CN1037763C - Method for preparation of pure cupric sulfate by using copper-contained waste liquid from preparation of guaiacol and treatment method for its waste liquid - Google Patents
Method for preparation of pure cupric sulfate by using copper-contained waste liquid from preparation of guaiacol and treatment method for its waste liquid Download PDFInfo
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- CN1037763C CN1037763C CN 95106987 CN95106987A CN1037763C CN 1037763 C CN1037763 C CN 1037763C CN 95106987 CN95106987 CN 95106987 CN 95106987 A CN95106987 A CN 95106987A CN 1037763 C CN1037763 C CN 1037763C
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Abstract
The present invention relates to a method for producing cupric sulfate by using copper-containing waste liquid used for preparing guaiacol and a waste liquid treating method. The waste liquid is cooled to be settled out crude cupric sulfate which is dissolved with water, cupric oxide can be prepared by filtering out insoluble substances, sulphuric acid is added to the cupric oxide to be prepared into a purified cupric sulfate solution which is recrystallized to obtain the pure cupric sulfate, and residual liquid is cooled to prepare sodium sulfate. The pure cupric sulfate prepared by the method can be reused in the production of the guaiacol, and other components are also sufficiently recovered and utilized.
Description
The invention relates to a treatment technology of copper-containing waste liquid generated in the production of synthetic vanillin.
In the production of synthetic vanillin, diazonium salt is hydrolyzed to prepare the intermediate product guaiacolThe nitrogen salt water solution takes copper sulfate as a catalyst and is hydrolyzed at a higher temperature to generate the guaiacol. After the reaction is finished, high-temperature mixed waste liquid containing copper sulfate, sulfuric acid, sodium sulfate and organic matters is generated. Along with the decrease of the liquid temperature, the dissolution amount of the copper sulfate and the sodium sulfate in the solution reaches saturation, and the massive crude copper sulfate is separated out, namely the crude copper sulfate and the sulfuric acid waste liquid containing the copper sulfate can be separated. The reaction equation for the preparation of guaiacol is as follows: (1) diazotizing o-aminoanisole into diazonium salt at low temperature
(2) The diazonium salt is hydrolyzed into the guaiacol in the medium of copper sulfate,distilling the hydrolysate to obtain the finished product. Leaving a waste solution containing copper sulfate, sulfuric acid, sodium sulfate and organic matter.The copper is recovered from the copper-containing waste liquid by replacing copper with iron. The "production of copper sulfate by using waste copper catalyst" in 1993 volume 13, page 117 introduces a method for preparing copper sulfate from camphor-synthesizing leftover material by using combustion and extraction method. The use of waste liquid of guaiacol to refine copper sulfate for reuse in production has not been reported.
The invention aims to provide a method for preparing pure copper sulfate, sodium sulfate and sulfuric acid by using copper-containing waste liquid for preparing guaiacol.
The method for preparing pure copper sulfate from the waste liquid for preparing the guaiacol comprises the following steps: (1) cooling or evaporating and cooling the waste liquid to precipitate crude copper sulfate; (2) the crude copper sulfate is prepared into a pure copper sulfate solution by the following method:
a. the crude copper sulfate is dissolved by adding water,
b. filtering the obtained water solution, filtering to remove insoluble substances,
c. adding sodium hydroxide into the obtained solution and heating to generate copper oxide precipitate,
d. filtering, separating out the copper oxide,
e. adding sulfuric acid into copper oxide and heating to obtain pure copper sulfate solution,
(3) and cooling the copper sulfate solution, and recrystallizing the copper sulfate to obtain the pure copper sulfate.
The method for preparing copper sulfate adopts the step of preparing copper oxide, and the copper oxide is filtered twice, wherein insoluble substances are removed once and dissolved substances are removed once, so that the obtained pure copper sulfate can meet the standard requirement of the first-grade product of the national standard GB 437-80. Can be reused in the production of vanillin.
FIG. 1 is a flow chart of the above process for preparing pure copper sulfate;
FIG. 2 is a process flow diagram of the waste acid solution;
FIG. 3 is a flow chart of the process for preparing anhydrous sodium sulfate.
As shown in fig. 1, waste heat copper sulfate solution is cooled to precipitate crude copper sulfate containing impurities, water is added to dissolve the crude copper sulfate, insoluble substances are filtered out, sodium hydroxide is added into the obtained solution, steam is introduced for heating to generate copper oxide precipitate, then the copper oxide precipitate is subjected to pressure filtration to separate out copper oxide solid, sulfuric acid is added and steam is introduced for heating to enable the copper oxide to fully react to form pure copper sulfate solution, the solution is cooled to crystallize and separate out pure copper sulfate, and then a refined copper sulfate finished product can be obtained by a centrifugal separation method. The mother liquor obtained by centrifugation is pure sulfuric acid and copper sulfate solution, and can be used for preparing sulfuric acid for dissolving copper oxide with concentrated sulfuric acid. The wholeThe chemical reaction equation of the preparation process is as follows:
after the waste copper sulfate solution is cooled and precipitated to obtain crude copper sulfate, the remaining copper-containing waste sulfuric acid solution can be treated according to the method of the flow chart shown in figure 2:
heating the copper-containing waste sulfuric acid solution, evaporating and concentrating, then cooling, and precipitating to obtain crude copper sulfate, wherein the copper sulfate can be refined in the step (2) of the process. The acid solution obtained by separation is sulfuric acid solution which can be used in the working procedure of dissolving copper oxide into copper sulfate.
As shown in fig. 3, the main component of the solution left in the copper oxide filter pressing process is sodium sulfate, and the solution is cooled to precipitate sodium sulfate decahydrate. Separating sodium sulfate decahydrate, and heating for dehydration to obtain anhydrous sodium sulfate product.
The refining method of copper sulfate and the treatment method of waste acid liquid can recycle more than 90 percent of copper sulfate, can obtain sulfuric acid and anhydrous sodium sulfate by-products, and reduce environmental pollution.
Several examples are presented below: example 1
Refining crude copper sulfate precipitated from waste heat copper sulfate solution by cooling:
250 kg of crude copper sulfate is weighed, 500 kg of water is added, the mixture is intermittently stirred and dissolved for about 2 hours, and insoluble impurities are filtered after the solution is saturated. Adding sodium hydroxide into the filtrate while stirring until the pH is 6, introducing steam, directly heating, and adding Cu (OH) at 80-90 deg.C2Dehydration produces a black precipitate of CuO. About 58 kg of CuO was obtained by pressure filtration. Diluting the recovered sulfuric acid with copper sulfate mother liquor at a ratio of 1: 1, and adding CuO when the temperature of the acid liquor rises to 90-95 ℃. Adding a little amount of materials within 30-40 min, and after the reaction is finished, the Baume degree of the solution is 38-42 Be', H2SO4The content is 3-4%, the mixture is sent into a crystallization kettle for crystallization, and the pure copper sulfate is obtained after the temperature is reduced to 30-35 ℃ and the material is discharged.Example 2
Preparing sulfuric acid from copper-containing waste sulfuric acid solution:
1000 kg of copper-containing waste sulfuric acid solution with the specific gravity of 1.36 is taken out, concentrated to the specific gravity of 1.56 by using a film evaporator, discharged and naturally cooled, and 135 kg of a mixture of solid copper sulfate and sodium sulfate is obtained, wherein the acid content of the solution is 62-68 percent. The solid is used for refining copper sulfate, the sulfuric acid solution is used for preparing copper sulfate from copper oxide, and the redundant part can be sold. Example 3
Preparation of sodium sulfate:
and (3) taking the sodium sulfate-containing waste liquid obtained by CuO filter pressing in the embodiment 1, and placing the waste liquid in a cooler for cooling to obtain sodium sulfate decahydrate. Heating sodium sulfate decahydrate for dehydration, drying and crushing to obtain anhydrous sodium sulfate. The recovery rate can reach 60 percent.
Claims (4)
1. A method for preparing pure copper sulfate from waste liquid of guaiacol preparation comprises the following steps:
(1) cooling the waste liquid, precipitating to obtain crude copper sulfate,
(2) the crude copper sulfate is prepared into a pure copper sulfate solution,
(3) the copper sulfate solution is cooled and the copper sulfate is crystallized again to obtain pure copper sulfate,
the method for preparing the pure copper sulfate solution from the crude copper sulfate is characterized by comprising the following steps:
a. the crude copper sulfate is dissolved by adding water,
b. filtering the obtained water solution, filtering to remove insoluble substances,
c. adding sodium hydroxide into the obtained solution and heating to generate copper oxide precipitate,
d. filtering, separating out the copper oxide,
e. adding sulfuric acid into the copper oxide and heating to obtain pure copper sulfate solution.
2. The method for producing pure copper sulfate from the copper-containing waste liquid from the production of guaiacol as claimed in claim 1, wherein the sulfuric acid added in said step e is a mixture of the acid solution obtained by separating copper sulfate in said step (3) and sulfuric acid.
3. The process for producing pure copper sulfate from waste liquid from the production of guaiacol as claimed in claim 1 or 2, wherein the copper-containing spent acid solution obtained after precipitating crude copper sulfate in the step (1) is concentrated by evaporation under heating, and then cooled to precipitate crude copper sulfate, and the separated acid solution is used in the step (2) for recycling the copper oxide to copper sulfate.
4. The method for preparing pure copper sulfate from the waste liquid containing the phenol from the production of the kaempferol as claimed in claim 1 or 2, wherein the sodium sulfate-containing waste liquid obtained in the step d is cooled to precipitate sodium sulfate decahydrate, and the sodium sulfate decahydrate is heated and dehydrated to obtain refined anhydrous sodium sulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95106987 CN1037763C (en) | 1995-07-13 | 1995-07-13 | Method for preparation of pure cupric sulfate by using copper-contained waste liquid from preparation of guaiacol and treatment method for its waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95106987 CN1037763C (en) | 1995-07-13 | 1995-07-13 | Method for preparation of pure cupric sulfate by using copper-contained waste liquid from preparation of guaiacol and treatment method for its waste liquid |
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| Publication Number | Publication Date |
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| CN1117947A CN1117947A (en) | 1996-03-06 |
| CN1037763C true CN1037763C (en) | 1998-03-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 95106987 Expired - Fee Related CN1037763C (en) | 1995-07-13 | 1995-07-13 | Method for preparation of pure cupric sulfate by using copper-contained waste liquid from preparation of guaiacol and treatment method for its waste liquid |
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| CN101549882B (en) * | 2008-04-03 | 2011-10-05 | 上海美维科技有限公司 | Method for preparing high-purity cupric oxide powder from acid cupriferous waste liquid |
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1995
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