CN107987045A - A kind of technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst - Google Patents

A kind of technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst Download PDF

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CN107987045A
CN107987045A CN201711288432.7A CN201711288432A CN107987045A CN 107987045 A CN107987045 A CN 107987045A CN 201711288432 A CN201711288432 A CN 201711288432A CN 107987045 A CN107987045 A CN 107987045A
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catalyst
membrane reactor
sodium dehydroacetate
ketene dimer
immobilized alcl
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CN107987045B (en
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庆九
俞新南
刘芳
朱小刚
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Nantong Acetic Acid Chemical Co Ltd
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Nantong Acetic Acid Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/34—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D309/36—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • 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
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B01J23/04—Alkali metals
    • 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
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/005—Separating solid material from the gas/liquid stream
    • B01J8/006—Separating solid material from the gas/liquid stream by filtration
    • 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

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a kind of technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, including first toluene is squeezed into the ceramic membrane reactor equipped with immobilized AlCl_3 catalyst, ketene dimer is added in 0.5h~1h, the mass ratio 1 that feeds intake of ketene dimer and toluene:5~15, controlling reaction temperature is 50~70 DEG C, and in 0.8~2MPa, catalyst loading is 0.5~3wt% of total amount of feeding for reactor pressure control；The solid-carried catalyst is prepared using infusion process；When reaction solution ketene dimer HPLC contents≤0.5%, polymerisation terminates, and penetrating fluid carries out extractive reaction, ketene dimer into extraction tower with sodium hydrate aqueous solution：Sodium hydroxide molar ratio=1:1~1.5, dehydroacetic acid sodium solution is concentrated, is dried, crushes and product packaging at 90~105 DEG C, obtained sodium dehydroacetate yield is >=99%, product content >=99.8%.The present invention effectively reduces production cost, reduces quantity of three wastes in production, obtained sodium dehydroacetate high income.

Description

A kind of technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst
Technical field
The present invention relates to chemical technology field, and in particular to a kind of preparation process of sodium dehydroacetate.
Background technology
Sodium dehydroacetate
Appearance characteristics：White crystalline powder.
Dissolubility：Water (25 DEG C of solubility 33g/100g) is dissolved in, is insoluble in the organic solvents such as ethanol.
Molecular weight：191.1
Fusing point：110℃
Purposes：
Food preservative, antistaling agent.The product has the saccharomycete in food, spoilage organisms, mould in stronger antibacterial work With being widely used in the anti-corrosion, fresh-keeping of meat, fish, greengrocery, fruits, beverage class, cake class etc., be New-type wide-spectrum suppression Microbial inoculum.
Prior art synthesis technique：
The conventional production process that industrially produces is at present：Ketene dimer is made in catalyst triethylene diamine, catechol Under, condensation generation dehydroactic acid, mother liquor use the dehydroacetic acid in highly basic and in mother liquor, obtained dehydrogenation in solvent toluene Sodium acetate solution prepares sodium dehydroacetate finished product through acid out, alkali soluble, and toluene layer is returned to steam and used, which receives Rate and content are relatively low, and water layer without decolourizing, easily bring into dehydroacetic acid by the by-product in toluenic mother liquor, and later separation is difficult, production Cost is higher.
Existing synthesis technique：
Patent document《A kind of preparation method of pharmaceutical grade dehydroactic acid sodium》The technique of report is：Three second of catalyst will be contained In the solvent benzol of alkene diamines, to be then slowly added to ketene dimer in the case where being stirred continuously, temperature control 50 degree with Interior, the crude product after complete reaction is cooled down, filtered and purified, and crude product is dissolved by heating with sodium carbonate liquor, then using activity Carbon decoloring, is then stirred using hydrochloric acid and neutralizes pH value, then precipitate is dried, adds distilled water in a kettle, is added For hot temperature to 48-52 DEG C, the dehydroactic acid of preparation puts into sodium hydroxide again, and drying is refiltered after reaction, and sodium dehydroacetate is made Finished product, this processing step is complicated, is first prepared into dehydroacetic acid dry product and is prepared into sodium dehydroacetate again, and operability is not strong, and Catalyst is not recyclable, and production cost is higher.
Patent document《A kind of method of membrane filtration manufacture pharmaceutical grade dehydroactic acid sodium》The technique of report is：Second is used first Ethyl acetoacetic acid ethyl ester method is prepared into dehydroacetic acid crude product, then dehydroacetic acid crude product is refined, and the dehydroacetic acid after refining is molten again Xie Hou, dehydroacetic acid sodium solution is prepared into alkaline reaction, then is decolourized to it, membrane filtration after decoloration, then is filtered dry Dry obtained sodium dehydroacetate, this technique is using the yield of ethyl acetoac etate process synthesis dehydroacetic acid compared with ketene dimer It is low, and operating procedure is complicated, is not suitable for industrialized production.
Patent document《A kind of dehydroactic acid sodium/dehydroacetic acid continuous producing method》The technique of report is：Ketene dimer and Toluene-triethylene diamine solution in mass ratio 1：10~25 continuously enter in pipeline reactor controlling reaction temperature at 45~75 DEG C Successive reaction, continuously enters extraction tower after 1.5~3h of residence time；With sodium hydrate aqueous solution continuous extraction, ketene dimer：Hydrogen Sodium oxide molybdena molar ratio=1：0.48~0.55；Water layer enters activated carbon tower continuous stripping, steams water crystallization and obtains the dehydrogenation vinegar of white Sour sodium finished product or water layer neutralize through decoloration acid and obtain white dehydroacetic acid finished product；Gained toluene layer enters continuous extraction water scrubber Water washing recycles toluene, then prepares triethylene diamine rear enclosure in proportion and uses in reaction.This process catalyst is not recyclable, and Organic layer can just be applied mechanically after need to distilling after alkali extraction, and water layer needs activated carbon decolorizing, and production cost is higher.
The content of the invention
Therefore, not recyclable for catalyst in sodium dehydroacetate production process, ketene dimer polymeric by-products are difficult to point From the problems such as, the technical problem to be solved in the present invention is, have developed a kind of use can reuse catalyst, be easily isolated The technique for preparing sodium dehydroacetate of ketene dimer polymeric by-products.
A kind of the technical scheme is that work for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst Skill, includes the following steps：
1) first toluene is squeezed into the ceramic membrane reactor equipped with immobilized AlCl_3 catalyst, open the circulation pump, is then turned on double second Ketenes dnockout pumps, adds ketene dimer in 0.5h~1h, the mass ratio 1 that feeds intake of ketene dimer and toluene:5~15, control Reaction temperature is 50~70 DEG C, reactor pressure control in 0.8~2MPa, catalyst loading for total amount of feeding (catalyst with The mixed solution gross mass of ketene dimer and toluene) 0.5~3wt%；
The solid-carried catalyst is prepared using infusion process, using KOH-NaOH as active component, the mass ratio of KOH and NaOH For 1~3:1, active component is weighed, is configured to 20~30wt% aqueous solutions, carrier Al2O3、SiO2With one kind in ZSM-5, By the carrier impregnation weighed in active component aqueous solution 12-48h, then carry out normal pressure steam water, steam water after at 100~110 DEG C Drying, then 2~5h is roasted at 250~300 DEG C；
2) when reaction solution ketene dimer HPLC contents≤0.5%, polymerisation terminates, and penetrating fluid enters extraction tower hydrogen Aqueous solution of sodium oxide carries out extractive reaction, ketene dimer：Sodium hydroxide molar ratio=1:1~1.5, by dehydroacetic acid sodium solution into Row concentration, is dried at 90~105 DEG C, crushes and product packaging, and obtained sodium dehydroacetate yield is >=99%, product Content >=99.8%.
The technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst according to the present invention, it is preferred that Nanofiltration membrane in the step 1) ceramic membrane reactor is by Al2O3With TiO2It is made, 1~2nm of membrane aperture.
The technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst according to the present invention, it is preferred that The particle size of the carrier is 100~300 mesh.
The technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst according to the present invention, it is preferred that The roasting carries out in Muffle furnace.
The technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst according to the present invention, it is preferred that The ratio that the active component accounts for catalyst gross mass is 5~15%.
Preferably, by the carrier impregnation weighed in active component aqueous solution 20-30h.
The technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst according to the present invention, it is preferred that In step 2), oil reservoir can be directly entered reactor and make solvent use after extraction.Oil reservoir after extraction contains toluene.
The technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst according to the present invention, it is preferred that Sodium hydrate aqueous solution mass concentration described in step 2) is 5~16%.
Present invention is generally directed to catalyst in sodium dehydroacetate production process is not recyclable, ketene dimer polymeric by-products are difficult The problems such as to separate, have developed a kind of technique for preparing sodium dehydroacetate in membrane reactor using immobilized AlCl_3 catalyst.
Membrane reactor principle is that the toluene solution of ketene dimer is circulated through circulating pump in reaction system, first passes through cooler, Enter back into membrane reactor, the pressure in reactor is controlled by pressure-control valve, and under a certain pressure, a part of circulation fluid is from film Pipe oozes out, and is got after penetrating fluid sampling is qualified on the outside of reactor by outlet valve, another part circulation fluid flows out again from control valve It is recycled to through circulating pump in membrane reactor.
For the material of the ceramic membrane reactor of the present invention on reacting without influence, nanofiltration membrane aperture is smaller, can retain macromolecular By-product high polymer, coloured groups, while can retain catalyst, catalyst repeats reaction, reacts detachable anti-after certain batch Device is answered to carry out membrane tube cleaning, activation of catalyst.
The active component of catalyst is inorganic base (potassium hydroxide and sodium hydroxide), and reaction principle is ketene dimer in alkalescence Polycondensation generation dehydroacetic acid is carried out under catalyst action.
Catalyst prepared by the present invention is to load active component over a molecular sieve, and there are soda acid activity for molecular sieve surface Position, has the characteristics that high mechanical strength, heat endurance are good and specific surface area is big, and potassium hydroxide is supported on molecular sieve with sodium hydroxide On, the solid base of certain base strength is can obtain after calcining, the membrane tube of the membrane reactor used in the present invention can efficiently separate Catalyst and the larger high polymer of molecular weight, catalyst can be circulated in membrane reactor always, and conventional basic catalyst exists Difficulty is separated in reaction process, and can act on forming accessory substance with dehydroacetic acid, so catalyst before is unable to Reusability, The active component of catalyst after the present invention is immobilized will not be lost in during the reaction and base strength is uniform, this is because activearm It is to be connected with chemical bond with molecular sieve to divide, and catalyst is reusable after membrane tube separates.
Beneficial effects of the present invention：
The present invention uses immobilized AlCl_3 catalyst, is immobilized on the larger molecular sieve of specific surface area by two kinds of inorganic bases are for composite On, catalyst has higher catalytic activity and reaction selectivity, can greatly improve the reaction yield of ketene dimer dimerization, and And the present invention is reacted using membrane reactor, has efficiently separated catalyst, catalyst can be repeated several times in membrane reactor Use, the coloured high polymer of macromolecular for reacting generation in addition is effectively trapped in membrane reactor, the mother liquor after reaction without into Row decoloration, the toluene layer after extraction can not be handled makees solvent use again, and water layer is effectively reduced and is produced into without decoloration This.
Brief description of the drawings
Fig. 1 is the process flow chart of the present invention.
Embodiment
Embodiment 1：
1) toluene is squeezed into the ceramic membrane reactor equipped with immobilized AlCl_3 catalyst first, open the circulation pump, be then turned on double Ketenes dnockout pumps, adds ketene dimer in 0.5h, the mass ratio 1 that feeds intake of ketene dimer and toluene:5, control reaction temperature Spend for 50 DEG C, in 0.8MPa, catalyst loading is total amount of feeding (catalyst and ketene dimer and toluene for reactor pressure control Mixed solution gross mass) 0.5wt%.The nanofiltration membrane is by Al2O3With TiO2It is made, 1~2nm of membrane aperture；
2) the solid-carried catalyst KOH-NaOH/Al described in step 12O3Prepared using infusion process, using KOH-NaOH as activearm Point, the mass ratio of KOH and NaOH are 1:1, active component is weighed, is configured to 20wt% aqueous solutions, carrier Al2O3, particle diameter is big Small is 100 mesh, and the ratio that active component accounts for catalyst gross mass is 5%, by the carrier impregnation weighed in active component aqueous solution Middle 24h, then carries out normal pressure and steams water, dried after steaming water at 100 DEG C, then carry out roasting 2h at 250 DEG C in Muffle furnace.
2) reaction solution ketene dimer HPLC content≤0.5%, polymerisation terminate, and penetrating fluid is extracted into extraction tower Reaction, ketene dimer：Sodium hydroxide molar ratio=1:1, sodium hydrate aqueous solution mass concentration is 5%, and oil reservoir can be straight after extraction Tap into and make solvent use into reactor, dehydroacetic acid sodium solution is concentrated, be dried, crush and product bag at 90 DEG C Dress, obtained sodium dehydroacetate yield are 99.2%, product content 99.8%.
Embodiment 2：
1) toluene is squeezed into the ceramic membrane reactor equipped with immobilized AlCl_3 catalyst first, open the circulation pump, be then turned on double Ketenes dnockout pumps, adds ketene dimer in 1h, the mass ratio 1 that feeds intake of ketene dimer and toluene:10, controlling reaction temperature For 60 DEG C, reactor pressure control in 1MPa, catalyst loading for total amount of feeding (catalyst and ketene dimer and toluene it is mixed Close solution gross mass) 0.5wt%.The nanofiltration membrane is by Al2O3With TiO2It is made, 1~2nm of membrane aperture；
2) the solid-carried catalyst KOH-NaOH/SiO described in step 12Prepared using infusion process, using KOH-NaOH as activearm Point, the mass ratio of KOH and NaOH are 2:1, active component is weighed, is configured to 25wt% aqueous solutions, carrier SiO2, particle size For 200 mesh, the ratio that active component accounts for catalyst gross mass is 10%, by the carrier impregnation weighed in active component aqueous solution 24h, then carries out normal pressure and steams water, dried after steaming water at 105 DEG C, then carry out roasting 3h at 280 DEG C in Muffle furnace.
3) when reaction solution ketene dimer HPLC contents≤0.5%, polymerisation terminates, and penetrating fluid is carried out into extraction tower Extractive reaction, ketene dimer：Sodium hydroxide molar ratio=1:1.2, sodium hydrate aqueous solution mass concentration is 10%, oily after extraction Layer can be directly entered reactor and make solvent use, and dehydroacetic acid sodium solution is concentrated, is dried, crushes at 100 DEG C And product packaging, obtained sodium dehydroacetate yield are 99.4%, product content 99.9%.
Embodiment 3：
1) toluene is squeezed into the ceramic membrane reactor equipped with immobilized AlCl_3 catalyst first, open the circulation pump, be then turned on double Ketenes dnockout pumps, adds ketene dimer in 1h, the mass ratio 1 that feeds intake of ketene dimer and toluene:15, controlling reaction temperature For 70 DEG C, reactor pressure control in 2MPa, catalyst loading for total amount of feeding (catalyst and ketene dimer and toluene it is mixed Close solution gross mass) 3wt%.The nanofiltration membrane is by Al2O3With TiO2It is made, 1~2nm of membrane aperture；
2) the solid-carried catalyst KOH-NaOH/ZSM-5 described in step 1 is prepared using infusion process, using KOH-NaOH as activity The mass ratio of component, KOH and NaOH are 3:1, active component is weighed, is configured to 30wt% aqueous solutions, carrier ZSM-5, particle diameter Size is 300 mesh, and the ratio that active component accounts for catalyst gross mass is 15%, and the carrier impregnation weighed is water-soluble in active component 24h in liquid, then carries out normal pressure and steams water, dried after steaming water at 110 DEG C, then carry out roasting 5h at 300 DEG C in Muffle furnace.
3) when reaction solution ketene dimer HPLC contents≤0.5%, polymerisation terminates, and penetrating fluid is carried out into extraction tower Extractive reaction, ketene dimer：Sodium hydroxide molar ratio=1:1.5, sodium hydrate aqueous solution mass concentration is 16%, oily after extraction Layer can be directly entered reactor and make solvent use, and dehydroacetic acid sodium solution is concentrated, is dried, crushes at 105 DEG C And product packaging, obtained sodium dehydroacetate yield are 99.3%, product content 99.8%.
The present invention have studied a kind of technique for preparing sodium dehydroacetate in membrane reactor using immobilized AlCl_3 catalyst, double second Ketenes carries out polymerisation with toluene in the membrane reactor equipped with immobilized AlCl_3 catalyst, reacts the coloured high polymer of macromolecular of generation Effectively it is trapped in membrane reactor, the mother liquor after reaction need not decolourize, and the toluene layer after extraction can not be handled to be made again Solvent uses, and water layer effectively reduces production cost, reduce quantity of three wastes in production, obtained dehydroacetic acid without decoloration Sodium yield is >=99%, product content >=99.8%.

Claims (8)

  1. A kind of 1. technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is characterised in that：Including as follows Step：
    1) first toluene is squeezed into the ceramic membrane reactor equipped with immobilized AlCl_3 catalyst, open the circulation pump, is then turned on ketene dimer Dnockout pumps, adds ketene dimer in 0.5h~1h, the mass ratio 1 that feeds intake of ketene dimer and toluene:5~15, control reaction Temperature is 50~70 DEG C, and in 0.8~2MPa, catalyst loading is total amount of feeding (catalyst and double second for reactor pressure control The mixed solution gross mass of ketenes and toluene) 0.5~3wt%；
    The solid-carried catalyst is prepared using infusion process, and using KOH-NaOH as active component, the mass ratio of KOH and NaOH are 1 ~3:1, active component is weighed, is configured to 20~30wt% aqueous solutions, carrier Al2O3、SiO2With one kind in ZSM-5, will claim The carrier impregnation taken 12-48h in active component aqueous solution, then carries out normal pressure and steams water, dried after steaming water at 100~110 DEG C, 2~5h is roasted at 250~300 DEG C again；
    2) when reaction solution ketene dimer HPLC contents≤0.5%, polymerisation terminates, and penetrating fluid enters extraction tower hydroxide Sodium water solution carries out extractive reaction, ketene dimer：Sodium hydroxide molar ratio=1:1~1.5, dehydroacetic acid sodium solution is carried out dense Contracting, is dried at 90~105 DEG C, crushes and product packaging, and obtained sodium dehydroacetate yield is >=99%, product content >=99.8%.
  2. 2. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is special Sign is：Nanofiltration membrane in the step 1) ceramic membrane reactor is by Al2O3With TiO2It is made, 1~2nm of membrane aperture.
  3. 3. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is special Sign is：The particle size of the carrier is 100~300 mesh.
  4. 4. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is special Sign is：The roasting carries out in Muffle furnace.
  5. 5. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is special Sign is：The ratio that the active component accounts for catalyst gross mass is 5~15%.
  6. 6. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is special Sign is：By the carrier impregnation weighed in active component aqueous solution 20-30h.
  7. 7. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is special Sign is：In step 2), oil reservoir can be directly entered reactor and make solvent use after extraction.
  8. 8. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is special Sign is：Sodium hydrate aqueous solution mass concentration described in step 2) is 5~16%.
CN201711288432.7A 2017-12-07 2017-12-07 A kind of technique preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst Active CN107987045B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113454056A (en) * 2021-05-28 2021-09-28 安徽金禾实业股份有限公司 Preparation method of acetoacetamide-N-sulfonic acid triethylamine salt

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558124A (en) * 2011-12-23 2012-07-11 蚌埠丰原医药科技发展有限公司 Method for preparing food-grade sodium dehydroacetate
CN105384714A (en) * 2015-12-18 2016-03-09 南京工业大学 Decolorization and purification technology for sodium dehydroacetate
CN106478573A (en) * 2016-08-26 2017-03-08 南通奥凯生物技术开发有限公司 A kind of preparation method of pharmaceutical grade dehydroactic acid sodium
CN106588843A (en) * 2016-12-08 2017-04-26 南通醋酸化工股份有限公司 Continuous production method of sodium dehydroacetate/dehydroacetic acid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102558124A (en) * 2011-12-23 2012-07-11 蚌埠丰原医药科技发展有限公司 Method for preparing food-grade sodium dehydroacetate
CN105384714A (en) * 2015-12-18 2016-03-09 南京工业大学 Decolorization and purification technology for sodium dehydroacetate
CN106478573A (en) * 2016-08-26 2017-03-08 南通奥凯生物技术开发有限公司 A kind of preparation method of pharmaceutical grade dehydroactic acid sodium
CN106588843A (en) * 2016-12-08 2017-04-26 南通醋酸化工股份有限公司 Continuous production method of sodium dehydroacetate/dehydroacetic acid

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
何丹丹 等: "固体碱催化合成脱氢乙酸", 《化工进展》 *
曾琦斐: "负载型固体碱NaF/NaX的制取及其在DHA制备中的应用", 《北华大学学报(自然科学版)》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113454056A (en) * 2021-05-28 2021-09-28 安徽金禾实业股份有限公司 Preparation method of acetoacetamide-N-sulfonic acid triethylamine salt

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