CN112159016A - Method for recovering and treating waste acid water generated in amantadine synthesis - Google Patents
Method for recovering and treating waste acid water generated in amantadine synthesis Download PDFInfo
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- CN112159016A CN112159016A CN202010970642.XA CN202010970642A CN112159016A CN 112159016 A CN112159016 A CN 112159016A CN 202010970642 A CN202010970642 A CN 202010970642A CN 112159016 A CN112159016 A CN 112159016A
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- Prior art keywords
- recovering
- amantadine
- sulfuric acid
- magnesium sulfate
- sulfate
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
- C01B21/16—Hydrazine; Salts thereof
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
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- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
-
- 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
- C02F2103/343—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 pharmaceutical industry, e.g. containing antibiotics
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Geology (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for recovering and treating waste acid water generated in the process of synthesizing amantadine, which comprises two schemes of recovering and utilizing sulfuric acid waste water generated in the process of synthesizing amantadine into hydrazine sulfate and magnesium sulfate with certain additional value. The method can effectively treat a large amount of sulfuric acid wastewater generated in the amantadine synthesis process, and simultaneously recycles the wastewater to convert the wastewater into magnesium sulfate and hydrazine sulfate with certain additional value. The method for recovering and treating the waste acid water reduces the cost and pressure of subsequent waste water treatment, lightens the environmental burden and realizes green and environment-friendly production.
Description
Technical Field
The invention belongs to the field of pharmacy, relates to a method for treating waste acid water generated by reaction, and particularly relates to a method for recovering and treating waste acid water generated in the process of preparing amantadine.
Background
The chemical name of amantadine is 1-amino adamantane, which is an antiviral drug and also an antiparkinsonian drug. It is often used for the production of synthetic adamantane derivative, amantadine hydrochloride, and the like. Amantadine is able to block uncoating of influenza a virus and release of its nucleic acid into respiratory epithelial cells, affecting early replication of the virus that has entered the cell. The product has no host specificity, and can prevent virus from entering host cell, influence virus dehydrogenation, and inhibit virus replication. The antiviral spectrum is narrow, and the compound has obvious inhibition effect on influenza A virus. Is mainly used for treating avian influenza, and can obviously reduce the death rate after being used. The product can promote brain tissue to release appropriate amount of dopamine, or delay its metabolism to maintain dopamine level in brain. Is suitable for primary Parkinson disease, Parkinson syndrome and extrapyramidal reaction induced by drugs. In addition, amantadine often forms compound anti-cold drugs with other drugs, so that the market demand is huge, and the market of the preparation is steadily increased.
The traditional preparation method of amantadine is obtained by brominating adamantane and then reacting with urea, and the method has the advantages of low conversion rate, high bromine price, difficult recovery and environmental friendliness. Acetic anhydride is used for nitration, resin nitration, metal salt ions participate in nitration and the like, and the reaction result is not ideal. Relatively more by-products are produced under acetic acid or acetic anhydride, which is not favorable for separation and purification.
Adamantane is dissolved in dichloromethane to serve as a substrate, acetonitrile and fuming sulfuric acid are used for dropwise adding oxidation, and then, the adamantanamine is hydrolyzed under the strong alkali condition to prepare the adamantanamine. Therefore, the timely treatment of sulfuric acid wastewater becomes extremely urgent and necessary.
Disclosure of Invention
The invention provides a method for recovering and treating waste acid water generated in the process of synthesizing amantadine, aiming at overcoming the defects in the prior art.
The invention is realized by the following technical scheme: the invention discloses a method for recovering and treating waste acid water generated in amantadine synthesis, which specifically comprises the following steps:
a. and (3) recovering hydrazine sulfate:
(1) adding a proper amount of sulfuric acid wastewater after extraction in the process of synthesizing amantadine into a reaction kettle, adding a proper amount of hydrazine hydrate, and adjusting the pH value to 3;
(2) after the feed liquid is added, opening the reaction kettle for stirring, opening the condenser, heating the reaction kettle, evaporating the dilute acid feed liquid to 1500kg, sampling and detecting distilled water, discharging after meeting the discharge standard, and applying the dilute acid feed liquid which does not meet the discharge standard;
(3) after distillation is finished, part of hydrazine hydrate is continuously added to adjust the pH value to 5;
(4) stirring, cooling to 75 deg.C with jacket-opened circulating water, reacting for 2 hr, cooling to 35 deg.C, stirring for 2 hr;
(5) after the heat preservation is finished, centrifugally separating, pumping the mother liquor back to the reaction kettle for use, and drying to obtain a wet hydrazine sulfate product;
b. recovering magnesium sulfate:
(1) adding a proper amount of sulfuric acid wastewater after extraction in the process of synthesizing amantadine into a reaction kettle, adding a proper amount of magnesia, and adjusting the pH value to 7;
(2) filtering the neutral liquid, transferring the neutral liquid into a distillation kettle, heating, distilling and concentrating at the temperature of 90-120 ℃, distilling out 1000L of the neutral liquid, and supplementing a new neutralizing liquid;
(3) when the solid-liquid ratio of the materials in the kettle is evaporated to a certain concentration, no new neutralization solution is added; cooling the temperature in the kettle to 35 ℃, and stirring at a low speed for crystallization for 30 min;
(4) centrifugally separating, recycling mother liquor, and drying to obtain a magnesium sulfate wet product.
The raw material formula proportion used in the step of recovering hydrazine sulfate is as follows: each 5000L of sulfuric acid wastewater needs 1600L-1800L of hydrazine hydrate, and 1900 kg-2100 kg of hydrazine sulfate is produced.
As a preferred embodiment of the invention, the proportion formula of the raw materials used in the step of recovering hydrazine sulfate is as follows: for every 5000L of treated sulfuric acid wastewater, 1680L of hydrazine hydrate is needed, and 1990kg of hydrazine sulfate is produced.
In the step of recovering the magnesium sulfate, 550 kg-650 kg of magnesia is required to be added for neutralization every 5000L of sulfuric acid wastewater, 2900 kg-3100 kg of magnesium sulfate is produced, and the solid-to-liquid ratio is controlled to be 1: 1.0-2.0 during distillation.
In the preferred embodiment of the invention, 625kg of magnesia is required to be added for neutralization to produce 3000kg of magnesium sulfate per 5000L of treated sulfuric acid wastewater in the step of recovering the magnesium sulfate, and the solid-to-liquid ratio during distillation is controlled to be 1: 1.0-1.5.
The invention has the beneficial effects that: the invention aims to provide a method for treating sulfuric acid wastewater generated in an amantadine synthesis process, which comprises two schemes of recovering and utilizing the sulfuric acid wastewater generated in the amantadine synthesis process into hydrazine sulfate and magnesium sulfate with certain additional values. The method can effectively treat a large amount of sulfuric acid wastewater generated in the amantadine synthesis process, and simultaneously recycles the wastewater to convert the wastewater into magnesium sulfate and hydrazine sulfate with certain additional value. The invention reduces the cost and pressure of subsequent wastewater treatment, lightens the environmental burden and realizes green and environment-friendly production.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
Example 1:
the invention discloses a method for recovering and treating waste acid water generated in amantadine synthesis, which specifically comprises the following steps:
a. and (3) recovering hydrazine sulfate: (1) 5000L of sulfuric acid wastewater after extraction in the process of synthesizing amantadine in a proper amount is added into a reaction kettle, 1680L of hydrazine hydrate is added, and the pH value is adjusted to 3; (2) after the feed liquid is added, opening the reaction kettle for stirring, opening the condenser, heating the reaction kettle, evaporating the dilute acid feed liquid to 1500kg, sampling and detecting distilled water, discharging after meeting the discharge standard, and applying the dilute acid feed liquid which does not meet the discharge standard; (3) after distillation is finished, part of hydrazine hydrate is continuously added to adjust the pH value to 5; (4) stirring, cooling to 75 deg.C with jacket-opened circulating water, reacting for 2 hr, cooling to 35 deg.C, stirring for 2 hr; (5) after the heat preservation is finished, centrifugally separating, pumping the mother liquor back to the reaction kettle for use, and spin-drying to obtain 1990kg of wet hydrazine sulfate;
b. recovering magnesium sulfate: (1) 5000L of sulfuric acid wastewater after extraction in the process of synthesizing amantadine with a proper amount is added into a reaction kettle, 625kg of magnesia is added, and the pH value is adjusted to 7; (2) filtering the neutral liquid, transferring the neutral liquid into a distillation kettle, heating, distilling and concentrating at the temperature of 90-120 ℃, distilling out 1000L of the neutral liquid, and supplementing a new neutralizing liquid; (3) when the solid-liquid ratio of the materials in the kettle is evaporated to 1: 1.0-1.5, no new neutralization solution is added; cooling the temperature in the kettle to 35 ℃, and stirring at a low speed for crystallization for 30 min; (4) centrifugal separation, mother liquor can be used mechanically, and 3000kg of magnesium sulfate wet product is obtained after drying.
Example 2:
the invention discloses a method for recovering and treating waste acid water generated in amantadine synthesis, which specifically comprises the following steps:
a. and (3) recovering hydrazine sulfate: (1) 5000L of sulfuric acid wastewater after reaction and extraction in the process of synthesizing amantadine, 1600L-1800L of hydrazine hydrate are added into a reaction kettle, and the pH value is adjusted to 3; (2) after the feed liquid is added, opening the reaction kettle for stirring, opening the condenser, heating the reaction kettle, evaporating the dilute acid feed liquid to 1500kg, sampling and detecting distilled water, discharging after meeting the discharge standard, and applying the dilute acid feed liquid which does not meet the discharge standard; (3) after distillation is finished, part of hydrazine hydrate is continuously added to adjust the pH value to 5; (4) stirring, cooling to 75 deg.C with jacket-opened circulating water, reacting for 2 hr, cooling to 35 deg.C, stirring for 2 hr; (5) after the heat preservation is finished, centrifugally separating, pumping the mother liquor back to the reaction kettle for use, and spin-drying to obtain 1900 kg-2100 kg of wet hydrazine sulfate;
b. recovering magnesium sulfate: (1) 5000L of sulfuric acid wastewater after extraction in the process of synthesizing amantadine with a proper amount is added into a reaction kettle, 550 kg-650 kg of magnesia is added, and the pH value is adjusted to 7; (2) filtering the neutral liquid, transferring the neutral liquid into a distillation kettle, heating, distilling and concentrating at the temperature of 90-120 ℃, distilling out 1000L of the neutral liquid, and supplementing a new neutralizing liquid; (3) when the solid-liquid ratio of the materials in the kettle is evaporated to 1: 1.0-2.0, no new neutralization solution is added; cooling the temperature in the kettle to 35 ℃, and stirring at a low speed for crystallization for 30 min; (4) centrifugally separating, wherein mother liquor can be used repeatedly, and obtaining 2900 kg-3100 kg of wet magnesium sulfate after drying.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. A method for recovering and treating waste acid water generated in the process of synthesizing amantadine is characterized by comprising the following steps: the method for recovering and treating the waste acid water generated in the amantadine synthesis process specifically comprises the following steps:
a. and (3) recovering hydrazine sulfate:
(1) adding a proper amount of sulfuric acid wastewater after extraction in the process of synthesizing amantadine into a reaction kettle, adding a proper amount of hydrazine hydrate, and adjusting the pH value to 3;
(2) after the feed liquid is added, opening the reaction kettle for stirring, opening the condenser, heating the reaction kettle, evaporating the dilute acid feed liquid to 1500kg, sampling and detecting distilled water, discharging after meeting the discharge standard, and applying the dilute acid feed liquid which does not meet the discharge standard;
(3) after distillation is finished, part of hydrazine hydrate is continuously added to adjust the pH value to 5;
(4) stirring, cooling to 75 deg.C with jacket-opened circulating water, reacting for 2 hr, cooling to 35 deg.C, stirring for 2 hr;
(5) after the heat preservation is finished, centrifugally separating, pumping the mother liquor back to the reaction kettle for use, and drying to obtain a wet hydrazine sulfate product;
b. recovering magnesium sulfate:
(1) adding a proper amount of sulfuric acid wastewater after extraction in the process of synthesizing amantadine into a reaction kettle, adding a proper amount of magnesia, and adjusting the pH value to 7;
(2) filtering the neutral liquid, transferring the neutral liquid into a distillation kettle, heating, distilling and concentrating at the temperature of 90-120 ℃, distilling out 1000L of the neutral liquid, and supplementing a new neutralizing liquid;
(3) when the solid-liquid ratio of the materials in the kettle is evaporated to a certain concentration, no new neutralization solution is added; cooling the temperature in the kettle to 35 ℃, and stirring at a low speed for crystallization for 30 min;
(4) centrifugally separating, recycling mother liquor, and drying to obtain a magnesium sulfate wet product.
2. The method according to claim 1, wherein the method comprises the steps of: the raw material formula proportion used in the step of recovering hydrazine sulfate is as follows: each 5000L of sulfuric acid wastewater needs 1600L-1800L of hydrazine hydrate, and 1900 kg-2100 kg of hydrazine sulfate is produced.
3. The method according to claim 2, wherein the method comprises the steps of: the raw material proportion formula used in the step of recovering hydrazine sulfate is as follows: for every 5000L of treated sulfuric acid wastewater, 1680L of hydrazine hydrate is needed, and 1990kg of hydrazine sulfate is produced.
4. The method according to claim 1, wherein the method comprises the steps of: in the step of recovering the magnesium sulfate, 550 kg-650 kg of magnesia is required to be added for neutralization every 5000L of sulfuric acid wastewater, 2900 kg-3100 kg of magnesium sulfate is produced, and the solid-to-liquid ratio is controlled to be 1: 1.0-2.0 during distillation.
5. The method according to claim 4, wherein the method comprises the steps of: in the step of recovering the magnesium sulfate, 625kg of magnesia is required to be added for neutralization every 5000L of sulfuric acid wastewater to be treated, 3000kg of magnesium sulfate is produced, and the solid-to-liquid ratio is controlled to be 1: 1.0-1.5 during distillation.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010970642.XA CN112159016A (en) | 2020-09-16 | 2020-09-16 | Method for recovering and treating waste acid water generated in amantadine synthesis |
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| CN202010970642.XA CN112159016A (en) | 2020-09-16 | 2020-09-16 | Method for recovering and treating waste acid water generated in amantadine synthesis |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115285952A (en) * | 2022-07-09 | 2022-11-04 | 黄淮学院 | Method for preparing hydrazine sulfate by utilizing waste water generated in synthesis of aromatic hydrazide compounds |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220970A (en) * | 1998-11-13 | 1999-06-30 | 化学工业部连云港设计研究院 | Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid |
| KR20010097371A (en) * | 2000-04-21 | 2001-11-08 | 우명우 | Manufacturing magnesium sulfate by waste sulfuric acid. |
| CN102101732A (en) * | 2011-01-14 | 2011-06-22 | 南京大学 | Method for recovering hydrazine sulfate and chromium hydroxide from chromium-containing waste acid |
| JP2011161365A (en) * | 2010-02-09 | 2011-08-25 | Kurita Water Ind Ltd | Hydrazine-containing wastewater treatment method |
-
2020
- 2020-09-16 CN CN202010970642.XA patent/CN112159016A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1220970A (en) * | 1998-11-13 | 1999-06-30 | 化学工业部连云港设计研究院 | Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid |
| KR20010097371A (en) * | 2000-04-21 | 2001-11-08 | 우명우 | Manufacturing magnesium sulfate by waste sulfuric acid. |
| JP2011161365A (en) * | 2010-02-09 | 2011-08-25 | Kurita Water Ind Ltd | Hydrazine-containing wastewater treatment method |
| CN102101732A (en) * | 2011-01-14 | 2011-06-22 | 南京大学 | Method for recovering hydrazine sulfate and chromium hydroxide from chromium-containing waste acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115285952A (en) * | 2022-07-09 | 2022-11-04 | 黄淮学院 | Method for preparing hydrazine sulfate by utilizing waste water generated in synthesis of aromatic hydrazide compounds |
| CN115285952B (en) * | 2022-07-09 | 2023-09-29 | 黄淮学院 | Method for preparing hydrazine sulfate by utilizing aromatic hydrazide compound synthetic wastewater |
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