CN116217430A - Separation and purification method of high-concentration anhydrous aldoxime - Google Patents
Separation and purification method of high-concentration anhydrous aldoxime Download PDFInfo
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- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000000746 purification Methods 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 title claims abstract description 23
- 238000005185 salting out Methods 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 76
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- LJHFIVQEAFAURQ-ZPUQHVIOSA-N (NE)-N-[(2E)-2-hydroxyiminoethylidene]hydroxylamine Chemical compound O\N=C\C=N\O LJHFIVQEAFAURQ-ZPUQHVIOSA-N 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 10
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 65
- 150000003839 salts Chemical class 0.000 claims description 62
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 42
- 239000007787 solid Substances 0.000 claims description 38
- 238000001914 filtration Methods 0.000 claims description 24
- 239000012267 brine Substances 0.000 claims description 23
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 23
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 239000002244 precipitate Substances 0.000 claims description 20
- 239000012266 salt solution Substances 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 18
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 claims description 17
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 15
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 13
- 239000002351 wastewater Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000000108 ultra-filtration Methods 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000011033 desalting Methods 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 5
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 238000005086 pumping Methods 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 2
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 claims description 2
- -1 aluminum sulfate octadecatriene Chemical compound 0.000 claims description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- 230000008569 process Effects 0.000 description 14
- 238000004821 distillation Methods 0.000 description 11
- FZENGILVLUJGJX-IHWYPQMZSA-N (Z)-acetaldehyde oxime Chemical compound C\C=N/O FZENGILVLUJGJX-IHWYPQMZSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- ZJOKNSFTHAWVKK-UHFFFAOYSA-K aluminum octadecanoate sulfate Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)[O-].[Al+3].S(=O)(=O)([O-])[O-] ZJOKNSFTHAWVKK-UHFFFAOYSA-K 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 229940103272 aluminum potassium sulfate Drugs 0.000 description 4
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000002923 oximes Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012465 retentate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000005916 Methomyl Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000005857 Trifloxystrobin Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- UHXUZOCRWCRNSJ-QPJJXVBHSA-N methomyl Chemical compound CNC(=O)O\N=C(/C)SC UHXUZOCRWCRNSJ-QPJJXVBHSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ONCZDRURRATYFI-TVJDWZFNSA-N trifloxystrobin Chemical compound CO\N=C(\C(=O)OC)C1=CC=CC=C1CO\N=C(/C)C1=CC=CC(C(F)(F)F)=C1 ONCZDRURRATYFI-TVJDWZFNSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/14—Separation; Purification; Stabilisation; Use of additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a separation and purification method of high-concentration anhydrous aldoxime, which comprises the steps of preparing an aldoxime reaction liquid by ammoximation, rectifying the aldoxime reaction liquid to remove a reaction solvent used in the ammoximation reaction, and obtaining a tower kettle reaction liquid after rectification; then the following steps are sequentially carried out: purifying the inorganic salt to obtain a salting-out agent; adding a salting-out agent into the reaction liquid in the tower kettle after rectification, heating, stirring, and standing to enable the reaction liquid to be layered; and (3) taking the obtained upper reaction liquid, separating water through primary rectification, and then carrying out secondary rectification to obtain the glyoxime serving as a product. The water content of the obtained anhydrous aldoxime is lower than 100ppm, and the purity is more than or equal to 99 percent.
Description
Technical Field
The invention belongs to the field of chemical industry, and in particular relates to a separation and purification method of high-concentration anhydrous aldoxime.
Background
The aldoxime is an organic intermediate and is mainly used for synthesizing pesticide methomyl and trifloxystrobin; meanwhile, the reagent is an important organic synthesis reagent and analysis reagent, is mainly used as a reducing agent and an deoxidizing agent, and has the advantages of low price, low toxicity, good deoxidizing effect and the like. The ammoximation process is a method for synthesizing aldoxime, and has the advantages of simple process, mild reaction conditions, high aldehyde-ketone conversion rate, few byproducts and the like, but the ammoximation process has the advantage that a large amount of water is contained in raw materials which are required to be added when oxime series products are synthesized, so that the oxime content in ammoximation reaction liquid is low. Therefore, the ammoximation reaction liquid is usually required to be separated and purified to obtain the glyoxime with high concentration.
The patent discloses a separation and purification method of acetaldehyde oxime (CN 110746316A), which mainly adopts cyclohexanone oxime and acetaldehyde to carry out oxime exchange reaction to prepare the acetaldehyde oxime. After the alkali of the glyoxime reaction liquid is neutralized, toluene is added, and the glyoxime and the cyclohexanone are separated by reduced pressure rectification. And then adding water into the obtained glyoxime-toluene mixed solution to extract glyoxime, thereby obtaining an glyoxime aqueous solution and toluene. Finally, removing the water in the aldoxime water solution by adopting a decompression rectification mode to obtain an aldoxime product with the mass fraction of 50 percent.
A process for preparing aldoxime (CN 112574063A) is disclosed for preparing and purifying aldoxime. The method adopts an ammoximation method to prepare the aldoxime. The obtained glyoxime reaction liquid is extracted by using methylene dichloride, the solvent is distilled off under normal pressure after the extraction liquid is dried by anhydrous sodium sulfate, and then the fraction is collected by reduced pressure distillation, so that the anhydrous glyoxime with the mass fraction of 99% is obtained. The extraction agent in the system uses a large amount of dichloromethane solvent, so that the process of fractionating the solvent at normal pressure has large energy consumption. In addition, certain product loss exists in the extraction process of the extractant, and the final system product yield is 92%.
The method adopts the extraction technology to purify the glyoxime product, a large amount of solvent is consumed, and the extraction is not complete, so that the product yield is low; the patent discloses a preparation method of anhydrous aldoxime (CN 101624353A) and a preparation and purification method of the anhydrous aldoxime. The method adopts hydroxylamine, acetaldehyde and alkali liquor to react, and utilizes the solubility reduction of aldoxime at low temperature and the salting-out effect of inorganic salt to realize the layering of aldoxime reaction liquid, thus preparing high-concentration aldoxime, but a large amount of byproduct ammonium sulfate salt is produced in the process of the patent.
In summary, in the current purification method of anhydrous aldoxime, the organic solvent extraction method needs to use a large amount of organic solvent, and the separation and purification energy consumption is high. A large amount of industrial waste salt is generated in the process of salting-out method, and the atomic economy utilization rate is low. Accordingly, improvements in the art are needed.
Disclosure of Invention
The invention aims to provide a separation and purification method of high-concentration anhydrous aldoxime, wherein the water content of the obtained anhydrous aldoxime is lower than 100ppm (detected by a Karl Fischer electric quantity method), and the purity is more than or equal to 99%.
In order to solve the technical problems, the invention provides a separation and purification method of high-concentration anhydrous aldoxime, which comprises the steps of preparing an aldoxime reaction liquid by ammoximation reaction, rectifying (normal pressure rectification) the aldoxime reaction liquid to remove a reaction solvent used in the ammoximation reaction, and obtaining a tower kettle reaction liquid after rectification; then the following steps are sequentially carried out:
1) Preparation of salting-out agent:
purifying the inorganic salt (thereby removing heavy metals) to obtain a salting-out agent;
2) Salting out and layering:
adding a salting-out agent into the reaction liquid in the tower kettle after rectification, heating to 80+/-10 ℃, stirring, standing, and layering the reaction liquid to obtain an upper-layer reaction liquid (an upper-layer organic phase) and a lower-layer reaction liquid respectively;
rectifying the reaction liquid in the tower kettle: salting-out agent = 3-5L/1 kg;
stirring for about 15+ -5 min;
3) And (3) rectifying and purifying:
separating water (separating redundant water) from the upper reaction liquid obtained in the step 2) through primary rectification (the temperature of the tower top is 60-100 ℃), and then carrying out secondary rectification (the temperature of the tower top is 80-110 ℃), so as to obtain the acetaldehyde oxime which is the product, namely the anhydrous acetaldehyde oxime (detected by a Karl Fischer electric quantity method, and the water content is lower than 100 ppm).
As the improvement of the separation and purification method of the high-concentration anhydrous aldoxime, the invention further comprises the following steps:
4) And (3) recovering salting-out agent:
cooling the lower reaction solution in the step 2) to 0-10 ℃, and standing until no new precipitate is generated (the standing time is about 30-60 min), wherein the precipitate is a recyclable salting-out agent; removing (filtering or centrifuging) the precipitate to obtain a reaction solution after desalting;
5) Stripping (80-160 ℃) the reaction liquid obtained in the step 4) after desalting, and condensing steam generated by stripping to be used as reaction wastewater; thereby realizing the removal of organic matters (including acetaldehyde, aldoxime and the like) in the reaction liquid after desalting;
6) Pumping the reaction wastewater obtained in the step 5) into an ultrafiltration device; filtering by an ultrafiltration membrane (aperture of 0.002-0.01 microns), and controlling the pressure difference of the ultrafiltration membrane to be less than or equal to 0.16Mpa; the filtered wastewater can be directly discharged (the filtered wastewater can be directly discharged because no salt exists in the filtered wastewater); the concentrated brine solution (the mass fraction of the salt is 30-40%) can be returned to the step 2 for recycling.
That is, the concentrated brine solution can be mixed with the reaction liquid in the tower kettle after rectification and then added with salting-out agent.
As a further improvement of the separation and purification method of the high concentration anhydrous aldoxime of the present invention, the preparation of the salting-out agent of step 1) comprises the steps of:
a) Pretreatment of salt:
600-850 kg of inorganic salt is dissolved in 1000-3600L of high-purity water, and the obtained salt solution is introduced into a high-pressure reaction kettle;
b) Under the stirring condition, introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a), wherein the flow is 10-50 cubic meters per hour, the introducing time is 5-10 min, and the stirring reaction is continued for 1-5 h after the hydrogen sulfide gas is introduced;
c) Filtering the reaction solution obtained after the reaction in the step b) to remove solid precipitates (including solid precipitates such as PbS, feS and the like) so as to obtain a purified brine solution;
d) Concentrating the salt water solution obtained in the step c) through rotary evaporation until a salt saturated water solution is obtained;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 1-8 hours at a low temperature (0-10 ℃) to separate out solid, and filtering to obtain salt solid;
f) And e), drying the salt solid obtained in the step e) at 30-60 ℃ for 2-5 h to obtain the salting-out agent.
As a further improvement of the separation and purification method of the high-concentration anhydrous aldoxime of the invention: the inorganic salt is at least one (one or a mixture of two or more) of aluminum potassium sulfate dodecahydrate, aluminum chloride, aluminum sulfate (aluminum sulfate octadecanoate), aluminum nitrate, aluminum sulfide and lithium carbonate.
As a further improvement of the separation and purification method of the high concentration aldoxime of the present invention: the inorganic salt is prepared from aluminum sulfate: lithium chloride: aluminum potassium sulfate dodecahydrate = 1:1.25:1.5 weight ratio.
As a further improvement of the separation and purification method of the high concentration aldoxime of the present invention:
the ammoximation reaction is as follows: adding 5-7 parts by mass of molecular sieve catalyst, 46-65 parts by mass of acetaldehyde, 21-30 parts by mass of ammonia gas and 78-111 parts by mass of tertiary butanol into a reaction kettle, stirring and mixing; after the reaction kettle is heated to 10-80 ℃, 71-100 parts of 50% hydrogen peroxide enters the reaction kettle in a dropwise manner, and the dropwise time is 20-60 min; stirring and reacting for 1-8 h after the dripping is finished to obtain an glyoxime reaction solution;
and (3) rectifying the glyoxime reaction liquid at normal pressure (the temperature of the top of the tower is 90-95 ℃), so that tertiary butanol serving as a reaction solvent is removed, and rectifying the reaction liquid at the bottom of the tower.
The tertiary butanol can be recycled.
The invention provides a novel salting-out method separation and purification process, which aims at the current situations that the concentration of glyoxime in the existing production process is low, the purification process is complex, a large amount of waste salt is generated in the process, and the like. The method has the advantages of simple operation, high concentration of the glyoxime after separation and concentration, no waste salt generation in the process and the like.
The purification mechanism of the invention mainly comprises: the strength of the salting-out agent in combination with water determines the salting-out effect. The hydration number is related to the size of cations in the salting-out agent, and the smaller the cations, the larger the hydration number, and the stronger the salting-out effect. The radius of aluminum ions and lithium ions in aluminum sulfate and lithium chloride is small, the charged ions are more, the influence on a hydration layer of the salted-out ions is large, and the dewatering capacity of the salted-out ions is enhanced. The salting-out agent is used as a salting-out agent, so that the salting-out effect is greatly improved.
The invention has the following technical advantages:
1) In the material separation and purification process, the invention realizes the layering of the glyoxime reaction liquid by utilizing the salting-out technology, replaces the method of using an extracting agent in the prior art, avoids the use of a large amount of organic solvents, and reduces the energy consumption of later purification.
2) Compared with the common salting-out agent, the salting-out agent used in the invention has obvious salting-out effect. After salting out and layering, the water content of the upper layer reaction liquid (upper layer organic phase) is only 10-20%. And obtaining the high-purity anhydrous aldoxime after simple rectification and water removal.
3) The salting-out agent of the invention has obvious salting-out effect after being purified by mixing one or more salts with smaller cation radius according to a certain proportion. The concentration of the aldoxime product is up to 99.8%.
4) The salting-out agent can be recycled, and no waste salt is generated in the whole process; is economical and environment-friendly.
In summary, the separation and purification method of high-concentration aldoxime comprises the steps of rectifying the aldoxime reaction liquid prepared by ammoximation to remove the tertiary butanol serving as a reaction solvent, adding a salting-out agent into the reaction liquid at a tower kettle after rectification, stirring and heating for a period of time, layering the reaction liquid, taking the upper reaction liquid, and carrying out reduced pressure rectification twice to obtain the anhydrous aldoxime product. The salting-out layered lower reaction liquid is subjected to cooling salting-out, centrifugation, filtration and other processes to realize the recycling of the salting-out agent. The method for preparing the aldoxime takes the salting-out agent as a core for separation and purification, thereby effectively simplifying the separation and purification process of the aldoxime. Realizes the separation of aldoxime and water and purifies anhydrous aldoxime. The salting-out agent can be recycled after filtration in a cooling salting-out mode. The finished product of the anhydrous aldoxime obtained after the preliminary separation of the aldoxime is subjected to a rectification process is colorless and transparent, and has high purity (the purity is more than or equal to 99%) and high yield (the yield is more than or equal to 95%).
Drawings
The following describes the embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be further described with reference to the following specific examples, but the scope of the invention is not limited thereto:
example 1, ammoximation reaction and rectification (prior art):
95KG of molecular sieve catalyst (TS-1, titanium silicalite), 882KG of acetaldehyde and 1500KG of tertiary butanol are added into a reaction kettle equipped with an electric stirring, dropping funnel, reflux condenser and thermometer, and the mixture is stirred and mixed, and 450 cubic meters (about 408 KG) of ammonia gas is introduced. After the reaction kettle is heated to 60 ℃,1360kg of 50% (mass%) hydrogen peroxide is added into the reaction kettle in a dropwise manner for 60min. After the dripping is finished, stirring and reacting for 1h to obtain the glyoxime reaction liquid.
Taking the prepared acetaldehyde oxime reaction liquid (for example 2000L) to carry out normal pressure rectification (the temperature of the top of the tower is 90-95 ℃) to remove the tertiary butanol which is a reaction solvent until no tertiary butanol is generated any more, obtaining the tower kettle reaction liquid after rectification, and recycling the tertiary butanol;
the reaction liquid in the column bottom after the rectification was used in each of examples 1 to 7.
The aluminum sulfate octadecanoate, lithium chloride, aluminum potassium sulfate dodecahydrate used in examples 2-1 to 2-7 below were all technical grade, with purities of: 98.5% of aluminum sulfate octadecatydrate, 98.2% of lithium chloride and 98.4% of aluminum potassium sulfate dodecahydrate. % is mass%.
The autoclave used in examples 2-1 to 2-7 had a capacity of 5000L.
Example 2-1, preparation of salting-out agent, the following steps were performed in order:
a) Pretreatment of salt:
aluminum sulfate octadecanoate is selected as salt, 600kg of aluminum sulfate octadecanoate is dissolved in 1500L of high-purity water, and after the aluminum sulfate octadecanoate is fully dissolved, the obtained salt solution is introduced into a high-pressure reaction kettle;
b) Introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a) under the stirring condition, wherein the flow rate is 20 cubic meters per hour, the introducing time is 10min, and stirring and reacting for 2h are continued after the hydrogen sulfide gas is introduced;
c) Filtering the reaction solution obtained after the reaction in the step b) to remove solid precipitates (including solid precipitates such as PbS, feS and the like) and obtain a purified brine solution;
d) Carrying out rotary evaporation and concentration on the purified brine solution obtained in the step c) at 50 ℃ and under the condition of minus 0.1Mpa until no distilled water is distilled, and ending the rotary evaporation and concentration to obtain a salt saturated water solution;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 3 hours at a low temperature (0-10 ℃) to separate out solid, and filtering to obtain salt solid;
f) And (3) drying the salt solid obtained in the step e) at 30-60 ℃ for 5 hours to obtain about 596kg of salting-out agent (aluminum sulfate with the purity of 99.2%).
Description: purity can be detected using chemical methods (HG_T3442-2014).
Example 2-2, preparation of salting-out agent, the following steps were performed in order:
a) Pretreatment of salt:
lithium chloride is selected as salt, 760kg of lithium chloride is dissolved in 1000L of high-purity water, and after the lithium chloride is fully dissolved, the obtained salt solution is introduced into a high-pressure reaction kettle;
b) Introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a) under the stirring condition, wherein the flow rate is 20 cubic meters per hour, the introducing time is 10min, and stirring and reacting for 2h are continued after the hydrogen sulfide gas is introduced;
c) Filtering the reaction solution obtained after the reaction in the step b) to remove solid precipitate, thereby obtaining purified brine solution;
d) Concentrating the purified brine solution obtained in the step c) by rotary distillation at 50 ℃ and minus 0.1Mpa until no distilled water is distilled off, and ending the rotary distillation concentration to obtain a salt saturated water solution;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 4 hours at a low temperature (0-10 ℃) to separate out solid, and filtering to obtain salt solid;
f) And e), drying the salt solid in the step e) at 30-60 ℃ for 5 hours to obtain the salting-out agent (lithium chloride with the purity of 99.05%).
Examples 2-3, preparation of salting-out agent, the following steps were performed in sequence:
a) Pretreatment of salt:
selecting aluminum potassium sulfate dodecahydrate as salt, dissolving 850kg of aluminum potassium sulfate dodecahydrate in 3600L of high-purity water, and introducing the obtained salt solution into a high-pressure reaction kettle after full dissolution;
b) Introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a) under the stirring condition, introducing the solution for 10min at the flow rate of 20 cubic meters per hour, and then continuing to stir and react for 2h;
c) Filtering the reaction solution after the reaction in the step b) to remove solid precipitate, thereby obtaining purified brine solution;
d) Concentrating the purified brine solution obtained in the step c) by rotary distillation at 50 ℃ and minus 0.1Mpa until no distilled water is distilled off, and ending the rotary distillation concentration to obtain a salt saturated water solution;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 4 hours at a low temperature (0-10 ℃) so as to precipitate solid, and filtering to obtain salt solid;
f) And e), drying the salt solid obtained in the step e) at 30-60 ℃ for 5 hours to obtain the salting-out agent (aluminum potassium sulfate with the purity of 99.08%).
Examples 2-4, preparation of salting-out agent, the following steps were performed in order:
a) Pretreatment of salt:
aluminum sulfate octadecatrier and lithium chloride are selected as salts, 300kg of aluminum sulfate octadecatrier and 400kg of lithium chloride are dissolved in 1000L of high-purity water, and after the solution is fully dissolved, the obtained salt solution is introduced into a high-pressure reaction kettle;
b) Introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a) under the stirring condition, introducing the solution for 10min at the flow rate of 20 cubic meters per hour, and then continuing to stir and react for 2h;
c) Filtering the reaction solution after the reaction in the step b) to remove solid precipitate, thereby obtaining purified brine solution;
d) Concentrating the purified brine solution obtained in the step c) by rotary distillation at 50 ℃ and minus 0.1Mpa until no distilled water is distilled off, and ending the rotary distillation concentration to obtain a salt saturated water solution;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 5 hours at a low temperature (0-10 ℃) so as to precipitate solids, and filtering to obtain salt solids;
f) And e), drying the salt solid in the step e) at 30-60 ℃ for 5 hours to obtain a salting-out agent (aluminum sulfate with the content of 42.5% and lithium chloride with the content of 56.56%).
Examples 2-5, preparation of salting-out agent, the following steps were performed in order:
a) Pretreatment of salt:
aluminum sulfate octadecatriend aluminum potassium sulfate dodecahydrate are selected as salts, 300kg of aluminum sulfate octadecatriend 450kg of aluminum potassium sulfate dodecahydrate are dissolved in 2600L of high-purity water, and after the aluminum sulfate octadecatriend aluminum potassium sulfate dodecahydrate are fully dissolved, the obtained salt solution is introduced into a high-pressure reaction kettle;
b) Introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a) at the flow rate of 20 cubic meters per hour for 10min, and then continuing to stir and react for 2h;
c) Filtering the reaction solution after the reaction in the step b) to remove solid precipitate, thereby obtaining purified brine solution;
d) Concentrating the purified brine solution obtained in the step c) at 50 ℃ and minus 0.1Mpa by rotary evaporation to obtain a salt saturated aqueous solution;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 5 hours at a low temperature (0-10 ℃) to separate out solid, and filtering to obtain salt solid;
f) And e), drying the salt solid in the step e) at 30-60 ℃ for 5 hours to obtain a salting-out agent (containing 39.82% of aluminum sulfate and 59.21% of aluminum potassium sulfate).
Examples 2-6, preparation of salting-out agent, the following steps were performed in order:
a) The pretreatment of the salt is carried out,
selecting lithium chloride and aluminum potassium sulfate dodecahydrate as salts, dissolving 350kg of lithium chloride and 400kg of aluminum potassium sulfate dodecahydrate in 2600L of high-purity water, and introducing the obtained salt solution into a high-pressure reaction kettle after the solution is fully dissolved;
b) Introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a) under the stirring condition, introducing the solution for 10min at the flow rate of 20 cubic meters per hour, and then continuing to stir and react for 2h;
c) Filtering the reaction solution after the reaction in the step b) to remove solid precipitate, thereby obtaining purified brine solution;
d) Concentrating the purified brine solution obtained in the step c) by rotary distillation at 50 ℃ and minus 0.1Mpa until no distilled water is distilled off, and ending the rotary distillation concentration to obtain a salt saturated water solution;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 5 hours at a low temperature (0-10 ℃) to separate out solid, and filtering to obtain salt solid;
f) And e), drying the salt solid in the step e) at 30-60 ℃ for 5 hours to obtain a salting-out agent (containing 39.84% of lithium chloride and 59.26% of aluminum potassium sulfate).
Examples 2-7, preparation of salting-out agent, the following steps were performed in order:
a) Pretreatment of salt:
aluminum sulfate octadecatriend, lithium chloride and aluminum potassium sulfate dodecahydrate are selected as salts, 200kg of aluminum sulfate octadecatriend 250kg of lithium chloride and 300kg of aluminum potassium sulfate dodecahydrate are dissolved in 2800L of high-purity water, and after the solution is fully dissolved, the obtained salt solution is introduced into a high-pressure reaction kettle;
b) Introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a) under the stirring condition, introducing the solution for 10min at the flow rate of 20 cubic meters per hour, and then continuing to stir and react for 2h;
c) Filtering the reaction solution after the reaction in the step b) to remove solid precipitate, thereby obtaining purified brine solution;
d) Concentrating the purified brine solution obtained in the step c) by rotary distillation at 50 ℃ and minus 0.1Mpa until no distilled water is distilled off, and ending the rotary distillation concentration to obtain a salt saturated water solution;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 5 hours at a low temperature (0-10 ℃) so as to precipitate solids, and filtering to obtain salt solids;
f) And e), drying the salt solid in the step e) at 30-60 ℃ for 5 hours to obtain the salting-out agent (the content of aluminum sulfate is 26.56%, the content of lithium chloride is 33.12% and the content of aluminum potassium sulfate is 39.45%) required by the process.
Example 1: a separation and purification method of high-concentration aldoxime comprises the following steps:
1) Salting out and layering:
adding 596kg of salting-out agent prepared in the example 2-1 into 2600L of the rectified tower kettle reaction solution, heating to 80 ℃, stirring for 15min, and standing to separate the reaction solution; respectively obtaining an upper layer reaction liquid (an upper layer organic phase) and a lower layer reaction liquid;
1) And (3) rectifying and purifying:
separating excessive water from the upper layer reaction liquid (upper layer organic phase) obtained in the step 1) through primary rectification (the temperature of the top of the tower is 95-97 ℃), and obtaining 1131.5kg (detected by a Karl Fischer electric quantity method) of anhydrous glyoxime product through secondary rectification (the temperature of the top of the tower is 97-99 ℃), wherein the water content is lower than 100 ppm;
the main components of the residue obtained by the secondary rectification are a small amount of salting-out agent, heavy components (acetaldehyde oxime polycondensate) and the like, and the residue is used as hazardous waste treatment.
3) And (3) recovering salting-out agent:
cooling (0-10 ℃) the lower layer reaction liquid obtained in the step 1), standing, and salting out a large amount of the lower layer reaction liquid when standing until no new precipitate is generated (standing time is about 30-60 min), wherein the precipitate is a salting-out agent recycled; removing precipitate by centrifugation (centrifugation for 10 minutes at 2500 rpm) to obtain reaction liquid after desalting;
4) Stripping (110-120 ℃) the reaction liquid obtained in the step 3) to remove organic matters in the wastewater, thereby removing the organic matters (acetaldehyde, acetaldehyde oxime and the like) in the reaction liquid after the desalination;
condensing steam generated by stripping to be used as reaction wastewater;
5) Pumping the reaction wastewater obtained in the step 4) into an ultrafiltration device; the ultrafiltration device is a tubular ultrafiltration membrane with the aperture of 0.005 micron;
filtering with ultrafiltration membrane (pore size of 0.005 μm), and controlling pressure difference of ultrafiltration membrane to be less than or equal to 0.16MPa. The filtered wastewater has no salt and can be directly discharged. The trapped liquid is a concentrated solution of aluminum sulfate octadecatydrate (the concentration of the aluminum sulfate octadecatydrate is about 30 percent), and the trapped liquid can be returned to the step 1) for recycling.
The aldoxime content obtained in example 1 was 99.3% and the yield was about 95%.
Example 2 "596 kg of salting-out agent prepared in example 2-1 was added in step 1) of example 1" 758kg of salting-out agent prepared in example 2-2 "was changed to" adding ". The remainder was identical to example 1.
1141kg of anhydrous glyoxime product with a moisture content of less than 100ppm is obtained.
The aldoxime content obtained in this example 2 was 99.5% and the yield was about 96%.
Example 3 "596 kg of salting-out agent prepared in example 2-1 was added in step 1) of example 1" 849kg of salting-out agent prepared in example 2-3 "was changed to" added. The remainder was identical to example 1.
The aldoxime content obtained in this example 3 was 99.4% and the yield was about 95%. The moisture content is less than 100ppm.
Example 4 "596 kg of salting-out agent prepared in example 2-1 was added in step 1) of example 1" 695kg of salting-out agent prepared in example 2-4 "was changed to" adding. The remainder was identical to example 1.
The aldoxime content obtained in this example 4 was 99.2% and the yield was about 94%. The moisture content is less than 100ppm.
Example 5 "596 kg of salting-out agent prepared in example 2-1 was added in step 1) of example 1" was changed to "746 kg of salting-out agent prepared in example 2-5". The remainder was identical to example 1.
The aldoxime content obtained in this example 5 was 99.5% and the yield was about 95%. The moisture content is less than 100ppm.
Example 6 "596 kg of salting-out agent prepared in example 2-1 was added in step 1) of example 1" to 747kg of salting-out agent prepared in example 2-6 ". The remainder was identical to example 1.
The aldoxime content obtained in example 6 was 99.6% and the yield was about 97%. The moisture content is less than 100ppm.
Example 7 "596 kg of salting-out agent prepared in example 2-1 was added in step 1) of example 1" 748kg of salting-out agent prepared in example 2-7 "was changed to" adding ". The remainder was identical to example 1.
The aldoxime content obtained in this example 7 was 99.8% and the yield was about 97%. The moisture content is less than 100ppm.
Recycling cases of example 8 and example 7:
the retentate (brine concentrated solution) obtained in step 5) of example 7 was tested, and the contents of the components were: aluminum sulfate octadecatydrate 7.97%, lithium chloride 9.94%, aluminum potassium sulfate dodecahydrate 11.84%.
The procedure of example 1 was repeated except that 2600L of the reaction solution in the column bottom after rectification was taken, 195L of the retentate (concentrated brine solution) obtained in step 5) of the procedure of example 7 was added, 350kg of the salting-out agent obtained in step 3) of example 7 was further added, and 350kg of the salting-out agent prepared in examples 2 to 7 was added.
The aldoxime content obtained in example 8 was 99.7% and the yield was about 97%. The moisture content is less than 100ppm.
Comparative example 1 the "salting-out agent" in example 1 was changed to "aluminum sulfate", the amount was kept substantially unchanged, i.e. 600kg, and the rest was identical to example 1.
The results obtained were: 1112.2Kg of aqueous glyoxime product was obtained, and the content of the prepared glyoxime was 86.8%, and the yield was about 84.5%.
Comparative example 2 the "salting-out agent" in example 1 was changed to ammonium sulfate as salting-out agent described in CN101624353A, the amount was kept substantially unchanged, namely 600kg, and the remainder was identical to example 1.
The results obtained were: 1145Kg of aqueous glyoxime product was obtained, and the content of the prepared glyoxime was 94.5% and the yield was 91.5%.
Description: by adopting the method of the invention, the concentration of the acetaldehyde oxime in the upper layer reaction liquid (upper layer organic phase) obtained in the step 1) of the example 1 reaches more than 85 percent; therefore, the water content of the product is effectively prevented from increasing due to azeotropic distillation of the aldoxime and water in the subsequent rectification.
Whereas the upper layer reaction liquid (upper organic phase) obtained in this comparative example 2 had an glyoxime concentration of only about 65%.
Comparative example 3-1, the hydrogen sulfide purification process in "preparation of salting-out agent of example 2-1" was removed, and the process was changed to be as described in the prior art, i.e., the salting-out agent was directly subjected to water washing, crystallization and purification; the method comprises the following steps:
600kg of aluminum sulfate octadecanoate was dissolved in 1500L of high purity water and filtered, and the filtrate obtained was substituted for the "purified brine solution obtained in step c)" and then subjected to d) to f) of example 2-1 in this order.
The "salting-out agent" in example 1 was changed to the above-obtained product, and the amount was kept constant, namely 596kg, and the rest was the same as in example 1.
The results obtained were: 1111Kg of aqueous glyoxime product was obtained, and the content of the prepared glyoxime was 99.2% and the yield was 93.2%.
Comparative example 3-2, the hydrogen sulfide purification process in "examples 2-7, preparation of salting-out agent" was removed, and was changed to be as described in the prior art, i.e., the salting-out agent was directly subjected to water washing, crystallization and purification; the method comprises the following steps:
200kg of aluminum sulfate octadecatydrate, 250kg of lithium chloride and 300kg of aluminum potassium sulfate dodecahydrate were dissolved in 2800L of high-purity water, and the filtrate obtained was filtered instead of "the purified brine solution obtained in step c)" and then subjected to examples 2 to 7 in this order.
The "salting-out agent" in example 7 was changed to the above-obtained product, and the amount was kept unchanged, namely 748kg, and the rest was the same as in example 7.
The results obtained were: 1128Kg of aqueous glyoxime product was obtained, the content of glyoxime produced was 98.5%, and the yield was 94%.
Comparative example 4 the temperature parameter of step 1) of example 1 was changed to normal temperature 25 ℃, i.e. to the following:
adding 596kg of salting-out agent prepared in the example 2-1 into 2600L of the rectified tower kettle reaction solution, stirring at room temperature of 25 ℃ for 15min, and standing to separate the reaction solution;
the remainder was identical to example 1.
The results obtained were: 1197Kg of aqueous glyoxime product was obtained, the content of the prepared glyoxime was 88.6%, and the yield was 89.7%.
Finally, it should also be noted that the above list is merely a few specific embodiments of the present invention. Obviously, the invention is not limited to the above embodiments, but many variations are possible. All modifications directly derived or suggested to one skilled in the art from the present disclosure should be considered as being within the scope of the present invention.
Claims (7)
1. A separation and purification method of high-concentration anhydrous aldoxime comprises the steps of preparing an aldoxime reaction solution by ammoximation, rectifying the aldoxime reaction solution to remove a reaction solvent used in the ammoximation reaction, and obtaining a tower kettle reaction solution after rectification; the method is characterized by comprising the following steps of:
1) Preparation of salting-out agent:
purifying the inorganic salt to obtain a salting-out agent;
2) Salting out and layering:
adding a salting-out agent into the reaction liquid in the tower kettle after rectification, heating to 80+/-10 ℃, stirring, standing, and layering the reaction liquid to obtain an upper-layer reaction liquid and a lower-layer reaction liquid respectively;
3) And (3) rectifying and purifying:
and 2) taking the upper layer reaction liquid obtained in the step 2), separating water through primary rectification, and then carrying out secondary rectification to obtain the glyoxime serving as a product.
2. The method for separating and purifying high-concentration anhydrous aldoxime according to claim 1, wherein in the step 2):
rectifying the reaction liquid in the tower kettle: salting-out agent = 3-5L/1 kg.
3. The method for separating and purifying high-concentration anhydrous aldoxime according to claim 1 or 2, further comprising the steps of:
4) And (3) recovering salting-out agent:
cooling the lower reaction solution in the step 2) to 0-10 ℃, and standing until no new precipitate is generated, wherein the precipitate is a recyclable salting-out agent; removing the precipitate to obtain a reaction solution after desalting;
5) Stripping the reaction liquid after desalting obtained in the step 4), thereby removing organic matters in the reaction liquid after desalting, and condensing steam generated by stripping to be used as reaction wastewater;
6) Pumping the reaction wastewater obtained in the step 5) into an ultrafiltration device; filtering with ultrafiltration membrane, and controlling the pressure difference of the ultrafiltration membrane to be less than or equal to 0.16Mpa; filtering the wastewater and discharging; the concentrated brine solution can be returned to the step 2) for recycling.
4. A method for separating and purifying high concentration anhydrous aldoxime according to any one of claims 1 to 3, wherein the preparation of the salting-out agent in step 1) comprises the steps of:
a) Pretreatment of salt:
600-850 kg of inorganic salt is dissolved in 1000-3600L of high-purity water, and the obtained salt solution is introduced into a high-pressure reaction kettle;
b) Under the stirring condition, introducing hydrogen sulfide gas into the salt solution in the high-pressure reaction kettle in the step a), wherein the flow is 10-50 cubic meters per hour, the introducing time is 5-10 min, and the stirring reaction is continued for 1-5 h after the hydrogen sulfide gas is introduced;
c) Filtering the reaction solution obtained after the reaction in the step b) to remove solid precipitates, thereby obtaining purified brine solution;
d) Concentrating the salt water solution obtained in the step c) through rotary evaporation until a salt saturated water solution is obtained;
e) Cooling and crystallizing the salt saturated aqueous solution obtained in the step d) for 1-8 hours at low temperature to separate out solid, thus obtaining salt solid;
f) And e), drying the salt solid obtained in the step e) at 30-60 ℃ for 2-5 h to obtain the salting-out agent.
5. The method for separating and purifying high-concentration anhydrous aldoxime according to claim 4, which is characterized in that: the inorganic salt is at least one of aluminum potassium sulfate dodecahydrate, aluminum chloride, aluminum sulfate, aluminum nitrate, aluminum sulfide, lithium carbonate and lithium chloride.
6. The method for separating and purifying high-concentration anhydrous aldoxime according to claim 5, which is characterized in that: the inorganic salt is prepared from aluminum sulfate octadecatriene water: lithium chloride: aluminum potassium sulfate dodecahydrate = 1:1.25:1.5 weight ratio.
7. The method for separating and purifying high-concentration aldoxime according to any one of claims 1 to 6, which is characterized in that:
the ammoximation reaction is as follows: adding 5-7 parts by mass of molecular sieve catalyst, 46-65 parts by mass of acetaldehyde, 21-30 parts by mass of ammonia gas and 78-111 parts by mass of tertiary butanol into a reaction kettle, stirring and mixing; after the reaction kettle is heated to 10-80 ℃, 71-100 parts of 50% hydrogen peroxide enters the reaction kettle in a dropwise manner, and the dropwise time is 20-60 min; stirring and reacting for 1-8 h after the dripping is finished to obtain an glyoxime reaction solution;
and rectifying the glyoxime reaction liquid at normal pressure so as to remove tertiary butanol serving as a reaction solvent, thereby obtaining the rectified tower kettle reaction liquid.
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