CN111204775A - Method for treating waste water from cefoperazone acid production - Google Patents

Method for treating waste water from cefoperazone acid production Download PDF

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Publication number
CN111204775A
CN111204775A CN202010031730.3A CN202010031730A CN111204775A CN 111204775 A CN111204775 A CN 111204775A CN 202010031730 A CN202010031730 A CN 202010031730A CN 111204775 A CN111204775 A CN 111204775A
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mother liquor
cefoperazone acid
treating
calcium
acid production
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吕敦生
张立明
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Shandong Xinquan Pharmaceutical Co ltd
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Shandong Xinquan Pharmaceutical Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/06—Boron halogen compounds
    • C01B35/063—Tetrafluoboric acid; Salts thereof
    • C01B35/066—Alkali metal tetrafluoborates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/20—Halides
    • C01F11/24—Chlorides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds

Abstract

The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for treating cefoperazone acid production wastewater. Adding alkali into the 7-TMCA mother liquor to adjust the pH value to 7-9, then adding potassium salt to cool and grow crystal, and centrifuging to obtain potassium fluoborate solid; adding calcium salt into the cefoperazone acid mother liquor, cooling, growing crystals, and centrifuging to obtain calcium phosphate; and (3) evaporating the water of the mother liquor after recovering the calcium phosphate, centrifuging to obtain calcium chloride, and performing post-treatment on the calcium chloride to obtain a pure calcium chloride product. The method for treating the cefoperazone acid production wastewater reduces the content of inorganic acid in the wastewater, reduces the sewage treatment pressure, and generates better economic benefit and environmental protection benefit.

Description

Method for treating waste water from cefoperazone acid production
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a method for treating cefoperazone acid production wastewater.
Background
The cefoperazone acid is white or off-white crystalline powder; no smell, moisture-attracting property. Easily soluble in acetone, slightly soluble in acetonitrile and practically insoluble in water. The molecular formula is as follows: c25H27N9O8S2The structural formula is as follows:
Figure BDA0002364561440000011
at present, 7-ACA (7-aminocephalosporanic acid) is used as an initial raw material and condensed with methylmercaptotetrazole under the catalytic action of boron trifluoride to generate 7-TMCA (cefmenoxime mother nucleus), and the 7-TMCA is activated and acylated with chlorinated HO-EPCP to generate cefoperazone acid.
The chemical reaction equation that occurs during the reaction is as follows:
Figure BDA0002364561440000012
Figure BDA0002364561440000021
the main links of waste water generation in the process are 7-TMCA crystallization and cefoperazone acid crystallization, 7-ACA is condensed with methylmercaptotetrazole under the catalytic action of boron trifluoride to generate 7-TMCA (shown in a chemical formula (1)), ammonia water is added into the solution for crystallization, the obtained 7-TMCA is used for further reaction in a chemical formula (2), and the 7-TMCA mother liquor mainly comprises fluoboric acid, acetic acid and organic matters, wherein the organic matters are a mixture of 7-ACA, methylmercaptotetrazole and 7-TMCA; after the reaction of the chemical formula (4) is finished, adding water for crystallization, wherein the obtained cefoperazone acid mother liquor is phosphoric acid, hydrochloric acid and other organic matters, and the organic matters are a mixture of reaction raw materials and reaction products in the chemical formula (4).
Disclosure of Invention
The purpose of the invention is: overcomes the defects of the prior art and provides a method for treating wastewater generated in cefoperazone acid production. The treatment method reduces the content of inorganic acid in the wastewater, reduces the sewage treatment pressure, and generates better economic benefit and environmental protection benefit.
The invention relates to a method for treating cefoperazone acid production wastewater, which comprises the following steps:
(1)7-TMCA mother liquor treatment
Adding alkali into the 7-TMCA mother liquor to adjust the pH value to 7-9, then adding potassium salt to cool and grow crystal, and centrifuging to obtain potassium fluoborate solid;
(2) cefoperazone acid mother liquor treatment
Adding calcium salt into the cefoperazone acid mother liquor, cooling, growing crystals, and centrifuging to obtain calcium phosphate; and (3) evaporating the water of the mother liquor after recovering the calcium phosphate, centrifuging to obtain calcium chloride, and performing post-treatment on the calcium chloride to obtain a pure calcium chloride product.
Wherein:
and (2) adding sodium hydroxide into the alkali in the step (1) to be used as acid in the 7-TMCA mother liquor.
The potassium salt in the step (1) is solid potassium nitrate, and aims to provide potassium ions to generate potassium fluoborate precipitate, and the mass of the added potassium nitrate accounts for 3-4% of the mass of the cefoperazone acid mother liquor.
Adding the potassium salt into the mixture obtained in the step (1), stirring the mixture for 30 to 60 minutes at a stirring speed of 80 to 120r/min, and cooling and growing the crystals; the stirring speed is preferably 100-120 r/min.
And (2) cooling to 0-5 ℃ in the step (1), and growing the crystals for 0.5-1.5 h.
The calcium salt in the step (2) is calcium carbonate or calcium oxide, preferably calcium carbonate, and the mass of the added calcium carbonate accounts for 5-7% of the mass of the cefoperazone acid mother liquor; the calcium salt is added for the purpose of neutralizing acid in the cefoperazone acid mother liquor and providing calcium ions to generate calcium phosphate precipitate.
Adding calcium salt in the step (2), stirring and reacting for 30-60min at the rotating speed of 80-120r/min, cooling to 0-10 ℃, and growing the crystal for 0.5-1.5 h.
The stirring time in the step (2) is preferably 1 hour.
And (3) the calcium chloride post-treatment in the step (2) is to wash calcium chloride by using dimethyl acetamide to obtain a pure calcium chloride product.
The potassium fluoborate recycled in the step (1) can be used for flux of welding flux, and can also be used for metallurgical industry and preparation of boron trifluoride and other fluoride salt raw materials.
The calcium phosphate recovered in step (2) may be used in anticaking agents, acidity regulators, nutritional supplements, flavoring agents, stabilizers, and moisture retention agents.
The calcium chloride can be used as solidifying agent, calcium enhancer, refrigerant for freezing, desiccant, anticaking agent, microbe inhibitor, pickling agent, and tissue modifier.
As a preferred technical scheme, the method for treating the cefoperazone acid production wastewater comprises the following steps:
(1)7-TMCA mother liquor treatment
Taking 7-TMCA mother liquor, adding alkali into the mother liquor to adjust the pH of the mother liquor to 7-9, adding a proper amount of potassium salt, stirring for reaction, cooling for crystallization, and centrifuging to obtain potassium fluoborate solid.
(2) Cefoperazone acid mother liquor treatment
Taking the cefoperazone acid mother liquor, adding calcium salt into the mother liquor, stirring for reaction, cooling for crystal growing, and centrifuging to obtain calcium phosphate solid. Evaporating water in the mother liquor after recovering the calcium phosphate, centrifuging to obtain calcium chloride, and washing with a small amount of dimethylacetamide to obtain relatively pure calcium chloride.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the method for treating the cefoperazone acid production wastewater, the 7-TMCA mother liquor and the cefoperazone acid mother liquor are subjected to desalination treatment, so that the salt in the wastewater is obviously reduced, and the wastewater treatment pressure is reduced.
(2) The method for treating the cefoperazone acid production wastewater recovers the phosphoric acid in the cefoperazone acid, can reduce the treatment pressure of sewage, and can also reduce the corrosion of equipment, thereby creating higher economic benefit and environmental protection benefit.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The method for treating cefoperazone acid production wastewater in the embodiment 1 comprises the following steps:
4000L of 7-TMCA mother liquor (about 116kg of fluoboric acid) is added into a reaction kettle, 65kg of sodium hydroxide is added into the mother liquor, the pH value is adjusted to 8, 133kg of potassium nitrate is added, the mixture is stirred and reacted for 40min at the rotating speed of 100r/min, the temperature is reduced to 3 ℃, crystal growth is carried out for 1h, and 177kg of wet potassium fluoborate (the moisture content is 7.5 percent, and the content is 93 percent) is obtained by centrifugation.
Adding 3500L of cefoperazone acid mother liquor (containing about 70kg of phosphoric acid and about 78kg of hydrochloric acid) into a reaction kettle, adding 215kg of calcium carbonate into the reaction kettle while stirring, stirring and reacting for 45min at the rotating speed of 100r/min, cooling to 5 ℃, growing crystals for 1h, and centrifuging to obtain 130kg of wet calcium phosphate product (with the water content of about 15% and the purity of 98%). The water content in the mother liquor from which the calcium phosphate was recovered was distilled off, followed by centrifugation to obtain calcium chloride, and the calcium chloride was washed with a small amount of dimethylacetamide to obtain 120kg (water content: about 8.0%, purity: about 94%) of a wet calcium chloride product.
Example 2
The method for treating cefoperazone acid production wastewater in the embodiment 2 comprises the following steps:
4000L of 7-TMCA mother liquor (about 115kg of fluoboric acid) is added into a reaction kettle, 64.5kg of sodium hydroxide is added into the mother liquor, the pH value is adjusted to 7, 133kg of potassium nitrate is added, the mixture is stirred and reacted for 60min at the rotating speed of 90r/min, the temperature is reduced to 2 ℃, crystal growth is carried out for 1.5h, and the wet potassium fluoborate product is obtained by centrifugation for 178kg (the moisture content is 8.3 percent, and the content is 92.5 percent).
3500L of cefoperazone acid mother liquor (containing about 71kg of phosphoric acid and 79kg of hydrochloric acid) is added into a reaction kettle, 218kg of calcium carbonate is added into the reaction kettle while stirring, the reaction kettle is stirred and reacted for 30min at the rotating speed of 90r/min, the temperature is reduced to 5 ℃, crystal growth is carried out for 0.5h, and the calcium phosphate wet product is obtained by centrifugation for 129kg (the moisture content is about 14 percent, and the purity is 97 percent). The water content in the mother liquor from which the calcium phosphate was recovered was distilled off, followed by centrifugation to obtain calcium chloride, and the calcium chloride was washed with a small amount of dimethylacetamide to obtain 118kg (water content: about 8.5%, purity: about 95%) of a wet calcium chloride product.
Example 3
The method for treating cefoperazone acid production wastewater in the embodiment 3 comprises the following steps:
4000L of 7-TMCA mother liquor (about 116kg of fluoboric acid) is added into a reaction kettle, 65kg of sodium hydroxide is added into the mother liquor, the pH value is adjusted to 9, 133.5kg of potassium nitrate is added, the mixture is stirred and reacted for 60min at the rotating speed of 110r/min, the temperature is reduced to 5 ℃, crystal growth is carried out for 1.5h, and 177kg of wet potassium fluoborate (the moisture content is 7.8 percent, and the content is 92.5 percent) is obtained through centrifugation.
3500L of cefoperazone acid mother liquor (containing about 70kg of phosphoric acid and about 78kg of hydrochloric acid) is added into a reaction kettle, 215kg of calcium carbonate is added into the reaction kettle while stirring, the reaction is carried out for 60min while stirring at the rotating speed of 110r/min, the temperature is reduced to 8 ℃, crystal growth is carried out for 1.5h, and the calcium phosphate wet product is obtained by centrifugation for 131kg (the moisture content is about 15.5 percent, and the purity is 96.5 percent). The water content in the mother liquor from which the calcium phosphate was recovered was distilled off, followed by centrifugation to obtain calcium chloride, and the calcium chloride was washed with a small amount of dimethylacetamide to obtain 119kg (water content: about 8.1%, purity: about 94%) of a wet calcium chloride product.
Example 4
The method for treating cefoperazone acid production wastewater in the embodiment 4 comprises the following steps:
4000L of 7-TMCA mother liquor (about 114kg of fluoboric acid) is added into a reaction kettle, 65kg of sodium hydroxide is added into the mother liquor, the pH value is adjusted to 8, 133kg of potassium nitrate is added, the mixture is stirred and reacted for 40min at the rotating speed of 110r/min, the temperature is reduced to 3 ℃, crystal growth is carried out for 1h, and 177kg of wet potassium fluoborate (the moisture content is 7.5 percent, and the content is 93 percent) is obtained through centrifugation.
Adding 3500L of cefoperazone acid mother liquor (containing about 70kg of phosphoric acid and about 78kg of hydrochloric acid) into a reaction kettle, adding 215kg of calcium carbonate into the reaction kettle while stirring, stirring and reacting for 90min at the rotating speed of 115r/min, cooling to 3 ℃, growing crystals for 1h, and centrifuging to obtain 130kg of wet calcium phosphate product (with the water content of about 15% and the purity of 97.5%). The water content in the mother liquor from which the calcium phosphate was recovered was distilled off, followed by centrifugation to obtain calcium chloride, and the calcium chloride was washed with a small amount of dimethylacetamide to obtain 120kg (water content: about 7.8%, purity: about 92.5%) of a wet calcium chloride product.

Claims (8)

1. A method for treating cefoperazone acid production wastewater is characterized by comprising the following steps: the method comprises the following steps:
(1)7-TMCA mother liquor treatment
Adding alkali into the 7-TMCA mother liquor to adjust the pH value to 7-9, then adding potassium salt to cool and grow crystal, and centrifuging to obtain potassium fluoborate solid;
(2) cefoperazone acid mother liquor treatment
Adding calcium salt into the cefoperazone acid mother liquor, cooling, growing crystals, and centrifuging to obtain calcium phosphate; and (3) evaporating the water of the mother liquor after recovering the calcium phosphate, centrifuging to obtain calcium chloride, and performing post-treatment on the calcium chloride to obtain a pure calcium chloride product.
2. The method for treating cefoperazone acid production wastewater according to claim 1, wherein the method comprises the following steps: the alkali in the step (1) is solid sodium hydroxide.
3. The method for treating cefoperazone acid production wastewater according to claim 1, wherein the method comprises the following steps: the potassium salt in the step (1) is solid potassium nitrate, and the mass of the potassium nitrate added accounts for 3-4% of the mass of the cefoperazone acid mother liquor.
4. The method for treating cefoperazone acid production wastewater according to claim 1, wherein the method comprises the following steps: adding the potassium salt into the mixture obtained in the step (1), stirring the mixture for 30 to 60 minutes at a stirring speed of 80 to 120r/min, and cooling and growing the crystals.
5. The method for treating cefoperazone acid production wastewater according to claim 1, wherein the method comprises the following steps: and (2) cooling to 0-5 ℃ in the step (1), and growing the crystals for 0.5-1.5 h.
6. The method for treating cefoperazone acid production wastewater according to claim 1, wherein the method comprises the following steps: the calcium salt in the step (2) is calcium carbonate or calcium oxide, and the mass of the added calcium carbonate accounts for 5-7% of the mass of the cefoperazone acid mother liquor.
7. The method for treating cefoperazone acid production wastewater according to claim 1, wherein the method comprises the following steps: adding calcium salt in the step (2), stirring and reacting for 30-60min at the rotating speed of 80-120r/min, cooling to 0-10 ℃, and growing the crystal for 0.5-1.5 h.
8. The method for treating cefoperazone acid production wastewater according to claim 1, wherein the method comprises the following steps: and (3) the calcium chloride post-treatment in the step (2) is to wash calcium chloride by using dimethyl acetamide to obtain a pure calcium chloride product.
CN202010031730.3A 2020-01-13 2020-01-13 Method for treating waste water from cefoperazone acid production Withdrawn CN111204775A (en)

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Application publication date: 20200529