CN105348154A - Method for recycling sulfosalicylic acid from doxycycline production waste liquid - Google Patents
Method for recycling sulfosalicylic acid from doxycycline production waste liquid Download PDFInfo
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- CN105348154A CN105348154A CN201510899634.XA CN201510899634A CN105348154A CN 105348154 A CN105348154 A CN 105348154A CN 201510899634 A CN201510899634 A CN 201510899634A CN 105348154 A CN105348154 A CN 105348154A
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- Prior art keywords
- acid
- waste liquid
- doxycycline
- sulfosalicylic acid
- recovery
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- 239000002699 waste material Substances 0.000 title claims abstract description 18
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 18
- 229960003722 doxycycline Drugs 0.000 title abstract description 9
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 title abstract 6
- XQTWDDCIUJNLTR-CVHRZJFOSA-N doxycycline monohydrate Chemical compound O.O=C1C2=C(O)C=CC=C2[C@H](C)[C@@H]2C1=C(O)[C@]1(O)C(=O)C(C(N)=O)=C(O)[C@@H](N(C)C)[C@@H]1[C@H]2O XQTWDDCIUJNLTR-CVHRZJFOSA-N 0.000 title abstract 6
- 238000004064 recycling Methods 0.000 title abstract 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- CSVUNXDXKHELCR-UHFFFAOYSA-L disodium;3-carboxy-4-oxidobenzenesulfonate Chemical compound [Na+].[Na+].OC(=O)C1=CC(S([O-])(=O)=O)=CC=C1[O-] CSVUNXDXKHELCR-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 230000008025 crystallization Effects 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 239000011780 sodium chloride Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 claims description 32
- HALQELOKLVRWRI-VDBOFHIQSA-N doxycycline hyclate Chemical compound O.[Cl-].[Cl-].CCO.O=C1C2=C(O)C=CC=C2[C@H](C)[C@@H]2C1=C(O)[C@]1(O)C(=O)C(C(N)=O)=C(O)[C@@H]([NH+](C)C)[C@@H]1[C@H]2O.O=C1C2=C(O)C=CC=C2[C@H](C)[C@@H]2C1=C(O)[C@]1(O)C(=O)C(C(N)=O)=C(O)[C@@H]([NH+](C)C)[C@@H]1[C@H]2O HALQELOKLVRWRI-VDBOFHIQSA-N 0.000 claims description 24
- 238000011084 recovery Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004098 Tetracycline Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000019364 tetracycline Nutrition 0.000 claims description 4
- 229940040944 tetracyclines Drugs 0.000 claims description 4
- -1 tetracyclines organic compound Chemical class 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 2
- 235000015320 potassium carbonate Nutrition 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract 2
- 239000003344 environmental pollutant Substances 0.000 abstract 1
- 231100000719 pollutant Toxicity 0.000 abstract 1
- PCTXBFQNMDKOSP-UHFFFAOYSA-M sodium;(2-carboxyphenyl) sulfate Chemical compound [Na+].OS(=O)(=O)OC1=CC=CC=C1C([O-])=O PCTXBFQNMDKOSP-UHFFFAOYSA-M 0.000 abstract 1
- 229960001172 doxycycline hyclate Drugs 0.000 description 12
- 239000000243 solution Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- SGKRLCUYIXIAHR-AKNGSSGZSA-N (4s,4ar,5s,5ar,6r,12ar)-4-(dimethylamino)-1,5,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4a,5,5a,6-tetrahydro-4h-tetracene-2-carboxamide Chemical compound C1=CC=C2[C@H](C)[C@@H]([C@H](O)[C@@H]3[C@](C(O)=C(C(N)=O)C(=O)[C@H]3N(C)C)(O)C3=O)C3=C(O)C2=C1O SGKRLCUYIXIAHR-AKNGSSGZSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000193738 Bacillus anthracis Species 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- 241000202934 Mycoplasma pneumoniae Species 0.000 description 1
- 239000006002 Pepper Substances 0.000 description 1
- 241000606701 Rickettsia Species 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- 206010044302 Tracheitis Diseases 0.000 description 1
- 241000607626 Vibrio cholerae Species 0.000 description 1
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 229940118696 vibrio cholerae Drugs 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/42—Separation; Purification; Stabilisation; Use of additives
- C07C303/44—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for recycling sulfosalicylic acid from doxycycline production waste liquid and belongs to the field of medicinal chemistry separation and purification. The method includes the following steps that alkali is added to doxycycline production waste liquid, the alkali reacts with sulfosalicylic acid in the doxycycline production waste liquid, sulfosalicylic acid sodium salt is formed, then ethyl alcohol is recycled, crystallization is conducted, and sodium sulfosalicylate is obtained; the recycled sulfosalicylic acid sodium salt is added to an alcohol solution and an acid solution, after a reaction is ended, filtering is conducted, sodium chloride is removed, filter liquor is concentrated, solvent is recycled, crystallization is conducted, sulfosalicylic acid is obtained, the recycling rate reaches 80% or more, and a product is acceptable in quality. Compared with a traditional recycling process, the sulfosalicylic acid is recycled from the doxycycline production waste liquid, emission of pollutants is reduced, environmental protection is facilitated, the sulfosalicylic acid can be recycled, the production cost is lowered, and the economic and social benefits of doxycycline are raised.
Description
Technical field
The present invention relates to the recovery method that a kind of Vibravenos produces sulphosalicylic acid in waste liquid, belong to pharmaceutical chemical separation and purification field.
Background technology
Vibravenos also known as doxycycline or deoxidation soil mould, it is the semi-synthetic tetracycline antibiotics of a kind of long-acting, broad-spectrum, except having effect to gram-positive microorganism and negative bacterium, also can suppress rickettsia, mycoplasma pneumoniae, sand holes mycoplasma, ameba etc., particularly the respiratory tract common bacteria of chronic tracheitis patient is all more responsive to Doxycycline Hyclate, act on length of holding time, absorbed following oral administration is very fast, and side effect is little.In recent years, researchist finds that Doxycycline Hyclate is comparatively responsive to anthrax bacteria, vibrio cholerae etc., and low dose of Doxycycline Hyclate can suppress the crown sclerosis of blood vessel, therefore excites the market requirement of Doxycycline Hyclate further.
At present, the production technique of Doxycycline Hyclate is all take terramycin as raw material, through techniques such as chloro, dehydration, hydrogenations, finally turns salt and generates Doxycycline Hyclate.Produce in Doxycycline Hyclate process, hydrogenated products utilizes sulphosalicylic acid selectivity to become salt-pepper noise, then neutralized by alkali, be converted into Vibravenos free alkali, sulphosalicylic acids a large amount of has in the process been left in mother liquor, the content of sulphosalicylic acid about 15% in this mother liquor.Sulphosalicylic acid is poisonous, difficult degradation, to environment, will damage human body if directly discharge or deal with improperly simultaneously.Due to water-soluble extremely strong, the easily decomposition of being heated of sulphosalicylic acid, recovery difficult is quite large.
Document (Chinese Journal of Pharmaceuticals, nineteen eighty-two, 10 phases, sulphosalicylic acid is reclaimed from the conversion mother liquor of doxycycline) report that to select trialkylamine to be complexing agent, n-Octanol and sulfonated kerosene be thinner, sodium hydroxide is strippant, carry out extracting-reextraction experimental study, after three grades of extractions, reclaim sulphosalicylic acid, extraction agent can recycle, the research is only limitted to the removing of a small amount of sulphosalicylic acid in mother liquor, the research is also only limitted to laboratory lab scale, does not carry out amplification test research.And the research technology is by complexometric extraction repeatedly, strip and be separated sulphosalicylic acid, equipment and complicated operation, do not have the value of industrialization.
Document (Environmental Pollution and Control, 2007,09(6), 463-466; Doxycycline factory effluent resource technology is studied) carry out reclaiming research to the sulphosalicylic acid in Doxycycline Hyclate production process, what the research adopted equally is first reclaim sulfosalicylic acid sodium salt, then sulfosalicylic acid sodium salt is made into the aqueous solution and carries out ion-exchange by polystyrene resin (H type) exchange column, outflow composition is carried out underpressure distillation, crystallization, reclaims the sulphosalicylic acid meeting production requirement.This technology equally also just completes the lab scale work in laboratory, adopt ion-exchange unit and resin cost high.The most important thing is must to obtain sulphosalicylic acid by a large amount of water of distillation removing, as everyone knows, hydro-thermal capacity is large, Interpolymer Association is firm, evaporation difficulty is large, consumption of calorie is large, the outflow concentration of adding ion-exchange is less, the cost reclaiming sulphosalicylic acid is higher, does not also have industrialization value.
For the sulphosalicylic acid in mother liquor, current domestic production Doxycycline Hyclate producer generally adopts the way of burning or enters Waste Water Treatment, and environmental protection pressure is huge.Usual production 1 ton of Doxycycline Hyclate consumes sulphosalicylic acid 1.8 tons, if can sulphosalicylic acid be recycled, not only can the discharge of decreasing pollution thing, and reduce three wastes pressure, and there is good economic benefit and social benefit.
Summary of the invention
Object of the present invention is exactly provide a kind of reduce production cost to overcome defect that above-mentioned prior art exists, be conducive to suitability for industrialized production, be conducive to the novel process that the Doxycycline Hyclate of environment protection produces sulphosalicylic acid in waste liquid.
The present invention solves the problems of the technologies described above adopted technical scheme and realizes especially by following steps:
(1) preparation of sulphosalicylic acid sodium salt: Vibravenos is produced waste liquid and first add alkali and react, pH value is adjusted to make tetracyclines organic compound crystallization, filter, filtrate adds activated carbon decolorizing, excessively filters gac, filtrate concentration and recovery ethanol, crystallization, filter, drying obtains sulphosalicylic acid sodium salt.
(2) recovery of sulphosalicylic acid: be added to by sulphosalicylic acid sodium salt in alcohol, acid solution, stirring heating makes it react, filtration from sodium chloride, filtrate concentration and recovery solvent, crystallization, filter, drying obtains sulfosalisylic acid product.
Alkali described in step (1) selects sodium carbonate, salt of wormwood, potassium hydroxide or sodium hydroxide; PH value scope is 7-9; Ethanol recovery volume ratio is 60%-80%.
Alcohol described in step (2) selects methyl alcohol, ethanol, Virahol or propyl carbinol; Hydrochloric acid or sulfuric acid are selected in acid; Acid mass percentage concentration scope is 10%-30%; Temperature of reaction is 70 DEG C-110 DEG C; Reaction times is 1-2 hour.
Compared with prior art tool of the present invention has the following advantages: (1) this recovery process is simple, is all general-purpose equipment; (2) utilize alkyd directly sulfosalicylic acid sodium salt to be converted into sulfosalisylic acid recovery, product is separated out with the form of crystallization, and energy feedstuff consumption is few, and cost obviously reduces; (3) reclaim the sulphosalicylic acid purity obtained high, meet quality standard, can meet secondary and use, it be applied in the production of Doxycycline Hyclate, the finished product are qualified, can reuse; (4) decrease the discharge of pollutent, make high concentrated organic wastewater quantity discharged decrease more than 78%, be conducive to environment protection.Be very beneficial for suitability for industrialized production, economic and social benefit is remarkable.
Embodiment
In order to implement the present invention better, now for embodiment, the invention will be further described, but embodiment is not limitation of the present invention.
embodiment 1:
(1) preparation of sulphosalicylic acid sodium salt
In the reaction flask of 5L, add the Vibravenos production waste liquid that 2L contains sulphosalicylic acid, then add sodium hydroxide, stir and make it react, PH=7 is adjusted again with a small amount of sodium hydrate solid, make solution no longer separate out solid, cross and filter insoluble tetracyclines organic compound, filtrate adds 40g gac, reflux 30 minutes, then filter, filtrate concentration and recovery ethanol, concentrated solution crystallisation by cooling, filter, dry 248g sulphosalicylic acid sodium salt.
(2) recovery of sulphosalicylic acid
The hydrochloric acid of 400g sulfosalicylic acid sodium salt and 2L mass percentage concentration 10%, ethanolic soln is added in the reaction flask of 5L, stirring makes it react, reflux 1 hour, after reaction terminates, filtration from sodium chloride, filtrate concentration and recovery ethanol, concentrated solution crystallisation by cooling, filter, dry 298g sulphosalicylic acid, yield 81%.
embodiment 2:
(1) preparation of sulphosalicylic acid sodium salt
In the reaction flask of 5L, add the Vibravenos production waste liquid that 2L contains sulphosalicylic acid, then add sodium carbonate, stir and make it react, PH=9 is adjusted again with a small amount of sodium carbonate solid, make solution no longer separate out solid, cross and filter insoluble tetracyclines organic compound, filtrate adds 40g gac, reflux 30 minutes, then filter, filtrate concentration and recovery ethanol, concentrated solution crystallisation by cooling, filter, dry 248g sulphosalicylic acid sodium salt.
(2) recovery of sulphosalicylic acid
The sulfuric acid of 400g sulfosalicylic acid sodium salt and 1L mass percentage concentration 20%, aqueous isopropanol is added in the reaction flask of 5L, stirring makes it react, reflux 1 hour, after reaction terminates, filtration from sodium chloride, filtrate concentration and recovery Virahol, concentrated solution crystallisation by cooling, filter, dry 287g sulphosalicylic acid, yield 78%.
The sulphosalicylic acid adopting present invention process to reclaim reaches following technical indicator: white solid, soluble in water and ethanol, fusing point 120 DEG C, content is greater than 99%, up-to-standard.
After adopting recovery process of the present invention, after testing, in Vibravenos production waste liquid, sulfosalisylic acid content is by original 15%, drops to less than 1%, is beneficial to waste liquid qualified discharge, is conducive to environment protection.
Claims (3)
1. Vibravenos produces a recovery method for sulphosalicylic acid in waste liquid, it is characterized in that, is realized by following steps:
(1) preparation of sulphosalicylic acid sodium salt: Vibravenos is produced waste liquid and first add alkali and react, pH value is adjusted to make tetracyclines organic compound crystallization, filter, filtrate adds activated carbon decolorizing, excessively filters gac, filtrate concentration and recovery ethanol, crystallization, filter, drying obtains sulphosalicylic acid sodium salt; Described alkali selects sodium carbonate, salt of wormwood, potassium hydroxide or sodium hydroxide; PH value scope is 7-9; Ethanol recovery volume ratio is 60%-80%;
(2) recovery of sulphosalicylic acid: be added to by sulphosalicylic acid sodium salt in the solution containing alcohol, acid, stirring heating makes it react, filtration from sodium chloride, filtrate concentration and recovery solvent, crystallization, and filter, drying obtains sulfosalisylic acid product;
Described alcohol selects methyl alcohol, ethanol, Virahol or propyl carbinol; Hydrochloric acid or sulfuric acid are selected in acid.
2. Vibravenos produces the recovery method of sulphosalicylic acid in waste liquid as claimed in claim 1, and it is characterized in that, the mass percentage concentration scope of selected acid is 10%-30%.
3. Vibravenos produces the recovery method of sulphosalicylic acid in waste liquid as claimed in claim 1, and it is characterized in that, step (2) temperature of reaction is 70 DEG C-110 DEG C; Reaction times is 1-2 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510899634.XA CN105348154B (en) | 2014-12-10 | 2015-12-09 | The recovery method of sulfosalicylic acid in a kind of Doxycycline production waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410748203 | 2014-12-10 | ||
| CN2014107482039 | 2014-12-10 | ||
| CN201510899634.XA CN105348154B (en) | 2014-12-10 | 2015-12-09 | The recovery method of sulfosalicylic acid in a kind of Doxycycline production waste liquid |
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| CN105348154A true CN105348154A (en) | 2016-02-24 |
| CN105348154B CN105348154B (en) | 2017-10-31 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107118138A (en) * | 2017-05-16 | 2017-09-01 | 扬州联博药业有限公司 | A kind of method that sulfosalicylic acid is reclaimed in the alkalization mother liquor from fortimicin |
| CN107417563A (en) * | 2017-04-12 | 2017-12-01 | 扬州联博药业有限公司 | A kind of method that Doxycycline Hyclate is reclaimed in the refinement mother liquor from Doxycycline Hyclate |
| CN110872241A (en) * | 2018-09-04 | 2020-03-10 | 山西卓联锐科科技有限公司 | Method for recovering sulfosalicylic acid and p-toluenesulfonic acid in doxycycline hydrogenation wastewater |
| CN110872166A (en) * | 2018-09-04 | 2020-03-10 | 山西卓联锐科科技有限公司 | Method for recovering p-toluenesulfonic acid from doxycycline dehydration wastewater |
| CN113135845A (en) * | 2021-04-22 | 2021-07-20 | 昆山华苏生物科技有限公司 | Method for extracting regenerated p-toluenesulfonic acid from doxycycline hydrochloride production wastewater |
| CN114073993A (en) * | 2020-08-13 | 2022-02-22 | 昆山华苏生物科技有限公司 | Method for cleaning waste catalyst in doxycycline hydrochloride hydrogenation reaction |
| CN114076758A (en) * | 2020-08-13 | 2022-02-22 | 昆山华苏生物科技有限公司 | Method for monitoring endpoint of doxycycline hydrochloride hydrogenation reaction |
| CN114956427A (en) * | 2022-06-17 | 2022-08-30 | 盐城苏海制药有限公司 | Treatment method for doxycycline hydrochloride wastewater solidification |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN107417563A (en) * | 2017-04-12 | 2017-12-01 | 扬州联博药业有限公司 | A kind of method that Doxycycline Hyclate is reclaimed in the refinement mother liquor from Doxycycline Hyclate |
| CN107118138A (en) * | 2017-05-16 | 2017-09-01 | 扬州联博药业有限公司 | A kind of method that sulfosalicylic acid is reclaimed in the alkalization mother liquor from fortimicin |
| CN107118138B (en) * | 2017-05-16 | 2022-06-28 | 扬州联博药业有限公司 | Method for recovering sulfosalicylic acid from doxycycline alkalization mother liquor |
| CN110872241A (en) * | 2018-09-04 | 2020-03-10 | 山西卓联锐科科技有限公司 | Method for recovering sulfosalicylic acid and p-toluenesulfonic acid in doxycycline hydrogenation wastewater |
| CN110872166A (en) * | 2018-09-04 | 2020-03-10 | 山西卓联锐科科技有限公司 | Method for recovering p-toluenesulfonic acid from doxycycline dehydration wastewater |
| CN114073993A (en) * | 2020-08-13 | 2022-02-22 | 昆山华苏生物科技有限公司 | Method for cleaning waste catalyst in doxycycline hydrochloride hydrogenation reaction |
| CN114076758A (en) * | 2020-08-13 | 2022-02-22 | 昆山华苏生物科技有限公司 | Method for monitoring endpoint of doxycycline hydrochloride hydrogenation reaction |
| CN114076758B (en) * | 2020-08-13 | 2023-12-05 | 昆山华苏生物科技有限公司 | End point monitoring method for doxycycline hydrochloride hydrogenation reaction |
| CN113135845A (en) * | 2021-04-22 | 2021-07-20 | 昆山华苏生物科技有限公司 | Method for extracting regenerated p-toluenesulfonic acid from doxycycline hydrochloride production wastewater |
| CN114956427A (en) * | 2022-06-17 | 2022-08-30 | 盐城苏海制药有限公司 | Treatment method for doxycycline hydrochloride wastewater solidification |
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