrolysis using the solid acid catalyst described above.
178.4g of sorbic acid was obtained in a yield of 89.2% and a purity of 99.3%, and 19.4g of tar was obtained as a by-product.
Comparative example 3
The procedure for preparing a solid acid catalyst of comparative example 3 is the same as in example 1 except that:
charge ratio (molar ratio) of Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：55：2.3：0.01：0.1：300。
The pore diameter of the prepared solid acid catalyst is 9.5 nm.
The same procedure as in example 1 was used to prepare a sorbic acid polyester by acid hydrolysis using the solid acid catalyst described above.
180.6g of sorbic acid was obtained in a yield of 90.3% and a purity of 99.1%, and 17g of tar was obtained as a by-product.
Claims (6)
1. A production method for preparing sorbic acid by acidolysis of sorbic acid polyester with a macroporous solid acid catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) putting 150 plus 200 parts of sorbic acid polyester into a reaction kettle, adding deionized water, putting 1-5 parts of solid acid catalyst, opening a stirring and steam valve, heating to the acidolysis temperature of 80-100 ℃, and carrying out acidolysis for 30-120 min;
(2) filtering while the solution is hot to obtain a sorbic acid aqueous solution;
(3) cooling, crystallizing, washing and drying to obtain sorbic acid;
wherein, the aperture of the solid acid catalyst in the step (1) is 8-50nm, and the specific surface area is 180-350m2The preparation method comprises the following steps:
1) preparation of macroporous support
Aging to form aluminosilicate gel by taking sodium metaaluminate as an aluminum source, silica sol as a silicon source, quaternary ammonium salt as a template agent and sodium bicarbonate as a pore-expanding agent, and hydrothermally synthesizing a catalyst carrier;
2) zirconia strong acid loading
Preparing 20-60% zirconium oxychloride solution, vacuum equivoluminal dipping for 10-24h, drying, and roasting to obtain the solid acid catalyst.
2. The method for producing sorbic acid by acid hydrolysis of sorbic acid polyester with the macroporous solid acid catalyst as claimed in claim 1, wherein: the step 1) is as follows:
preparing an aluminum source solution: putting sodium metaaluminate into the prepared sulfuric acid solution, and stirring and dissolving;
preparing a silicon source solution: adding silica sol, quaternary ammonium salt and sodium bicarbonate into deionized water, and uniformly stirring;
dropwise adding an aluminum source solution into a silicon source solution, stirring for 1-5h, and aging for 2-20h to obtain aluminosilicate gel;
putting the aluminosilicate gel into a hydrothermal synthesis kettle, and reacting at the temperature of 100 ℃ and 180 ℃ for 10-36 h;
filtering, drying at 150 ℃ under 100-;
the feeding molar ratio is as follows:
Al2O3：SiO2：H2SO4: quaternary ammonium salts: pore-expanding agent: h2O＝1：45-230：2-6：0.01-1：0.5-1：300-650。
3. The method for producing sorbic acid by acid hydrolysis of sorbic acid polyester with the macroporous solid acid catalyst as claimed in claim 2, wherein: the quaternary ammonium salt is tetrapropylammonium bromide.
4. The method for producing sorbic acid by acid hydrolysis of sorbic acid polyester with the macroporous solid acid catalyst as claimed in claim 1, wherein: in the step 2), the drying temperature is 100-.
5. The method for producing sorbic acid by acid hydrolysis of sorbic acid polyester with the macroporous solid acid catalyst as claimed in claim 4, wherein: in the step 2), the drying temperature is 120 ℃, and the drying time is 3 hours.
6. The method for producing sorbic acid by acid hydrolysis of sorbic acid polyester with the macroporous solid acid catalyst as claimed in claim 1, wherein: in the step 2), the roasting temperature is 550-650 ℃, and the roasting time is 3-5 h.
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| CN113578347A (en) * | 2021-08-31 | 2021-11-02 | 重庆工商大学 | Porous magnetic carbon-based solid acid catalyst and preparation method and application thereof |
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