CN114684842B - Method for preparing sodium hydrosulfide and co-producing calcium sulfate - Google Patents
Method for preparing sodium hydrosulfide and co-producing calcium sulfate Download PDFInfo
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- CN114684842B CN114684842B CN202210464290.XA CN202210464290A CN114684842B CN 114684842 B CN114684842 B CN 114684842B CN 202210464290 A CN202210464290 A CN 202210464290A CN 114684842 B CN114684842 B CN 114684842B
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- 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
- C01F11/46—Sulfates
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
- C01B17/32—Hydrosulfides of sodium or potassium
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- 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
Abstract
The invention discloses a method for preparing sodium hydrosulfide and co-producing calcium sulfate, which takes hydrogen sulfide gas, calcium hydroxide, sodium hydrosulfide and sodium sulfate as raw materials and has high conversion rate. The method comprises the steps of introducing hydrogen sulfide gas into an emulsion of calcium hydroxide, and reacting to obtain calcium hydrosulfide and basic calcium hydrosulfide; dissolving calcium hydrosulfide in water, precipitating basic calcium hydrosulfide, separating solid from liquid, reacting the solid with sodium bisulfate to obtain sodium hydrosulfide, and reacting the liquid with sodium sulfate to obtain sodium hydrosulfide. The method realizes the utilization of cheaper raw materials to a great extent, generates no waste in the reaction process, reduces the production cost, is environment-friendly, and is worthy of popularization and application.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a method for preparing sodium hydrosulfide and co-producing calcium sulfate.
Background
Sodium hydrosulfide is an important inorganic chemical product and has wide application. Auxiliaries which are used, for example, in the dye industry for the synthesis of organic intermediates and for the preparation of sulfur dyes; the tanning industry is used for dehairing and tanning hides; the fertilizer industry is used for removing the monomer sulfur in the activated carbon desulfurizer. Is a raw material for preparing ammonium sulfide and a semi-finished product of pesticide ethanethiol; the mining industry uses a large number of beneficiation reagents; the method is used for sulfurous acid dyeing and the like in the production of artificial fibers, and can also be used for wastewater treatment and the like. The sodium hydrosulfide product has a plurality of application values, and the development of a production process of the sodium hydrosulfide with high conversion rate is very important.
Most of the traditional sodium hydrosulfide production processes are absorption methods. Introducing hydrogen sulfide gas into sodium sulfide or caustic soda solution, and obtaining pure sodium hydrosulfide liquid by using a separation means. The most varied of these processes are the way the hydrogen sulfide gas is produced and the effect of hydrogen sulfide gas purity on the reaction. The production process has certain dangerousness, and the reaction production raw materials have no economy, and the product conversion rate is not ideal. In order to pursue higher product conversion and to select cheaper production raw materials. A method for producing sodium hydrosulfide using hydrogen sulfide gas, calcium hydroxide, and sodium sulfate as raw materials has been reported. The production method is completed in two steps. Firstly, hydrogen sulfide reacts with calcium hydroxide to prepare calcium hydrosulfide, and the calcium hydrosulfide is separated; and secondly, reacting the calcium hydrosulfide with sodium sulfate to obtain the sodium hydrosulfide. The reaction formula is as follows:
2H 2 S + Ca(OH) 2 = Ca(HS) 2 +2 H 2 O
Ca(HS) 2 + Na 2 SO 4 = 2NaHS + CaSO 4 ↓
the production process uses cheaper industrial raw materials, does not have causticization reaction, has mild reaction conditions, meets the requirement of green chemistry, and provides a method for industrially producing sodium hydrosulfide. However, in the actual production process, the first step reaction of the process is found to generate the difficultly soluble basic calcium hydrosulfide, so that the conversion rate of the generated calcium hydrosulfide is not ideal, and the conversion rate of the generated sodium hydrosulfide is not ideal. And the by-product can be treated as waste of the reaction, so that the raw materials cannot be utilized to a great extent, thereby greatly increasing the production cost, being difficult to treat the waste generated by the reaction and bringing certain harm to the environment.
The invention aims to provide a method for preparing sodium hydrosulfide, which is low in production cost and environment-friendly on the basis of the known method.
Disclosure of Invention
The invention aims to provide a method for preparing sodium hydrosulfide and co-producing calcium sulfate with high conversion rate.
The invention relates to a method for preparing sodium hydrosulfide and co-producing calcium sulfate, which is realized by the following steps:
1) Introducing hydrogen sulfide gas into the calcium hydroxide emulsion under the condition of continuous stirring;
2) Continuously introducing hydrogen sulfide gas at a constant speed for 1-3 hours to ensure that the calcium hydroxide emulsion is completely converted into basic calcium hydrosulfide and calcium hydrosulfide, and stopping introducing the hydrogen sulfide gas;
3) Carrying out suction filtration and separation on the solid-liquid mixture to obtain basic calcium hydrosulfide solid and a calcium hydrosulfide solution;
4) Under the condition of continuous stirring, adding sodium sulfate solid into the calcium bisulfide obtained in the step 3 to obtain a sodium bisulfide solution and calcium sulfate solid, and respectively obtaining calcium sulfate and the sodium bisulfide solution;
5) And (3) adding 200ml of ultrapure water into the basic calcium hydrosulfide solid obtained in the step (3), adding the sodium bisulfate solid into the ultrapure water under the condition of continuous stirring, and separating a solid product and a liquid product to respectively obtain calcium sulfate and a sodium hydrosulfide solution.
The principle of the invention is as follows:
3H 2 S + 2Ca(OH) 2 = Ca(HS) 2 + Ca(HS)OH↓+3H 2 O
Ca(HS)OH +NaHSO 4 =CaSO 4 ↓+NaHS+H 2 O
Ca(HS) 2 + Na 2 SO 4 = 2NaHS + CaSO 4 ↓
the invention has the beneficial effects that: the invention provides a production method for co-producing sodium hydrosulfide and calcium sulfate by taking hydrogen sulfide gas, calcium hydroxide, sodium hydrosulfide and sodium sulfate as raw materials and high conversion rate. The method comprises the steps of introducing hydrogen sulfide gas into an emulsion of calcium hydroxide, and reacting to obtain calcium hydrosulfide and basic calcium hydrosulfide; dissolving calcium hydrosulfide in water, precipitating basic calcium hydrosulfide, separating solid from liquid, reacting the solid with sodium bisulfate to obtain sodium hydrosulfide, reacting the liquid with sodium sulfate to obtain sodium hydrosulfide, and utilizing and converting intermediate product into final product. The method realizes the utilization of cheaper raw materials to a great extent, generates no waste in the reaction process, reduces the production cost, is environment-friendly, and is worthy of popularization and application.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The invention provides a method for preparing sodium hydrosulfide and co-producing calcium sulfate, which is realized by the following steps:
1) Introducing hydrogen sulfide gas into 29 mass percent calcium hydroxide emulsion under the condition of continuous stirring;
2) Continuously introducing hydrogen sulfide gas at a constant speed for 1-3 hours to ensure that the calcium hydroxide emulsion is completely converted into basic calcium hydrosulfide and calcium hydrosulfide, and stopping introducing the hydrogen sulfide gas;
3) Carrying out suction filtration and separation on the solid-liquid mixture to obtain basic calcium hydrosulfide solid and a calcium hydrosulfide solution;
4) Under the condition of continuous stirring, adding sodium sulfate solid into the calcium bisulfide solution obtained in the step 3 to obtain a sodium bisulfide solution and calcium sulfate solid, and respectively obtaining calcium sulfate and the sodium bisulfide solution;
5) And (3) adding 200ml of ultrapure water into the basic calcium hydrosulfide solid obtained in the step (3), adding the sodium bisulfate solid into the ultrapure water under the condition of continuous stirring, and separating a solid product and a liquid product to respectively obtain calcium sulfate and a sodium hydrosulfide solution.
In the step 1, the stirring speed is 700-900r/min.
In step 1, the preparation method of the calcium hydroxide emulsion comprises the following steps: 126g of calcium hydroxide solid having a purity of 95% was slowly added to a round-bottomed flask containing 300mL of ultrapure water under continuous stirring to obtain a calcium hydroxide emulsion.
In the step 4, the molar mass ratio of the calcium hydrosulfide solid to the sodium sulfate solid is in a range of 1:1 to 1.05.
In the step 5, the molar mass ratio of the added sodium bisulfate solid to the basic calcium bisulfide solid is 1-1.046: 1.
and (5) washing the calcium sulfate obtained in the step 5 with a 10% sulfuric acid solution for purification.
The hydrogen sulfide gas has a purity of more than 98 percent and does not contain carbon dioxide, and the gas pressure is 0.1-0.3 MPa.
Example 1
Adding 300ml of ultrapure water into a 500ml round bottom bottle, continuously stirring at the speed of 700r/min, and slowly adding 126g of calcium hydroxide solid with the purity of 95% into the 500ml round bottom bottle to obtain a calcium hydroxide emulsion; and continuously introducing hydrogen sulfide gas with the air pressure of 0.2MPa and the purity of more than 98% into the calcium hydroxide emulsion at a constant speed for 1 hour, so that the calcium hydroxide emulsion is completely converted into a solid-liquid mixture of basic calcium hydrosulfide and calcium hydrosulfide, and stopping introducing the hydrogen sulfide gas. And carrying out suction filtration and separation on the solid-liquid mixture to obtain 95g of basic calcium hydrosulfide solid and 342g of calcium hydrosulfide solution. Under the condition of continuous stirring, 57.6g of sodium sulfate solid is added into the calcium bisulfide solution for suction filtration, 320g of liquid product, namely sodium bisulfide solution, is obtained by separation, 49.7g of solid product, namely calcium sulfate, is obtained by washing the solid product with 10% sulfuric acid solution, and the calcium sulfate product with the purity of 98% is obtained; adding 200ml of ultrapure water into the basic calcium hydrosulfide solid, adding 126.6g of sodium bisulfate solid into the basic calcium hydrosulfide solid under the condition of continuous stirring, performing suction filtration and separation to obtain 250g of liquid product, namely sodium hydrosulfide solution, 129.2g of solid product, namely calcium sulfate, and washing the solid product with 10% sulfuric acid solution to obtain a calcium sulfate product with the purity of 98%. And combining liquid products, wherein the concentration of sodium hydrosulfide is 146g/L, and the reaction conversion rate is 90%. And washing and refining the liquid product to obtain 97g of sodium hydrosulfide product with the purity of 75%.
And (3) combining the calcium sulfate to obtain 179g of calcium sulfate product with the purity of 98%.
Example 2
Adding 300ml of ultrapure water into a 500ml round bottom bottle, continuously stirring at the speed of 800r/min, and slowly adding 126g of calcium hydroxide solid with the purity of 95% into the 500ml round bottom bottle to obtain a calcium hydroxide emulsion; and continuously introducing hydrogen sulfide gas with the air pressure of 0.1 MPa and the purity of more than 98% into the calcium hydroxide emulsion at a constant speed for 2 hours, so that the calcium hydroxide emulsion is completely converted into a solid-liquid mixture of basic calcium hydrosulfide and calcium hydrosulfide, and stopping introducing the hydrogen sulfide gas. And carrying out suction filtration and separation on the solid-liquid mixture to obtain 93g of basic calcium hydrosulfide solid and 360g of calcium hydrosulfide solution. Under the condition of continuous stirring, adding 80.4g of sodium sulfate solid into a calcium bisulfide solution, carrying out suction filtration, separating to obtain 325g of liquid product, namely sodium bisulfide solution, 69.3g of solid product, namely calcium sulfate, and washing the solid product by using 10% sulfuric acid solution to obtain a calcium sulfate product with the purity of 98%; adding 200ml of ultrapure water into the basic calcium hydrosulfide solid, adding 125.6g of sodium bisulfate solid into the basic calcium hydrosulfide solid under the condition of continuous stirring, performing suction filtration and separation to obtain 350g of liquid product, namely sodium hydrosulfide solution, 129g of solid product, namely calcium sulfate, and washing the solid product with 10% sulfuric acid solution to obtain a calcium sulfate product with the purity of 98%. And combining liquid products, wherein the concentration of sodium hydrosulfide is 162g/L, and the reaction conversion rate is 90%. And washing and refining the liquid product to obtain 93g of sodium hydrosulfide product with the purity of 77%.
And (3) combining the calcium sulfate to obtain 206.7g of calcium sulfate product with the purity of 98%.
Example 3
Adding 300ml of ultrapure water into a 500ml round bottom bottle, continuously stirring at the speed of 900r/min, and slowly adding 126g of calcium hydroxide solid with the purity of 95% into the 500ml round bottom bottle to obtain a calcium hydroxide emulsion; and continuously introducing hydrogen sulfide gas with the air pressure of 0.3MPa and the purity of more than 98% into the calcium hydroxide emulsion at a constant speed for 3 hours, so that the calcium hydroxide emulsion is completely converted into a solid-liquid mixture of basic calcium hydrosulfide and calcium hydrosulfide, and stopping introducing the hydrogen sulfide gas. And carrying out suction filtration and separation on the solid-liquid mixture to obtain 95g of basic calcium hydrosulfide solid and 362g of calcium hydrosulfide solution. Under the condition of continuous stirring, adding 84.4g of sodium sulfate solid into a calcium hydrosulfide solution, carrying out suction filtration, separating to obtain 331g of liquid product, namely sodium hydrosulfide solution, 75.4g of solid product, namely calcium sulfate, washing the solid product by using a 10% sulfuric acid solution, and obtaining a calcium sulfate product with the purity of 98%; adding 200ml of ultrapure water into the basic calcium bisulfide solid, adding 132.2g of sodium bisulfate solid into the basic calcium bisulfide solid under the condition of continuous stirring, performing suction filtration and separation to obtain 257g of liquid product, namely sodium bisulfide solution, 140.7g of solid product, namely calcium sulfate, and washing the solid product with 10% sulfuric acid solution to obtain a calcium sulfate product with the purity of 98%. Liquid products are combined, the concentration of sodium hydrosulfide is 178g/L, and the reaction conversion rate is 98%. And washing and refining the liquid product to obtain 98g of sodium hydrosulfide product with the purity of 80%.
The calcium sulfate was combined to give 216.4g of calcium sulfate product with a purity of 98%.
Claims (7)
1. A method for preparing sodium hydrosulfide and co-producing calcium sulfate is characterized by comprising the following steps:
1) Introducing hydrogen sulfide gas into the calcium hydroxide emulsion under the condition of continuous stirring;
2) Continuously introducing hydrogen sulfide gas at a constant speed for 1-3 hours to ensure that the calcium hydroxide emulsion is completely converted into basic calcium hydrosulfide and calcium hydrosulfide, and stopping introducing the hydrogen sulfide gas;
3) Carrying out suction filtration and separation on the solid-liquid mixture to obtain basic calcium hydrosulfide solid and a calcium hydrosulfide solution;
4) Under the condition of continuous stirring, adding sodium sulfate solid into the calcium bisulfide solution obtained in the step 3) to obtain a sodium bisulfide solution and calcium sulfate solid, and respectively obtaining calcium sulfate and the sodium bisulfide solution;
5) Adding ultrapure water into the solid basic calcium hydrosulfide obtained in the step 3), adding solid sodium bisulfate into the solid basic calcium hydrosulfide under the condition of continuous stirring, and separating a solid product from a liquid product to respectively obtain calcium sulfate and a sodium hydrosulfide solution.
2. The method as claimed in claim 1, wherein the stirring speed in step 1) is 700-900r/min.
3. The method of claim 1, wherein the calcium hydroxide emulsion is formulated as follows: 126g of calcium hydroxide solid having a purity of 95% was slowly added to a round-bottomed flask containing 300mL of ultrapure water under continuous stirring to obtain a calcium hydroxide emulsion.
4. The method according to claim 1, wherein the molar ratio of the calcium hydrosulfide to the sodium sulfate solid in the step 4) is within a range from 1 to 1.05.
5. The method according to claim 1, wherein the molar ratio of the solid sodium bisulfate to the solid basic calcium hydrosulfide added in the step 5) is 1 to 1.046.
6. The method according to claim 1, characterized in that the calcium sulphate obtained in step 5) is purified by washing with a 10% sulphuric acid solution.
7. The method according to claim 1, wherein the hydrogen sulfide gas is a gas having a purity of more than 98% and containing no carbon dioxide, and the gas pressure is 0.1 to 0.3MPa.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342600A (en) * | 2001-11-05 | 2002-04-03 | 唐培堃 | Process for preparing hydrogen sulfide |
| CN101186280A (en) * | 2007-11-29 | 2008-05-28 | 青岛奥海科工贸有限公司 | Method for preparing sodium sulfhydrate from hydrogen sulfide tail gas |
| CN101372319A (en) * | 2008-10-16 | 2009-02-25 | 云南省化工研究院 | Method for producing sulfurated hydrogen and calcium salt with calcium sulphide |
| CN113373271A (en) * | 2021-06-08 | 2021-09-10 | 安徽工业大学 | Method for recycling steel ladle refining waste residues after treatment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6657082B2 (en) * | 1998-03-24 | 2003-12-02 | Council Of Scientific And Industrial Research | Process for the preparation of thiourea |
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- 2022-04-29 CN CN202210464290.XA patent/CN114684842B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342600A (en) * | 2001-11-05 | 2002-04-03 | 唐培堃 | Process for preparing hydrogen sulfide |
| CN101186280A (en) * | 2007-11-29 | 2008-05-28 | 青岛奥海科工贸有限公司 | Method for preparing sodium sulfhydrate from hydrogen sulfide tail gas |
| CN101372319A (en) * | 2008-10-16 | 2009-02-25 | 云南省化工研究院 | Method for producing sulfurated hydrogen and calcium salt with calcium sulphide |
| CN113373271A (en) * | 2021-06-08 | 2021-09-10 | 安徽工业大学 | Method for recycling steel ladle refining waste residues after treatment |
Non-Patent Citations (1)
| Title |
|---|
| 硫氢化钠新制法的探讨;张鹏博;《无机盐工业》;19830531(第06期);第4-5页 * |
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