CN102115114B - Method for preparing copper sulfide, calcium carbonate and sodium hydroxide from sodium sulfide waste - Google Patents

Method for preparing copper sulfide, calcium carbonate and sodium hydroxide from sodium sulfide waste Download PDF

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CN102115114B
CN102115114B CN 201010615463 CN201010615463A CN102115114B CN 102115114 B CN102115114 B CN 102115114B CN 201010615463 CN201010615463 CN 201010615463 CN 201010615463 A CN201010615463 A CN 201010615463A CN 102115114 B CN102115114 B CN 102115114B
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sodium
carbonate
sodium hydroxide
waste residue
calcium carbonate
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CN102115114A (en
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谢善情
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Nantong Botao Chemical Co ltd
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Abstract

The invention provides a method for preparing copper sulfide, calcium carbonate and sodium hydroxide from sodium sulfide waste. The sodium sulfide waste mixes and reacts with copper bicarbonate to produce a mixture containing copper sulfide, sodium carbonate and sodium bicarbonate; the mixture is filtered to produce a clear filtrate containing sodium carbonate and sodium bicarbonate and a filter cake containing copper sulfide; the filter cake containing copper sulfide is washed, dried and pulverized to obtain a copper sulfide product; the filtrate containing sodium carbonate and sodium bicarbonate reacts with an excessive amount of calcium hydroxide solution to produce a mixture containing calcium carbonate precipitates and sodium hydroxide solution; the mixture is filtered to obtain a filter cake of calcium carbonate and a liquid containing sodium hydroxide; and the filter cake of calcium carbonate is washed, dried and pulverized to obtain a calcium carbonate product; and the liquid containing sodium hydroxide is distilled to produce a supersaturated solution of sodium hydroxide, and the supersaturated solution of sodium hydroxide is spray-dried to obtain a sodium hydroxide product. The method eliminates the environmental pollution due to sodium sulfide waste, makes the best use of the potential value of the sodium sulfide waste, achieves the purpose of turning waste into treasure, and has a high practical value.

Description

The method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue
Technical field
The present invention relates to the improvement of barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue and the technical field of utilization, be particularly related to the method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue, its raw material is barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue .
Background technology
The industrial process of Sodium Sulphide (sodium sulphite) mainly contains coal reduction mirabilite method, gas reduction method, barium sulfate by-product sodium sulfide method and hydrogen sulfide method.Wherein, barium sulfate by-product sodium sulfide method is to produce barium sulphide with coal reduction barium sulfate, then adds metabisulfite solution to process, and generates sodium sulphite and process white, separates evaporation concentration and obtaining through suction filtration.The method is discharged a large amount of Sodium Sulphide waste residues, wherein most of from carbon contained in coal, and fails the sodium sulphite separated.After testing, the content of sodium carbonate in this Sodium Sulphide waste residue reaches 12-15%, and sodium sulphite is 25-30%.
Total institute is known, and sodium sulphite is very easily water-soluble, and the aqueous solution is strong basicity, and extremely strong pungency and corrodibility are arranged while contacting with mucous membrane with skin, while touching skin and hair, can cause and burn.Especially react the hydrogen sulfide generated with water, after absorbing human body, thereby cause poisoning extremely death, therefore, if the Sodium Sulphide waste residue is not used and administers, not only can cause environmental pollution, also have certain potential safety hazard.
Therefore, be necessary to explore the method for extracting sodium sulphite from the Sodium Sulphide waste residue, thereby effectively excavate the potential value of Sodium Sulphide waste residue, eliminate environmental pollution and potential safety hazard.
Summary of the invention
The object of the invention is to, the method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue is provided, its raw material is barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue, the method is simple to operate, facility investment is few, take full advantage of the potential value of barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue, realized turning waste into wealth, eliminated the pollution of Sodium Sulphide waste residue to environment.
Technical scheme of the present invention is as follows: prepare the method for cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue, its raw material is barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue, comprises the steps:
Steps A: carbonate content in conversion Sodium Sulphide waste residue, and configuration Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions;
Step B: Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions are successively dropped in the protection against corrosion reactor with the ratio 1:0.8 of sodium sulphite and molar content with hydrogen-carbonate copper pure substance~1.2, carry out chemical reaction, now, because being combined into cupric sulfide, cupric ion and sulfonium ion precipitate, thereby, be reacted to last, copper ions or containing the cupric ion of minute quantity not in solution, thus obtain the mixture of Containing Sulfur copper, sodium carbonate and sodium bicarbonate;
Step C: step B gained mixture is filtered, filter clarification containing sodium carbonate and the solution of sodium bicarbonate and the filter cake of Containing Sulfur copper;
Step D: the filter cake of the Containing Sulfur copper that step C is obtained, through washing, dry, pulverize, and obtains copper sulphide product;
Step e: configuration aqua calcis, the solution containing sodium carbonate and sodium bicarbonate that step C is obtained mixes with the excessive hydrogen calcium oxide solution, follow the hydrogen in ion with hydrogen-carbonate in hydroxide ion, thereby the release carbanion, then calcium ion and carbonic acid are that calcium carbonate precipitates with ionic bond, thereby, be reacted to last, contain sodium ion in solution, hydroxide ion, thus obtain the mixture containing carbonic acid calcium deposit and sodium hydroxide solution;
Step F: step e gained mixture is filtered, obtain calcium carbonate filter cake and containing the solution of sodium hydroxide;
Step G: calcium carbonate filter cake, through washing, be dry, pulverize, obtain calcium carbonate product;
Step H: will be the sodium hydroxide supersaturated solution containing the solution distillation of sodium hydroxide, spraying drying, obtain the sodium hydroxide product.
Before configuration Sodium Sulphide waste residue suspension liquid, first described Sodium Sulphide waste residue is ground into to the 80-100 order.
The principle of the chemical reaction of the method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue of the present invention is:
Na2S+?Cu(HCO3)2=====?CuS↓+2?NaHCO3
2NaHCO3++?Ca(OH)2?=====?CaCO3↓+Na2CO3?+2H2O
Na2CO3+?Ca(OH)2?=====?CaCO3↓+2?NaOH
The invention has the beneficial effects as follows: the method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue of the present invention, the method will be converted into industrial raw material cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue of barium sulfate by-product sodium sulfide method gained, thereby eliminated the pollution of sodium sulphite to environment in the Sodium Sulphide waste residue, effectively utilized the potential value of Sodium Sulphide waste residue, having realized turning waste into wealth, is a method of great practical value.
Embodiment
Embodiment 1
The method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue, its raw material is barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue, comprises the steps:
Steps A: carbonate content in conversion Sodium Sulphide waste residue, and be 80 orders by the pulverizing of Sodium Sulphide waste residue, then configure Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions;
Step B: Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions are successively dropped in the protection against corrosion reactor with the ratio 1:0.8 of molar content with hydrogen-carbonate copper pure substance with sodium sulphite, carry out chemical reaction, obtain the mixture of Containing Sulfur copper, sodium carbonate and sodium bicarbonate;
Step C: step B gained mixture is filtered, filter clarification containing sodium carbonate and the solution of sodium bicarbonate and the filter cake of Containing Sulfur copper;
Step D: the filter cake of the Containing Sulfur copper that step C is obtained, through washing, dry, pulverize, and obtains copper sulphide product;
Step e: the configuration aqua calcis, the solution containing sodium carbonate and sodium bicarbonate that step C is obtained mixes with the excessive hydrogen calcium oxide solution, obtains the mixture containing carbonic acid calcium deposit and sodium hydroxide solution;
Step F: step e gained mixture is filtered, obtain calcium carbonate filter cake and containing the solution of sodium hydroxide;
Step G: calcium carbonate filter cake, through washing, be dry, pulverize, obtain calcium carbonate product;
Step H: will be the sodium hydroxide supersaturated solution containing the solution distillation of sodium hydroxide, spraying drying, obtain the sodium hydroxide product.
Embodiment 2
The method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue, its raw material is barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue, comprises the steps:
Steps A: carbonate content in conversion Sodium Sulphide waste residue, and be 90 orders by the pulverizing of Sodium Sulphide waste residue, then configure Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions;
Step B: Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions are successively dropped in the protection against corrosion reactor with the ratio 1:1 of molar content with hydrogen-carbonate copper pure substance with sodium sulphite, carry out chemical reaction, obtain the mixture of Containing Sulfur copper, sodium carbonate and sodium bicarbonate;
Step C: step B gained mixture is filtered, filter clarification containing sodium carbonate and the solution of sodium bicarbonate and the filter cake of Containing Sulfur copper;
Step D: the filter cake of the Containing Sulfur copper that step C is obtained, through washing, dry, pulverize, and obtains copper sulphide product;
Step e: the configuration aqua calcis, the solution containing sodium carbonate and sodium bicarbonate that step C is obtained mixes with the excessive hydrogen calcium oxide solution, obtains the mixture containing carbonic acid calcium deposit and sodium hydroxide solution;
Step F: step e gained mixture is filtered, obtain calcium carbonate filter cake and containing the solution of sodium hydroxide;
Step G: calcium carbonate filter cake, through washing, be dry, pulverize, obtain calcium carbonate product;
Step H: will be the sodium hydroxide supersaturated solution containing the solution distillation of sodium hydroxide, spraying drying, obtain the sodium hydroxide product.
Embodiment 3
The method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue, its raw material is barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue, comprises the steps:
Steps A: carbonate content in conversion Sodium Sulphide waste residue, and be 100 orders by the pulverizing of Sodium Sulphide waste residue, then configure Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions;
Step B: Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions are successively dropped in the protection against corrosion reactor with the ratio 1:1.2 of molar content with hydrogen-carbonate copper pure substance with sodium sulphite, carry out chemical reaction, obtain the mixture of Containing Sulfur copper, sodium carbonate and sodium bicarbonate;
Step C: step B gained mixture is filtered, filter clarification containing sodium carbonate and the solution of sodium bicarbonate and the filter cake of Containing Sulfur copper;
Step D: the filter cake of the Containing Sulfur copper that step C is obtained, through washing, dry, pulverize, and obtains copper sulphide product;
Step e: the configuration aqua calcis, the solution containing sodium carbonate and sodium bicarbonate that step C is obtained mixes with the excessive hydrogen calcium oxide solution, obtains the mixture containing carbonic acid calcium deposit and sodium hydroxide solution;
Step F: step e gained mixture is filtered, obtain calcium carbonate filter cake and containing the solution of sodium hydroxide;
Step G: calcium carbonate filter cake, through washing, be dry, pulverize, obtain calcium carbonate product;
Step H: will be the sodium hydroxide supersaturated solution containing the solution distillation of sodium hydroxide, spraying drying, obtain the sodium hydroxide product.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, its framework form can be flexible and changeable, can the subseries method.Just make some simple deduction or replace, all should be considered as belonging to the present invention's scope of patent protection definite by submitted to claims .

Claims (2)

1. prepare the method for cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue, it is characterized in that, its raw material is barium sulfate by-product sodium sulfide method gained Sodium Sulphide waste residue, comprises the steps:
Steps A: carbonate content in conversion Sodium Sulphide waste residue, and configuration Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions;
Step B: Sodium Sulphide waste residue suspension liquid and hydrogen-carbonate copper solutions are successively dropped in the protection against corrosion reactor with the ratio 1:0.8 of sodium sulphite and molar content with hydrogen-carbonate copper pure substance~1.2, carry out chemical reaction, obtain the mixture of Containing Sulfur copper, sodium carbonate and sodium bicarbonate;
Step C: step B gained mixture is filtered, filter clarification containing sodium carbonate and the solution of sodium bicarbonate and the filter cake of Containing Sulfur copper;
Step D: the filter cake of the Containing Sulfur copper that step C is obtained, through washing, dry, pulverize, and obtains copper sulphide product;
Step e: the configuration aqua calcis, the solution containing sodium carbonate and sodium bicarbonate that step C is obtained mixes with the excessive hydrogen calcium oxide solution, obtains the mixture containing carbonic acid calcium deposit and sodium hydroxide solution;
Step F: step e gained mixture is filtered, obtain calcium carbonate filter cake and containing the solution of sodium hydroxide;
Step G: calcium carbonate filter cake, through washing, be dry, pulverize, obtain calcium carbonate product;
Step H: will be the sodium hydroxide supersaturated solution containing the solution distillation of sodium hydroxide, spraying drying, obtain the sodium hydroxide product.
2. the method for preparing cupric sulfide, calcium carbonate and sodium hydroxide with the Sodium Sulphide waste residue as claimed in claim 1, is characterized in that, before configuration Sodium Sulphide waste residue suspension liquid, first described Sodium Sulphide waste residue is ground into to the 80-100 order.
CN 201010615463 2010-12-31 2010-12-31 Method for preparing copper sulfide, calcium carbonate and sodium hydroxide from sodium sulfide waste Expired - Fee Related CN102115114B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421850A (en) * 1965-07-02 1969-01-14 Anaconda Co Separate recovery of copper sulfide and zinc sulfide from aqueous solutions containing water-soluble salts of copper and zinc
CN1948153A (en) * 2006-10-31 2007-04-18 赵志军 New method of producing sodium sulfite and sodium sulfide using alkali sulfide reduction waste water
CN101898771A (en) * 2010-08-03 2010-12-01 王嘉兴 Method for preparing caustic soda and carbon/sulfur calcium mixture from sodium sulfide waste residues

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58141346A (en) * 1982-02-15 1983-08-22 Dowa Mining Co Ltd Collecting method of metal from industrial by-product

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421850A (en) * 1965-07-02 1969-01-14 Anaconda Co Separate recovery of copper sulfide and zinc sulfide from aqueous solutions containing water-soluble salts of copper and zinc
CN1948153A (en) * 2006-10-31 2007-04-18 赵志军 New method of producing sodium sulfite and sodium sulfide using alkali sulfide reduction waste water
CN101898771A (en) * 2010-08-03 2010-12-01 王嘉兴 Method for preparing caustic soda and carbon/sulfur calcium mixture from sodium sulfide waste residues

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JP昭58-141346A 1983.08.22

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