CN105348154B - The recovery method of sulfosalicylic acid in a kind of Doxycycline production waste liquid - Google Patents
The recovery method of sulfosalicylic acid in a kind of Doxycycline production waste liquid Download PDFInfo
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- CN105348154B CN105348154B CN201510899634.XA CN201510899634A CN105348154B CN 105348154 B CN105348154 B CN 105348154B CN 201510899634 A CN201510899634 A CN 201510899634A CN 105348154 B CN105348154 B CN 105348154B
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- sulfosalicylic acid
- acid
- recovery
- doxycycline
- waste liquid
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- 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 claims abstract description 33
- 238000011084 recovery Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 229960003722 doxycycline Drugs 0.000 title claims abstract description 17
- 239000007788 liquid Substances 0.000 title claims abstract description 17
- 239000002699 waste material Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 10
- 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 claims abstract 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 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 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 10
- 238000002425 crystallisation Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 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
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- -1 Sulfosalicylic acid sodium salt Chemical class 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims 2
- 239000001103 potassium chloride Substances 0.000 claims 2
- 235000011164 potassium chloride Nutrition 0.000 claims 2
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000003344 environmental pollutant Substances 0.000 abstract description 2
- 231100000719 pollutant Toxicity 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 229960001172 doxycycline hyclate Drugs 0.000 description 11
- 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 description 11
- 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 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229930195503 Fortimicin Natural products 0.000 description 3
- BIDUPMYXGFNAEJ-APGVDKLISA-N astromicin Chemical compound O[C@@H]1[C@H](N(C)C(=O)CN)[C@@H](OC)[C@@H](O)[C@H](N)[C@H]1O[C@@H]1[C@H](N)CC[C@@H]([C@H](C)N)O1 BIDUPMYXGFNAEJ-APGVDKLISA-N 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical class OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000004098 Tetracycline Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000019364 tetracycline Nutrition 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000224489 Amoeba Species 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- 206010006458 Bronchitis chronic Diseases 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 241000204031 Mycoplasma Species 0.000 description 1
- 241000202934 Mycoplasma pneumoniae Species 0.000 description 1
- 241000607598 Vibrio Species 0.000 description 1
- 206010047400 Vibrio infections Diseases 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 208000007451 chronic bronchitis Diseases 0.000 description 1
- 239000008139 complexing agent Substances 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
- 239000003085 diluting agent Substances 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 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
- 238000000746 purification Methods 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
- 239000004576 sand Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 229940063650 terramycin Drugs 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 229940072172 tetracycline antibiotic Drugs 0.000 description 1
- 150000003522 tetracyclines Chemical class 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000005292 vacuum distillation Methods 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 the recovery method of sulfosalicylic acid in a kind of Doxycycline production waste liquid, belong to pharmaceutical chemical and isolate and purify field.This method comprises the following steps：Alkali and sulfosalisylic acid reaction therein are added into Doxycycline production waste liquid, sulfosalicylic acid sodium salt is formed, ethanol is reclaimed afterwards, crystallization obtains sulfosalicylic acid sodium salt；The sulfosalicylic acid sodium salt of recovery is added in alcohol, acid solution, after reaction terminates, filtration from sodium chloride, filtrate concentration and recovery solvent, crystallization obtains sulfosalicylic acid, and the rate of recovery reaches more than 80%, qualified product.Compared with traditional recovery process; the present invention passes through the recovery to sulfosalicylic acid in Doxycycline production waste liquid; not only reduce the discharge of pollutant; be conducive to environmental protection; and sulfosalicylic acid is recyclable to be recycled; production cost is reduced, the economic and social benefit of Doxycycline production is improved.
Description
Technical field
The present invention relates to the recovery method of sulfosalicylic acid in a kind of Doxycycline production waste liquid, belong to pharmaceutical chemical separation
Purification art.
Background technology
Doxycycline is also known as fortimicin or deoxidation soil is mould, is a kind of semi-synthetic tetracycline antibiotics of long-acting, broad-spectrum, removes
There is effect outer to gram-positive bacteria and negative bacterium, may also suppress Richettsia, mycoplasma pneumoniae, sand holes mycoplasma, amoeba
The respiratory tract common bacteria of protozoon etc., particularly chronic bronchitis patient is all more sensitive to Doxycycline Hyclate, and effect is maintained
Time is long, and absorbed following oral administration is very fast, Small side effects.In recent years, researcher has found Doxycycline Hyclate to anthrax bacteria, cholera
Vibrios etc. is more sensitive, and low dose of Doxycycline Hyclate can suppress the coronal hardening of blood vessel, therefore further excite hydrochloric acid
The market demand of Doxycycline.
At present, the production technology of Doxycycline Hyclate is using terramycin as raw material, through works such as chloro, dehydration, hydrogenations
Skill, finally turns salt generation Doxycycline Hyclate.Produce during Doxycycline Hyclate, hydrogenated products are to utilize sulfosalicylic acid choosing
Selecting property is crystallized into salt, is then neutralized by alkali, is converted into Doxycycline free alkali, in the process substantial amounts of sulfosalicylic acid quilt
Stay in mother liquor, the content of sulfosalicylic acid about 15% in the mother liquor.Sulfosalicylic acid is poisonous, difficult degradation, if directly discharged
Or deal with improperly and environment will be polluted, while being damaged to human body.Because sulfosalicylic acid water solubility is extremely strong, by
Hot easily to decompose, recovery difficult is quite big.
Document（Chinese Journal of Pharmaceuticals, nineteen eighty-two, 10 phases, sulfosalisylic is reclaimed from the conversion mother liquor of fortimicin
Acid）It is that complexing agent, n-octyl alcohol and sulfonated kerosene are that diluent, sodium hydroxide are strippant to report from trialkylamine, is entered
Row extraction-back extraction experimental study, after being extracted by three-level, reclaims sulfosalicylic acid, extractant can be recycled, this
Research is only limitted to the removing of a small amount of sulfosalicylic acid in mother liquor, and the research is also only limitted to laboratory lab scale, is not amplified
Experimental study.And the research technology is by complexometric extraction repeatedly, back extraction separation sulfosalicylic acid, equipment and operation
Complexity, the value without industrialization.
Document（Environmental Pollution and Control, 2007,09（6）, 463-466；Fortimicin production waste water reclaiming technology is ground
Study carefully）Sulfosalicylic acid in Doxycycline Hyclate production process is carried out to reclaim research, the research equally uses elder generation
Sulfosalicylic acid sodium salt is reclaimed, sulfosalicylic acid sodium salt is then made into the aqueous solution and passes through polystyrene resin（H types）Exchange column is carried out
Ion exchange, vacuum distillation is carried out by outflow composition, and the sulfosalicylic acid for meeting production requirement is reclaimed in crystallization.The technology is same
Also the lab scale work in laboratory is simply completed, it is high using ion-exchange unit and resin cost.It is most important to have to be by
Substantial amounts of water, which is distilled off, can just access sulfosalicylic acid, it is well known that hydro-thermal capacity is big, Interpolymer Association is firm, evaporation is difficult
Degree is big, consumption of calorie is big, along with the outflow concentration of ion exchange is smaller, and the cost for reclaiming sulfosalicylic acid is higher, does not also have
Industrialization value.
For the sulfosalicylic acid in mother liquor, current domestic production Doxycycline Hyclate producer is typically using the method for burning
Or entering Waste Water Treatment, environmental protection pressure is huge.Generally 1 ton of Doxycycline Hyclate of production consumes 1.8 tons of sulfosalicylic acid,
If sulfosalicylic acid can be recycled, the discharge of pollutant can be not only reduced, three wastes pressure is reduced, and with preferable
Economic benefit and social benefit.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind reduction production cost,
Be conducive to industrialized production, be conducive to the Doxycycline Hyclate of environmental protection to produce the new technology of sulfosalicylic acid in waste liquid.
The technical scheme that present invention solution above-mentioned technical problem is used is realized especially by following steps：
（1）The preparation of sulfosalicylic acid sodium salt：First add alkali to be reacted Doxycycline production waste liquid, adjust pH value to make Fourth Ring
Plain class organic compound crystallization is separated out, and filtering, filtrate adds activated carbon decolorizing, is filtered to remove activated carbon, filtrate concentration and recovery ethanol,
Crystallization, filtering, is dried to obtain sulfosalicylic acid sodium salt.
（2）The recovery of sulfosalicylic acid：Sulfosalicylic acid sodium salt is added in alcohol, acid solution, agitating and heating reacts it,
Filtration from sodium chloride, filtrate concentration and recovery solvent is crystallized, and filtering is dried to obtain sulfosalisylic acid product.
Step（1）Described in alkali select sodium carbonate, potassium carbonate, potassium hydroxide or sodium hydroxide；PH range be 7-
9；Ethanol recovery volume ratio is 60% -80%.
Step（2）Described in alcohol select methanol, ethanol, isopropanol or n-butanol；Acid selects hydrochloric acid or sulfuric acid；Sour matter
It is 10% -30% to measure concentration range；Reaction temperature is 70 DEG C -110 DEG C；Reaction time is 1-2 hours.
Compared with prior art the invention has the advantages that：（1）The recovery process is simple, all common apparatus；（2）
Sulfosalicylic acid sodium salt is directly converted into sulfosalisylic acid recovery using alkyd, product is separated out in the form of crystallizing, energy feedstuff
Consumption is few, and cost is substantially reduced；（3）Reclaim obtained sulfosalicylic acid purity high, meet quality standard, disclosure satisfy that secondary make
With being had been applied in the production of Doxycycline Hyclate, final products are qualified, can be reused；（4）Reduce pollution
The discharge of thing so that high concentrated organic wastewater discharge capacity reduces more than 78%, is conducive to environmental protection.It is very beneficial for industry
Metaplasia is produced, and economic and social benefit is notable.
Embodiment
In order to preferably implement the present invention, now for embodiment, the invention will be further described, but embodiment is not to this
The limitation of invention.
Embodiment 1：
（1）The preparation of sulfosalicylic acid sodium salt
The Doxycycline production waste liquid that 2L contains sulfosalicylic acid is added in 5L reaction bulb, hydroxide is then added
Sodium, stirring reacts it, then adjusts PH=7 with a small amount of sodium hydrate solid, solution is no longer separated out solid, is filtered to remove insoluble
Tetracyclines organic compound, filtrate adds 40g activated carbons, is heated to reflux 30 minutes, then filters, filtrate concentration and recovery second
Alcohol, concentrate crystallisation by cooling, filtering, dry 248g sulfosalicylic acid sodium salts.
（2）The recovery of sulfosalicylic acid
400g sulfosalicylic acid sodium salts and hydrochloric acid, the ethanol solution of 2L mass percentage concentrations 10% are added in 5L reaction bulb,
Stirring reacts it, flows back 1 hour, after reaction terminates, filtration from sodium chloride, filtrate concentration and recovery ethanol, concentrate cooling
Crystallization, filtering, dry 298g sulfosalicylic acids, yield 81%.
Embodiment 2：
（1）The preparation of sulfosalicylic acid sodium salt
The Doxycycline production waste liquid that 2L contains sulfosalicylic acid is added in 5L reaction bulb, sodium carbonate is then added,
Stirring reacts it, then adjusts PH=9 with a small amount of sodium carbonate solid, solution is no longer separated out solid, is filtered to remove insoluble tetracycline
Class organic compound, filtrate adds 40g activated carbons, is heated to reflux 30 minutes, then filters, filtrate concentration and recovery ethanol, concentration
Liquid crystallisation by cooling, filtering, dry 248g sulfosalicylic acid sodium salts.
（2）The recovery of sulfosalicylic acid
400g sulfosalicylic acid sodium salts are added in 5L reaction bulb and sulfuric acid, the isopropanol of 1L mass percentage concentrations 20% are molten
Liquid, stirring reacts it, flows back 1 hour, after reaction terminates, filtration from sodium chloride, filtrate concentration and recovery isopropanol, concentrate
Crystallisation by cooling, filtering, dry 287g sulfosalicylic acids, yield 78%.
The sulfosalicylic acid reclaimed using present invention process reaches following technical indicator：White solid, soluble in water and second
Alcohol, 120 DEG C of fusing point, content is up-to-standard more than 99%.
After recovery process of the present invention, after testing, sulfosalisylic acid content is by original in Doxycycline production waste liquid
15%, drop to less than 1%, beneficial to waste liquid qualified discharge, be conducive to environmental protection.
Claims (2)
1. the recovery method of sulfosalicylic acid in a kind of Doxycycline production waste liquid, it is characterised in that realized by following steps：
（1）The preparation of sulfosalicylic acid sodium salt or sylvite：First add alkali to be reacted Doxycycline production waste liquid, adjust pH value to make four
Ring element class organic compound crystallization is separated out, and filtering, filtrate adds activated carbon decolorizing, is filtered to remove activated carbon, filtrate concentration and recovery second
Alcohol, is crystallized, and filtering is dried to obtain sulfosalicylic acid sodium salt or sulfosalisylic acid potassium salt；The alkali from sodium carbonate, potassium carbonate,
Potassium hydroxide or sodium hydroxide；PH range is 7-9；Ethanol recovery volume ratio is 60% -80%；
（2）The recovery of sulfosalicylic acid：Sulfosalicylic acid sodium salt or sulfosalisylic acid potassium salt are added to the solution containing alcohol, acid
In, agitating and heating reacts it, filtration from sodium chloride or potassium chloride, filtrate concentration and recovery solvent, crystallizes, filtering, dry
To sulfosalisylic acid product；
Described alcohol selects methanol, ethanol, isopropanol or n-butanol；Acid selects hydrochloric acid or sulfuric acid,
Selected sour mass percentage concentration scope is 10% -30%.
2. the recovery method of sulfosalicylic acid in Doxycycline production waste liquid as claimed in claim 1, it is characterised in that step
(2) reaction temperature is 70 DEG C -110 DEG C；Reaction time is 1-2 hours.
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| 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 |
|---|---|---|---|
| CN2014107482039 | 2014-12-10 | ||
| CN201410748203 | 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 CN105348154A (en) | 2016-02-24 |
| CN105348154B true CN105348154B (en) | 2017-10-31 |
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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 |
| 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 |
| 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 |
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| 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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| IT956668B (en) * | 1971-06-21 | 1973-10-10 | Fmc Corp | PROCEDURE FOR THE PRODUCTION OF SUBSTITUTED ALCOXISULPHONATES AND POLYESTERS CONTAINING SUCH ALCOS SULFONATES |
| CN1137517A (en) * | 1996-01-27 | 1996-12-11 | 河南省科学院化学研究所 | Preparing reagent grade sulfosalicylic acid and its sodium salt by industrial product epuration |
| CN101786971B (en) * | 2010-03-01 | 2013-11-06 | 扬州联博药业有限公司 | Preparation process of doxycycline hydrochloride |
| CN103274971B (en) * | 2013-06-19 | 2014-08-06 | 太仓沪试试剂有限公司 | Purification method of 5-sulfosalicylic acid |
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