CN107987045B - A kind of technique preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst - Google Patents

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

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CN107987045B
CN107987045B CN201711288432.7A CN201711288432A CN107987045B CN 107987045 B CN107987045 B CN 107987045B CN 201711288432 A CN201711288432 A CN 201711288432A CN 107987045 B CN107987045 B CN 107987045B
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catalyst
membrane reactor
sodium dehydroacetate
ketene dimer
immobilized alcl
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CN107987045A (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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    • 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)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

The invention discloses a kind of techniques 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, mass ratio 1:5~15 that feed intake of ketene dimer and toluene, controlling reaction temperature is 50~70 DEG C, 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 content≤0.5%, polymerization reaction terminates, penetrating fluid enters extraction tower and carries out extraction reaction with sodium hydrate aqueous solution, ketene dimer: sodium hydroxide molar ratio=1:1~1.5, dehydroacetic acid sodium solution is concentrated, it is dried, crushes and product packaging at 90~105 DEG C, sodium dehydroacetate yield obtained is >=99%, product content >=99.8%.The present invention effectively reduces production cost, reduces quantity of three wastes in production, sodium dehydroacetate high income obtained.

Description

A kind of technique preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst
Technical field
The present invention relates to chemical technology fields, and in particular to a kind of preparation process of sodium dehydroacetate.
Background technique
Sodium dehydroacetate
Appearance characteristics: white crystalline powder.
Dissolubility: it is dissolved in water (25 DEG C of solubility 33g/100g), is insoluble in the organic solvents such as ethyl alcohol.
Molecular weight: 191.1
Fusing point: 110 DEG C
Purposes:
Food preservative, antistaling agent.The product has stronger antibacterial work to the saccharomycete in food, spoilage organisms, mould 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 technology:
The conventional production process industrially produced at present are as follows: ketene dimer is made in catalyst triethylene diamine, catechol Under, condensation generates dehydroactic acid in solvent toluene, and mother liquor is using the dehydroacetic acid in highly basic and in mother liquor, obtained dehydrogenation Sodium acetate solution prepares sodium dehydroacetate finished product through acid out, alkali soluble, and toluene layer is returned to steam and be used, which receives Rate and content are lower, and water layer without decolourizing, easily bring into dehydroacetic acid by the by-product in toluenic mother liquor, and later separation is difficult, production Higher cost.
Existing synthesis technology:
The technique of patent document " a kind of preparation method of pharmaceutical grade dehydroactic acid sodium " report are as follows: 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 reacting completely is cooled down, filtered and is purified, and crude product is dissolved by heating with sodium carbonate liquor, then using activity Then carbon decoloring neutralizes pH value using hydrochloric acid stirring, is then dried to precipitate, distilled water is added in a kettle, add For hot temperature to 48-52 DEG C, the dehydroactic acid of preparation puts into sodium hydroxide again, refilters drying 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 not can be recycled, and production cost is higher.
The technique of patent document " a kind of method of film filtering manufacture pharmaceutical grade dehydroactic acid sodium " report are as follows: use second first Ethyl acetoacetic acid ethyl ester method is prepared into dehydroacetic acid crude product, then refines to dehydroacetic acid crude product, and the dehydroacetic acid after purification is molten again Xie Hou is prepared into dehydroacetic acid sodium solution with alkaline reaction, then decolourizes to it, decoloration caudacoria filtering, 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 " report technique are as follows: ketene dimer and Toluene-triethylene diamine solution 1:10~25 in mass ratio, which continuously enter, controls reaction temperature at 45~75 DEG C in pipeline reactor 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, which are neutralized through decoloration with acid, obtains 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 not can be recycled, and Organic layer can just be applied after need to distilling after alkali extraction, and water layer needs active carbon decoloring, and production cost is higher.
Summary of the invention
Therefore, it not can be recycled 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 that, catalyst can be reused, be easily isolated by having developed a kind of use The technique for preparing sodium dehydroacetate of ketene dimer polymeric by-products.
The technical scheme is that a kind of 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, opens circulating pump, be then turned on double second Ketenes dnockout pumps, add ketene dimer in 0.5h~1h, mass ratio 1:5~15 that feed intake of ketene dimer and toluene, control Reaction temperature is 50~70 DEG C, reactor pressure control in 0.8~2MPa, catalyst loading be 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 solution, carrier Al2O3、SiO2One of with ZSM-5, By weighed carrier impregnation 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 content≤0.5%, polymerization reaction terminates, and penetrating fluid enters extraction tower hydrogen Aqueous solution of sodium oxide carries out extraction 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 sodium dehydroacetate yield obtained is >=99%, product Content >=99.8%.
The technique according to the present invention for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, 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 according to the present invention for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is preferred that The particle size of the carrier is 100~300 mesh.
The technique according to the present invention for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is preferred that The roasting carries out in Muffle furnace.
The technique according to the present invention for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is preferred that The ratio that the active component accounts for catalyst gross mass is 5~15%.
Preferably, by weighed carrier impregnation in active component aqueous solution 20-30h.
The technique according to the present invention for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, it is preferred that In step 2), oil reservoir can be directly entered reactor and make solvent use after extraction.Oil reservoir extracted is containing toluene.
The technique according to the present invention for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, 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 not can be recycled, and ketene dimer polymeric by-products are difficult The problems such as to separate, has 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 recycled through circulating pump in reaction system, first passes through cooler, It enters 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 exudation is got on the outside of reactor by outlet valve after penetrating fluid sampling is qualified, and another part circulation fluid flows out again from control valve It is recycled in membrane reactor through circulating pump.
For the material of ceramic membrane reactor of the invention on reaction without influence, nanofiltration membrane aperture is smaller, can retain macromolecular By-product high polymer, coloured groups, while can retain catalyst, the repeatable reaction of catalyst react 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 alkalinity Polycondensation is carried out under catalyst action generates dehydroacetic acid.
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, thermal stability are good and large specific surface area, potassium hydroxide and sodium hydroxide are supported on molecular sieve On, the solid base of certain base strength can be obtained after calcining, the membrane tube of the membrane reactor used in the present invention can efficiently separate Catalyst and the biggish high polymer of molecular weight, catalyst can circulate in membrane reactor always, and previous basic catalyst exists Difficulty is separated in reaction process, and can act on forming by-product 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 during the reaction and base strength is uniform, this is because active group Dividing is to be connected with chemical bond with molecular sieve, and catalyst is reusable after membrane tube separates.
Beneficial effects of the present invention:
The present invention uses immobilized AlCl_3 catalyst, and two kinds of inorganic bases are carried out compound to be immobilized on the biggish molecular sieve of specific surface area On, catalyst catalytic activity with higher 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 furthermore reacting generation is effectively trapped in membrane reactor, the mother liquor after reaction be not necessarily into Row decoloration, toluene layer extracted can not be handled makees solvent use again, and water layer is effectively reduced and is produced into without decoloration This.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1:
1) toluene is squeezed into the ceramic membrane reactor equipped with immobilized AlCl_3 catalyst first, opens circulating pump, be then turned on double Ketenes dnockout pumps, add ketene dimer in 0.5h, the mass ratio 1:5 that feeds intake of ketene dimer and toluene, control reaction temperature Degree is 50 DEG C, and 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 12O3It is prepared using infusion process, using KOH-NaOH as active group Point, the mass ratio of KOH and NaOH is 1:1, weighs active component, is configured to 20wt% aqueous solution, and carrier Al2O3, partial size is big Small is 100 mesh, and the ratio that active component accounts for catalyst gross mass is 5%, by weighed carrier impregnation in active component aqueous solution In for 24 hours, then carry out normal pressure and steam 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%, polymerization reaction terminate, and penetrating fluid enters extraction tower and extracted Reaction, ketene dimer: sodium hydroxide molar ratio=1:1, sodium hydrate aqueous solution mass concentration are 5%, and oil reservoir can be straight after extraction It taps into and makees solvent use into reactor, dehydroacetic acid sodium solution is concentrated, be dried, crush and product packet at 90 DEG C Dress, sodium dehydroacetate yield obtained 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, opens circulating pump, be then turned on double Ketenes dnockout pumps, add ketene dimer in 1h, the mass ratio 1:10 that feeds intake of ketene dimer and toluene, control reaction temperature Be 60 DEG C, reactor pressure control in 1MPa, catalyst loading be 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 12It is prepared using infusion process, using KOH-NaOH as active group Point, the mass ratio of KOH and NaOH are 2:1, weigh active component, are configured to 25wt% aqueous solution, carrier SiO2, particle size For 200 mesh, the ratio that active component accounts for catalyst gross mass is 10%, by weighed carrier impregnation in active component aqueous solution For 24 hours, it 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 content≤0.5%, polymerization reaction terminates, and penetrating fluid enters extraction tower progress Extraction 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, sodium dehydroacetate yield obtained 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, opens circulating pump, be then turned on double Ketenes dnockout pumps, add ketene dimer in 1h, the mass ratio 1:15 that feeds intake of ketene dimer and toluene, control reaction temperature Be 70 DEG C, reactor pressure control in 2MPa, catalyst loading be 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, is activity with KOH-NaOH The mass ratio of component, KOH and NaOH are 3:1, weigh active component, are configured to 30wt% aqueous solution, carrier ZSM-5, partial size Size is 300 mesh, and the ratio that active component accounts for catalyst gross mass is 15%, and weighed carrier impregnation is water-soluble in active component In liquid for 24 hours, it 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 content≤0.5%, polymerization reaction terminates, and penetrating fluid enters extraction tower progress Extraction 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, sodium dehydroacetate yield obtained are 99.3%, product content 99.8%.
The present invention has studied a kind of technique for preparing sodium dehydroacetate in membrane reactor using immobilized AlCl_3 catalyst, double second Ketenes and toluene react the coloured high polymer of macromolecular of generation in the membrane reactor progress polymerization reaction equipped with immobilized AlCl_3 catalyst It is effectively trapped in membrane reactor, without decolourizing, toluene layer extracted can not be handled to be made the mother liquor after reaction again Solvent uses, and water layer effectively reduces production cost without decoloration, reduces quantity of three wastes in production, dehydroacetic acid obtained Sodium yield is >=99%, product content >=99.8%.

Claims (8)

1. a kind of 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, opens circulating pump, is then turned on ketene dimer Dnockout pumps add ketene dimer in 0.5h~1h, mass ratio 1:5~15 that feed intake of ketene dimer and toluene, control 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, and using KOH-NaOH as active component, the mass ratio of KOH and NaOH are 1 ~3:1, weighs active component, is configured to 20~30wt% aqueous solution, carrier Al2O3、SiO2One of with ZSM-5, will claim Then the carrier impregnation taken 12-48h in active component aqueous solution carries out normal pressure and steams water, dries 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 content≤0.5%, polymerization reaction terminates, and penetrating fluid enters extraction tower hydroxide Sodium water solution carries out extraction 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 sodium dehydroacetate yield obtained is >=99%, product content >=99.8%.
2. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, special Sign is: the nanofiltration membrane in the step 1) ceramic membrane reactor is by Al2O3With TiO2It is made, 1~2nm of membrane aperture.
3. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, special Sign is: the particle size of the carrier is 100~300 mesh.
4. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, special Sign is: the roasting carries out in Muffle furnace.
5. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, special Sign is: the ratio that the active component accounts for catalyst gross mass is 5~15%.
6. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, special Sign is: by weighed carrier impregnation in active component aqueous solution 20-30h.
7. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, special Sign is: in step 2), oil reservoir can be directly entered reactor and make solvent use after extraction.
8. the technique according to claim 1 for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst, special Sign is: sodium hydrate aqueous solution mass concentration described in step 2) is 5~16%.
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