CN117105833A - Preparation method of L-cystine - Google Patents
Preparation method of L-cystine Download PDFInfo
- Publication number
- CN117105833A CN117105833A CN202310818669.0A CN202310818669A CN117105833A CN 117105833 A CN117105833 A CN 117105833A CN 202310818669 A CN202310818669 A CN 202310818669A CN 117105833 A CN117105833 A CN 117105833A
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- China
- Prior art keywords
- activated carbon
- cystine
- solution
- adsorption
- hydrochloric acid
- Prior art date
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- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 title claims abstract description 102
- 229960003067 cystine Drugs 0.000 title claims abstract description 101
- 239000004158 L-cystine Substances 0.000 title claims abstract description 27
- 235000019393 L-cystine Nutrition 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 244
- 238000001179 sorption measurement Methods 0.000 claims abstract description 89
- 238000000034 method Methods 0.000 claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 37
- 238000001035 drying Methods 0.000 claims abstract description 32
- 230000007062 hydrolysis Effects 0.000 claims abstract description 28
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 28
- 238000001556 precipitation Methods 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 21
- 238000004140 cleaning Methods 0.000 claims abstract description 18
- 238000007670 refining Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000001953 recrystallisation Methods 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 67
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 54
- 238000001914 filtration Methods 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 239000003513 alkali Substances 0.000 claims description 28
- 238000010438 heat treatment Methods 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 27
- 239000000413 hydrolysate Substances 0.000 claims description 24
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000012043 crude product Substances 0.000 claims description 21
- 238000000967 suction filtration Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000006386 neutralization reaction Methods 0.000 claims description 17
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 238000010992 reflux Methods 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000012065 filter cake Substances 0.000 claims description 10
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 9
- 238000011010 flushing procedure Methods 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000003301 hydrolyzing effect Effects 0.000 claims description 7
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 6
- 239000004323 potassium nitrate Substances 0.000 claims description 6
- 235000010333 potassium nitrate Nutrition 0.000 claims description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 239000012459 cleaning agent Substances 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000004519 grease Substances 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000012467 final product Substances 0.000 abstract description 2
- 229940024606 amino acid Drugs 0.000 description 39
- 235000001014 amino acid Nutrition 0.000 description 38
- 150000001413 amino acids Chemical class 0.000 description 38
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 11
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000004475 Arginine Substances 0.000 description 6
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 6
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 6
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 239000004220 glutamic acid Substances 0.000 description 5
- 235000013922 glutamic acid Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 5
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 4
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005457 optimization Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 102000011782 Keratins Human genes 0.000 description 3
- 108010076876 Keratins Proteins 0.000 description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 3
- AGPKZVBTJJNPAG-WHFBIAKZSA-N L-isoleucine Chemical compound CC[C@H](C)[C@H](N)C(O)=O AGPKZVBTJJNPAG-WHFBIAKZSA-N 0.000 description 3
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 3
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 3
- 239000004472 Lysine Substances 0.000 description 3
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000003704 aspartic acid Nutrition 0.000 description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004042 decolorization Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004153 Potassium bromate Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 description 2
- 239000004473 Threonine Substances 0.000 description 2
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005903 acid hydrolysis reaction Methods 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 2
- 229960000310 isoleucine Drugs 0.000 description 2
- AGPKZVBTJJNPAG-UHFFFAOYSA-N isoleucine Natural products CCC(C)C(N)C(O)=O AGPKZVBTJJNPAG-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 235000019396 potassium bromate Nutrition 0.000 description 2
- 229940094037 potassium bromate Drugs 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 description 1
- 239000004201 L-cysteine Substances 0.000 description 1
- 235000013878 L-cysteine Nutrition 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- COLNVLDHVKWLRT-QMMMGPOBSA-N L-phenylalanine Chemical compound OC(=O)[C@@H](N)CC1=CC=CC=C1 COLNVLDHVKWLRT-QMMMGPOBSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000729 antidote Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008081 blood perfusion Effects 0.000 description 1
- 235000008429 bread Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 235000013365 dairy product Nutrition 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003172 expectorant agent Substances 0.000 description 1
- 230000003419 expectorant effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/354—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of L-cystine, which comprises the steps of removing impurities from collected pig hair, cleaning, drying and cutting off; then the L-cystine finished product is obtained after hydrolysis, isoelectric point precipitation, decoloration refining and recrystallization and drying. According to the preparation method of cystine, the pig hair can be hydrolyzed, cystine is collected from the hydrolyzed solution through repeated isoelectric precipitation, and meanwhile, in the decoloring and refining crystallization processes, modified activated carbon is adopted to realize that the adsorption effect on the product cystine is reduced while the adsorption of other impurities is not influenced, so that the total yield of a final product is improved, the loss is reduced, and the industrial benefit of product production is remarkably improved.
Description
Technical Field
The invention relates to the technical field of amino acid preparation methods, in particular to a preparation method of L-cystine.
Background
L-cystine is an organic substance with a molecular weight of 240.3, and is a white hexagonal plate crystal or white crystal powder, which is soluble in dilute acid and alkaline solution, extremely insoluble in water, and insoluble in ethanol. Proteins are present in small amounts, and are contained in keratin such as hair and fingers. The product is used as raw material for producing antidote and expectorant, and can be used as dairy product additive and bread quick-forming promoter in food industry, and can generate various special fragrances after heating with saccharides in food, prevent oxidation of oil and fat, and has wide application in food processing process; the cosmetic industry is a raw material for producing cold-ironing essence.
The preparation method of L-cystine mainly comprises three steps:
(1) Air is used to oxidize the alkaline aqueous solution of L-cysteine.
(2) The content of the extract from pig hair, especially horsehair, can reach 8%. Hydrolyzing pig hair in acid at 110deg.C or keratin, removing impurities, neutralizing with alkali to pH=5.1, crystallizing to obtain crude product, dissolving in hydrochloric acid under heating, decolorizing with activated carbon, filtering, neutralizing the filtrate with ammonia, recrystallizing, and washing until no chloride ion or iron ion is contained.
The method comprises the following steps: adding 720kg of hydrochloric acid with the concentration of 10mol/L into a hydrolysis tank, heating to 70-80 ℃, rapidly adding 400kg of human hair or pig, continuously heating to 100 ℃, heating to 110-117 ℃ within 1-1.5 h, hydrolyzing for 6.5-7 h (counted from 100 ℃), cooling and filtering. Adding 30% -40% industrial sodium hydroxide solution into the filtrate under stirring, adding alkaline solution at a reduced speed until the pH value reaches 3.0, standing for 36h until the pH value reaches 4.9, separating precipitate, and centrifuging to spin-dry to obtain cystine crude product (I), wherein the mother liquor contains glutamic acid, arginine, leucine and the like. Weighing 150kg of cystine crude product (I), adding about 90kg of 10mol/L hydrochloric acid, 360kg of water, heating to 65-70 ℃, stirring and dissolving for 0.5h, adding 12kg of active carbon, heating to 80-90 ℃, preserving heat for 0.5h, and carrying out plate-frame filter pressing. Heating the filtrate to 80-85 ℃, adding 30% sodium hydroxide while stirring, and stopping until ph is 4.8. Standing to precipitate crystals, siphoning supernatant, separating out bottom precipitate, and centrifuging to spin dry to obtain cystine crude product (II). Weighing 100kg of cystine crude product (II), adding 500L of 1mol/L hydrochloric acid, heating to 70 ℃, and adding 3-5 kg of active carbon. Then heating to 85 ℃, preserving heat, stirring for 0.5h, and carrying out plate-frame filter pressing. Adding distilled water into the filtrate, which is about 1.5 times of the volume of the filtrate, heating to 75-80 ℃, and neutralizing with 12% ammonia water until ph is 3.5-4.0 under stirring, wherein cystine is crystallized and separated out. And (3) crystallizing, centrifuging, drying, washing with distilled water until no chloride ions exist, and drying in vacuum to obtain the cystine finished product. The yield of human hair can reach 8 percent and the yield of pig hair can reach 5 percent.
The prior art is one of the preparation methods disclosed above, hydrochloric acid hydrolysis, first filtering to remove impurities, adding sodium hydroxide to adjust the pH value to the isoelectric point of cystine for precipitation, carrying out second filtering after precipitation to obtain a crude product, adding hydrochloric acid into the crude product for dissolution, adding activated carbon for decolorization and adsorption, carrying out third filtering, adding hydrochloric acid again for dissolution and decolorization and adsorption after filtration, adding ammonia water for neutralization until crystallization is separated out after the last decolorization, and washing and vacuum drying to obtain cystine.
In the prior art, the activated carbon is often used for refining the amino acid solution, and impurities in the crude amino acid solution are adsorbed by utilizing the physical and chemical adsorption properties of the activated carbon. The applicant has found that the adsorption capacity of the activated carbon to each amino acid in the amino acid solution is different, i.e. the adsorption capacity of the same activated carbon to different amino acids is different.
Document 1: preparation of related amino acids from pig hair
Document 1 discloses the following information: pig hair is a keratin that contains various amino acids necessary for various animal bodies including human bodies. The amino acid and content of the pig hair are as follows: arginine 10.9%, glutamic acid 15.3%, histidine 1.1%, isoleucine 4.7%, threonine 6.3%, valine 5.9%, cystine 14.4%, aspartic acid 8.0%, leucine 8.3%, lysine 3.8%, tyrosine 3.5%.
The content ratio of amino acids and isoelectric point of the pig hair are as follows
| Name of the name | Content of | Isoelectric point |
| Glutamic acid glu | 15.3％ | 3.22 |
| Arginine Arg | 10.9％ | 10.76 |
| Cystine Cys | 14.4％ | 4.9 |
| Aspartic acid asp | 8.0％ | 2.97 |
| Isoleucine Ile | 4.7％ | 6.02 |
| Threonine Thr | 6.3％ | 6.53 |
| Leucine Leu | 8.3％ | 5.98 |
| Lysine Lys | 3.8％ | 9.74 |
| Tyrosine Tyr | 3.5％ | 5.6 |
| Valvaline Val | 5.9％ | 5.96 |
It is known from the prior art that cystine is prepared by adjusting the solution to the isoelectric point of cystine to minimize the solubility of cystine and then precipitating to obtain crude product. Most of other amino acids have higher solubility at the isoelectric point of cystine and are in a dissolved state, so that solid-liquid separation can be carried out. The isoelectric points of the rest amino acids in the pig hair are obviously different from those of cystine, so that the rest amino acids basically do not form floccules or form a blend with the crude cystine when cystine is separated out.
Document 2: discussion of problems in extraction of cystine by isoelectric point method
As can be seen from table 1, the total yield loss of cystine extraction was measured in document 2, and the cystine content in the hydrolysate was 142g, which means that the cystine content was 14.2%, which is in agreement with the data of 14.4% cystine content of the pig hair disclosed in document 2, indicating that the cystine hydrolysis was complete. However, in the process of forming the refined product, the hydrolysate is subjected to isoelectric point precipitation, and then subjected to multiple times of activated carbon adsorption to finally form refined cystine; the loss of cystine mainly exists in precipitation loss at isoelectric point and multiple adsorption loss of activated carbon. It can be seen from table 1 of document 2 that the loss amount of the crude product prepared from the hydrolysate is 20g, and that 71g of cystine is lost by adsorption of activated carbon in the process of obtaining the refined product from the crude product in the isoelectric point precipitation step, and that the yield of cystine is seriously affected by adsorption of activated carbon.
Document 3: influence of active carbon pore structure and surface chemical property on nitrobenzene adsorption
By reacting activated carbon HNO 3 Oxidation and subsequent N 2 The heat treatment in the atmosphere is carried out, and the influence of the property of the activated carbon on the nitrobenzene adsorption performance is studied. Cryogenic liquid nitrogen (N) 2 77K) adsorption to determine the specific surface area and pore volume, pore size distribution, SEM observation of the surface morphology of the activated carbon, boehm titration, FTIR zero charge point pHPZC determination andelemental analysis quantitatively characterizes the change of oxygen-containing functional groups on the surface of the activated carbon. The results indicate HNO 3 The oxidation can obviously change the surface chemical property of the activated carbon, increase the number of acidic oxygen-containing functional groups on the surface of the activated carbon, and has little influence on the pore structure of the activated carbon. Then N 2 The heat treatment in the atmosphere can cause the decomposition of acidic oxygen-containing functional groups on the surface of the activated carbon, the external surface area is increased, and micropores are ablated into mesopores. The adsorption of nitrobenzene on activated carbon substantially conforms to Langmuir's equation. The suitable number of mesopores and the smaller acidic oxygen-containing functional groups are the main reasons for the higher adsorption capacity of ACNO-T on nitrobenzene.
It can be seen from document 3 that the adsorption effect of activated carbon can be greatly affected by the chemical modification method, so that the activated carbon is changed from a lower adsorption amount to a higher adsorption amount.
Document 4: adsorption research of activated carbon on common physiological amino acid
Literature 1 discloses an adsorption test of PVB coated spherical activated carbon and bare carbon particles on amino acid in 18, and adopts a dynamic adsorption mode to verify the adsorption capacity of PVB coated activated carbon and bare carbon particles (the activated carbon not coated with PVB) on different amino acids.
As can be seen from table 1 of document 1, the adsorption capacity of the coated carbon was reduced to a different extent than that of the bare carbon, except for phenylalanine, but the reduction degree of the different amino acids was also significantly different. For example, the decrease in aspartic acid is 99% and the decrease in tryptophan is 9.13%; the reduction of cystine was 47.27% for 56.38% for glutamic acid and 34.12% for arginine; 11.72% of tyrosine.
In addition, as can be seen from the maximum adsorption scale of the activated carbon on the amino acid, the adsorption amount of the same activated carbon on different amino acids also has significant difference, for example, the adsorption amount of the activated carbon on cystine is 40.57 mu mol/g, the adsorption amount of the glutamic acid is 13.66 mu mol/g, the adsorption amount of the arginine is 65.21 mu mol/g, and the adsorption amount of the tyrosine is 371.86 mu mol/g; the adsorption amount of tryptophan was 338.3. Mu. Mol/g.
It can be seen from document 4 that the differences in the physicochemical properties of different amino acids result in significant differences and selectivities in the adsorption capacity of activated carbon for different amino acids, so that the refining effect of an amino acid solution can be improved by the selection of activated carbon in the refining process.
Secondly, the coated activated carbon is a good modification method, however, as the coated activated carbon is generally spherical, the spherical activated carbon is not easy to form scraps after being coated, and is beneficial to safer in blood perfusion. However, in the industrial production process, since the cost of spherical activated carbon is slightly higher than that of powdered activated carbon and the powdered activated carbon has higher adsorption efficiency, powdered activated carbon is generally used in the process of preparing cystine, but powdered activated carbon is generally not suitable for coating treatment.
It can be seen that the adsorption amount of cystine to activated carbon can be reduced by 47% by the coating treatment, but since the coating treatment is not suitable for powdered activated carbon, the adsorption amount of cystine to powdered activated carbon can be reduced by chemical-physical modification.
Disclosure of Invention
The invention aims to provide a preparation method of L-cystine based on acid hydrolysis.
The technical problems to be solved by the invention are as follows:
and (3) reducing the loss rate of cystine in the process of preparing the refined product from the crude cystine, and improving the total yield or the total yield of the product.
In order to achieve the above object, in one embodiment of the present invention, there is provided a method for preparing L-cystine, comprising the steps of:
removing impurities from collected pig hair, cleaning the pig hair by using hot water and a cleaning agent, removing dust and grease on the surface of the pig hair until the pig hair is cleaned, and drying and cutting off the pig hair after cleaning;
step (2) hydrolysis
Heating industrial hydrochloric acid to 100-110 ℃, adding pig hair, hydrolyzing, cooling and filtering after the hydrolysis is completed to obtain hydrolysate;
step (3) isoelectric precipitation
Adding alkali liquor into the hydrolysate under stirring operation to neutralize the hydrolysate until the pH value of the hydrolysate is 4.8-4.9; stopping stirring after the hydrolysis is finished, standing to enable the cystine to be completely precipitated, and then carrying out suction filtration to obtain a cystine crude product and a precipitation mother solution;
step (4) decoloring refining
Adding the cystine crude product into dilute hydrochloric acid, dissolving, adding modified activated carbon and EDTA, boiling and refluxing for 20-30 min; adding alkali liquor into the solution for neutralization after suction filtration, adjusting the pH value to be 4.8-4.9 until precipitation is achieved, standing and suction filtration to obtain a refined filter cake;
step (5) recrystallization
Dissolving the refined filter cake in dilute hydrochloric acid, adding modified activated carbon for adsorption treatment, filtering after adsorption for 30-60 min, adding alkali liquor for neutralization after filtering, regulating the pH value to precipitate, standing, carrying out suction filtration, flushing for a plurality of times by using hot water, and drying to obtain an L-cystine finished product;
preparation of modified activated carbon in step (6)
(A1) Immersing activated carbon powder in a potassium nitrate solution; then the activated carbon is placed in high-temperature steam with the temperature of 500-600 ℃ for treatment, and the volume fraction of oxygen in the high-temperature steam is 5-10%; after the treatment is finished, cleaning by using hot water to obtain active carbon A1;
(A2) Adding activated carbon A1 into 0.5-1.2 mol/L propylene glycol methyl ether acetate aqueous solution, and then treating for 60-90 min; adding ammonia water for continuous treatment after the treatment is finished; then filtering, sequentially flushing with ethanol and water, and drying to obtain active carbon A2;
(A3) Adding activated carbon A2 into a mixed solution of triethylenetetramine and acetic acid, controlling the temperature of the mixed solution to be 60-70 ℃, stirring for 3-6 h, and then filtering, washing and drying to obtain activated carbon A3;
(A4) The benzoyl chloride, the diethyl ether and the phosphorus trichloride are proportioned according to the volume ratio of 10-20:30-50:2-5 to obtain diethyl ether mixed solution, the activated carbon A3 is added into the diethyl ether mixed solution, heating, stirring and reflux treatment are carried out, after the treatment is finished, the washing is carried out by using tetrahydrofuran, then the washing is carried out by using ethanol, finally the washing is carried out by using hot water, and the modified activated carbon is obtained after filtration and drying.
In the optimized scheme of the invention, the industrial hydrochloric acid in the step (2) is 9-11 mol/L hydrochloric acid, and the hydrolysis time is 9-10 h; hydrochloric acid is refluxed during the hydrolysis.
In the optimized scheme of the invention, the alkali liquor in the step (3) is 30-35% sodium hydroxide solution and ammonia water; continuously detecting the pH value of the hydrolysate in the neutralization process; the alkali liquor added in the initial stage is sodium hydroxide solution, the alkali liquor is slowly added after the pH value reaches 3.0, and ammonia water is selected as the alkali liquor to be slowly added until the pH value reaches 4.9 after the pH value reaches 4.0; the temperature is kept between 40 ℃ and 50 ℃ in the hydrolysis process.
In the optimized scheme of the invention, the dilute hydrochloric acid in the step (4) is 1 mon/L-3 mol/L hydrochloric acid solution, and the adsorption temperature after adding the modified activated carbon is 22-28 ℃; the addition amount of the modified activated carbon is 7-9% of the mass of the refined solution.
In the optimized scheme of the invention, the dilute hydrochloric acid in the step (5) is 1 mon/L-3 mol/L hydrochloric acid solution, and the adsorption temperature after adding the modified activated carbon is 30-40 ℃; the addition amount of the modified activated carbon is 10-12% of the mass of the refined solution.
In the optimization scheme of the invention, the specific method of (A1) in the step (6) is as follows:
immersing activated carbon powder in 1-2 mol/L potassium nitrate solution for 2-3 h; then placing the activated carbon in high-temperature steam with the temperature of 500-600 ℃ for 30-45 min, wherein the volume fraction of oxygen in the high-temperature steam is 5-10%; after the treatment, the activated carbon A1 is obtained by cleaning with hot water.
In the optimization scheme of the invention, the specific method of (A2) in the step (6) is as follows:
(A2) Adding activated carbon A1 into 0.5-1.2 mol/L propylene glycol methyl ether acetate aqueous solution, and then heating to 30-35 ℃ for 60-90 min; adding ammonia water to continue to treat for 30-60 min after the treatment is finished; and then filtering, washing by using ethanol and water in sequence, and drying to obtain the activated carbon A2.
In the optimization scheme of the invention, the specific method of (A3) in the step (6) is as follows:
(A3) Adding active carbon A2 into a mixed solution of triethylenetetramine and acetic acid, wherein the mixed solution contains 0.5-1 mol/L of triethylenetetramine, the pH value is 3.0-4.0, the temperature of the mixed solution is controlled to be 60-70 ℃, stirring is carried out for 3-6 h, and then the active carbon A3 is obtained after filtering, washing and drying.
In the optimization scheme of the invention, the specific method of (A4) in the step (6) is as follows:
(A4) And (3) proportioning benzoyl chloride, diethyl ether and phosphorus trichloride according to a volume ratio of 12:33:4 to obtain diethyl ether mixed solution, adding active carbon A3 into the diethyl ether mixed solution, heating, stirring and refluxing for 3-5 hours, washing with tetrahydrofuran, washing with ethanol, washing with hot water, filtering and drying to obtain the modified active carbon.
In summary, the invention has the following advantages:
according to the preparation method of cystine, the pig hair can be hydrolyzed, cystine is collected from the hydrolyzed solution through repeated isoelectric precipitation, and meanwhile, in the decoloring and refining crystallization processes, modified activated carbon is adopted to realize that the adsorption effect on the product cystine is reduced while the adsorption of other impurities is not influenced, so that the total yield of a final product is improved, the loss is reduced, and the industrial benefit of product production is remarkably improved.
Detailed Description
The invention provides a preparation method of L-cystine, which comprises the following steps:
removing impurities from collected pig hair, cleaning the pig hair by using hot water and a cleaning agent, removing dust and grease on the surface of the pig hair until the pig hair is cleaned, and drying and cutting off the pig hair after cleaning;
step (2) hydrolysis
Heating industrial hydrochloric acid to 100-110 ℃, adding pig hair, hydrolyzing, cooling and filtering after the hydrolysis is completed to obtain hydrolysate;
step (3) isoelectric precipitation
Adding alkali liquor into the hydrolysate under stirring operation to neutralize the hydrolysate until the pH value of the hydrolysate is 4.8-4.9; stopping stirring after the hydrolysis is finished, standing to enable the cystine to be completely precipitated, and then carrying out suction filtration to obtain a cystine crude product and a precipitation mother solution;
step (4) decoloring refining
Adding the cystine crude product into dilute hydrochloric acid, dissolving, adding modified activated carbon and EDTA, boiling and refluxing for 20-30 min; adding alkali liquor into the solution for neutralization after suction filtration, adjusting the pH value to be 4.8-4.9 until precipitation is achieved, standing and suction filtration to obtain a refined filter cake;
step (5) recrystallization
Dissolving the refined filter cake in dilute hydrochloric acid, adding modified activated carbon for adsorption treatment, filtering after adsorption for 30-60 min, adding alkali liquor for neutralization after filtering, regulating the pH value to precipitate, standing, carrying out suction filtration, flushing for a plurality of times by using hot water, and drying to obtain an L-cystine finished product;
preparation of modified activated carbon in step (6)
(A1) Immersing activated carbon powder in a potassium nitrate solution; then the activated carbon is placed in high-temperature steam with the temperature of 500-600 ℃ for treatment, and the volume fraction of oxygen in the high-temperature steam is 5-10%; after the treatment is finished, cleaning by using hot water to obtain active carbon A1;
(A2) Adding activated carbon A1 into 0.5-1.2 mol/L propylene glycol methyl ether acetate aqueous solution, and then treating for 60-90 min; adding ammonia water for continuous treatment after the treatment is finished; then filtering, sequentially flushing with ethanol and water, and drying to obtain active carbon A2;
(A3) Adding activated carbon A2 into a mixed solution of triethylenetetramine and acetic acid, controlling the temperature of the mixed solution to be 60-70 ℃, stirring for 3-6 h, and then filtering, washing and drying to obtain activated carbon A3;
(A4) The benzoyl chloride, the diethyl ether and the phosphorus trichloride are proportioned according to the volume ratio of 10-20:30-50:2-5 to obtain diethyl ether mixed solution, the activated carbon A3 is added into the diethyl ether mixed solution, heating, stirring and reflux treatment are carried out, after the treatment is finished, the washing is carried out by using tetrahydrofuran, then the washing is carried out by using ethanol, finally the washing is carried out by using hot water, and the modified activated carbon is obtained after filtration and drying.
Example 1:
the invention provides a preparation method of L-cystine, which comprises the following steps:
removing impurities from collected pig hair, cleaning the pig hair by using hot water and a cleaning agent, removing dust and grease on the surface of the pig hair until the pig hair is cleaned, and drying and cutting off the pig hair after cleaning;
step (2) hydrolysis
Heating 10mol/L industrial hydrochloric acid to 100deg.C, adding pig hair, hydrolyzing for 10 hr, and refluxing hydrochloric acid during hydrolysis; cooling and filtering after the hydrolysis is completed to obtain hydrolysate;
step (3) isoelectric precipitation
Adding alkaline sodium hydroxide solution into the hydrolysate under stirring operation for neutralization, and continuously detecting the pH value of the hydrolysate in the neutralization process; after the pH value reaches 3.0, the alkali solution sodium hydroxide solution is added in a decelerating way. After the pH value reaches 4.0, ammonia water is selected as alkali liquor to be slowly added until the pH value reaches 4.9; the temperature was maintained at 45℃during the hydrolysis. Stopping stirring after the hydrolysis is finished, standing to enable the cystine to be completely precipitated, and then carrying out suction filtration to obtain a cystine crude product and a precipitation mother solution.
Step (4) decoloring refining
Adding the cystine crude product into 2mol/L dilute hydrochloric acid, dissolving, adding modified activated carbon and EDTA, wherein the mass ratio of the modified activated carbon to the refined solution is 8%, and the adding mass ratio of the EDTA is 0.1%. Boiling and refluxing for 30min, and controlling the adsorption temperature to be 28 ℃; and (3) after the solution is subjected to suction filtration, adding alkali liquor for neutralization, adjusting the pH value to be 4.8-4.9 until precipitation is separated out, standing, and performing suction filtration to obtain a refined filter cake. The alkali liquor can be added in the same manner as in the step (3) in the decoloring, refining and recrystallization processes.
Step (5) recrystallization
Adding the refined filter cake into 2mol/L dilute hydrochloric acid for dissolution, adding modified activated carbon for adsorption treatment, wherein the adsorption temperature of the modified activated carbon is 35 ℃; the addition amount of the modified activated carbon is 12% of the mass of the refined solution. And (3) filtering after 30min of adsorption, adding alkali liquor for neutralization after filtering, regulating the pH value until precipitation is separated out, standing, performing suction filtration, flushing for a plurality of times by using hot water, and drying to obtain the L-cystine finished product.
The modified activated carbon used in example 1 was prepared by the method disclosed in example 2.
Example 2: preparation method of modified activated carbon
(A1) Immersing activated carbon powder in a potassium nitrate solution with the concentration of 2mol/L for 3 hours; then the activated carbon is placed in high-temperature steam with 520 ℃ for treatment for 40min, and the volume fraction of oxygen in the high-temperature steam is 6%; after the treatment, the activated carbon A1 is obtained by cleaning with hot water.
(A2) Adding activated carbon A1 into 0.8mol/L propylene glycol methyl ether acetate aqueous solution, and then heating to 32 ℃ for treatment for 80min; adding ammonia water after the treatment is finished, and continuing the treatment for 40min; and then filtering, washing by using ethanol and water in sequence, and drying to obtain the activated carbon A2.
(A3) Adding activated carbon A2 into a mixed solution of triethylenetetramine and acetic acid, wherein the mixed solution contains 0.6mol/L triethylenetetramine, the pH value is 3.6, controlling the temperature of the mixed solution to 65 ℃, stirring for 5 hours, and then filtering, washing and drying to obtain activated carbon A3.
(A4) And (3) proportioning benzoyl chloride, diethyl ether and phosphorus trichloride according to a volume ratio of 12:33:4 to obtain diethyl ether mixed solution, adding activated carbon A3 into the diethyl ether mixed solution, heating, stirring and refluxing, washing with tetrahydrofuran, washing with ethanol, washing with hot water, filtering and drying to obtain the modified activated carbon.
The adsorption effect of the activated carbon and the amino acid is the sum of physical adsorption and chemical adsorption, the cystine contains sulfhydryl, and the surface acidity and alkalinity and the porous structure of the activated carbon can be changed by adjusting the types and the quantity of the nitrogen-containing and oxygen-containing functional groups on the surface of the activated carbon, so that the adsorption performance of the modified activated carbon on the amino acid is changed.
Experimental example one: quality inspection of finished products
The modified activated carbon in the embodiment 2 of the invention is applied to the embodiment to obtain the L-cystine finished product of the invention, and the finished product is detected according to the related standards of pharmacopoeia, and the detection categories and results are as follows.
1. Acidity detection
Taking 1.0g of the product, adding 100ml of water, fully shaking, and detecting the pH value of the product to be 5.8; meets 5.0 to 6.5 of pharmacopoeia standards.
2. Transmittance of solution
1.0g of the product is taken, 20ml of 1mol/L hydrochloric acid solution is added for dissolution, and the light transmittance is measured at a wavelength of 430nm according to an ultraviolet-visible spectrophotometry. The light transmittance of the product is 99.2%.
3. Chloride detection
0.50g of the product is taken, 10ml of dilute nitric acid is added for dissolution, water is added for 50ml, 25ml is separated, and the product is compared with a control solution prepared from 5.0ml of standard sodium chloride solution. The product is shallower than standard.
4. Sulfate detection
Taking 0.70g of the product, adding 5ml of diluted hydrochloric acid, shaking to dissolve, adding water to 40ml, and comparing with a control solution prepared by adding 5ml of diluted hydrochloric acid into 1.4ml of standard potassium sulfate solution. The product is shallower than standard.
5. Specific rotation detection
And (5) measuring by adopting an automatic polarimeter, and cleaning the sample tube. And (5) turning on the light source to perform measurement, repeating the measurement, and averaging. The specific rotation value of the product is-226 degrees, and the specific rotation value of the standard sample is-225 degrees, so that the product can be determined to be cystine.
6. Content determination
The detection method comprises the following steps: taking about 80mg of the product, precisely weighing, placing the product into an iodine bottle, adding 2ml of sodium hydroxide test solution and 10ml of water, shaking for dissolution, adding 10ml of potassium bromide solution, precisely adding 50ml of potassium bromate titration solution and 15ml of dilute hydrochloric acid, sealing, placing the product in an ice bath for 10 minutes in a dark place, adding 1.5g of potassium iodide, shaking uniformly, titrating with sodium thiosulfate titration solution (0.1 mol/L) after 1 minute, adding 2ml of starch indicator when the product is near the end point, continuing to titrate until blue disappears, and correcting the titration result by a blank test. Each 1ml of potassium bromate titrant (0.01667 mol/L) corresponds to 2.403mg of cystine.
Experimental example two, influence of different preparation processes on total yield
Example 2:
a method for preparing L-cystine, comprising the following steps:
removing impurities from collected pig hair, cleaning the pig hair by using hot water and a cleaning agent, removing dust and grease on the surface of the pig hair until the pig hair is cleaned, and drying and cutting off the pig hair after cleaning;
step (2) hydrolysis
Heating 10mol/L industrial hydrochloric acid to 100deg.C, adding pig hair, hydrolyzing for 10 hr, and refluxing hydrochloric acid during hydrolysis; cooling and filtering after the hydrolysis is completed to obtain hydrolysate;
step (3) isoelectric precipitation
Adding alkaline sodium hydroxide solution into the hydrolysate under stirring operation for neutralization, and continuously detecting the pH value of the hydrolysate in the neutralization process; after the pH value reaches 3.0, the alkali solution sodium hydroxide solution is added in a decelerating way. After the pH value reaches 4.0, ammonia water is selected as alkali liquor to be slowly added until the pH value reaches 4.9; the temperature was maintained at 45℃during the hydrolysis. Stopping stirring after the hydrolysis is finished, standing to enable the cystine to be completely precipitated, and then carrying out suction filtration to obtain a cystine crude product and a precipitation mother solution.
Step (4) decoloring refining
Adding the cystine crude product into 2mol/L dilute hydrochloric acid, dissolving, adding active carbon and EDTA, wherein the mass ratio of the active carbon to the refined solution is 8%, and the adding mass ratio of the EDTA is 0.1%. Boiling and refluxing for 30min, and controlling the adsorption temperature to be 28 ℃; and (3) after the solution is subjected to suction filtration, adding alkali liquor for neutralization, adjusting the pH value to be 4.8-4.9 until precipitation is separated out, standing, and performing suction filtration to obtain a refined filter cake. The alkali liquor can be added in the same manner as in the step (3) in the decoloring, refining and recrystallization processes.
Step (5) recrystallization
Adding the refined filter cake into 2mol/L dilute hydrochloric acid for dissolution, adding activated carbon for adsorption treatment, wherein the adsorption temperature of the activated carbon is 35 ℃; the addition amount of the activated carbon is 12% of the mass of the refined solution. And (3) filtering after 30min of adsorption, adding alkali liquor for neutralization after filtering, regulating the pH value until precipitation is separated out, standing, performing suction filtration, flushing for a plurality of times by using hot water, and drying to obtain the L-cystine finished product.
The activated carbon used in example 2 was wood powder activated carbon purchased from Chongqing macro-range activated carbon Co., ltd, and the activated carbon used in example 2 was unmodified ordinary activated carbon.
Experiments were performed with 2000g of pig hair, and the production was performed by the method of example 1 and example 2, to prepare a cystine finished product, the total yield of the two examples being as follows:
the pig hair itself has a lower cystine content than human hair and horsehair, but is easier to collect due to the greater yield of pig hair. As can be seen from the comparison of the total yields of the example 1 and the example 2, the adsorption capacity of the modified activated carbon to cystine in the adsorption process is reduced, so that the total yield is increased to a certain extent. Meanwhile, the quality detection of the finished product also shows that the quality of the finished product obtained in the embodiment 1 of the invention meets the national requirements.
Experimental example III, comparison of adsorption capacities of modified activated carbon on different amino acids
The experimental method comprises the following steps:
(1) Selecting a plurality of amino acids, and respectively preparing 1000ml of amino acid solution with the mass fraction of 15%;
(2) The experimental group 1 adopts 30g of modified activated carbon for adsorption, stirring is carried out continuously in the adsorption process, the adsorption is carried out for 30min at normal temperature, then the filtration is carried out, and the content change of amino acid in the filtrate is detected.
(3) The control group is adsorbed by 30g of common activated carbon, stirring is carried out continuously in the adsorption process, the adsorption is carried out for 30min at normal temperature, then the filtration is carried out, and the content change of the amino acid in the filtrate is detected.
The test results of the experimental group 1 and the control group are shown in the following table:
| amino acid name | Adsorption rate of control group | Adsorption rate of Experimental group 1 |
| Cystine (cystine) | 86％ | 62％ |
| Arginine (Arg) | 99％ | 99％ |
| Histidine | 99％ | 98％ |
| Tryptophan | 89％ | 86％ |
| Glycine (Gly) | 82％ | 73％ |
| Lysine | 92％ | 92％ |
| Tyrosine | 84％ | 85％ |
Adsorption ratio= (amino acid before adsorption content-amino acid after adsorption content)/amino acid before adsorption content. The adsorption amount of the activated carbon to the amino acid is generally related to the type of the amino acid, the adsorption time, the adsorption concentration, the use amount of the activated carbon, whether stirring is carried out or not and the acid-base property of the adsorption solution. The invention sets the uniform solution concentration and other parameters, so that the amino acid type becomes the only variable, and the adsorption condition of different amino acids can be detected. From the above experimental results, it can be seen that when different activated carbons are used for adsorption, the adsorption rates of cystine and glycine are significantly changed, wherein the difference of the changes of cystine is the largest; the adsorption rate of the other amino acids is not changed greatly when different activated carbon is adopted for adsorption, which shows that the adsorption performance of the modified activated carbon has no obvious influence on the amino acids, and only has a certain influence on cystine and glycine. As the isoelectric points of cystine and glycine have large difference, when the isoelectric point of cystine is precipitated, glycine is dissolved in a solution in a free state, and the adsorption of cystine is not influenced. The reduction of the cystine adsorption rate in the experimental group 1 shows that after the modified activated carbon is adopted, the activated carbon reduces the adsorption of cystine in the adsorption process, and simultaneously, the adsorption of other impurities by the activated carbon is not influenced, so that the storage of cystine in the hydrolysate or the crude product solution is more, the total yield of cystine is more favorable to be improved, and the problem that a large amount of cystine is carried away by the activated carbon in the repeated activated carbon adsorption process is avoided, so that the yield of cystine in each step can be improved, and the total yield is improved.
Claims (9)
1. A method for preparing L-cystine, comprising the steps of:
removing impurities from collected pig hair, cleaning the pig hair by using hot water and a cleaning agent, removing dust and grease on the surface of the pig hair until the pig hair is cleaned, and drying and cutting off the pig hair after cleaning;
step (2) hydrolysis
Heating industrial hydrochloric acid to 100-110 ℃, adding pig hair, hydrolyzing, cooling and filtering after the hydrolysis is completed to obtain hydrolysate;
step (3) isoelectric precipitation
Adding alkali liquor into the hydrolysate under stirring operation to neutralize the hydrolysate until the pH value of the hydrolysate is 4.8-4.9; stopping stirring after the hydrolysis is finished, standing to enable the cystine to be completely precipitated, and then carrying out suction filtration to obtain a cystine crude product and a precipitation mother solution;
step (4) decoloring refining
Adding the cystine crude product into dilute hydrochloric acid, dissolving, adding modified activated carbon and EDTA, boiling and refluxing for 20-30 min; adding alkali liquor into the solution for neutralization after suction filtration, adjusting the pH value to be 4.8-4.9 until precipitation is achieved, standing and suction filtration to obtain a refined filter cake;
step (5) recrystallization
Dissolving the refined filter cake in dilute hydrochloric acid, adding modified activated carbon for adsorption treatment, filtering after adsorption for 30-60 min, adding alkali liquor for neutralization after filtering, regulating the pH value to precipitate, standing, carrying out suction filtration, flushing for a plurality of times by using hot water, and drying to obtain an L-cystine finished product;
preparation of modified activated carbon in step (6)
(A1) Immersing activated carbon powder in a potassium nitrate solution; then the activated carbon is placed in high-temperature steam with the temperature of 500-600 ℃ for treatment, and the volume fraction of oxygen in the high-temperature steam is 5-10%; after the treatment is finished, cleaning by using hot water to obtain active carbon A1;
(A2) Adding activated carbon A1 into 0.5-1.2 mol/L propylene glycol methyl ether acetate aqueous solution, and then treating for 60-90 min; adding ammonia water for continuous treatment after the treatment is finished; then filtering, sequentially flushing with ethanol and water, and drying to obtain active carbon A2;
(A3) Adding activated carbon A2 into a mixed solution of triethylenetetramine and acetic acid, controlling the temperature of the mixed solution to be 60-70 ℃, stirring for 3-6 h, and then filtering, washing and drying to obtain activated carbon A3;
(A4) The benzoyl chloride, the diethyl ether and the phosphorus trichloride are proportioned according to the volume ratio of 10-20:30-50:2-5 to obtain diethyl ether mixed solution, the activated carbon A3 is added into the diethyl ether mixed solution, heating, stirring and reflux treatment are carried out, after the treatment is finished, the washing is carried out by using tetrahydrofuran, then the washing is carried out by using ethanol, finally the washing is carried out by using hot water, and the modified activated carbon is obtained after filtration and drying.
2. The method for producing L-cystine according to claim 1, wherein: the industrial hydrochloric acid in the step (2) is 9-11 mol/L hydrochloric acid, and the hydrolysis time is 9-10 h; hydrochloric acid is refluxed during the hydrolysis.
3. The method for producing L-cystine according to claim 1, wherein: the alkali liquor in the step (3) is 30-35% of sodium hydroxide solution and ammonia water; continuously detecting the pH value of the hydrolysate in the neutralization process; the alkali liquor added in the initial stage is sodium hydroxide solution, the alkali liquor is slowly added after the pH value reaches 3.0, and ammonia water is selected as the alkali liquor to be slowly added until the pH value reaches 4.9 after the pH value reaches 4.0; the temperature is kept between 40 ℃ and 50 ℃ in the hydrolysis process.
4. The method for producing L-cystine according to claim 1, wherein: the dilute hydrochloric acid in the step (4) is 1 mon/L-3 mol/L hydrochloric acid solution, and the adsorption temperature after adding the modified activated carbon is 22-28 ℃; the addition amount of the modified activated carbon is 7-9% of the mass of the refined solution.
5. The method for producing L-cystine according to claim 1, wherein: the dilute hydrochloric acid in the step (5) is 1 mon/L-3 mol/L hydrochloric acid solution, and the adsorption temperature after adding the modified activated carbon is 30-40 ℃; the addition amount of the modified activated carbon is 10-12% of the mass of the refined solution.
6. The method for producing L-cystine according to claim 1, wherein: the specific method of (A1) in the step (6) is as follows:
immersing activated carbon powder in 1-2 mol/L potassium nitrate solution for 2-3 h; then placing the activated carbon in high-temperature steam with the temperature of 500-600 ℃ for 30-45 min, wherein the volume fraction of oxygen in the high-temperature steam is 5-10%; after the treatment, the activated carbon A1 is obtained by cleaning with hot water.
7. The method for producing L-cystine according to claim 1, wherein: the specific method of (A2) in the step (6) is as follows:
(A2) Adding activated carbon A1 into 0.5-1.2 mol/L propylene glycol methyl ether acetate aqueous solution, and then heating to 30-35 ℃ for 60-90 min; adding ammonia water to continue to treat for 30-60 min after the treatment is finished; and then filtering, washing by using ethanol and water in sequence, and drying to obtain the activated carbon A2.
8. The method for producing L-cystine according to claim 1, wherein: the specific method of (A3) in the step (6) is as follows:
(A3) Adding active carbon A2 into a mixed solution of triethylenetetramine and acetic acid, wherein the mixed solution contains 0.5-1 mol/L of triethylenetetramine, the pH value is 3.0-4.0, the temperature of the mixed solution is controlled to be 60-70 ℃, stirring is carried out for 3-6 h, and then the active carbon A3 is obtained after filtering, washing and drying.
9. The method for producing L-cystine according to claim 1, wherein: the specific method of (A4) in the step (6) is as follows:
(A4) And (3) proportioning benzoyl chloride, diethyl ether and phosphorus trichloride according to a volume ratio of 12:33:4 to obtain diethyl ether mixed solution, adding active carbon A3 into the diethyl ether mixed solution, heating, stirring and refluxing for 3-5 hours, washing with tetrahydrofuran, washing with ethanol, washing with hot water, filtering and drying to obtain the modified active carbon.
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