CN109336755A - A kind of preparation method of medicine intermediate succinic acid - Google Patents
A kind of preparation method of medicine intermediate succinic acid Download PDFInfo
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- CN109336755A CN109336755A CN201811420831.9A CN201811420831A CN109336755A CN 109336755 A CN109336755 A CN 109336755A CN 201811420831 A CN201811420831 A CN 201811420831A CN 109336755 A CN109336755 A CN 109336755A
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention discloses a kind of preparation methods of medicine intermediate succinic acid, specifically include following steps, are combined using coprecipitation and sol-gal process first and are prepared composite catalyst, then prepare the sodium chloride solution that mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added in the three-necked flask with condenser pipe, 80-120 DEG C is warming up to when after then addition sodium chloride solution, catalyst being stirred slowly and is stirred to react, filter after reaction, collect filtrate；The pH to 2-3 that hydrochloric acid solution adjusts filtrate is added into filtrate, filtering is dry by the solid obtained after filter, and succinic acid is made.This method is easy to operate, and product yield is high.
Description
Technical field:
The present invention relates to medicine intermediate preparation fields, are specifically related to a kind of preparation side of medicine intermediate succinic acid
Method.
Background technique:
Succinic acid is also known as succinic acid, decomposes at 235 DEG C, vacuum distillation can distil, water can be dissolved in, be slightly soluble in ethyl alcohol,
In ether and acetone.Industrially, succinic acid is often made by butene dioic acid catalysis reduction, and succinic acid can also be hydrolyzed by succinonitrile and be made
It is standby.In the lab, the sodium salt and Iod R of two molecule diethyl malonates can be used in succinic acid, and then hydrolysis decarboxylation is made.Amber
Amber acid has anti-spasm, eliminating the phlegm and diuresis in medicine.Diethyl succinate is the important intermediate of organic synthesis.
Chinese patent (201210339366.2) discloses the preparation method of succinic acid, is with the biomass containing cellulose
Raw material is successively hydrolyzed, succinic acid production bacterium carries out the obtained succinic acid that ferments.Chinese patent (201510772386.2) is open
A kind of method of fermentation method production succinic acid, specifically: with glucose, corn pulp, basic magnesium carbonate etc. for raw material, pass through hair
Ferment method produces fermentation culture, and obtained succinic acid is then acidified to it using sulfuric acid.Chinese patent (201210293009.7) is public
A kind of method for preparing succinic acid has been opened, has successively been esterified and is hydrolyzed obtained succinic acid as raw material using ammonium succinate.Above-mentioned side
Law article part is more difficult to control, and product yield is lower.
Summary of the invention:
In view of the deficiencies of the prior art, it is an object of the present invention to provide a kind of preparation method of medicine intermediate succinic acid,
This method process is simple, and product is easily isolated, high income.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of medicine intermediate succinic acid, comprising the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；
(2) graphene, silane coupling agent and deionized water are mixed, dispersion liquid is made in ultrasonic treatment；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydrogen is added dropwise while stirring
Sodium hydroxide solution precipitating, continues stir process 1-3h, is cooled to room temperature after completion of dropwise addition, filter, and the solid after filter successively uses
It is directly scattered in hexamethylene after dehydrated alcohol, deionized water washing, butyl titanate is then added dropwise, turns mixed liquor after stirring
It moves in reaction kettle, 15-22h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, after the solid after filter is dry again
Catalyst is made in calcination processing at 600-800 DEG C；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added
Into the three-necked flask with condenser pipe, 80- is warming up to when after then addition sodium chloride solution, catalyst being stirred slowly
120 DEG C are stirred to react, and filter after reaction, collect filtrate；The pH to 2-3 that hydrochloric acid solution adjusts filtrate is added into filtrate,
Filtering, the solid obtained after filter is dry, succinic acid is made.
As a preferred embodiment of the above technical solution, in step (1), the molar concentration of each metal ion in mixed salt solution
It is respectively as follows: cerium ion 0.55-1.35mol/L, copper ion 1.5-2mol/L.
As a preferred embodiment of the above technical solution, in step (2), the graphene, silane coupling agent mass ratio be 1:
(0.005-0.01)。
As a preferred embodiment of the above technical solution, in step (2), the power of the ultrasonic treatment is 500-1000W, described super
The time of sonication is 20-60min.
As a preferred embodiment of the above technical solution, in step (3), the time of calcination processing is 1-6h.
As a preferred embodiment of the above technical solution, in step (3), in the catalyst, graphene, nano-titanium oxide, oxidation
The mass ratio of cerium is 0.7:(1.3-1.6): 1.
As a preferred embodiment of the above technical solution, in step (4), the revolving speed being stirred to react is 1500-4500rpm, institute
Stating the time being stirred to react is 2-6h.
As a preferred embodiment of the above technical solution, in step (4), the levulic acid, sodium chloride, catalyst mass ratio be
1:(0.15-0.33): (0.01-0.02).
As a preferred embodiment of the above technical solution, in step (4), the mass concentration of the hydrochloric acid solution is 8-13%.
The invention has the following advantages:
Succinic acid is made using levulic acid as raw material, by non-oxide process in the present invention, and reaction route is simple, and condition is easy to
Control, product yield is high, and purifying products are simple.
The present invention combines to prepare catalyst using coprecipitation and sol-gal process, prepares mixed metal salt first
It is mixed with graphene dispersing solution, sodium hydroxide pellets is then added dropwise by solution, the metal oxide precursor dispersion after precipitating
It is not dry to be directly scattered in the reaction solution for preparing nano-titanium oxide in graphene surface, butyl titanate is then added one
Determine to be hydrolyzed at temperature, nano-titanium oxide obtained is also stably dispersed in the surface of graphene, the catalyst stability
Good, surface-active is big, can effectively facilitate the generation of reaction, and the preparation condition of catalyst is also easy to control, low for equipment requirements.
Specific embodiment:
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of medicine intermediate succinic acid, comprising the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；Wherein, each metal from
The molar concentration of son is respectively as follows: cerium ion 0.55mol/L, copper ion 1.5mol/L；
(2) graphene, silane coupling agent and deionized water are mixed, is ultrasonically treated 20min under 500W power, dispersion is made
Liquid；Wherein, the graphene, silane coupling agent mass ratio be 1:0.005；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydrogen is added dropwise while stirring
Sodium hydroxide solution precipitating, continues stir process 1h, is cooled to room temperature after completion of dropwise addition, filter, and the solid after filter successively uses nothing
It is directly scattered in hexamethylene after water-ethanol, deionized water washing, butyl titanate is then added dropwise, shifts mixed liquor after stirring
Into reaction kettle, 15h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, 600-800 again after solid after filter is dry
Catalyst is made in calcination processing 1h at DEG C；Wherein, graphene, nano-titanium oxide, cerium oxide mass ratio be 0.7:1.3:1；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added
Into the three-necked flask with condenser pipe, 80 DEG C are warming up to when after then addition sodium chloride solution, catalyst being stirred slowly
It is stirred to react 2h, is filtered after reaction, filtrate is collected；The pH to 2-3 that hydrochloric acid solution adjusts filtrate, mistake are added into filtrate
Filter, the solid obtained after filter is dry, succinic acid is made；Wherein, the levulic acid, sodium chloride, catalyst mass ratio be
1:0.15:0.01.
The yield of succinic acid is 97.3%.
Embodiment 2
A kind of preparation method of medicine intermediate succinic acid, comprising the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；Wherein, each metal from
The molar concentration of son is respectively as follows: cerium ion 1.35mol/L, copper ion 2mol/L；
(2) graphene, silane coupling agent and deionized water are mixed, is ultrasonically treated 60min under 1000W power, be made and divide
Dispersion liquid；Wherein, the graphene, silane coupling agent mass ratio be 1:0.01；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydrogen is added dropwise while stirring
Sodium hydroxide solution precipitating, continues stir process 3h, is cooled to room temperature after completion of dropwise addition, filter, and the solid after filter successively uses nothing
It is directly scattered in hexamethylene after water-ethanol, deionized water washing, butyl titanate is then added dropwise, shifts mixed liquor after stirring
Into reaction kettle, 22h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, 600-800 again after solid after filter is dry
Catalyst is made in calcination processing 6h at DEG C；Wherein, graphene, nano-titanium oxide, cerium oxide mass ratio be 0.7:1.6:1；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added
Into the three-necked flask with condenser pipe, 120 DEG C are warming up to when after then addition sodium chloride solution, catalyst being stirred slowly
It is stirred to react 6h, is filtered after reaction, filtrate is collected；The pH to 2-3 that hydrochloric acid solution adjusts filtrate, mistake are added into filtrate
Filter, the solid obtained after filter is dry, succinic acid is made；Wherein, the levulic acid, sodium chloride, catalyst mass ratio be
1:0.33:0.02.
The yield of succinic acid is 98.2%.
Embodiment 3
A kind of preparation method of medicine intermediate succinic acid, comprising the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；Wherein, each metal from
The molar concentration of son is respectively as follows: cerium ion 0.75mol/L, copper ion 1.6mol/L；
(2) graphene, silane coupling agent and deionized water are mixed, is ultrasonically treated 30min under 600W power, dispersion is made
Liquid；Wherein, the graphene, silane coupling agent mass ratio be 1:0.006；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydrogen is added dropwise while stirring
Sodium hydroxide solution precipitating, continues stir process 1h, is cooled to room temperature after completion of dropwise addition, filter, and the solid after filter successively uses nothing
It is directly scattered in hexamethylene after water-ethanol, deionized water washing, butyl titanate is then added dropwise, shifts mixed liquor after stirring
Into reaction kettle, 16h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, 600-800 again after solid after filter is dry
Catalyst is made in calcination processing 2h at DEG C；Wherein, graphene, nano-titanium oxide, cerium oxide mass ratio be 0.7:1.4:1；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added
Into the three-necked flask with condenser pipe, 90 DEG C are warming up to when after then addition sodium chloride solution, catalyst being stirred slowly
It is stirred to react 3h, is filtered after reaction, filtrate is collected；The pH to 2-3 that hydrochloric acid solution adjusts filtrate, mistake are added into filtrate
Filter, the solid obtained after filter is dry, succinic acid is made；Wherein, the levulic acid, sodium chloride, catalyst mass ratio be
1:0.2:0.012.
The yield of succinic acid is 97.5%.
Embodiment 4
A kind of preparation method of medicine intermediate succinic acid, comprising the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；Wherein, each metal from
The molar concentration of son is respectively as follows: cerium ion 0.95mol/L, copper ion 1.7mol/L；
(2) graphene, silane coupling agent and deionized water are mixed, is ultrasonically treated 40min under 700W power, dispersion is made
Liquid；Wherein, the graphene, silane coupling agent mass ratio be 1:0.007；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydrogen is added dropwise while stirring
Sodium hydroxide solution precipitating, continues stir process 2h, is cooled to room temperature after completion of dropwise addition, filter, and the solid after filter successively uses nothing
It is directly scattered in hexamethylene after water-ethanol, deionized water washing, butyl titanate is then added dropwise, shifts mixed liquor after stirring
Into reaction kettle, 19h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, 600-800 again after solid after filter is dry
Catalyst is made in calcination processing 3h at DEG C；Wherein, graphene, nano-titanium oxide, cerium oxide mass ratio be 0.7:1.45:1；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added
Into the three-necked flask with condenser pipe, 100 DEG C are warming up to when after then addition sodium chloride solution, catalyst being stirred slowly
It is stirred to react 4h, is filtered after reaction, filtrate is collected；The pH to 2-3 that hydrochloric acid solution adjusts filtrate, mistake are added into filtrate
Filter, the solid obtained after filter is dry, succinic acid is made；Wherein, the levulic acid, sodium chloride, catalyst mass ratio be
1:0.25:0.014.
The yield of succinic acid is 96.9%.
Embodiment 5
A kind of preparation method of medicine intermediate succinic acid, comprising the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；Wherein, each metal from
The molar concentration of son is respectively as follows: cerium ion 1.05mol/L, copper ion 1.8mol/L；
(2) graphene, silane coupling agent and deionized water are mixed, is ultrasonically treated 50min under 800W power, dispersion is made
Liquid；Wherein, the graphene, silane coupling agent mass ratio be 1:0.008；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydrogen is added dropwise while stirring
Sodium hydroxide solution precipitating, continues stir process 2h, is cooled to room temperature after completion of dropwise addition, filter, and the solid after filter successively uses nothing
It is directly scattered in hexamethylene after water-ethanol, deionized water washing, butyl titanate is then added dropwise, shifts mixed liquor after stirring
Into reaction kettle, 20h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, 600-800 again after solid after filter is dry
Catalyst is made in calcination processing 5h at DEG C；Wherein, graphene, nano-titanium oxide, cerium oxide mass ratio be 0.7:1.5:1；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added
Into the three-necked flask with condenser pipe, 110 DEG C are warming up to when after then addition sodium chloride solution, catalyst being stirred slowly
It is stirred to react 5h, is filtered after reaction, filtrate is collected；The pH to 2-3 that hydrochloric acid solution adjusts filtrate, mistake are added into filtrate
Filter, the solid obtained after filter is dry, succinic acid is made；Wherein, the levulic acid, sodium chloride, catalyst mass ratio be
1:0.28:0.016.
The yield of succinic acid is 98.5%.
Embodiment 6
A kind of preparation method of medicine intermediate succinic acid, comprising the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；Wherein, each metal from
The molar concentration of son is respectively as follows: cerium ion 1.15mol/L, copper ion 1.9mol/L；
(2) graphene, silane coupling agent and deionized water are mixed, is ultrasonically treated 55min under 900W power, dispersion is made
Liquid；Wherein, the graphene, silane coupling agent mass ratio be 1:0.009；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydrogen is added dropwise while stirring
Sodium hydroxide solution precipitating, continues stir process 2.5h, is cooled to room temperature after completion of dropwise addition, filter, and the solid after filter successively uses
It is directly scattered in hexamethylene after dehydrated alcohol, deionized water washing, butyl titanate is then added dropwise, turns mixed liquor after stirring
It moves in reaction kettle, 21h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, 600- again after solid after filter is dry
Catalyst is made in calcination processing 5h at 800 DEG C；Wherein, graphene, nano-titanium oxide, cerium oxide mass ratio be 0.7:1.5:
1；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added
Into the three-necked flask with condenser pipe, 120 DEG C are warming up to when after then addition sodium chloride solution, catalyst being stirred slowly
It is stirred to react 5h, is filtered after reaction, filtrate is collected；The pH to 2-3 that hydrochloric acid solution adjusts filtrate, mistake are added into filtrate
Filter, the solid obtained after filter is dry, succinic acid is made；Wherein, the levulic acid, sodium chloride, catalyst mass ratio be
1:0.31:0.018.
The yield of succinic acid is 97.9%.
Claims (9)
1. a kind of preparation method of medicine intermediate succinic acid, which comprises the following steps:
(1) six nitric hydrate cerium, copper nitrate are dissolved in and mixed salt solution are made in particle water；
(2) graphene, silane coupling agent and deionized water are mixed, dispersion liquid is made in ultrasonic treatment；
(3) after mixed salt solution, dispersion liquid being mixed evenly, it is warming up to 35-45 DEG C, hydroxide is added dropwise while stirring
Sodium solution precipitating, continues stir process 1-3h, is cooled to room temperature after completion of dropwise addition, filter, the solid after filter successively uses anhydrous
It is directly scattered in hexamethylene after ethyl alcohol, deionized water washing, butyl titanate is then added dropwise, is transferred to mixed liquor after stirring
In reaction kettle, 15-22h is reacted at 150 DEG C, is cooled to room temperature after reaction, filter, 600- again after solid after filter is dry
Catalyst is made in calcination processing at 800 DEG C；
(4) sodium chloride solution that preparation mass concentration is 20-30%；Levulic acid, n,N-Dimethylformamide are added to band
Have in the three-necked flask of condenser pipe, is warming up to 80-120 DEG C when after then addition sodium chloride solution, catalyst being stirred slowly
It is stirred to react, filters after reaction, collect filtrate；The pH to 2-3 that hydrochloric acid solution adjusts filtrate is added into filtrate, filters,
The solid obtained after filter is dry, succinic acid is made.
2. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (1), mix
The molar concentration for closing each metal ion in metal salt solution is respectively as follows: cerium ion 0.55-1.35mol/L, copper ion 1.5-2mol/
L。
3. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (2), institute
State graphene, the mass ratio of silane coupling agent is 1:(0.005-0.01).
4. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (2), institute
The power for stating ultrasonic treatment is 500-1000W, and the time of the ultrasonic treatment is 20-60min.
5. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (3), forge
The time for burning processing is 1-6h.
6. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (3), institute
State in catalyst, the mass ratio of graphene, nano-titanium oxide, cerium oxide is 0.7:(1.3-1.6): 1.
7. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (4), institute
Stating the revolving speed being stirred to react is 1500-4500rpm, and the time being stirred to react is 2-6h.
8. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (4), institute
State levulic acid, sodium chloride, catalyst mass ratio be 1:(0.15-0.33): (0.01-0.02).
9. a kind of preparation method of medicine intermediate succinic acid as described in claim 1, it is characterised in that: in step (4), institute
The mass concentration for stating hydrochloric acid solution is 8-13%.
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| CN110227455A (en) * | 2019-06-26 | 2019-09-13 | 内蒙古大学 | A kind of preparation method of two-dimensional layer glycerol oxidation nanometer catalyst |
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| CN110227455A (en) * | 2019-06-26 | 2019-09-13 | 内蒙古大学 | A kind of preparation method of two-dimensional layer glycerol oxidation nanometer catalyst |
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