CN114437101A - Preparation method of isosorbide - Google Patents
Preparation method of isosorbide Download PDFInfo
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- CN114437101A CN114437101A CN202210362604.5A CN202210362604A CN114437101A CN 114437101 A CN114437101 A CN 114437101A CN 202210362604 A CN202210362604 A CN 202210362604A CN 114437101 A CN114437101 A CN 114437101A
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- molecular sieve
- deionized water
- isosorbide
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- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 title claims abstract description 47
- 229960002479 isosorbide Drugs 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 14
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 239000002808 molecular sieve Substances 0.000 claims abstract description 70
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims abstract description 31
- 239000000600 sorbitol Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000000376 reactant Substances 0.000 claims abstract description 12
- 238000001179 sorption measurement Methods 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 239000013543 active substance Substances 0.000 claims abstract description 6
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 45
- 229910021641 deionized water Inorganic materials 0.000 claims description 45
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 36
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000002791 soaking Methods 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 27
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 20
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 230000007935 neutral effect Effects 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 15
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- VFZQATFTQAZCMO-UHFFFAOYSA-N 6-chlorochromen-4-one Chemical compound O1C=CC(=O)C2=CC(Cl)=CC=C21 VFZQATFTQAZCMO-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 239000012043 crude product Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 238000005299 abrasion Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000009834 vaporization Methods 0.000 claims description 5
- 230000008016 vaporization Effects 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims 1
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 229960001484 edetic acid Drugs 0.000 description 8
- 238000006297 dehydration reaction Methods 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 239000003377 acid catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/12—Oxidising
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/34—Reaction with organic or organometallic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/40—Special temperature treatment, i.e. other than just for template removal
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
A process for preparing isosorbide, belonging to the technical field of fine chemical engineering, comprises the steps of molecular sieve cleaning, molecular sieve modification, active substance adsorption and calcination and isosorbide synthesis. The preparation method of the isosorbide has the advantages of mild reaction conditions, simple operation, high conversion rate of the reactant sorbitol, high selectivity and high yield of the product isosorbide, the reaction temperature is 130-230 ℃, the conversion rate of the sorbitol is 95.32-97.93%, the selectivity of the isosorbide is 75.47-77.43%, and the yield of the isosorbide is 72.89-75.74%.
Description
Technical Field
The invention relates to a preparation method of isosorbide, belonging to the technical field of fine chemical engineering.
Background
Based on structural characteristics such as functional binary hydroxyl, rigid structure, chiral center and the like, isosorbide and derivatives thereof are widely used in the fields of food, cosmetics, medicines, high polymer materials and the like. Isosorbide is obtained by catalytic dehydration of sorbitol in general, and the raw material sorbitol can be prepared in large quantities by catalytic hydrogenation of glucose, so that the raw material source of isosorbide is very rich and the price is very low. Catalytic dehydration of sorbitol is usually carried out with a liquid acid (e.g. H)2SO4Etc.) is a catalyst, and the liquid acid catalyst not only corrodes equipment, pollutes the environment and is difficult to separate from products, but also has the defects of more side reactions, dark color of the obtained products and the like. To avoid the above problems with liquid acid catalysts, researchers in this field have developed many ways to avoid the use of liquid acid catalysts.
Chinese patent CN108117560A discloses a method for preparing isosorbide, which comprises the steps of firstly adding a phosphorus modified HZSM-5 molecular sieve into sorbitol solution, carrying out dehydration reaction to obtain a solid-liquid mixture, then filtering to obtain filtrate, carrying out activated carbon decoloration on the filtrate, and filtering again to obtain filtrate; then the filtrate is sequentially subjected to ion exchange by D301 anion resin, 001 × 7 cation resin and D301 anion resin to obtain ion exchange solution; condensing the ion exchange liquid to Brix of 75-90%, and performing primary cooling crystallization; after centrifugation, crude isosorbide crystals are obtained; adding water into the coarse isosorbide crystals, heating and melting the coarse isosorbide crystals to ensure that the Brix of the coarse isosorbide crystals is 70-85%, and carrying out secondary cooling crystallization; centrifuging and drying to obtain the isosorbide crystal product. The preparation process is complex, the operation is complex, the yield of the isosorbide is low, the dehydration reaction temperature is 150-300 ℃, the reaction pressure is 3-10 MPa, the conditions are harsh, and the energy consumption is high.
Chinese patent CN101492457A discloses a method for preparing isosorbide, which takes sorbitol as raw material and H3PO4The modified tetravalent metal oxide is used as a catalyst to prepare the isosorbide through dehydration reaction. The selectivity of isosorbide is 63.49%, the yield is 62.23%, the dehydration reaction temperature is 250-300 ℃, and the preparation method disclosed by the patent is high in reaction temperature, high in energy consumption and low in product selectivity and yield.
It can be seen from the above patents that, in the preparation method of isosorbide by catalytic dehydration using sorbitol as raw material, although many methods have been developed to avoid the use of liquid acid catalyst, the problems of harsh reaction conditions, complex process operation, low selectivity and yield of isosorbide, etc. still exist.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of isosorbide, which realizes the following purposes: the preparation method has the advantages of mild reaction conditions, simple operation, high sorbitol conversion rate, high isosorbide selectivity and high yield.
In order to realize the purpose, the invention adopts the following technical scheme:
a process for preparing isosorbide includes washing molecular sieve, modifying molecular sieve, adsorbing active substance, calcining and synthesizing isosorbide.
The following is a further improvement of the above technical solution:
step 1 molecular sieve cleaning
Mixing hydrogen peroxide and concentrated sulfuric acid into a strong oxidation solution according to a volume ratio of 3:7, putting a molecular sieve into the strong oxidation solution, soaking for 1-6 minutes, taking out, soaking and washing the molecular sieve with deionized water until an eluate is neutral, soaking the molecular sieve into the mixed solution at a temperature of 50-80 ℃, soaking for 12-26 hours, taking out, washing with deionized water until the eluate is neutral, and drying at 100-130 ℃ for 1-3 hours to obtain the washed molecular sieve;
the hydrogen peroxide is prepared from hydrogen peroxide, wherein the mass concentration of the hydrogen peroxide is 30 wt%;
the mass concentration of the concentrated sulfuric acid is 98 wt%;
the mass ratio of the molecular sieve to the strong oxidation solution is 20-50: 100;
the molecular sieve is spherical, the particle size is 1.6-2.5 mm, the pore diameter is 10-40 nm, the bulk density is 0.64g/mL, the abrasion rate is 0.1%, the compressive strength is 35N, and the silicon-aluminum ratio is 1: 1;
the mass ratio of the molecular sieve to the mixed liquid is 15-40: 100;
the mixed solution consists of bis (2-hydroxyethyl) dimethylammonium chloride, tetramethylammonium hydroxide, potassium hydroxide and deionized water;
the mass ratio of the bis (2-hydroxyethyl) dimethylammonium chloride to the tetramethylammonium hydroxide to the potassium hydroxide to the deionized water is 1-7: 2-8: 1-6: 70-100.
Step 2 modification of molecular sieves
Mixing citric acid, ethylenediamine tetraacetic acid, trifluoroacetic acid and deionized water to obtain acid liquor, immersing the cleaned molecular sieve into the acid liquor, heating to 80-110 ℃, soaking for 2-4 hours, filtering out the molecular sieve, washing with deionized water until the eluate is neutral, and drying at 90-120 ℃ for 1-4 hours to obtain the modified molecular sieve;
the mass ratio of the cleaned molecular sieve to the acid liquor is 20-35: 100;
the mass ratio of the citric acid to the ethylene diamine tetraacetic acid to the trifluoroacetic acid to the deionized water is 10-19: 5-9: 1-6: 80-110.
Step 3 active material adsorption and calcination
Dissolving ammonium metavanadate and zirconium sulfate in deionized water to obtain a mixed salt solution, putting the modified molecular sieve into the mixed salt solution, dipping for 30-50 hours, taking out, drying at 80-110 ℃ for 2-5 hours, transferring to a muffle furnace, heating to 280-380 ℃ at a heating rate of 2-4 ℃/min, calcining at constant temperature for 1-3.5 hours, and cooling to room temperature to obtain a catalyst;
the mass ratio of the modified molecular sieve to the mixed salt solution is 20-36: 100;
in the mixed salt solution, the mass ratio of ammonium metavanadate, zirconium sulfate and deionized water is 12-18: 13-20: 80-100.
Step 4 Synthesis of isosorbide
Loading a catalyst into a constant temperature section of a tubular fixed bed reactor, controlling the temperature of the constant temperature section at 130-230 ℃ under the protection of nitrogen, preheating a reactant sorbitol aqueous solution to 100-130 ℃ through a preheating section of the reactor, sending the reactant sorbitol aqueous solution into the constant temperature section after vaporization, cooling a gas-liquid mixture after reaction through an ice water bath, separating gas from liquid, collecting the obtained liquid into a crude product tank, and sampling and analyzing the liquid collected in the crude product tank within 3 hours after the reaction is stable;
the mass concentration of the sorbitol in the sorbitol aqueous solution is 10-14 wt%.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method of the isosorbide has the advantages of mild reaction conditions, simple operation, high conversion rate of the reactant sorbitol, high selectivity and high yield of the product isosorbide;
2. according to the preparation method of the isosorbide, the reaction temperature is 130-230 ℃, the conversion rate of the sorbitol is 95.32-97.93%, the selectivity of the isosorbide is 75.47-77.43%, and the yield of the isosorbide is 72.89-75.74%.
Detailed Description
The following description of the preferred embodiments of the present invention is provided for the purpose of illustration and description, and is in no way intended to limit the invention.
Example 1: preparation method of isosorbide
The method comprises the following steps:
1. molecular sieve cleaning
Mixing hydrogen peroxide and concentrated sulfuric acid into a strong oxidation solution according to a volume ratio of 3:7, putting a molecular sieve into the strong oxidation solution, soaking for 4 minutes, taking out, soaking and washing the molecular sieve with deionized water until an eluate is neutral, soaking the molecular sieve into the mixed solution, controlling the temperature to be 70 ℃, soaking for 20 hours, taking out, washing with the deionized water until the eluate is neutral, and drying at 120 ℃ for 2 hours to obtain the washed molecular sieve;
the hydrogen peroxide is prepared from hydrogen peroxide, wherein the mass concentration of the hydrogen peroxide is 30 wt%;
the mass concentration of the concentrated sulfuric acid is 98 wt%;
the mass ratio of the molecular sieve to the strong oxidation solution is 40: 100;
the molecular sieve is spherical, the particle size is 2mm, the aperture is 30nm, the bulk density is 0.64g/mL, the abrasion rate is 0.1%, the compressive strength is 35N, and the silica-alumina ratio is 1: 1;
the mass ratio of the molecular sieve to the mixed solution is 25: 100;
the mixed solution consists of bis (2-hydroxyethyl) dimethylammonium chloride, tetramethylammonium hydroxide, potassium hydroxide and deionized water;
the mass ratio of the bis (2-hydroxyethyl) dimethylammonium chloride to the tetramethylammonium hydroxide to the potassium hydroxide to the deionized water is 5:6:4: 90.
2. Modification of molecular sieves
Mixing citric acid, ethylenediamine tetraacetic acid, trifluoroacetic acid and deionized water to obtain acid liquor, immersing the cleaned molecular sieve into the acid liquor, heating to 100 ℃, soaking for 3 hours, filtering out the molecular sieve, washing with the deionized water until the eluate is neutral, and drying at 110 ℃ for 3 hours to obtain the modified molecular sieve;
the mass ratio of the cleaned molecular sieve to the acid liquor is 30: 100;
the mass ratio of the citric acid to the ethylenediamine tetraacetic acid to the trifluoroacetic acid to the deionized water is 13:7:4: 100.
3. Active substance adsorption and calcination
Dissolving ammonium metavanadate and zirconium sulfate in deionized water to obtain a mixed salt solution, putting the modified molecular sieve in the mixed salt solution, soaking for 40 hours, taking out, drying at 100 ℃ for 4 hours, transferring to a muffle furnace, heating to 320 ℃ at a heating rate of 3 ℃/min, calcining at constant temperature for 2 hours, and cooling to room temperature to obtain a catalyst;
the mass ratio of the modified molecular sieve to the mixed salt solution is 30: 100;
in the mixed salt solution, the mass ratio of ammonium metavanadate, zirconium sulfate and deionized water is 15:17: 90.
4. Synthesis of isosorbide
Loading a catalyst into a constant temperature section of a tubular fixed bed reactor, controlling the temperature of the constant temperature section at 180 ℃ under the protection of nitrogen, preheating a reactant sorbitol aqueous solution to 120 ℃ through a preheating section of the reactor, sending the heated reactant sorbitol aqueous solution into the constant temperature section after vaporization, collecting the obtained liquid into a crude product tank after cooling a gas-liquid mixture after reaction in an ice water bath and carrying out gas-liquid separation, and sampling and analyzing the liquid collected in the crude product tank within 3 hours after the reaction is stable;
in the sorbitol aqueous solution, the mass concentration of sorbitol is 13 wt%.
Example 2: preparation method of isosorbide
The method comprises the following steps:
1. molecular sieve cleaning
Mixing hydrogen peroxide and concentrated sulfuric acid into a strong oxidation solution according to a volume ratio of 3:7, putting a molecular sieve into the strong oxidation solution, soaking for 1 minute, taking out, soaking and washing the molecular sieve with deionized water until an eluate is neutral, soaking the molecular sieve into the mixed solution, controlling the temperature to be 50 ℃, soaking for 12 hours, taking out, washing with the deionized water until the eluate is neutral, and drying at 100 ℃ for 1 hour to obtain the washed molecular sieve;
the hydrogen peroxide is prepared from hydrogen peroxide, wherein the mass concentration of the hydrogen peroxide is 30 wt%;
the mass concentration of the concentrated sulfuric acid is 98 wt%;
the mass ratio of the molecular sieve to the strong oxidation solution is 20: 100;
the molecular sieve is spherical, the particle size is 1.6mm, the aperture is 10nm, the bulk density is 0.64g/mL, the abrasion rate is 0.1%, the compressive strength is 35N, and the silicon-aluminum ratio is 1: 1;
the mass ratio of the molecular sieve to the mixed solution is 15: 100;
the mixed solution consists of bis (2-hydroxyethyl) dimethylammonium chloride, tetramethylammonium hydroxide, potassium hydroxide and deionized water;
the mass ratio of the bis (2-hydroxyethyl) dimethylammonium chloride to the tetramethylammonium hydroxide to the potassium hydroxide to the deionized water is 1:2:1: 70.
2. Modification of molecular sieves
Mixing citric acid, ethylenediamine tetraacetic acid, trifluoroacetic acid and deionized water to obtain acid liquor, immersing the cleaned molecular sieve into the acid liquor, heating to 80 ℃, soaking for 2 hours, filtering out the molecular sieve, washing with deionized water until the eluate is neutral, and drying at 90 ℃ for 1 hour to obtain the modified molecular sieve;
the mass ratio of the cleaned molecular sieve to the acid liquor is 20: 100;
the mass ratio of the citric acid to the ethylenediamine tetraacetic acid to the trifluoroacetic acid to the deionized water is 10:5:1: 80.
3. Active substance adsorption and calcination
Dissolving ammonium metavanadate and zirconium sulfate in deionized water to obtain a mixed salt solution, putting the modified molecular sieve into the mixed salt solution, soaking for 30 hours, taking out, drying at 80 ℃ for 2 hours, transferring to a muffle furnace, heating to 280 ℃ at a heating rate of 2 ℃/min, calcining at constant temperature for 1 hour, and cooling to room temperature to obtain a catalyst;
the mass ratio of the modified molecular sieve to the mixed salt solution is 20: 100;
in the mixed salt solution, the mass ratio of ammonium metavanadate, zirconium sulfate and deionized water is 12:13: 80.
4. Synthesis of isosorbide
Loading a catalyst into a constant temperature section of a tubular fixed bed reactor, controlling the temperature of the constant temperature section at 130 ℃ under the protection of nitrogen, preheating a reactant sorbitol aqueous solution to 100 ℃ through a preheating section of the reactor, sending the heated reactant sorbitol aqueous solution into the constant temperature section after vaporization, collecting the obtained liquid into a crude product tank after cooling a gas-liquid mixture after reaction in an ice water bath and carrying out gas-liquid separation, and sampling and analyzing the liquid collected in the crude product tank within 3 hours after the reaction is stable;
the mass concentration of the sorbitol in the sorbitol aqueous solution is 10 wt%.
Example 3: preparation method of isosorbide
The method comprises the following steps:
1. molecular sieve cleaning
Mixing hydrogen peroxide and concentrated sulfuric acid into a strong oxidation solution according to a volume ratio of 3:7, putting a molecular sieve into the strong oxidation solution, soaking for 6 minutes, taking out, soaking and washing the molecular sieve with deionized water until an eluate is neutral, soaking the molecular sieve into the mixed solution, controlling the temperature to be 80 ℃, soaking for 26 hours, taking out, washing with the deionized water until the eluate is neutral, and drying at 130 ℃ for 3 hours to obtain the washed molecular sieve;
the hydrogen peroxide is prepared from hydrogen peroxide, wherein the mass concentration of the hydrogen peroxide is 30 wt%;
the mass concentration of the concentrated sulfuric acid is 98 wt%;
the mass ratio of the molecular sieve to the strong oxidation solution is 50: 100;
the molecular sieve is spherical, the particle size is 2.5mm, the aperture is 40nm, the bulk density is 0.64g/mL, the abrasion rate is 0.1%, the compressive strength is 35N, and the silicon-aluminum ratio is 1: 1;
the mass ratio of the molecular sieve to the mixed solution is 40: 100;
the mixed solution consists of bis (2-hydroxyethyl) dimethylammonium chloride, tetramethylammonium hydroxide, potassium hydroxide and deionized water;
the mass ratio of the bis (2-hydroxyethyl) dimethylammonium chloride to the tetramethylammonium hydroxide to the potassium hydroxide to the deionized water is 7:8:6: 100.
2. Modification of molecular sieves
Mixing citric acid, ethylenediamine tetraacetic acid, trifluoroacetic acid and deionized water to obtain acid liquor, immersing the cleaned molecular sieve into the acid liquor, heating to 110 ℃, soaking for 4 hours, filtering out the molecular sieve, washing with the deionized water until the eluate is neutral, and drying at 120 ℃ for 4 hours to obtain the modified molecular sieve;
the mass ratio of the cleaned molecular sieve to the acid liquor is 35: 100;
the mass ratio of the citric acid to the ethylenediamine tetraacetic acid to the trifluoroacetic acid to the deionized water is 19:9:6: 110.
3. Active substance adsorption and calcination
Dissolving ammonium metavanadate and zirconium sulfate in deionized water to obtain a mixed salt solution, putting the modified molecular sieve into the mixed salt solution, soaking for 50 hours, taking out, drying at 110 ℃ for 5 hours, transferring to a muffle furnace, heating to 380 ℃ at a heating rate of 4 ℃/min, calcining at constant temperature for 3.5 hours, and cooling to room temperature to obtain a catalyst;
the mass ratio of the modified molecular sieve to the mixed salt solution is 36: 100;
in the mixed salt solution, the mass ratio of ammonium metavanadate, zirconium sulfate and deionized water is 18:20: 100.
4. Synthesis of isosorbide
Loading a catalyst into a constant temperature section of a tubular fixed bed reactor, controlling the temperature of the constant temperature section at 230 ℃ under the protection of nitrogen, preheating a reactant sorbitol aqueous solution to 130 ℃ through a preheating section of the reactor, sending the heated reactant sorbitol aqueous solution into the constant temperature section after vaporization, collecting the obtained liquid into a crude product tank after cooling a gas-liquid mixture after reaction in an ice water bath and separating the gas from the gas, and sampling and analyzing the liquid collected in the crude product tank within 3 hours after the reaction is stable;
in the sorbitol aqueous solution, the mass concentration of sorbitol is 14 wt%.
Comparative example 1: based on example 1, two steps of molecular sieve cleaning and molecular sieve modification are not carried out
Step 1 and step 2 are not carried out;
step 3 and step 4 were the same as in example 1.
Comparative example 2: example 1 on the basis of the equivalent replacement of ammonium metavanadate by zirconium sulfate in the active material adsorption and calcination step
The operation of step 1 and step 2 is the same as that of example 1;
in step 3, 15 parts of ammonium metavanadate is replaced with 15 parts of zirconium sulfate in equal amount, and the rest of the operation is the same as in example 1;
step 4 was performed as in example 1.
Comparative example 3: example 1 on the basis of the equivalent substitution of zirconium sulfate for ammonium metavanadate in the active material adsorption and calcination step
The operation of step 1 and step 2 is the same as that of example 1;
in step 3, 17 parts of zirconium sulfate was replaced with 17 parts of ammonium metavanadate in equal amount, and the rest of the procedure was the same as in example 1;
step 4 was performed as in example 1.
The results of sampling tests of examples 1, 2, 3 and comparative examples 1, 2, 3 are shown in Table 1:
TABLE 1
Claims (5)
1. A method for preparing isosorbide is characterized in that:
comprises the steps of molecular sieve cleaning, molecular sieve modification, active substance adsorption and calcination and isosorbide synthesis;
the molecular sieve cleaning method comprises the steps of mixing hydrogen peroxide and concentrated sulfuric acid into a strong oxidation solution according to a volume ratio of 3:7, putting the molecular sieve into the strong oxidation solution, soaking for 1-6 minutes, taking out, soaking and washing the molecular sieve with deionized water until an eluate is neutral, soaking the molecular sieve into the mixed solution, controlling the temperature to be 50-80 ℃, taking out after soaking for 12-26 hours, washing with deionized water until the eluate is neutral, and drying at 100-130 ℃ for 1-3 hours to obtain the cleaned molecular sieve;
the molecular sieve is spherical, the particle size is 1.6-2.5 mm, the pore diameter is 10-40 nm, the bulk density is 0.64g/mL, the abrasion rate is 0.1%, the compressive strength is 35N, and the silicon-aluminum ratio is 1: 1;
the mixed solution consists of bis (2-hydroxyethyl) dimethylammonium chloride, tetramethylammonium hydroxide, potassium hydroxide and deionized water;
the mass ratio of the bis (2-hydroxyethyl) dimethyl ammonium chloride to the tetramethyl ammonium hydroxide to the potassium hydroxide to the deionized water is 1-7: 2-8: 1-6: 70-100;
the molecular sieve is modified, wherein citric acid, ethylenediamine tetraacetic acid, trifluoroacetic acid and deionized water are mixed to obtain acid liquor, the cleaned molecular sieve is immersed in the acid liquor, the temperature is increased to 80-110 ℃, the molecular sieve is filtered and washed by the deionized water after being immersed for 2-4 hours until eluate is neutral, and the molecular sieve is dried for 1-4 hours at the temperature of 90-120 ℃ to obtain the modified molecular sieve;
the mass ratio of the cleaned molecular sieve to the acid liquor is 20-35: 100;
the mass ratio of the citric acid to the ethylenediamine tetraacetic acid to the trifluoroacetic acid to the deionized water is 10-19: 5-9: 1-6: 80-110;
dissolving ammonium metavanadate and zirconium sulfate in deionized water to obtain a mixed salt solution, putting the modified molecular sieve into the mixed salt solution, soaking for 30-50 hours, taking out, drying at 80-110 ℃ for 2-5 hours, transferring to a muffle furnace, heating to 280-380 ℃, calcining at constant temperature for 1-3.5 hours, and cooling to room temperature to obtain a catalyst;
the mass ratio of the modified molecular sieve to the mixed salt solution is 20-36: 100;
in the mixed salt solution, the mass ratio of ammonium metavanadate, zirconium sulfate and deionized water is 12-18: 13-20: 80-100.
2. The method for preparing isosorbide according to claim 1, wherein:
the mass concentration of the hydrogen peroxide is 30 wt%;
the mass concentration of the concentrated sulfuric acid is 98 wt%;
the mass ratio of the molecular sieve to the strong oxidation solution is 20-50: 100;
the mass ratio of the molecular sieve to the mixed liquid is 15-40: 100.
3. The method for preparing isosorbide according to claim 1, wherein:
in the active material adsorption and calcination steps, the temperature rise rate is 2-4 ℃/min.
4. The method for preparing isosorbide according to claim 1, wherein:
the method for synthesizing the isosorbide comprises the steps of filling a catalyst into a constant temperature section of a tubular fixed bed reactor, controlling the temperature of the constant temperature section at 130-230 ℃ under the protection of nitrogen, preheating a reactant sorbitol aqueous solution to 100-130 ℃ through a preheating section of the reactor, sending the reactant sorbitol aqueous solution into the constant temperature section after vaporization, cooling a gas-liquid mixture after reaction through an ice water bath, separating gas from liquid, and collecting the obtained liquid into a crude product tank.
5. The method for producing isosorbide according to claim 4, wherein:
the mass concentration of the sorbitol in the sorbitol aqueous solution is 10-14 wt%.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2238017A1 (en) * | 2004-01-21 | 2005-08-01 | Universidad Politecnica De Valencia | Method of preparing monoesters of polyhydroxyl alcohols |
CN101492458A (en) * | 2009-02-27 | 2009-07-29 | 南京工业大学 | Method for preparing isosorbide by using tetravalent metal phosphate as catalyst |
CN101691376A (en) * | 2009-09-22 | 2010-04-07 | 南京工业大学 | Method for preparing isosorbide by taking solid-supported heteropoly acid as catalyst |
CN108675317A (en) * | 2018-08-22 | 2018-10-19 | 江西西林科新材料有限公司 | A kind of synthetic method of low cost S APO-34 molecular sieves |
CN109261202A (en) * | 2018-09-30 | 2019-01-25 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and its preparation method and application preparing isobide for sorb dehydration of alcohols |
CN113289672A (en) * | 2021-06-02 | 2021-08-24 | 南通大学 | Improved process of molecular sieve catalyst |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
ES2238017A1 (en) * | 2004-01-21 | 2005-08-01 | Universidad Politecnica De Valencia | Method of preparing monoesters of polyhydroxyl alcohols |
CN101492458A (en) * | 2009-02-27 | 2009-07-29 | 南京工业大学 | Method for preparing isosorbide by using tetravalent metal phosphate as catalyst |
CN101691376A (en) * | 2009-09-22 | 2010-04-07 | 南京工业大学 | Method for preparing isosorbide by taking solid-supported heteropoly acid as catalyst |
CN108675317A (en) * | 2018-08-22 | 2018-10-19 | 江西西林科新材料有限公司 | A kind of synthetic method of low cost S APO-34 molecular sieves |
CN109261202A (en) * | 2018-09-30 | 2019-01-25 | 中国科学院山西煤炭化学研究所 | A kind of catalyst and its preparation method and application preparing isobide for sorb dehydration of alcohols |
CN113289672A (en) * | 2021-06-02 | 2021-08-24 | 南通大学 | Improved process of molecular sieve catalyst |
Non-Patent Citations (1)
Title |
---|
李澜鹏等: "山梨醇催化脱水制备异山梨醇研究进展", 《现代化工》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023193430A1 (en) * | 2022-04-08 | 2023-10-12 | 山东天力药业有限公司 | Method for preparing isosorbide |
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