CN105384714A - Decolorization and purification technology for sodium dehydroacetate - Google Patents
Decolorization and purification technology for sodium dehydroacetate Download PDFInfo
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- CN105384714A CN105384714A CN201510968041.4A CN201510968041A CN105384714A CN 105384714 A CN105384714 A CN 105384714A CN 201510968041 A CN201510968041 A CN 201510968041A CN 105384714 A CN105384714 A CN 105384714A
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- 239000004288 Sodium dehydroacetate Substances 0.000 title claims abstract description 42
- 229940079839 sodium dehydroacetate Drugs 0.000 title claims abstract description 42
- 235000019259 sodium dehydroacetate Nutrition 0.000 title claims abstract description 42
- DSOWAKKSGYUMTF-GZOLSCHFSA-M sodium;(1e)-1-(6-methyl-2,4-dioxopyran-3-ylidene)ethanolate Chemical compound [Na+].C\C([O-])=C1/C(=O)OC(C)=CC1=O DSOWAKKSGYUMTF-GZOLSCHFSA-M 0.000 title claims abstract description 42
- 238000005516 engineering process Methods 0.000 title claims abstract description 25
- 238000004042 decolorization Methods 0.000 title abstract description 7
- 238000000746 purification Methods 0.000 title abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 55
- 230000008025 crystallization Effects 0.000 claims abstract description 52
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 38
- 239000013078 crystal Substances 0.000 claims abstract description 31
- 238000001728 nano-filtration Methods 0.000 claims abstract description 30
- 239000000047 product Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000004287 Dehydroacetic acid Substances 0.000 claims abstract description 19
- 229940061632 dehydroacetic acid Drugs 0.000 claims abstract description 19
- 235000019258 dehydroacetic acid Nutrition 0.000 claims abstract description 19
- JEQRBTDTEKWZBW-UHFFFAOYSA-N dehydroacetic acid Chemical compound CC(=O)C1=C(O)OC(C)=CC1=O JEQRBTDTEKWZBW-UHFFFAOYSA-N 0.000 claims abstract description 19
- PGRHXDWITVMQBC-UHFFFAOYSA-N dehydroacetic acid Natural products CC(=O)C1C(=O)OC(C)=CC1=O PGRHXDWITVMQBC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims abstract description 8
- 239000012043 crude product Substances 0.000 claims abstract description 8
- 238000010828 elution Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 35
- YIOCQGHBBNGBND-UHFFFAOYSA-N sodium;3-acetyl-6-methylpyran-3-ide-2,4-dione Chemical compound [Na+].CC(=O)[C-]1C(=O)C=C(C)OC1=O YIOCQGHBBNGBND-UHFFFAOYSA-N 0.000 claims description 17
- 239000012530 fluid Substances 0.000 claims description 8
- 230000000149 penetrating effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 230000008033 biological extinction Effects 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000011026 diafiltration Methods 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000012466 permeate Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000011084 recovery Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- 239000000049 pigment Substances 0.000 description 12
- 230000008901 benefit Effects 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 2
- -1 highly basic Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- OGNSCSPNOLGXSM-UHFFFAOYSA-N (+/-)-DABA Natural products NCCC(N)C(O)=O OGNSCSPNOLGXSM-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003260 anti-sepsis Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000012407 engineering method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229960003692 gamma aminobutyric acid Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
Abstract
The invention relates to a decolorization and purification technology for sodium dehydroacetate. The decolorization and purification technology includes the steps that with a dehydroacetic acid crude product as the raw material, synthesis of sodium dehydroacetate is performed; after a reaction is finished, the material enters a ceramic nanofiltration membrane decolorization device in a heat-preserved state, and a permeation side solution enters a crystallization kettle for cooling crystallization; a concentration side solution enters a ceramic nanofiltration membrane elution device, hot deionized water is added to elute a product, and evaporative crystallization is performed; crystals are dehydrated, washed, dried, smashed and packaged to form the product. The purity of the product reaches 99.9%, and the recovery rate of sodium dehydroacetate reaches up to 99% or above in the whole process. By adopting the ceramic nanofiltration membrane decolorization and purification technology, product quality can be obviously improved, operation intensity can be relieved, a field operation environment can be improved, and production cost can be reduced.
Description
Technical field
The present invention relates to a kind of sodium dehydroacetate decolor refined technology, particularly relate to a kind of decolor refined technology of the sodium dehydroacetate based on nanofiltration membrane separation technique, belong to Field of Fine Chemicals.
Background technology
Sodium dehydroacetate is a kind of Novel safe food, feedstuff mildew antisepsis antistaling agent.It can the growth of mould fungus inhibition and bacterium effectively, contributes to the stability improving product, greatly extends the shelf lives of product.Under normal temperature, sodium dehydroacetate is white crystalline powder, and its molecular formula is C
8h
7naO
4h
2o, molecular weight is 208.15, soluble in water, the impact of acid and alkali basicity, and fast light, thermotolerance is better, is therefore used widely.
The method that dehydro-acetic acid process for producing sodium adopts is: the synthesis of (1) dehydro-acetic acid.Under inert solvent and catalyzer existent condition, there are two molecule aggregation reactions by diketene, generate dehydro-acetic acid, because the solubleness of dehydro-acetic acid in water is lower, can filter reaction solution after cooling, the dehydro-acetic acid of separating out is washed and filtered and can obtain dehydro-acetic acid; (2) preparation of sodium dehydroacetate.Add dehydro-acetic acid, water and the sodium hydroxide etc. that prepare in a kettle., dehydro-acetic acid and sodium hydroxide generation neutralization reaction, generate sodium dehydroacetate, its principle be dehydro-acetic acid with sodium hydroxide in generate sodium dehydroacetate, reaction formula is:
(3) sodium dehydroacetate is refining.After complete reaction, add the gac of about 5% in a kettle., and with pressure filter, gac is separated by the mode of filtering while hot; Filtrate crystallisation, washing, drying obtain the finished product.
In process of production, synthesis dehydro-acetic acid is often with the generation of side reaction, and ketene dimer at high temperature inevitably occurs high poly-, and the higher color of the polymerization degree is darker.Therefore pigment is carried secretly in the finished product, has had a strong impact on the color and luster of product, has reduced the quality of product.In industry, the normal gac that adopts decolours, but still there are some problems: (1) decolorizing effect is poor, and percent of decolourization is not high; (2) also cause portioned product to run off while charcoal absorption pigment and affect economic benefit; (3) tiny activated carbon granule is separated not exclusively then can enter product, causes quality product to decline; (4), after charcoal absorption pigment impurity, regeneration difficulty, aftertreatment can improve production cost further.(5) use of Powdered Activated Carbon can cause workshop airborne dust large, and operating environment is poor, is harmful to the person.
Ceramic Membranes Separating Technique is a new and effective isolation technique, compared with traditional isolation technique, has the advantages such as separation efficiency is high, energy consumption is low, operation is relatively simple, is widely used in fields such as food, medicine, environmental protection.Ceramic membrane due to its main material be metal oxide, have resistance to strong acid, highly basic, organic solvent, the advantages such as thermo-chemical stability is high, will without the need to lowering the temperature to material and regulating pH in use procedure, significantly reduce the addition of energy consumption in production process and auxiliary material, have using value.In material, the molecular weight of sodium dehydroacetate is 190.15, and the molecular weight of pigment molecular is generally at 500-1000Da, by selecting the ceramic membrane in suitable aperture then effectively can to retain pigment in system, and then reaches the effect to the decolouring of dehydro-acetic acid sodium solution.Nanofiltration membrane decolouring technology is applied in sodium dehydroacetate decolor refined technology the yield that greatly can reduce production cost and raising sodium dehydroacetate in industry, remarkable in economical benefits.
Chinese patent (CN201110151741.6) discloses a kind of method utilizing enzyme engineering method to produce γ-aminobutyric acid, adopts rolling organic membrane to decolour to material, can remove most of organic pigment in material, reach the object of purification.Chinese patent (CN103667383A) discloses a kind of preparation method of L-glutaminate, adopt the organic pigment in nanofiltration membrane technology removing feed liquid and small organic molecule, organic impurity in feed liquid is reduced greatly, improve the transmittance of feed liquid, reduce the consumption of gac.Nanofiltration membrane has had more application in the decolorizing and refining of Chemicals, nanofiltration membrane is compared to organic nanofiltration membrane, it is high that it has physical strength, the advantages such as chemical stability is good, high temperature resistant, high pressure, are particularly suitable for severe rugged environment as systems such as high temperature, high pressure, strong acid and strong base, high saliferous, organic solvents.Chinese patent (CN102219770A) discloses a kind of manufacture method of high purity sodium dehydroacetate, first add activated carbon decolorizing, " laminar nano film " is adopted to concentrate active substance for the solution after decolouring again, but Chinese patent (CN103788041A) thinks employing this method, and product purity does not still reach requirement.Meanwhile, it is not enough also to there are three aspects in the method: the first, does not replace the use of gac, and what mainly play decolorization is charcoal absorption, and film just eliminates gac; The second, gac fail remove pigment composition, " laminar nano level film " be also difficult to remove.3rd, charcoal absorption pigment has also taken away portioned product simultaneously, have impact on economic benefit.The present invention directly adopts nanofiltration membrane to decolour to reaction feed liquid, has got rid of the use of gac, has decreased processing step.Product purity is high, and the rate of recovery is high, creates huge economic benefit.
Summary of the invention
The object of the invention is to run off to solve product existing in dehydro-acetic acid process for producing sodium, operating environment is poor, the problems such as labour intensity is high, propose a kind of decolor refined technology of the sodium dehydroacetate based on nanofiltration membrane separation technique, effectively the pigment impurity in synthesis material liquid can be removed, and reclaim sodium dehydroacetate, environmental pollution is reduced while obtaining high-quality product, save energy, improves operating environment, reduces the novel sodium dehydroacetate decolor refined technology of production cost.
Technical scheme of the present invention is as follows: a kind of decolor refined technology of sodium dehydroacetate, and its concrete steps are as follows:
(1) synthesis of sodium dehydroacetate: dehydro-acetic acid crude product and water are added in reactor, under whipped state, add sodium hydroxide solution, control pH is alkalescence, after in groove to be batched, sodium hydroxide solution adds, be warming up to 80-90 DEG C, and continue stirring reaction in this case;
(2) decolouring of dehydro-acetic acid sodium water solution: the mass transport of reaction is concentrated to nanofiltration membrane decoloration device, penetrating fluid enters crystallization kettle crystallisation by cooling, concentrated solution is concentrated further after all returning and mixing with stoste, is collected by concentrated solution after concentration process terminates;
(3) wash-out of sodium dehydroacetate: the concentrated solution of collection is delivered in nanofiltration membrane percolating device, by adding the deionized water of heat by product wash-out out, per-meate side solution enters crystallization kettle evaporative crystallization;
(4) after crystallization, dehydro-acetic acid sodium crystal is through dehydration, oven dry, pulverizing, and packaging becomes the finished product.
The mass ratio of the dehydro-acetic acid crude product described in preferred above-mentioned steps (1) and water is 1:(1-1.5); Sodium hydroxide solution mass concentration is 10%-30%; Described pH is 8-10; In whole process, stir speed (S.S.) is 100-300rpm; Continue stirring reaction 0.5-2h.
Preferred above-mentioned steps (2) and the nanofiltration membrane described in step (3) are porous ceramic film; The configuration of film is chip, one of single passage tubular type or hyperchannel tubular type are planted; The material of film is ZrO
2, TiO
2or Al
2o
3in the matrix material of one or more; The molecular weight cut-off of film is 200-400Da.
The decoloration process of the dehydro-acetic acid sodium water solution described in preferred steps (2) adopts the mode of recycle to extinction cross flow filter, cycles of concentration to be 1-10 times; Working pressure is 0.5-3.0MPa; Temperature is 20-90 DEG C; Crossflow velocity is 0.5-5m/s.More preferably the cycles of concentration of decoloration process is 5-10 times; Working pressure the best is 0.5-1.5MPa; Temperature the best is 80-90 DEG C; Crossflow velocity the best is 3-5m/s.
Cooling and crystallizing process in preferred steps (2), its stirring intensity initial stage is 100-300rpm, first be chilled to 50-55 DEG C in advance, after having crystal to separate out, growing the grain 30-60min, stirring intensity reduces to 50-100rpm, then drops to 15-20 DEG C with 0.2-0.5 DEG C/min rate of temperature fall, when presenting starchiness in crystallization kettle crystallization terminate and suction filtration obtain dehydro-acetic acid sodium crystal.
The elution processes of the sodium dehydroacetate in preferred steps (3) adopts the mode of continuous countercurrent diafiltration, and the temperature of deionized water is 80-90 DEG C; The addition of deionized water and the concentrated solution mass ratio of collection are 1:(1-5); Working pressure is 0.5-3.0MPa; Temperature is 25-90 DEG C; Crossflow velocity is 0.5-5m/s.The working pressure of the elution processes of the sodium dehydroacetate more preferably in step (3) is 0.5-1.5MPa; Temperature the best is 80-90 DEG C; Crossflow velocity the best is 3-5m/s.
Evaporative crystallization technique in preferred steps (3), its evaporative crystallization temperature controls at 50-55 DEG C, the stirring intensity initial stage is 100-300rpm, crystal seed is added in time having crystal to separate out, stirring intensity reduces to 50-100rpm, crystal seed is pure dehydro-acetic acid sodium crystal, and the addition of crystal seed is 1% ~ 2% of sodium dehydroacetate quality in evaporative crystallization liquid; Simultaneously drop to 15-20 DEG C with 0.2-0.5 DEG C/min rate of temperature fall, when presenting starchiness in crystallization kettle, crystallization terminates and suction filtration obtains dehydro-acetic acid sodium crystal.
Described bake out temperature in preferred steps (4) controls at 90-105 DEG C, and drying time is 2-3h.
Adopt aforesaid method, can obtain the sodium dehydroacetate product refined, its purity reaches 99.9%, and in whole process the rate of recovery of sodium dehydroacetate up to more than 99%.
Beneficial effect:
A kind of sodium dehydroacetate decolor refined technology based on nanofiltration membrane separation technique that the present invention proposes, sodium dehydroacetate can be synthesized pigment impurity etc. in material and sodium dehydroacetate crystalline mother solution to remove, and the rate of recovery of sodium dehydroacetate is up to more than 99% in whole process, the sodium dehydroacetate product of high-quality can be obtained.
Accompanying drawing explanation
Fig. 1 is present invention process schema;
Fig. 2 is the decoloration process schema of embodiment 1;
Fig. 3 is the elution processes schema of embodiment 2;
Fig. 4 is the decoloration process schema of embodiment 1;
Fig. 5 is the elution processes schema of embodiment 2.
Embodiment
Below in conjunction with accompanying drawing embodiment, the present invention is further elaborated, it will be appreciated by those skilled in the art that described embodiment is only for example, and any restriction is not formed to the present invention.Present invention process schema as shown in Figure 1.
Embodiment 1:
(1) in reactor, drop into the dehydro-acetic acid crude product 1000g of 1000g deionized water and massfraction about 95%, open and stir, adjustment stirring intensity is 100rpm, and slowly drip the aqueous sodium hydroxide solution 1250g that massfraction is 18%, after sodium hydroxide solution dropwises in groove to be batched, open steam jacket, progressively be warming up to 90 DEG C, and stir 1h at this temperature, now recording pH value of solution is 8.1, and transmittance is 50%;
(2) the sodium dehydroacetate synthesis material upper step obtained is delivered to nanofiltration membrane decoloration device (as shown in Figure 2), adopts molecular weight cut-off to be the ZrO of 200Da
2chip nanofiltration membrane, red-tape operati pressure is 1MPa, and system running temperature is 90 DEG C, and crossflow velocity is 3m/s, pigment impurity in material etc. is concentrated 5 times, obtains penetrating fluid 2600g, concentrated solution 650g.Be input to by penetrating fluid in crystallization kettle, control stirring intensity is 200rpm, is chilled to 50 DEG C in advance, after having crystal to separate out, growing the grain 30min, stirring intensity reduces to 50rpm, drop to 20 DEG C with 0.2 DEG C/min rate of temperature fall again, when becoming starchiness in crystallization kettle, crystallization terminates.Open crystallization kettle bottom valve, material is put into suction filter, open vacuum pump, until mother liquor is drained;
(3) the concentrated solution 650g that upper step obtains is delivered to nanofiltration membrane percolating device (as shown in Figure 3), adopts molecular weight cut-off to be the TiO of 300Da
2single passage nanofiltration membrane, red-tape operati pressure is 0.5MPa, system running temperature is 90 DEG C, crossflow velocity is 4m/s, impeller pump remains a constant speed and add 90 DEG C of deionized water 650g in head tank, reclaim in membrane permeation side and obtain dehydro-acetic acid sodium solution 650g, and be input in crystallization kettle, controlling evaporative crystallization temperature controls at 50 DEG C, and the stirring intensity initial stage is 200rpm, adds 1% crystal seed in time having crystal to separate out, stirring intensity reduces to 50rpm, drop to 20 DEG C with 0.3 DEG C/min rate of temperature fall again, when becoming starchiness in observation crystallization kettle, crystallization terminates.Open crystallization kettle bottom valve, material is put into suction filter, open vacuum pump, until mother liquor is drained;
(4) crystal that obtains in step (2) and step (3) is put into supercentrifuge dehydration, dry 3h under the hot blast of 90 DEG C, pulverize, be packaged into the finished product.In product, moisture is 8.8%, high purity 99.88%, the rate of recovery 98.85%.
Embodiment 2:
(1) in reactor, drop into the dehydro-acetic acid crude product 1000g of 1200g deionized water and massfraction about 92.5%, open and stir, adjustment stirring intensity is 200rpm, and slowly drip the aqueous sodium hydroxide solution 1050g that massfraction is 23%, in groove to be batched, sodium hydroxide solution dropwises rear unlatching steam jacket, is progressively warming up to 85 DEG C, and stirs 1.5h at this temperature, now recording pH value of solution is 9.2, and transmittance is 41%;
(2) the sodium dehydroacetate synthesis material upper step obtained is delivered to nanofiltration membrane decoloration device (as shown in Figure 4), and employing molecular weight cut-off is the 19 passage Al of 400Da
2o
3nanofiltration membrane, red-tape operati pressure is 1MPa, and system running temperature is 85 DEG C, and crossflow velocity is 4m/s, pigment impurity in material etc. is concentrated 8 times, obtains penetrating fluid 2850g, concentrated solution 400g.Be input to by penetrating fluid in crystallization kettle, control stirring intensity is 250rpm, is chilled to 52 DEG C in advance, after having crystal to separate out, growing the grain 45min, stirring intensity reduces to 75rpm, drop to 18 DEG C with 0.3 DEG C/min rate of temperature fall again, when becoming starchiness in crystallization kettle, crystallization terminates.Open crystallization kettle bottom valve, material is put into suction filter, open vacuum pump, until mother liquor is drained;
(3) the concentrated solution 400g that upper step obtains is delivered to nanofiltration membrane percolating device (as shown in Figure 5), employing molecular weight cut-off is the chip ZrO of 200Da
2-TiO
2nanofiltration membrane, red-tape operati pressure is 1MPa, system running temperature is 85 DEG C, crossflow velocity is 4m/s, impeller pump remains a constant speed and adds 85 DEG C of deionized water 1300g in charging place of third stage film, reclaim in membrane permeation side and obtain dehydro-acetic acid sodium solution 1300g, and be input in crystallization kettle, controlling evaporative crystallization temperature controls at 52 DEG C, and stirring intensity is 250rpm, adds 1.5% crystal seed in time having crystal to separate out, stirring intensity reduces to 50rpm, drop to 18 DEG C with 0.4 DEG C/min rate of temperature fall again, when becoming starchiness in observation crystallization kettle, crystallization terminates.Open crystallization kettle bottom valve, material is put into suction filter, open vacuum pump, until mother liquor is drained;
(4) crystal that obtains in step (2) and step (3) is put into supercentrifuge dehydration, dry 2.5h under the hot blast of 95 DEG C, pulverize, be packaged into the finished product.In product, moisture is 8.6%, high purity 99.9%, the rate of recovery 98.9%.
Embodiment 3
(1) in reactor, drop into the dehydro-acetic acid crude product 1400g of 2100g deionized water and massfraction about 90%, open and stir, adjustment stirring intensity is 300rpm, and slowly drip the aqueous sodium hydroxide solution 1200g that massfraction is 30%, in groove to be batched, sodium hydroxide solution dropwises rear unlatching steam jacket, is progressively warming up to 80 DEG C, and stirs 1h at this temperature, now recording pH value of solution is 9, and transmittance is 34%;
(2) the sodium dehydroacetate synthesis material upper step obtained is delivered to nanofiltration membrane decoloration device, and employing molecular weight cut-off is the 19 passage ZrO of 300Da
2-TiO
2nanofiltration membrane, membrane module arrangement mode is 1 grade 5 sections, and red-tape operati pressure is 1.5MPa, and system running temperature is 80 DEG C, and crossflow velocity is 5m/s, pigment impurity in material etc. is concentrated 10 times, obtains penetrating fluid 4250g, concentrated solution 450g.Be input to by penetrating fluid in crystallization kettle, control stirring intensity is 300rpm, is chilled to 50 DEG C in advance, after having crystal to separate out, growing the grain 60min, stirring intensity reduces to 100rpm, drop to 15 DEG C with 0.5 DEG C/min rate of temperature fall again, when becoming starchiness in crystallization kettle, crystallization terminates.Open crystallization kettle bottom valve, material is put into suction filter, open vacuum pump, until mother liquor is drained;
(3) concentrated solution that upper step obtains is delivered to nanofiltration membrane percolating device, employing molecular weight cut-off is the 61 passage Al of 400Da
2o
3nanofiltration membrane, red-tape operati pressure is 1.5MPa, system running temperature is 80 DEG C, crossflow velocity is 3m/s, impeller pump remains a constant speed and add 80 DEG C of deionized water 2250g before level V membrane module, reclaim in membrane permeation side and obtain dehydro-acetic acid sodium solution 2250g, and be input in crystallization kettle, controlling evaporative crystallization temperature controls at 50 DEG C, and the stirring intensity initial stage is 300rpm, adds 2% crystal seed in time having crystal to separate out, stirring intensity reduces to 50rpm, drop to 15 DEG C with 0.5 DEG C/min rate of temperature fall again, when becoming starchiness in observation crystallization kettle, crystallization terminates.Open crystallization kettle bottom valve, material is put into suction filter, open vacuum pump, until mother liquor is drained;
(4) crystal that obtains in step (2) and step (3) is put into supercentrifuge dehydration, dry 2h under the hot blast of 105 DEG C, pulverize, be packaged into the finished product.In product, moisture is 8.1%, high purity 99.92%, the rate of recovery 99%.
Claims (10)
1. a decolor refined technology for sodium dehydroacetate, its concrete steps are as follows:
(1) synthesis of sodium dehydroacetate: dehydro-acetic acid crude product and water are added in reactor, under whipped state, add sodium hydroxide solution, control pH is alkalescence, after in groove to be batched, sodium hydroxide solution adds, be warming up to 80-90 DEG C, and continue stirring reaction in this case;
(2) decolouring of dehydro-acetic acid sodium water solution: the mass transport of reaction is concentrated to nanofiltration membrane decoloration device, penetrating fluid enters crystallization kettle crystallisation by cooling, concentrated solution is concentrated further after all returning and mixing with stoste, is collected by concentrated solution after concentration process terminates;
(3) wash-out of sodium dehydroacetate: the concentrated solution of collection is delivered in nanofiltration membrane percolating device, by adding the deionized water of heat by product wash-out out, per-meate side solution enters crystallization kettle evaporative crystallization;
(4) after crystallization, dehydro-acetic acid sodium crystal is through dehydration, oven dry, pulverizing, and packaging becomes the finished product.
2. decolor refined technology according to claim 1, is characterized in that the mass ratio of the dehydro-acetic acid crude product described in step (1) and water is 1:(1-1.5); Sodium hydroxide solution mass concentration is 10%-30%; Described pH is 8-10; In whole process, stir speed (S.S.) is 100-300rpm; Continue stirring reaction 0.5-2h.
3. decolor refined technology according to claim 1, is characterized in that step (2) and the nanofiltration membrane described in step (3) are porous ceramic film; The configuration of film is chip, one of single passage tubular type or hyperchannel tubular type are planted; The material of film is ZrO
2, TiO
2or Al
2o
3in the matrix material of one or more; The molecular weight cut-off of film is 200-400Da.
4. decolor refined technology according to claim 1, it is characterized in that the decoloration process of the dehydro-acetic acid sodium water solution described in step (2) adopts the mode of recycle to extinction cross flow filter, cycles of concentration is 1-10 times; Working pressure is 0.5-3.0MPa; Temperature is 20-90 DEG C; Crossflow velocity is 0.5-5m/s.
5. decolor refined technology according to claim 1, is characterized in that the cycles of concentration of the decoloration process of the dehydro-acetic acid sodium water solution described in step (2) is 5-10 times; Working pressure the best is 0.5-1.5MPa; Temperature the best is 80-90 DEG C; Crossflow velocity the best is 3-5m/s.
6. decolor refined technology according to claim 1, it is characterized in that the cooling and crystallizing process in step (2), its stirring intensity initial stage is 100-300rpm, first be chilled to 50-55 DEG C in advance, after having crystal to separate out, growing the grain 30-60min, stirring intensity reduces to 50-100rpm, drop to 15-20 DEG C with 0.2-0.5 DEG C/min rate of temperature fall again, when presenting starchiness in crystallization kettle crystallization terminate and suction filtration obtain dehydro-acetic acid sodium crystal.
7. decolor refined technology according to claim 1, it is characterized in that the elution processes of the sodium dehydroacetate in step (3) adopts the mode of continuous countercurrent diafiltration, the temperature of deionized water is 80-90 DEG C; The addition of deionized water and the concentrated solution mass ratio of collection are 1:(1-5); Working pressure is 0.5-3.0MPa; Temperature is 25-90 DEG C; Crossflow velocity is 0.5-5m/s.
8. decolor refined technology according to claim 1, is characterized in that the working pressure of the elution processes of the sodium dehydroacetate in step (3) is 0.5-1.5MPa; Temperature the best is 80-90 DEG C; Crossflow velocity the best is 3-5m/s.
9. decolor refined technology according to claim 1, it is characterized in that the evaporative crystallization technique in step (3), its evaporative crystallization temperature controls at 50-55 DEG C, the stirring intensity initial stage is 100-300rpm, crystal seed is added in time having crystal to separate out, stirring intensity reduces to 50-100rpm, and crystal seed is pure dehydro-acetic acid sodium crystal, and the addition of crystal seed is 1% ~ 2% of sodium dehydroacetate quality in evaporative crystallization liquid; Simultaneously drop to 15-20 DEG C with 0.2-0.5 DEG C/min rate of temperature fall, when presenting starchiness in crystallization kettle, crystallization terminates and suction filtration obtains dehydro-acetic acid sodium crystal.
10. decolor refined technology according to claim 1, it is characterized in that the described bake out temperature in step (4) controls at 90-105 DEG C, drying time is 2-3h.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349203A (en) * | 2016-08-26 | 2017-01-25 | 南通奥凯生物技术开发有限公司 | Method for producing pharmaceutical grade sodium dehydroacetate by membrane filtration |
| CN106366060A (en) * | 2016-08-26 | 2017-02-01 | 南通奥凯生物技术开发有限公司 | Pharmaceutical-grade sodium dehydroacetate purification method |
| CN107987045A (en) * | 2017-12-07 | 2018-05-04 | 南通醋酸化工股份有限公司 | A kind of technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst |
| CN108191802A (en) * | 2018-01-03 | 2018-06-22 | 江苏润普食品科技股份有限公司 | The production technology of dehydroactic acid sodium |
| CN108217794A (en) * | 2018-03-22 | 2018-06-29 | 兰州节能环保工程有限责任公司 | It is a kind of can simultaneously a variety of waste liquids of crystallization treatment method and device |
| CN108530338A (en) * | 2018-05-03 | 2018-09-14 | 南京翃翌陶瓷纳滤膜有限公司 | A method of extending the refined tryptophan of equipment life |
| WO2019061213A1 (en) * | 2017-09-29 | 2019-04-04 | 南通奥凯生物技术开发有限公司 | Method for preparing sodium acetate |
| CN112876440A (en) * | 2019-11-29 | 2021-06-01 | 南通醋酸化工股份有限公司 | Synthesis method of sodium dehydroacetate |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106349203A (en) * | 2016-08-26 | 2017-01-25 | 南通奥凯生物技术开发有限公司 | Method for producing pharmaceutical grade sodium dehydroacetate by membrane filtration |
| CN106366060A (en) * | 2016-08-26 | 2017-02-01 | 南通奥凯生物技术开发有限公司 | Pharmaceutical-grade sodium dehydroacetate purification method |
| WO2019061213A1 (en) * | 2017-09-29 | 2019-04-04 | 南通奥凯生物技术开发有限公司 | Method for preparing sodium acetate |
| CN107987045A (en) * | 2017-12-07 | 2018-05-04 | 南通醋酸化工股份有限公司 | A kind of technique for preparing sodium dehydroacetate in membrane reactor with immobilized AlCl_3 catalyst |
| CN108191802A (en) * | 2018-01-03 | 2018-06-22 | 江苏润普食品科技股份有限公司 | The production technology of dehydroactic acid sodium |
| CN108191802B (en) * | 2018-01-03 | 2021-02-09 | 江苏润普食品科技股份有限公司 | Production process of sodium dehydroacetate |
| CN108217794A (en) * | 2018-03-22 | 2018-06-29 | 兰州节能环保工程有限责任公司 | It is a kind of can simultaneously a variety of waste liquids of crystallization treatment method and device |
| CN108530338A (en) * | 2018-05-03 | 2018-09-14 | 南京翃翌陶瓷纳滤膜有限公司 | A method of extending the refined tryptophan of equipment life |
| CN112876440A (en) * | 2019-11-29 | 2021-06-01 | 南通醋酸化工股份有限公司 | Synthesis method of sodium dehydroacetate |
| CN112876440B (en) * | 2019-11-29 | 2023-09-29 | 南通醋酸化工股份有限公司 | Synthetic method of sodium dehydroacetate |
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