CN115385797A - Resource utilization treatment method for chloride production mother liquor of anecortave acetate - Google Patents
Resource utilization treatment method for chloride production mother liquor of anecortave acetate Download PDFInfo
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- CN115385797A CN115385797A CN202211120626.7A CN202211120626A CN115385797A CN 115385797 A CN115385797 A CN 115385797A CN 202211120626 A CN202211120626 A CN 202211120626A CN 115385797 A CN115385797 A CN 115385797A
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- 229960001232 anecortave Drugs 0.000 title claims abstract description 86
- YUWPMEXLKGOSBF-GACAOOTBSA-N Anecortave acetate Chemical compound O=C1CC[C@]2(C)C3=CC[C@]4(C)[C@](C(=O)COC(=O)C)(O)CC[C@H]4[C@@H]3CCC2=C1 YUWPMEXLKGOSBF-GACAOOTBSA-N 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 44
- 239000012452 mother liquor Substances 0.000 title claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims description 21
- 239000007788 liquid Substances 0.000 claims abstract description 113
- 239000002699 waste material Substances 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000003379 elimination reaction Methods 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 106
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 60
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 57
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- 239000012074 organic phase Substances 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000007791 liquid phase Substances 0.000 claims description 29
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 28
- 239000011780 sodium chloride Substances 0.000 claims description 28
- 239000012071 phase Substances 0.000 claims description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 229940043279 diisopropylamine Drugs 0.000 claims description 21
- 239000007790 solid phase Substances 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 18
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 239000004593 Epoxy Substances 0.000 claims description 12
- URAZVWXGWMBUGJ-UHFFFAOYSA-N di(propan-2-yl)azanium;chloride Chemical compound [Cl-].CC(C)[NH2+]C(C)C URAZVWXGWMBUGJ-UHFFFAOYSA-N 0.000 claims description 12
- CBMYJHIOYJEBSB-UHFFFAOYSA-N (10S)-3t.17t-Dihydroxy-10r.13c-dimethyl-(5cH.8cH.9tH.14tH)-hexadecahydro-1H-cyclopenta[a]phenanthren Natural products C1C(O)CCC2(C)C3CCC(C)(C(CC4)O)C4C3CCC21 CBMYJHIOYJEBSB-UHFFFAOYSA-N 0.000 claims description 10
- RAJWOBJTTGJROA-UHFFFAOYSA-N (5alpha)-androstane-3,17-dione Natural products C1C(=O)CCC2(C)C3CCC(C)(C(CC4)=O)C4C3CCC21 RAJWOBJTTGJROA-UHFFFAOYSA-N 0.000 claims description 10
- RAJWOBJTTGJROA-WZNAKSSCSA-N 5alpha-androstane-3,17-dione Chemical compound C1C(=O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC[C@H]21 RAJWOBJTTGJROA-WZNAKSSCSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000008346 aqueous phase Substances 0.000 claims description 9
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 8
- 108010009736 Protein Hydrolysates Proteins 0.000 claims description 6
- 229960002537 betamethasone Drugs 0.000 claims description 6
- UREBDLICKHMUKA-DVTGEIKXSA-N betamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-DVTGEIKXSA-N 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229960003957 dexamethasone Drugs 0.000 claims description 6
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 claims description 6
- 239000000413 hydrolysate Substances 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- OSVMTWJCGUFAOD-KZQROQTASA-N formestane Chemical compound O=C1CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1O OSVMTWJCGUFAOD-KZQROQTASA-N 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000010865 sewage Substances 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- HIOHRZIAENJDHP-UHFFFAOYSA-N CC(O)=O.N#CC#N Chemical compound CC(O)=O.N#CC#N HIOHRZIAENJDHP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N glycolonitrile Natural products N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract 2
- 230000008025 crystallization Effects 0.000 abstract 2
- 230000008020 evaporation Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- WJGAPUXHSQQWQF-UHFFFAOYSA-N acetic acid;hydrochloride Chemical compound Cl.CC(O)=O WJGAPUXHSQQWQF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- -1 anecortave acetate chlorine compound Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/74—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by halogenation, hydrohalogenation, dehalogenation, or dehydrohalogenation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/20—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0003—Androstane derivatives
- C07J1/0011—Androstane derivatives substituted in position 17 by a keto group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J7/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms
- C07J7/008—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms substituted in position 21
- C07J7/0085—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of two carbon atoms substituted in position 21 by an halogen atom
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Abstract
The invention discloses a resource utilization treatment method of anecortave acetate chlorine production mother liquor, which comprises the following steps: liquid-liquid layering, precipitation reaction, solid-liquid separation, pH value adjustment, liquid-liquid layering, evaporation concentration, cooling crystallization, solid-liquid separation, normal-pressure concentration, solid-liquid separation, elimination reaction, pH value adjustment, solid-liquid separation, reduced-pressure concentration, cooling crystallization and solid-liquid separation. The process method can fully recycle valuable components in the waste liquid, and the process is reasonable, the product quality is good, and the utilization rate of the valuable components is high.
Description
Technical Field
The invention belongs to the field of medical environment chemical industry, and particularly relates to a resource utilization treatment method of a chloride production mother solution of anecortave acetate.
Background
The production process of anecortave acetate uses anecortave acetate cyano as initial raw material, and adopts the processes of silicon etherification reaction to obtain anecortave acetate silicon ether substance, chlorination reaction to obtain anecortave acetate epichloride substance and displacement reaction to obtain anecortave acetate, and its specific synthetic route is as follows:
the synthesis process of the anecortave acetate chloridate is briefly described as follows:
preparation of LDA: adding metal lithium into a mixed solution of tetrahydrofuran and diisopropylamine, adding a mixed solution of styrene and tetrahydrofuran, and stirring until the metal lithium completely reacts.
Synthesis of anecortave acetate epichloride: adding anecortave acetate etherate into tetrahydrofuran, transferring into prepared LDA, and reacting under heat preservation;
transferring the reaction solution into dilute hydrochloric acid, stirring for reaction, and adding sodium hydroxide to adjust the pH value;
adding water and n-heptane, centrifuging, and drying.
When the chloride on the anecortave acetate is produced in a workshop, the feeding amount of the anecortave acetate etherate is 500kg, and the production waste liquid of the chloride on the anecortave acetate is about 10 tons.
Due to the reaction characteristics, in the synthesis reaction of chloride on the anecortave acetate, the anecortave acetate etherate (converted into the anecortave acetate cyanide compound under the acidic condition of post-treatment) has about 5 percent of residue; due to the relatively high solubility of the anecortave acetate chloride in tetrahydrofuran, about 5% of the anecortave acetate chloride remains in the centrifuged mother liquor. If the cyanide and the chloride of the anecortave acetate in the waste liquid can be recycled, the production cost of the anecortave acetate can be greatly reduced.
The mother liquor generated in the synthesis process of the anecortave acetate chloride comprises an aqueous phase and an organic phase, wherein the aqueous phase accounts for about 60 percent, and the organic phase accounts for about 40 percent; the aqueous phase comprises: 10-15% of diisopropylamine hydrochloride, 10-15% of sodium chloride, 3-5% of lithium chloride and the balance of water; the organic phase comprises: tetrahydrofuran 55-60 wt%, n-heptane 31-36 wt%, styrene 8 wt%, anecortave acetate chloride 0.5 wt% and anecortave acetate cyano 0.5 wt%.
In order to reduce the raw material consumption, reduce the production cost and meet the environmental protection requirement, the waste liquid generated in the production process of the anecortave acetate chlorine compound is necessary to be recycled and treated.
Disclosure of Invention
In order to solve the problem of resource waste in the production process, the invention provides a resource utilization treatment method of anecortave acetate chlorine production mother liquor, wherein the mother liquor comprises a water phase and an organic phase, the water phase accounts for about 60 percent, and the organic phase accounts for about 40 percent; the aqueous phase comprises: 10-15% of diisopropylamine hydrochloride, 10-15% of sodium chloride and 3-5% of lithium chloride; the organic phase comprises: tetrahydrofuran 55-60 wt%, n-heptane 31-36 wt%, styrene 8 wt%, anecortave acetate chloride 0.5 wt% and anecortave acetate cyano 0.5 wt%;
the resource utilization treatment method of the mother liquor comprises the following steps:
step (1), liquid-liquid layering: standing and layering the mother solution of the chloride production of anecortave acetate, treating an organic phase, and carrying out the next step on a water phase;
step (2), precipitation reaction: adding sodium carbonate into the water phase obtained in the step (1) to ensure that lithium chloride in the water phase reacts with the sodium carbonate to be converted into lithium carbonate precipitate and sodium chloride, and feeding the materials to the next step;
and (3) recovering lithium carbonate in the step (2): after solid-liquid separation is carried out on the material obtained in the step (2), the solid phase is lithium carbonate, and the liquid phase material enters the next step;
step (4), adjusting the pH value: adding sodium hydroxide into the liquid-phase material obtained in the step (3), adjusting the pH value to 11.5-12.5, converting diisopropylamine hydrochloride into diisopropylamine and sodium chloride, and enabling the material to enter the next step;
step (5), recovering the diisopropylamine in the step (4): layering the material liquid obtained in the step (4), wherein the upper layer is diisopropylamine, the material liquid is further dehydrated and then applied to the production process of the acetonicostat acetate chloride, and the material liquid at the lower layer enters the next step;
and (6) recovering sodium chloride in the waste liquid: evaporating and concentrating the residual materials in the step (3) until the weight of the residual materials is 30-40% of the total weight of the water phase, cooling to 20-30 ℃, performing solid-liquid separation, recovering sodium chloride, and treating a small amount of waste liquid in sewage treatment;
step (7), recovering tetrahydrofuran and n-heptane in the waste liquid: adding p-tert-butyl catechol into the organic phase obtained in the step (1) to prevent styrene in the waste liquid from polymerizing, concentrating under normal pressure, condensing the fraction at the temperature of 65-70 ℃, recovering tetrahydrofuran, condensing the fraction at the temperature of 95-100 ℃, recovering n-heptane, and enabling the solid-liquid mixed material to enter the next step;
and (8) recovering styrene in the waste liquid: carrying out solid-liquid separation on the solid-liquid mixed material in the step (6), wherein the liquid-phase material is styrene, and can be applied to the production procedure of the alecortave acetate chloratum after further treatment, and the solid-phase material is a mixture of the alecortave acetate chloratum and the alecortave acetate cyanogen base, and entering the next step;
step (9), elimination reaction: adding the solid-phase material obtained in the step (7) into a reaction solvent, adding liquid alkali with the mass fraction of 30%, adjusting the pH value to 12-13, controlling the temperature to be 25-35 ℃, reacting for 1-3 h, converting the anecortave acetate cyano-group into 4, 9-diene androstane-3, 17-diketone, adding glacial acetic acid to adjust the pH value to 6-7, and enabling the material to enter the next step;
step (10), recovering the anecortave acetate chloride in the waste liquid: after the solid-liquid separation is carried out on the material obtained in the step (8), the solid-phase material is chloride on the anecortave acetate, the solid-phase material can be applied to the production procedure of the anecortave acetate, and the liquid-phase material enters the next step;
step (11) and recovering the 4, 9-diene androstane-3, 17-dione in the step (8): and (2) concentrating the liquid-phase material obtained in the step (10) under reduced pressure until the weight of the residual material liquid is 1.0-3.0% of that of the organic phase, cooling to 0-5 ℃, performing solid-liquid separation, wherein the solid-phase material is 4, 9-diene androstane-3, 17-dione, can be applied to the production process of betamethasone epoxy hydrolysate and dexamethasone epoxy hydrolysate, and a small amount of liquid-phase material is worthless and is treated as waste liquid.
Preferably, in the step (2), the weight ratio of the sodium carbonate to the water phase is 0.047-0.078.
Preferably, in the step (7), the weight ratio of the p-tert-butylcatechol to the organic phase is 0.0005-0.001.
Preferably, in the step (9), the reaction solvent is at least one of methanol, isopropanol or ethyl acetate;
the weight ratio of the used amount of the reaction solvent to the organic phase is 0.04-0.1.
The invention has the beneficial effects that:
the method can realize resource utilization and treatment of the waste liquid generated in the production process of the anecortave acetate chlorinated mass, has the characteristics of reasonable process, environmental protection, energy conservation and high utilization rate of valuable components, and is particularly shown in the following aspects:
(1) In view of the fact that the solubility of the anecortave acetate cyanide compound is similar to that of the anecortave acetate chloride and the anecortave acetate chloride is not easy to separate, the anecortave acetate cyanide compound is converted into 4, 9-dienandrostane-3, 17-dione with high solubility under alkaline conditions (the reaction principle is as follows), so that the anecortave acetate chloride and the 4, 9-dienandrostane-3, 17-dione can be conveniently recovered;
(2) The method fully utilizes the characteristic of low solubility of lithium carbonate in water, adds sodium carbonate into the water phase, and converts lithium chloride into lithium carbonate and sodium chloride through a precipitation reaction;
(3) The invention adopts a pH value adjusting technology to convert diisopropylamine hydrochloride in a water phase into diisopropylamine, and then utilizes the characteristic that the diisopropylamine and water are immiscible, and adopts a liquid-liquid layering technology to recover the diisopropylamine from waste liquid;
(4) The invention fully utilizes the characteristics of large difference of boiling points of tetrahydrofuran (the boiling point is 66 ℃), n-heptane (the boiling point is 98.5 ℃) and styrene (the boiling point is 146 ℃), and adopts the normal pressure concentration technology to separate;
(5) In order to prevent the polymerization of the styrene, the p-tert-butyl catechol is added into the organic phase to be recovered, so that the styrene is in a stable state and is convenient to recover and reuse;
(6) The anecortave acetate epichlorohydrite recovered from the mother liquor can be used in the production process of anecortave acetate, and the 4, 9-diene androstane-3, 17-diketone recovered from the waste liquor can be used in the production process of betamethasone epoxy hydrolysate and dexamethasone epoxy hydrolysate, so that the cost is reduced to a great extent;
(7) After further dehydration treatment, the diisopropylamine, tetrahydrofuran, n-heptane and styrene recovered from the mother liquor can be applied to the production process of the chloride on the anecortave acetate, so that the production cost is reduced;
(8) Lithium carbonate and sodium chloride recovered from the mother liquor can be sold as byproducts, so that additional value is generated, and the production cost is reduced;
(9) The method has the characteristics of reasonable process, environmental protection, energy conservation and high utilization rate of valuable components, and the treated mother liquor is basically returned for recycling. The process method fully utilizes the characteristics of substances in the mother liquor and the particularity of the process. The invention solves the technical problems of mother liquor treatment and recycling, and simultaneously changes waste into valuable.
Drawings
The above and other features, characteristics and advantages of the present invention will become more apparent from the following description in conjunction with the accompanying drawings and embodiments, in which like reference numerals denote like features throughout the figures, and in which:
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments of the present invention will now be described in detail. It should be apparent that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
Example 1 the mother liquor to be treated was 10 tons, with about 6 tons of aqueous phase and about 4 tons of organic phase; the aqueous phase comprises: 600kg of diisopropylamine hydrochloride, 900kg of sodium chloride and 180kg of lithium chloride; the organic phase comprises: 2200kg tetrahydrofuran, 1440kg n-heptane, 320kg styrene, 20kg anecortave acetate epichloro-ride and 20kg anecortave acetate cyano.
The method for recycling mother liquor comprises the following steps:
step (1), liquid-liquid layering: standing and layering the mother solution of the chloride production of anecortave acetate, treating an organic phase, and carrying out the next step on a water phase;
step (2), precipitation reaction: adding 224.5kg of sodium carbonate into the water phase obtained in the step (1) to enable lithium chloride in the water phase to react with the sodium carbonate and convert the lithium chloride into 156.7kg of lithium carbonate precipitate and 247.8kg of sodium chloride, and enabling the materials to enter the next step;
and (3) recovering lithium carbonate in the step (2): after solid-liquid separation is carried out on the material obtained in the step (2), the solid phase is 156.7kg of lithium carbonate, and the liquid phase material enters the next step;
step (4), adjusting the pH value: adding sodium hydroxide into the liquid-phase material obtained in the step (3), adjusting the pH value to 11.5, converting diisopropylamine hydrochloride into 440kg diisopropylamine and 255kg sodium chloride, and enabling the material to enter the next step;
step (5), recovering the diisopropylamine in the step (4): layering the material liquid obtained in the step (4), wherein the upper layer is 440kg of diisopropylamine, the material liquid is further dehydrated and then applied to the production process of the anecortave acetate epichloride, and the material liquid at the lower layer enters the next step;
and (6) recovering sodium chloride in the waste liquid: evaporating and concentrating the residual materials in the step (3) to 1800kg, cooling to 30 ℃, performing solid-liquid separation, recovering 1300kg of sodium chloride, and treating a small amount of waste liquid in sewage treatment;
step (7), recovering tetrahydrofuran and n-heptane in the waste liquid: adding 2kg of p-tert-butyl catechol into the organic phase obtained in the step (1) to prevent styrene in the waste liquid from polymerizing, concentrating under normal pressure, condensing fractions at the temperature of 65-70 ℃, recovering 1900kg of tetrahydrofuran, condensing fractions at the temperature of 95-100 ℃, recovering 1300kg of n-heptane, and feeding the solid-liquid mixed material to the next step;
and (8) recovering styrene in the waste liquid: carrying out solid-liquid separation on the solid-liquid mixed material in the step (6), wherein the liquid-phase material is 320kg of styrene, the liquid-phase material can be applied to the production procedure of the anecortave acetate chloride after further treatment, and the solid-phase material is a mixture of the anecortave acetate chloride and the anecortave acetate cyanide, and entering the next step;
step (9), elimination reaction: adding the solid-phase material obtained in the step (7) into 160kg of methanol, adding 30% by mass of liquid alkali, adjusting the pH value to 12, controlling the temperature to be 35 ℃, reacting for 3 hours, converting the anecortave acetate cyano-group into 4, 9-diene androstane-3, 17-diketone, adding glacial acetic acid to adjust the pH value to 6, and enabling the material to enter the next step;
step (10), recovering the chloride on anecortave acetate in the waste liquid: after the solid-liquid separation is carried out on the material obtained in the step (8), 20kg of the anecortave acetate epichloro compound can be applied to the production procedure of the anecortave acetate, and the liquid-phase material enters the next step;
step (11) and recovering the 4, 9-diene androstane-3, 17-dione in the step (8): and (2) concentrating the liquid-phase material obtained in the step (10) under reduced pressure until the weight of the residual material liquid is 1.0 percent of that of the organic phase, cooling to 5 ℃, and performing solid-liquid separation to obtain 18kg of 4, 9-diene androstane-3, 17-dione, which can be applied to the production procedures of betamethasone epoxy hydrolysate and dexamethasone epoxy hydrolysate, wherein the liquid-phase material is worthless and is used for waste liquid treatment.
Example 2
The mother liquor to be treated is 10 tons, wherein the water phase is about 6 tons, and the organic phase is about 4 tons; the aqueous phase comprises: 900kg of diisopropylamine hydrochloride, 600kg of sodium chloride and 300kg of lithium chloride; the organic phase comprises: 2400kg tetrahydrofuran, 1240kg n-heptane, 320kg styrene, 20kg anecortave acetate epichlorophdride and 20kg anecortave acetate cyanogroup.
The method for recycling mother liquor comprises the following steps:
step (1), liquid-liquid layering: standing and layering the mother solution of the chloride production of anecortave acetate, treating an organic phase, and carrying out a water phase in the next step;
step (2), precipitation reaction: 374.1kg of sodium carbonate is added into the water phase obtained in the step (1) to ensure that lithium chloride in the water phase reacts with the sodium carbonate to be converted into 261.2kg of lithium carbonate precipitate and 412.9kg of sodium chloride, and the materials enter the next step;
and (3) recovering lithium carbonate in the step (2): after solid-liquid separation is carried out on the material obtained in the step (2), the solid phase is 261.2kg of lithium carbonate, and the liquid phase material enters the next step;
step (4), adjusting the pH value: adding sodium hydroxide into the liquid-phase material obtained in the step (3), adjusting the pH value to 12.5, converting diisopropylamine hydrochloride into 440kg diisopropylamine and 255kg sodium chloride, and enabling the material to enter the next step;
step (5), recovering the diisopropylamine in the step (4): layering the material liquid obtained in the step (4), wherein the upper layer is 440kg of diisopropylamine, the material liquid is further dehydrated and then applied to the production process of the anecortave acetate epichloride, and the material liquid at the lower layer enters the next step;
and (6) recovering sodium chloride in the waste liquid: evaporating and concentrating the residual materials in the step (3) to 2400kg, cooling to 20 ℃, carrying out solid-liquid separation, recovering 1100kg of sodium chloride, and introducing a small amount of waste liquid into sewage treatment;
step (7), recovering tetrahydrofuran and n-heptane in the waste liquid: adding 4kg of p-tert-butylcatechol into the organic phase obtained in the step (1) to prevent styrene in the waste liquid from polymerizing, concentrating under normal pressure, condensing fractions at a temperature range of 65-70 ℃, recovering 2100kg of tetrahydrofuran, condensing fractions at a temperature range of 95-100 ℃, recovering 1100kg of n-heptane, and feeding the solid-liquid mixed material to the next step;
and (8) recovering styrene in the waste liquid: carrying out solid-liquid separation on the solid-liquid mixed material in the step (6), recovering 320kg of styrene, further treating the styrene, and applying the styrene to the production process of the anecortave acetate chloride, wherein the solid-phase material is a mixture of the anecortave acetate chloride and the anecortave acetate cyanide, and entering the next step;
step (9), elimination reaction: adding the solid-phase material obtained in the step (7) into 400kg of isopropanol, adding 30% by mass of liquid alkali, adjusting the pH value to 13, controlling the temperature at 30 ℃, reacting for 1h, converting the anecortave acetate cyano-group into 4, 9-dienoandrost-3, 17-dione, adding glacial acetic acid to adjust the pH value to 7, and enabling the material to enter the next step;
step (10), recovering the anecortave acetate chloride in the waste liquid: carrying out solid-liquid separation on the material obtained in the step (8) to obtain 20kg of the chloride on the anecortave acetate, wherein the chloride can be applied to the production procedure of the anecortave acetate, and the liquid-phase material enters the next step;
step (11) and recovering the 4, 9-diene androstane-3, 17-dione in the step (8): and (3) concentrating the liquid-phase material obtained in the step (10) under reduced pressure until the weight of the residual material liquid is 3.0 percent of that of the organic phase, cooling to 0 ℃, and performing solid-liquid separation to obtain 18.5kg of 4, 9-diene androstane-3, 17-dione which can be applied to the production procedures of betamethasone epoxy hydrolysate and dexamethasone epoxy hydrolysate, wherein the liquid-phase material is worthless and is used as waste liquid for treatment.
Example 3
The mother liquor to be treated is 10 tons, wherein the water phase is about 6 tons, and the organic phase is about 4 tons; the aqueous phase comprises: 720kg of diisopropylamine hydrochloride, 780kg of sodium chloride and 240kg of lithium chloride; the organic phase comprises: 2280kg of tetrahydrofuran, 1360kg of n-heptane, 320kg of styrene, 20kg of anecortave acetate epichloro and 20kg of anecortave acetate cyano.
The method for recycling mother liquor comprises the following steps:
step (1), liquid-liquid layering: standing and layering the mother solution of the chloride production of anecortave acetate, treating an organic phase, and carrying out a water phase in the next step;
step (2), precipitation reaction: adding 299.3kg of sodium carbonate into the water phase obtained in the step (1) to enable lithium chloride in the water phase to react with the sodium carbonate and convert the lithium chloride into 208.9kg of lithium carbonate precipitate and 330.4kg of sodium chloride, and enabling the materials to enter the next step;
and (3) recovering lithium carbonate in the step (2): after solid-liquid separation is carried out on the material obtained in the step (2), the solid phase is 208.9kg of lithium carbonate, and the liquid phase material enters the next step;
step (4), adjusting the pH value: adding sodium hydroxide into the liquid-phase material obtained in the step (3), adjusting the pH value to 12.0, converting diisopropylamine hydrochloride into 440kg diisopropylamine and 255kg sodium chloride, and enabling the material to enter the next step;
step (5), recovering the diisopropylamine in the step (4): layering the material liquid obtained in the step (4), wherein the upper layer is 440kg of diisopropylamine, the material liquid is further dehydrated and then applied to the production process of the anecortave acetate epichloride, and the material liquid at the lower layer enters the next step;
and (6) recovering sodium chloride in the waste liquid: evaporating and concentrating the residual materials in the step (3) to 2100kg, cooling to 25 ℃, carrying out solid-liquid separation, recovering 1200kg of sodium chloride, and introducing a small amount of waste liquid into sewage treatment;
step (7), recovering tetrahydrofuran and n-heptane in the waste liquid: adding 3kg of p-tert-butyl catechol into the organic phase obtained in the step (1) to prevent styrene in the waste liquid from polymerizing, concentrating under normal pressure, condensing fractions at the temperature of 65-70 ℃, recovering 2000kg of tetrahydrofuran, condensing fractions at the temperature of 95-100 ℃, recovering 1200kg of n-heptane, and feeding the solid-liquid mixed material to the next step;
and (8) recovering styrene in the waste liquid: carrying out solid-liquid separation on the solid-liquid mixed material in the step (6) to obtain 320kg of styrene, further treating the styrene, and applying the styrene to a production procedure of the anecortave acetate chloride, wherein the solid-phase material is a mixture of the anecortave acetate chloride and the anecortave acetate cyanide, and entering the next step;
step (9), elimination reaction: adding the solid-phase material obtained in the step (7) into 280kg of ethyl acetate, adding 30% by mass of liquid alkali, adjusting the pH value to 12.5, controlling the temperature to be 33 ℃, reacting for 2 hours, converting the anecortave acetate cyano-compound into 4, 9-dienoandrost-3, 17-dione, adding glacial acetic acid to adjust the pH value to 6.5, and enabling the material to enter the next step;
step (10), recovering the anecortave acetate chloride in the waste liquid: carrying out solid-liquid separation on the material obtained in the step (8) to obtain 20kg of the chloride on the anecortave acetate, wherein the chloride can be applied to the production procedure of the anecortave acetate, and the liquid-phase material enters the next step;
step (11) and recovering the 4, 9-diene androstane-3, 17-dione in the step (8): and (3) concentrating the liquid-phase material obtained in the step (10) under reduced pressure until the weight of the residual material liquid is 2.0 percent of that of the organic phase, cooling to 2 ℃, and performing solid-liquid separation to obtain 18.5kg of 4, 9-diene androstane-3, 17-dione which can be applied to the production procedures of betamethasone epoxy hydrolysate and dexamethasone epoxy hydrolysate, wherein the liquid-phase material is worthless and is used as waste liquid for treatment.
The method for resource utilization and treatment of the waste liquid from production of chloride on anecortave acetate is described in detail, and the principle and the implementation mode of the invention are explained by applying specific examples, and the description of the examples is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (4)
1. A resource utilization treatment method of a mother liquor for production of anecortave acetate is characterized in that the mother liquor comprises a water phase and an organic phase, wherein the water phase accounts for 60 percent, and the organic phase accounts for 40 percent; the aqueous phase comprises: 10-15% of diisopropylamine hydrochloride, 10-15% of sodium chloride, 3-5% of lithium chloride and the balance of water; the organic phase comprises: tetrahydrofuran with the mass fraction of 55-60%, n-heptane with the mass fraction of 31-36%, styrene with the mass fraction of 8%, anecortave acetate epichloro compound with the mass fraction of 0.5% and anecortave acetate cyanogen compound with the mass fraction of 0.5%;
the resource utilization treatment method comprises the following steps:
step (1), liquid-liquid layering: standing and layering the mother solution of the chloride production of anecortave acetate, treating an organic phase, and carrying out the next step on a water phase;
step (2), precipitation reaction: adding sodium carbonate into the water phase obtained in the step (1) to enable lithium chloride in the water phase to react with the sodium carbonate to be converted into lithium carbonate precipitate and sodium chloride, and enabling the materials to enter the next step;
and (3) recovering lithium carbonate in the step (2): after solid-liquid separation is carried out on the material obtained in the step (2), the solid phase is lithium carbonate, and the liquid phase material enters the next step;
step (4), adjusting the pH value: adding sodium hydroxide into the liquid-phase material obtained in the step (3), adjusting the pH value to 11.5-12.5, converting diisopropylamine hydrochloride into diisopropylamine and sodium chloride, and enabling the material to enter the next step;
step (5), recovering the diisopropylamine in the step (4): layering the material liquid obtained in the step (4), wherein the upper layer is diisopropylamine, the diisopropylamine is further dehydrated and then is applied to the production procedure of the chloride on the anecortave acetate, and the material on the lower layer enters the next step;
and (6) recovering sodium chloride in the waste liquid: evaporating and concentrating the residual materials in the step (3) until the weight of the residual materials is 30-40% of the total weight of the water phase, cooling to 20-30 ℃, performing solid-liquid separation, recovering sodium chloride, and treating a small amount of waste liquid in sewage treatment;
step (7), recovering tetrahydrofuran and n-heptane in the waste liquid: adding p-tert-butyl catechol into the organic phase obtained in the step (1) to prevent styrene in the waste liquid from polymerizing, concentrating under normal pressure, condensing the fraction at the temperature of 65-70 ℃, recovering tetrahydrofuran, condensing the fraction at the temperature of 95-100 ℃, recovering n-heptane, and enabling the solid-liquid mixed material to enter the next step;
and (8) recovering styrene in the waste liquid: carrying out solid-liquid separation on the solid-liquid mixed material in the step (6), wherein the liquid-phase material is styrene, and can be applied to the production procedure of the alecortave acetate chloratum after further treatment, and the solid-phase material is a mixture of the alecortave acetate chloratum and the alecortave acetate cyanogen base, and entering the next step;
step (9), elimination reaction: adding the solid-phase material obtained in the step (7) into a reaction solvent, adding 30% by mass of liquid alkali, adjusting the pH value to 12-13, controlling the temperature to 25-35 ℃, reacting for 1-3 h, converting the anecortave acetate cyano-group into 4, 9-diene androstane-3, 17-dione, adding glacial acetic acid to adjust the pH value to 6-7, and enabling the material to enter the next step;
step (10), recovering the anecortave acetate chloride in the waste liquid: after the solid-liquid separation is carried out on the material obtained in the step (8), the solid-phase material is chloride on the anecortave acetate, the solid-phase material can be applied to the production procedure of the anecortave acetate, and the liquid-phase material enters the next step;
step (11) and recovering the 4, 9-diene androstane-3, 17-dione in the step (8): and (2) concentrating the liquid-phase material obtained in the step (10) under reduced pressure until the weight of the residual material liquid is 1.0-3.0% of that of the organic phase, cooling to 0-5 ℃, and performing solid-liquid separation, wherein the solid-phase material is 4, 9-dienestosterone-3, 17-dione, and can be applied to the production procedures of betamethasone epoxy hydrolysate and dexamethasone epoxy hydrolysate, and a small amount of liquid-phase material has no value and is used as waste liquid treatment.
2. The resource utilization treatment method according to claim 1, wherein in the step (2), the weight ratio of the sodium carbonate to the water phase is 0.047-0.078.
3. The resource utilization treatment method according to claim 1, wherein in the step (7), the weight ratio of the p-tert-butylcatechol to the organic phase is from 0.0005 to 0.001.
4. The resource utilization treatment method according to claim 1, wherein in the step (9), the reaction solvent is at least one of methanol, isopropanol, and ethyl acetate;
the weight ratio of the amount of the reaction solvent to the organic phase is 0.04-0.1.
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