CN115105863A - Liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and method for separating oil phase in methionine production - Google Patents
Liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and method for separating oil phase in methionine production Download PDFInfo
- Publication number
- CN115105863A CN115105863A CN202210473690.7A CN202210473690A CN115105863A CN 115105863 A CN115105863 A CN 115105863A CN 202210473690 A CN202210473690 A CN 202210473690A CN 115105863 A CN115105863 A CN 115105863A
- Authority
- CN
- China
- Prior art keywords
- liquid
- phase
- solid
- methionine
- oil phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229930182817 methionine Natural products 0.000 title claims abstract description 73
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 title claims abstract description 72
- 239000007788 liquid Substances 0.000 title claims abstract description 65
- 238000000926 separation method Methods 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000007787 solid Substances 0.000 title claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 52
- 239000012071 phase Substances 0.000 claims description 66
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 24
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 18
- 235000019253 formic acid Nutrition 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 8
- 239000012530 fluid Substances 0.000 claims description 8
- 230000020477 pH reduction Effects 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000008346 aqueous phase Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 229910000343 potassium bisulfate Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims 2
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 claims 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 239000012452 mother liquor Substances 0.000 abstract description 15
- 238000002425 crystallisation Methods 0.000 abstract description 14
- 230000008025 crystallization Effects 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000000701 coagulant Substances 0.000 abstract description 3
- 208000028659 discharge Diseases 0.000 abstract description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 15
- 229940091173 hydantoin Drugs 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 229910052938 sodium sulfate Inorganic materials 0.000 description 11
- 235000011152 sodium sulphate Nutrition 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- 239000000413 hydrolysate Substances 0.000 description 7
- CLUWOWRTHNNBBU-UHFFFAOYSA-N 3-methylthiopropanal Chemical compound CSCCC=O CLUWOWRTHNNBBU-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 5
- 238000000909 electrodialysis Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 235000011181 potassium carbonates Nutrition 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000007127 saponification reaction Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 238000013375 chromatographic separation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 150000002741 methionine derivatives Chemical class 0.000 description 4
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SBKRXUMXMKBCLD-UHFFFAOYSA-N 5-(2-methylsulfanylethyl)imidazolidine-2,4-dione Chemical compound CSCCC1NC(=O)NC1=O SBKRXUMXMKBCLD-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 108010009736 Protein Hydrolysates Proteins 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- -1 carbon anions Chemical class 0.000 description 2
- 238000009264 composting Methods 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 235000020776 essential amino acid Nutrition 0.000 description 2
- 239000003797 essential amino acid Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VWWOJJANXYSACS-UHFFFAOYSA-N 2-hydroxy-4-methylsulfanylbutanenitrile Chemical compound CSCCC(O)C#N VWWOJJANXYSACS-UHFFFAOYSA-N 0.000 description 1
- WWILHZQYNPQALT-UHFFFAOYSA-N 2-methyl-2-morpholin-4-ylpropanal Chemical compound O=CC(C)(C)N1CCOCC1 WWILHZQYNPQALT-UHFFFAOYSA-N 0.000 description 1
- KKYSBGWCYXYOHA-UHFFFAOYSA-N 3-methylthiopropylamine Chemical compound CSCCCN KKYSBGWCYXYOHA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101100425892 Danio rerio tpma gene Proteins 0.000 description 1
- 108010016626 Dipeptides Proteins 0.000 description 1
- 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 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 101150048952 TPM-1 gene Proteins 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0208—Separation of non-miscible liquids by sedimentation
- B01D17/0214—Separation of non-miscible liquids by sedimentation with removal of one of the phases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/02—Settling tanks with single outlets for the separated liquid
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
Abstract
The invention relates to the field of chemical industry, in particular to liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and a separation method of an oil phase in methionine production. Compared with the prior art, the method has the advantages that beneficial substances of the impurity enriched liquid are respectively separated in a mode of acidifying the crystallization mother liquor which is circulated for multiple times in methionine production, discharge treatment of the beneficial substances is avoided, low-grade alcohol or a coagulant is not introduced, separation equipment is simple, cost is low, energy consumption is low, and the maximization of the economic environment is realized.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and a separation method of an oil phase in methionine production.
Background
Methionine, also known by the name methionine, abbreviated Met, is one of the basic units for the biosynthesis of proteins, also an essential amino acid and a limiting amino acid. Met is the only sulfur-containing amino acid in the essential amino acids, the animal can obviously promote growth by taking a small amount of Met, the feeding period is shortened, the egg and milk yield can be increased, if the Met is not taken sufficiently, other amino acids in the body can be insufficiently utilized, the unused amino acids are converted into energy molecules and urea through deamination, and the burden of the liver and the kidney is increased. Methionine is widely used in the fields of feed, medicine, food, cosmetics and the like.
The known methionine production process is to synthesize 5- (beta-methylthioethyl) hydantoin, which can also be called hydantoin or hydantoin for short, by taking 3-methylthiopropanal, hydrocyanic acid, ammonia and carbon dioxide as raw materials. The hydantoin is hydrolyzed by alkali to obtain hydrolysate of methionine salt and carbonate mixture. Acidifying the hydrolysate to obtain methionine and filtrate containing large amount of useful components, and circulating after treatment; the difference between the acidifying medium and the base determines the difference in the return of the filtrate to the process, either to hydrolysis of the hydantoin or to the crystallization step.
Hydantoin is a necessary intermediate for the main production process of methionine, and bases such as potassium carbonate, sodium hydroxide, calcium hydroxide, potassium bicarbonate, sodium bicarbonate and the like can be used for hydantoin hydrolysis. The production process flow of the methionine is long, and no matter which alkali is used for hydrolyzing hydantoin, the generation of impurities cannot be avoided, wherein the impurities comprise formic acid, acrolein polymeric derivative, 3-methylmercapto propionaldehyde polymeric derivative, methionine hydroxy analogue, methionine derivative precursor, polycarboxylic acid impurities and the like, and the impurities are similar to the structure of the methionine: or carbon chains or amino or carboxyl, most impurities have similar and compatible effects with methionine, and are difficult to separate from the methionine completely, the quality of extracted methionine is reduced in the circulating process, and the yield of the reaction is affected, so that the separation of the impurities is a necessary operation.
Patent publication CN106748932A uses a microporous membrane filter to remove polymers from a mixed solution of methionine and bicarbonate, and then uses a cation exchange resin to separate the mixture into a methionine solution and a sulfate solution, and uses electrodialysis or stripping and/or an anion exchange resin to separate formic acid from the methionine solution. Firstly, the impurities in the crystallization mother liquor are not enriched, and the alkaline potassium is directly changed into neutral potassium by using cation resin, which is waste; secondly, the impurities in the crystallization mother liquor are small molecules and have viscosity, and the microporous membrane filter is difficult to filter the impurities and even blocked.
The patent publication CN102796033B uses organic solvent to extract hydrolysate, part of impurities are extracted to organic phase, the organic phase is recycled after distillation, and the residual liquid is treated as waste liquid. Firstly, methionine salt and carbonate in the saponified solution have high concentration, and an organic solvent is mixed with part of the saponified solution, so that part of products are wasted; secondly, the organic solvent is partially dissolved in the saponification solution, so that the subsequent organic solvent is accumulated; thirdly, the saponification liquid has low impurity proportion and low extraction efficiency, the part of impurities are basically 3-methylmercapto-propionaldehyde polymer and water phase are immiscible, and TPMA dimer can be controlled to a very low level in the preparation of 5- (2-methylmercapto-ethyl) -hydantoin; fourthly, the saponification liquid is strongly alkaline, carboxyl impurities are more soluble in a water phase, and the organic extraction effect is not obvious, but the impurities are one of main components. The comprehensive organic solvent extraction saponification liquid can only extract a very small amount of impurities in the saponification liquid, and no operation scheme is provided for the enrichment of formic acid.
The patent publication CN110678445A uses electrodialysis to remove 1-5 carbon anions in the methionine crystallization mother liquor. Within acceptable time and energy consumption of industrial production, electrodialysis cannot achieve the purpose well; methionine can enter the anolyte due to osmotic pressure or potential difference, and the anolyte still needs further treatment; furthermore, the concentration of impurities in the crystallization mother liquor may cause clogging of the membrane, which eventually leads to poor electrodialysis efficiency or even breakdown.
CN401693082A points out that methionine generates impurities such as dimethyldisulfide, allylamine, 3-methylthiopropylamine and the like during heating, but the heating time, the heating frequency and the heating temperature are not mentioned. The hydantoin hydrolysis process uses alkali metal or alkaline earth metal, and acidification salt and methionine mixture, because the content and solubility of the two are different, the subsequent concentration has multiple limits, thus the concentration has to be repeated. In order to reduce the number of concentration times, the methionine practitioner proposed the following protocol.
The hydrolysis liquid in CN107531621A is firstly concentrated to extract partial sodium carbonate to be returned to the hydrolysis of hydantoin, and then the methionine is extracted by sulfuric acid acidification, thus reducing the consumption of alkaline sodium and sulfuric acid for hydrolysis and also reducing the generation of sodium sulfate. Sodium carbonate is easily dissolved in water, and the hydrolysate is not easy to operate by concentrating to a high multiple and then filtering, so that a large amount of energy is consumed for concentration, and the treatment of impurities is not mentioned.
CN104693082A uses chromatographic separation technique to separate the mixed solution of sodium sulfate and methionine, and CN106432018A uses chromatographic separation technique to separate the mixed solution of potassium bicarbonate and methionine. The chromatographic separation technology needs to additionally introduce a large amount of water, so that the concentration of the methionine solution is reduced; secondly, the chromatographic separation has large investment and low separation efficiency, and most importantly, impurities generated in the methionine preparation are not treated, and the part of impurities (relative to impurities generated by thermal decomposition) are important to treat; furthermore, the separation effect of the chromatography on bicarbonate and methionine is considerable.
CN104926701A and CN103772246A use resin separation technology to separate the hydrolysate into methionine solution and sodium sulfate solution, and then the methionine and sodium sulfate are obtained by separate treatment. However, due to the solubility of methionine and the heat resistance of ion exchange resin, the saponified solution entering the ion exchange resin column must be diluted to a low concentration, and the subsequent crystallization and concentration operations are costly; the ion exchange resin is only used for separating sodium sulfate from other components, the intermediates of 3-methylmercapto propionaldehyde, 2-acrylic acid and acrolein and the polymers thereof, formate, methionine dipeptide and pigment mostly enter methionine solution, and the concentration and crystallization for a long time cause the enrichment of impurities to influence the quality of methionine; the sodium sulfate mother liquor is evaporated and crystallized, so that the enrichment of impurities can be caused, and the product quality of sodium sulfate is influenced; finally, the ion exchange technology needs to introduce a large amount of water, and subsequent operation generates a large amount of wastewater, which is not favorable for environmental protection and economy, and the cost for the main process flow is high.
CN109734637A, CN103922980A, CN103933861A, CN106432020B, CN104130169A, CN103922980A and CN105671587A, the mixed solution of methionine and carbonate/bicarbonate is separated into methionine and alkali liquor by using a bipolar membrane. Firstly, methionine has limited solubility and needs to be diluted by water, and the separated methionine solution needs to be concentrated and crystallized or crystallized at low temperature; secondly, the mixed solution contains a plurality of impurities, which has influence on the electron utilization efficiency of the bipolar membrane and the service life of the bipolar membrane; thirdly, the bipolar membrane is used for generating low-concentration alkali which still needs to be concentrated for use; fourthly, the generated carbon dioxide is neutral molecules, so that the solution resistance is increased, the electrodialysis efficiency is low, and the investment of equipment used for the main process flow is large and the operation cost is high.
Hydrolyzing with carbon dioxide in CN1923807A, CN101602700A, CN101602701A and CN110536881A to extract methionine and mother liquor, concentrating part of the mother liquor, adding lower alcohol to separate the mixture of methionine and potassium carbonate, returning the mixture to hydrolysis of hydantoin, and treating the secondary mother liquor for disposal. The introduction of lower alcohols is also problematic in that the system is subject to residual recovery.
If the impurities can be separated, they can be treated in a manner that maximizes the resource benefits and is not incinerated or biochemically treated.
In summary, the treatment can be divided into two concepts of extracting impurities or extracting methionine/salt, because methionine and salt have larger solubility in water, the extraction of impurities is not an alternative, however, the following problems still exist in the known published patents:
(1) the handling of impurities produced in the production of methionine is not explicitly mentioned;
(2) in order to reduce the separation of methionine and salt by a small part of impurities generated by subsequent treatment, a high-cost and high-energy-consumption equipment technology is used;
(3) treating the methionine crystallization mother liquor, and introducing lower alcohol or a coagulant;
(4) after the methionine crystallization mother liquor is treated, a part of crystallization mother liquor still needs to be discarded, and beneficial substances cannot be recovered;
(5) the waste of partial crystallization mother liquor is treated into low-value substances by using beneficial resources, and the cost is increased for the second time.
Disclosure of Invention
In order to solve the problems mentioned in the background art, the invention aims to provide a liquid-liquid two-phase or liquid-solid three-phase continuous separation device and a separation method of an oil phase in methionine production.
On one hand, the invention provides liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment, which is characterized in that: the solid-liquid separator comprises a housing, the inside of casing is from last to being divided into subsidence area and dense district down, the overflow mouth has been seted up on the upper portion of casing, chassis bottom pipe connection has solid-liquid separator, the overflow mouth the subsidence area with communicate through the three-phase separator between the dense district. In actual operation, the acidizing fluid flows and is separated between the settling zone and the thickening zone through the three-phase separator, the oil phase on the upper layer of the settling zone flows out of the overflow port, and the acid-containing aqueous solution and the solid mixture in the thickening zone are separated through the solid-liquid separator.
Preferably, the three-phase separator comprises a bypass pipe and a plurality of inclined pipes, the bypass pipe is vertically arranged, the upper end and the lower end of the bypass pipe are respectively communicated with the overflow port and the dense area, the upper end and the lower end of each inclined pipe are respectively communicated with the bypass pipe and the settling area, the settling area is provided with a plurality of inclined plates in parallel from top to bottom, and each inclined plate is arranged above the inclined pipe outlet in a one-to-one correspondence manner. During actual operation, the inclined pipe can reduce liquid flow stress, two liquid phases with different densities are automatically transferred into the bypass pipe for further separation, the oil phase flows out from the overflow port, the acid-containing aqueous solution with high density and a small amount of solid naturally settle to a dense area, and continuous separation of liquid-liquid two phases or liquid-solid three phases is realized.
Preferably, a feed inlet of the solid-liquid separator is communicated with the bottom of the thickening zone, and a liquid outlet of the solid-liquid separator is communicated with the upper part of the thickening zone. In actual operation, in order to ensure the liquid level of the upper layer and enable the oil phase to overflow, part of separated liquid flows back to the dense area.
On the other hand, the key point of the method for separating the oil phase in methionine production is that the method comprises the following steps:
s1, adding acid into the impurity enrichment solution for acidification until the pH value of the acidification solution is less than 4;
s2, distilling the acidified liquid at 60-100 ℃ to remove formic acid;
s3. separating the acidified liquid with formic acid removal into an oil phase, an aqueous phase and a solid phase using the apparatus of claims 1 to 3. In actual operation, the mother liquor which is recycled for multiple times in methionine production is used as the impurity-enriched liquid, and the impurity-enriched liquid contains one or more of the following components except solvent water: methionine, methionine derivatives, 3-methylthiopropanal, polymers and derivatives, potassium carbonate, potassium bicarbonate, potassium hydroxide, sodium sulfate, sodium carbonate, sodium bicarbonate, hydrocyanic acid derivatives and hydrolysis products of the derivatives, and hydrocyanic acid hydrolysis product formic acid, most of impurities generated in methionine production contain carboxyl, the impurities can be layered with a system after being enriched in the system by adjusting pH, the upper layer is a red-black oil phase, the lower layer is a system water solution, the oil phase impurities are completely adsorbed on other impurities, even the water solution is changed from original black red to light yellow, the methionine is changed into methionine acid salt in the acid system, and the methionine has high solubility in water, so that the oil phase impurities are completely/completely separated.
Preferably, the acid in S1 is one or more of hydrochloric acid, phosphoric acid, sulfuric acid, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium hydrogen sulfate, sodium hydrogen phosphate, disodium hydrogen phosphate, potassium hydrogen phosphate, dipotassium hydrogen phosphate, and ammonium hydrogen phosphate.
Preferably, the pH of the acidified solution in S1 is < 3. In practical operation, because the formic acid is dissolved in both the water phase and the organic phase, the formate in the acidification liquid is removed after being changed into the formic acid, and the organic phase and the water phase are separated more thoroughly and rapidly.
Preferably, S2 specifically is: extracting the acidizing fluid by using steam and circulating gas at the temperature of 60-100 ℃, wherein the extraction time is 10-100min, and returning the formic acid-containing gas phase into the acidizing fluid after the formic acid-containing gas phase is absorbed by alkali liquor. In practical operation, after circular extraction, the alkali liquor can be concentrated to prepare formate, the concentrated effluent can be used for supplementing water in the acidizing fluid, and the pH value of the acidizing fluid can be stabilized to a certain value.
Preferably, the recycle gas is carbon dioxide gas.
Preferably, the alkali liquor is prepared by dissolving one or more of oxides, hydroxides and carbonates of alkali metals and alkaline earth metals in water.
Preferably, in S3, the acidified liquid is introduced into a separation device, the temperature is controlled at 30-80 ℃, and continuous liquid-liquid or liquid-solid separation is performed, wherein the upper layer of a settling zone of the separation device is oil phase impurities, the middle layer is an acid-containing aqueous solution, and the lower layer is a solid. In actual operation, the temperature of the acidizing fluid needs to be controlled, the pH value of the overflowed oil phase needs to be adjusted to 5-7, and the fluidity of oil phase impurities can be increased, wherein the oil phase impurities mainly comprise 2-hydroxy-4-methylthiobutyronitrile, 3-methylthiopropanal, polymers of hydrocyanic acid, polymer hydrolysate and hydrolysate, water, potassium sulfate and the like.
Has the advantages that: compared with the prior art, the method has the advantages that beneficial substances of the impurity enriched liquid are respectively separated in a mode of acidifying the crystallization mother liquor which is circulated for multiple times in methionine production, discharge treatment of the beneficial substances is avoided, low-grade alcohol or a coagulant is not introduced, separation equipment is simple, cost is low, energy consumption is low, and the maximization of the economic environment is realized.
Drawings
FIG. 1 is a schematic structural diagram of the present invention.
Detailed Description
The present invention is described in detail in the following examples, which are given for the purpose of illustration only and are not to be construed as limiting the scope of the invention, which is defined in the claims. Except for special description, the parts are parts by weight, the percentages are mass percentages, and the concentration is mass percentage concentration.
Example 1
The utility model provides a liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment, includes casing 1, the inside of casing 1 is from last to being divided into settling zone an and dense district b down, overflow mouth 2 has been seted up on the upper portion of casing 1, casing 1 bottom pipe connection has solid-liquid separator 3, overflow mouth 2 the settling zone a with communicate through the three-phase separator between the dense district b.
Example 2
A liquid-liquid two-phase or liquid-solid three-phase continuous separation device comprises a machine shell 1, the interior of the machine shell 1 is divided into a settling area a and a dense area b from top to bottom, an overflow port 2 is formed in the upper portion of the machine shell 1, a solid-liquid separator 3 is connected to the bottom of the machine shell 1 through a pipeline, a feed inlet of the solid-liquid separator 3 is communicated with the bottom of the dense area b, a liquid outlet of the solid-liquid separator 3 is communicated with the upper portion of the dense area b, and the overflow port 2, the settling area a and the dense area b are communicated through a three-phase separator; the three-phase separator comprises a bypass pipe 4 and a plurality of inclined pipes 5 which are vertically arranged, the upper end and the lower end of the bypass pipe 4 are respectively communicated with the overflow port 2 and the dense area b, the upper end and the lower end of each inclined pipe 5 are respectively communicated with the bypass pipe 4 and the settling area a, the settling area a is provided with a plurality of inclined plates 6 in parallel from top to bottom, and each inclined plate 6 is arranged above the outlet of each inclined pipe 5 in a one-to-one correspondence manner.
Example 3
The apparatus of example 2 was used for separation of the oil phase in the production of isolated methionine.
The source of the impurity-enriched liquid is a mother liquid obtained by acidifying sodium hydroxide hydrolysate of hydantoin with sulfuric acid to extract methionine, concentrating and extracting sodium sulfate and then repeatedly extracting methionine and sodium sulfate for multiple times until impurities are enriched in the process of hydrolyzing hydantoin with sodium hydroxide, wherein the content of methionine is 0.5-3 wt%, the content of formate is 1-5 wt%, the content of sodium sulfate is 10-30 wt%, and the content of impurities containing methylthio groups is 1-10 wt%.
Adjusting the pH value of the impurity-enriched liquid to 2.4 by using sulfuric acid, removing formic acid from the acidified liquid by using carbon dioxide/steam at 60-100 ℃, absorbing the removed gas by using alkali liquor, returning to gas stripping of the acidified liquid, removing formic acid for 40-60min, continuously transferring the acidified liquid into separation equipment when the pH value of the acidified liquid is stable to 2.7, controlling the temperature of materials in the separation equipment to be 35-45 ℃, adjusting the pH value of overflowing oil phase substances to 5-7 by using ammonia, wherein the oil phase substances contain N, S, and the method is particularly suitable for composting.
Example 4
The apparatus of example 2 was used for separation of the oil phase in the production of isolated methionine.
The source of the impurity-enriched liquid is a crystallization mother liquid for extracting methionine by carbon dioxide acidification of potassium carbonate hydrolysate of hydantoin in a process of hydrolyzing hydantoin with potassium carbonate or a mother liquid for repeatedly regenerating hydrolyzed hydantoin and extracting methionine to enrich impurities, wherein the content of methionine is 0.5-3 wt%, the content of formate is 1-5 wt%, the content of alkaline potassium is 0.2-2 wt%, and the content of impurities containing methylthio groups is 1-10 wt%.
Adjusting the pH value of the impurity-enriched liquid to 2.2 by using sulfuric acid, removing formic acid from the acidified liquid by using carbon dioxide/steam at 60-100 ℃, absorbing the removed gas by using alkali liquor, returning to gas stripping of the acidified liquid, removing formic acid for 10-30min, continuously transferring into separation equipment when the pH value of the acidified liquid is stabilized to 2.4, controlling the temperature of materials in the separation equipment to be 30-60 ℃, adjusting the pH value of overflowing oil phase substances to 5-7 by using ammonia, and adjusting the pH value of the overflowing oil phase substances to N, S, K at the moment, so that the method is particularly suitable for composting.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (10)
1. A liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment is characterized in that: including casing (1), the inside of casing (1) is from last to dividing into subsidence area (a) and dense district (b) down, overflow mouth (2) have been seted up on the upper portion of casing (1), casing (1) bottom pipe connection has solid-liquid separator (3), overflow mouth (2) subside district (a) with communicate through the three-phase separator between the dense district (b).
2. A liquid-liquid two-phase or liquid-solid three-phase continuous separation apparatus according to claim 1, characterized in that: the three-phase separator comprises a bypass pipe (4) and a plurality of inclined pipes (5), wherein the bypass pipe (4) and the inclined pipes (5) are vertically arranged, the upper end and the lower end of the bypass pipe (4) are respectively communicated with the overflow port (2) and the dense area (b), the upper end and the lower end of each inclined pipe (5) are respectively communicated with the bypass pipe (4) and the sedimentation area (a), the sedimentation area (a) is parallelly provided with a plurality of inclined plates (6) from top to bottom, and each inclined plate (6) is arranged above an outlet of each inclined pipe (5) in a one-to-one correspondence mode.
3. A liquid-liquid two-phase or liquid-solid three-phase continuous separation apparatus according to claim 1 or 2, characterized in that: the feed inlet of the solid-liquid separator (3) is communicated with the bottom of the dense area (b), and the liquid outlet of the solid-liquid separator (3) is communicated with the upper part of the dense area (b).
4. A method for separating oil phase in methionine production is characterized by comprising the following steps:
s1, adding acid into the impurity enrichment solution for acidification until the pH value of the acidification solution is less than 4;
s2, distilling the acidified liquid at 60-100 ℃ to remove formic acid;
s3. separating the acidified liquid with formic acid removal into an oil phase, an aqueous phase and a solid phase using the apparatus of claims 1 to 3.
5. The method for separating an oil phase in methionine production according to claim 4, wherein: the acid in S1 is one or more of hydrochloric acid, phosphoric acid, sulfuric acid, sodium bisulfate, potassium bisulfate, ammonium bisulfate, sodium hydrogen phosphate, disodium hydrogen phosphate, potassium hydrogen phosphate, dipotassium hydrogen phosphate and ammonium hydrogen phosphate.
6. The method for separating an oil phase in methionine production according to claim 4, wherein: the pH of the acidified liquid in S1 is less than 3.
7. The method for separating the oil phase in methionine production according to claim 4, wherein S2 specifically comprises: extracting the acidizing fluid by using steam and circulating gas at the temperature of 60-100 ℃, wherein the extraction time is 10-100min, and returning the formic acid-containing gas phase into the acidizing fluid after the formic acid-containing gas phase is absorbed by alkali liquor.
8. The method for separating an oil phase in methionine production according to claim 7, wherein: the circulating gas is carbon dioxide gas.
9. The method for separating oil phase in methionine production according to claim 7, wherein the alkali solution is prepared by dissolving one or more of oxide, hydroxide and carbonate of alkali metal and alkaline earth metal in water.
10. The method for separating the oil phase in the methionine production according to claim 7, wherein in S3, the acidified liquid is introduced into a separation device, the temperature is controlled to be 30-80 ℃, continuous liquid-liquid or liquid-solid separation is performed, the upper layer of a settling zone of the separation device is oil phase impurities, the middle layer is an acid-containing aqueous solution, and the lower layer is a solid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210473690.7A CN115105863B (en) | 2022-04-29 | 2022-04-29 | Liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and separation method of oil phase in methionine production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210473690.7A CN115105863B (en) | 2022-04-29 | 2022-04-29 | Liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and separation method of oil phase in methionine production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115105863A true CN115105863A (en) | 2022-09-27 |
| CN115105863B CN115105863B (en) | 2023-10-24 |
Family
ID=83326431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210473690.7A Active CN115105863B (en) | 2022-04-29 | 2022-04-29 | Liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and separation method of oil phase in methionine production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115105863B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110233144A1 (en) * | 2007-10-14 | 2011-09-29 | Mccabe Derald L | Solids removal system and method |
| US20130206684A1 (en) * | 2010-07-08 | 2013-08-15 | Paques I.P. B.V. | Purifier comprising a solids separation device, and method for wastewater purification |
| CN106512491A (en) * | 2017-01-23 | 2017-03-22 | 太原市润民环保节能有限公司 | Turnover precipitation separation device |
| CN206142879U (en) * | 2016-09-10 | 2017-05-03 | 盘锦金宇众和工程服务有限公司 | Oil field filter -pressing water oil -water separator |
| CN211383924U (en) * | 2019-08-14 | 2020-09-01 | 上海洗霸科技股份有限公司 | Double-layer filler precipitation device |
| CN113698002A (en) * | 2021-09-23 | 2021-11-26 | 中国矿业大学 | Novel reverse osmosis strong brine recovery treatment process |
| CN114149351A (en) * | 2021-12-10 | 2022-03-08 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine optimized preparation method based on sulfuric acid direct acidification method and sodium sulfate washing equipment |
-
2022
- 2022-04-29 CN CN202210473690.7A patent/CN115105863B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110233144A1 (en) * | 2007-10-14 | 2011-09-29 | Mccabe Derald L | Solids removal system and method |
| US20130206684A1 (en) * | 2010-07-08 | 2013-08-15 | Paques I.P. B.V. | Purifier comprising a solids separation device, and method for wastewater purification |
| CN206142879U (en) * | 2016-09-10 | 2017-05-03 | 盘锦金宇众和工程服务有限公司 | Oil field filter -pressing water oil -water separator |
| CN106512491A (en) * | 2017-01-23 | 2017-03-22 | 太原市润民环保节能有限公司 | Turnover precipitation separation device |
| CN211383924U (en) * | 2019-08-14 | 2020-09-01 | 上海洗霸科技股份有限公司 | Double-layer filler precipitation device |
| CN113698002A (en) * | 2021-09-23 | 2021-11-26 | 中国矿业大学 | Novel reverse osmosis strong brine recovery treatment process |
| CN114149351A (en) * | 2021-12-10 | 2022-03-08 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine optimized preparation method based on sulfuric acid direct acidification method and sodium sulfate washing equipment |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115105863B (en) | 2023-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107055712B (en) | Method for recovering ammonia nitrogen, phosphorus and volatile fatty acid in livestock and poultry excrement hydrolysate by using two-stage bipolar membrane electrodialysis | |
| CN108658345B (en) | Method and system for refining salt from high-salt wastewater | |
| CN108658821B (en) | Clean production method of D, L-methionine and product thereof | |
| CN109721471B (en) | Method for purifying glycerin from by-product of biodiesel production | |
| CN110526839B (en) | Improved process for preparing taurine by ethylene oxide method | |
| CN112661682B (en) | Method for producing DL-methionine | |
| CN114149351A (en) | Methionine optimized preparation method based on sulfuric acid direct acidification method and sodium sulfate washing equipment | |
| CN106316832A (en) | Method for obtaining high-purity lactic acid by separating non-calcium salt lactic acid fermentation broth | |
| CN112661683A (en) | DL-methionine production method without discharged wastewater | |
| CN101108815B (en) | Method of recycling precipitating agent in production of L-leueine | |
| CN114044748A (en) | Methionine optimized preparation method based on carbon dioxide acidification method | |
| CN110713297A (en) | Caffeine wastewater treatment and recovery process | |
| CN108658757B (en) | Method for recovering phenylacetic acid from 6-aminopenicillanic acid enzymatic aqueous solution | |
| CN106748932B (en) | A kind of post-processing approach and device preparing methionine | |
| CN101870639A (en) | Method for producing kelp mannitol with low energy consumption | |
| CN110342559A (en) | A kind of system and method being recycled evaporated waste ammonia liquid joint-producing anhydrous sodium carbonate | |
| CN115105863B (en) | Liquid-liquid two-phase or liquid-solid three-phase continuous separation equipment and separation method of oil phase in methionine production | |
| CN208586063U (en) | A kind of system being recycled evaporated waste ammonia liquid joint-producing anhydrous sodium carbonate | |
| CN104876817B (en) | A kind of method that use succinic acid fermentation liquor extracts succinic acid | |
| CN106588641B (en) | A kind of recovery method of 2-KLG primary crystallization mother liquor | |
| CN101353337B (en) | Vitamin c clean production method | |
| CN112811647B (en) | Method for treating waste liquid in DL-methionine production | |
| CN104211270B (en) | The processing method of cyclization waste water in production process of lipoic acid | |
| CN106117012B (en) | A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination | |
| KR101073726B1 (en) | Economical manufacturing process of xylose from biomass hydrolysate using electrodialysis and direct recovery method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |