CN110105271B - Method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater - Google Patents
Method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater Download PDFInfo
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- CN110105271B CN110105271B CN201910461264.XA CN201910461264A CN110105271B CN 110105271 B CN110105271 B CN 110105271B CN 201910461264 A CN201910461264 A CN 201910461264A CN 110105271 B CN110105271 B CN 110105271B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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- Environmental & Geological Engineering (AREA)
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a method for preparing copper quinolinate by purifying and regenerating copper elements in the production wastewater of quinolinic acid, and belongs to the technical field of treatment of the production wastewater of quinolinic acid. The method comprises the following steps: (1) adjusting the pH value of the wastewater by using alkali, then slowly adding sodium sulfide while stirring, detecting the value by using a pH reagent, and performing filter pressing to collect black CuS precipitate; (2) adding the recovered CuS and water into an oxidation reaction kettle, and then stirring and adding a sodium chlorate aqueous solution for oxidation reaction; (3) and then adding copper sulfate pentahydrate, the recovered copper hydroxide, quinoline and sulfuric acid into the oxidation reaction kettle, dropwise adding a sodium chlorate aqueous solution, heating the reaction kettle, carrying out heat preservation reaction, cooling after the heat preservation is finished, crystallizing to separate out a solid, and filtering to obtain the quinolinic acid copper salt. The technology reduces the copper in the wastewater to below 2ppm, improves the utilization rate of the copper, can change waste into valuable, and solves the problem of discharge of the wastewater with high copper ions.
Description
Technical Field
The invention belongs to the technical field of quinolinic acid oxidation wastewater treatment, and particularly relates to a method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater.
Background
The production process of quinalinic acid comprises the following steps: adding copper sulfate pentahydrate, copper hydroxide (regenerated paste) and water into a reaction kettle, then slowly adding concentrated sulfuric acid, heating to 55 ℃, preserving heat and stirring for 1 h; adding quinoline, slowly dropwise adding a sodium chlorate aqueous solution, starting heating the reaction kettle, keeping the temperature of the kettle of the reaction kettle at 90-95 ℃, reacting for 22h, stopping heating, adding cooling water, reducing the temperature to 20-25 ℃, and crystallizing to separate out a solid. Then filtering to obtain copper quinolinate salt and wastewater; and neutralizing the quinolinic acid copper salt with alkali to obtain quinolinic acid sodium salt, recycling copper hydroxide for reuse, acidifying the quinolinic acid sodium salt with acid, and filtering to obtain quinolinic acid.
The process has two parts of wastewater generation: 1. in the wastewater in the oxidation stage, because the copper sulfate is excessive, a large amount of copper ions exist in the wastewater; 2. although copper hydroxide is recovered in the alkaline hydrolysis process of the copper quinolinate, part of copper ions still enter an acidification stage along with the sodium quinolinate; the traditional production method is to directly discharge the wastewater into a sewage station for treatment, so that the waste of copper ions is caused.
Chinese patent discloses a method for producing quinolinic acid (patent No. 2016105717166), wherein copper ions are recovered in the form of basic copper carbonate in the oxidation stage, copper is recovered in the form of copper oxide when quinolinic acid copper salt is alkaline hydrolyzed, the thorough degree of copper ions recovery cannot be known for basic copper carbonate because its Ksp constant has no data, copper hydroxide generated in alkaline hydrolysis needs to be converted into copper oxide by heating, and the process requirement is high and has certain difficulty.
Disclosure of Invention
The invention aims to provide a method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater, which aims to solve the practical technical problem that the copper element pollutes water bodies due to the discharge of the quinolinic acid oxidation wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater comprises the following steps:
(1) adjusting the pH value of the wastewater by using alkali, then slowly adding sodium sulfide while stirring, detecting the value by using a pH reagent, and performing filter pressing to collect black CuS precipitate;
(2) adding the recovered CuS and water into an oxidation reaction kettle, and then stirring and adding sodium chlorate to carry out oxidation reaction;
(3) and then, adding copper sulfate pentahydrate, the recovered copper hydroxide, quinoline and sulfuric acid into the oxidation reaction kettle, then dropwise adding a sodium chlorate aqueous solution, heating the reaction kettle, carrying out heat preservation reaction, cooling after the heat preservation is finished, crystallizing to separate out a solid, and then filtering to obtain the quinolinic acid copper salt.
Further, in the step (1), the pH value of the wastewater is adjusted to 6.8-7.2 by alkali.
Further, the pH value is more than 10 by using a pH reagent in the step (1).
Further, the weight ratio of the CuS recovered in step (2) to the sodium chlorate charge was 7 to 12.5.
Further, the weight ratio of the CuS recovered in the step (3) to the supplemented copper sulfate pentahydrate is 7 to 1.
Further, the temperature for the heat-preservation reaction in the step (3) is 90 to 95 ℃.
Further, the reaction is carried out for 2 hours at the temperature of 90-95 ℃ under the condition of heat preservation reaction
The invention has the following beneficial effects:
the principle is expressed by the following chemical equation:
the invention uses sodium sulfide with low price as raw material to lead copper ions and sulfur in the waste water to generate copper sulfide precipitate, and the Ksp constant of the copper sulfide is 1.3 multiplied by 10-36Therefore, the treatment depth of copper ions is more thorough, the strong oxidizing property of sodium chlorate is utilized to oxidize the divalent sulfur in the copper sulfide, and the copper is replaced and recovered.
The invention reduces the copper in the waste water to below 2ppm, improves the utilization rate of the copper, changes waste into valuable and solves the problem of discharge of the high-copper ion waste water.
Detailed Description
For a better understanding of the contents of the present invention, reference will now be made to the following examples, which are included to illustrate, but not to limit the scope of the present invention.
Example 1
Pumping 4 cubic volumes of collected wastewater into 6000L reaction kettle, adjusting pH to 6.8-7.2 with 30% sodium hydroxide solution alkali, adding sodium sulfide in batches, sampling and filtering, measuring pH to 10, testing whether there is excess sulfur ion in filtrate with 1% silver nitrate reagent, and testing whether silver sulfide Ksp1.09 × 10-49And stopping adding the sodium sulfide after the black precipitate exists, reacting for 15 minutes, detecting the existence of the black precipitate again, performing pressure filtration to obtain copper sulfide, drying and warehousing for later use or testing the moisture content of the wet product and warehousing for later use.
Feeding 900 kg of metered water, 7 kg of recovered copper sulfide (dry basis) and 12.5 kg of sodium chlorate in the kettle according to the original process, heating to 50 ℃, reacting for 2 hours, feeding 244 kg of 80% of sulfuric acid metered by the process, 1 kg of copper sulfate pentahydrate and 88 kg of copper hydroxide (dry basis) recovered from the upper batch, keeping the temperature at less than or equal to 50 ℃, stirring for 30 minutes, then feeding 140 kg of quinoline required by the original process, dropwise adding 400 kg of prepared sodium chlorate solution required by the original process at 90-95 ℃, keeping the temperature for reacting for 2 hours after dropwise adding, cooling, and centrifuging to obtain the quinolinic acid copper salt.
By detecting that the copper in the wastewater is reduced to 2ppm, the method not only improves the utilization rate of the copper, but also changes waste into valuable and solves the problem of discharge of the wastewater with high copper ions.
The above description should not be taken as limiting the invention to the embodiments, but rather, as will be apparent to those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to fall within the scope of the invention as defined by the claims appended hereto.
Claims (1)
1. A method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater is characterized by comprising the following steps:
(1) adjusting the pH value of the wastewater to 6.8-7.2 by using alkali, then slowly adding sodium sulfide while stirring, detecting that the pH value is more than 10 by using a pH reagent, and performing filter pressing to collect black CuS precipitate;
(2) adding the recovered CuS and water into an oxidation reaction kettle, and then stirring and adding a sodium chlorate aqueous solution for oxidation reaction, wherein the weight ratio of the recovered CuS to the sodium chlorate feeding is 7 to 12.5;
(3) and then, replenishing copper sulfate pentahydrate, recovered copper hydroxide, quinoline and sulfuric acid into the oxidation reaction kettle, dropwise adding a sodium chlorate aqueous solution, wherein the weight ratio of the recovered CuS to the replenished copper sulfate pentahydrate is 7: 1, carrying out heat preservation reaction for 2 hours at 90-95 ℃ after the temperature of the reaction kettle is raised, cooling after the heat preservation is finished, crystallizing to separate out a solid, and then filtering to obtain the quinolinic acid copper salt.
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| CN201910461264.XA CN110105271B (en) | 2019-05-30 | 2019-05-30 | Method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater |
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| CN201910461264.XA CN110105271B (en) | 2019-05-30 | 2019-05-30 | Method for preparing quinolinic acid copper salt by purifying and regenerating copper element in quinolinic acid oxidation wastewater |
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| CN110105271B true CN110105271B (en) | 2021-04-06 |
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| CN103388074B (en) * | 2012-05-09 | 2015-01-21 | 荆门市格林美新材料有限公司 | Method for treating spent tin stripping solution of waste circuit board |
| CN106187877B (en) * | 2016-07-19 | 2018-11-23 | 湖北金玉兰医药科技有限公司 | A kind of production method of quinolinic acid |
| CN107215984A (en) * | 2017-07-04 | 2017-09-29 | 连云港致诚化工有限公司 | The technique for recycling sodium chlorate oxidative synthesis quinolinic acid waste water |
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