CN112875726B - Method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate - Google Patents
Method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate Download PDFInfo
- Publication number
- CN112875726B CN112875726B CN202110294221.4A CN202110294221A CN112875726B CN 112875726 B CN112875726 B CN 112875726B CN 202110294221 A CN202110294221 A CN 202110294221A CN 112875726 B CN112875726 B CN 112875726B
- Authority
- CN
- China
- Prior art keywords
- calcium
- sodium bicarbonate
- solution
- sodium
- sulfate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/02—Preparation by double decomposition
-
- 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
Abstract
The invention disclosesA method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate uses sodium sulfate as raw material, ammonium bicarbonate and CO 2 And NH 3 The method comprises the steps of preparing sodium sulfate, calcium oxide or/and calcium hydroxide, ammonium salt, ammonium bicarbonate, ammonium sulfate, ammonium chloride or ammonium nitrate, and performing interconversion between the ammonium bicarbonate, the ammonium sulfate and the ammonium chloride or the ammonium nitrate.
Description
Technical Field
The invention belongs to the field of alkali preparation and secondary resource utilization, and particularly relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate.
Background
Sodium sulfate is an inorganic compound, also known as mirabilite in the form of decahydrate, and anhydrous sodium sulfate. Sodium sulfate is a by-product with huge yield formed in the production process of many metallurgical and chemical industries. At present, the market demand of sodium sulfate is limited, and an economical and effective comprehensive utilization method is lacked. With the improvement of the national requirements on environmental protection treatment, sodium sulfate generated in the environmental protection treatment process of many enterprises accumulates like a mountain, and the reservoir is full of sodium sulfate which is a disease and cannot be said. Therefore, a great deal of research on the comprehensive utilization of sodium sulfate is carried out at home and abroad, and the research mainly focuses on the research on the double decomposition of sodium sulfate and ammonium bicarbonate to produce sodium bicarbonate and sodium carbonate.
CN105712382A discloses a method for producing sodium bicarbonate by mirabilite, which adopts double decomposition crystallization of ammonium bicarbonate and sodium sulfate to separate out sodium bicarbonate, then adds lime into sodium bicarbonate crystallization mother liquor to adjust pH, heats up and collects ammonia, and filters to obtain solid waste which contains calcium sulfate, calcium carbonate and calcium hydroxide and is difficult to utilize.
CN103754898A discloses a method for preparing pure sodium chloride solution by using calcium chloride to react with sodium sulfate in salt well water and for producing sodium carbonate by combining a combined alkali-making method, wherein the method uses calcium chloride to remove the sodium sulfate in the solution, gypsum is precipitated, and the obtained purified sodium chloride solution is used for producing sodium carbonate by adopting the combined alkali-making method.
CN104355326A discloses a method for preparing sodium bicarbonate and co-producing ammonium sulfate by double decomposition of ammonium bicarbonate and sodium sulfate, which comprises mixing ammonium bicarbonate and sodium sulfate, crystallizing to separate out sodium bicarbonate, heating to remove ammonia from the mother liquid of sodium bicarbonate, evaporating, concentrating, crystallizing to separate sodium sulfate, freezing the mother liquid of sodium sulfate to crystallize sodium sulfate/ammonium sulfate double salt, and finally evaporating and crystallizing the mother liquid of double salt crystal to obtain ammonium sulfate product. The method has the advantages of long process flow, complex operation process, repeated heating/cooling, high energy consumption, low utilization rate of raw materials and high cost, and does not have a precedent for industrial implementation at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the method for preparing the sodium bicarbonate and the calcium sulfate dihydrate by the sodium sulfate, which has the advantages of simple process, high comprehensive utilization rate of raw materials and convenient operation.
The invention relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate, which comprises the following steps:
the method comprises the following steps: production of sodium bicarbonate by sodium ion
The purified sodium sulfate solution is used as a raw material for comprehensive utilization, ammonium bicarbonate is used as a secondary decomposition reactant, and Na is controlled + /NH 4 + Molar ratio of>1, using Na + The ion-generated homoionic effect forces the sodium bicarbonate to crystallize out, and sodium bicarbonate crystals and the first crystals are obtained by filtrationMother liquor, crystallizing the obtained first crystallization mother liquor for 2-12 h at-14 ℃ directly or by adding mirabilite seed crystal, filtering to obtain mirabilite and second crystallization mother liquor, returning the obtained mirabilite to be used as raw materials for comprehensive utilization, and using the obtained second crystallization mother liquor for producing calcium sulfate dihydrate or
With CO 2 And NH 3 The mixed gas is used as a secondary decomposition reactant to control NH 3 Molar ratio of Na>1, and introducing CO 2 Acidifying under pressure until the pH is 3.5-6.9, and using HCO 3 - The ion-producing uniionic effect forces sodium bicarbonate to crystallize and separate out, the liquid-solid separation obtains sodium bicarbonate crystal and acidified liquid, the acidified liquid is decompressed to force dissolved CO therein 2 And NH 3 Volatilized CO 2 And NH 3 Returning to be continuously used as a double decomposition reaction agent, and using the obtained volatile residual liquid for producing calcium sulfate dihydrate;
step two: production of calcium sulfate dihydrate from sulfate radical
According to Ca 2+ /SO 4 2- Adding soluble calcium salt as precipitant and SO into the second crystallization mother liquor or volatile residual liquid obtained in step one at a molar ratio of 1 4 2- With Ca 2+ Combining to form calcium sulfate precipitate, filtering to obtain calcium sulfate dihydrate product and precipitated solution, adding calcium oxide or/and calcium hydroxide into the precipitated solution, heating to remove ammonia, controlling the final pH of the solution to be not less than 10.5, and volatilizing NH 3 Returning to the first step for continuously serving as a double decomposition reaction agent, and introducing CO into final liquid obtained by removing ammonia 2 And adjusting the pH value to 7-9, filtering to obtain a calcium salt solution, and returning the obtained calcium salt solution to be continuously used as a precipitator.
The invention relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate, wherein in the step one, the purified sodium sulfate solution is obtained by adding sodium carbonate or/and sodium hydroxide into the sodium sulfate solution, adjusting the pH value to 8.5-9.5, purifying and transforming (converting ammonium sulfate into sodium sulfate) or removing impurities (such as calcium, magnesium, iron and other impurities), and filtering to obtain a solution containing Na 2 SO 4 80-480 g/L of solution.
The invention relates to a method for preparing sodium bicarbonate and dihydrate sulfuric acid by comprehensively utilizing sodium sulfateThe process for preparing sodium bicarbonate by using ammonium bicarbonate as secondary decomposition reactant includes the first step of controlling Na content + /NH 4 + Molar ratio of>1, preferably Na + /NH 4 + The molar ratio is 1.1-1.5, the pH of the solution is adjusted to 7-9, the solution is stirred for 1-4 hours at the temperature of 15-45 ℃, and Na is utilized + The ion produces the same ion effect, forces the sodium bicarbonate to crystallize out.
The invention relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate, wherein in the step one, CO is used 2 And NH 3 The technological process of preparing sodium bicarbonate with mixed gas as re-decomposing reactant includes controlling NH 3 Molar ratio of Na>1, preferably NH 3 The mol ratio of Na to CO is 1.1-2.0 2 Adjusting the pH value of the solution to 3.5-6.9, stirring for 1-4 h at 15-45 ℃, and using HCO 3 - The ion produces the same ion effect, forces the sodium bicarbonate to crystallize out.
The invention relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate, wherein in the step one, the pressure reduction of acidified liquid refers to stirring for 1-4 h at 25-65 ℃ under the condition that the liquid surface pressure is less than or equal to 0.1Mpa, preferably 0.02-0.1 Mpa, so as to force CO in the acidified liquid to be forced 2 And NH 3 And volatilizing.
In the second step, the soluble calcium salt is selected from at least one of calcium chloride, calcium bromide, calcium nitrate, calcium nitrite, calcium chlorate, calcium bromate, calcium acetate and calcium perchlorate, and preferably calcium chloride or calcium nitrate.
In the step two, the precipitation of the calcium sulfate refers to that Ca is used as the basis 2+ /SO 4 2- Adding soluble calcium salt as a precipitator into the second crystallization mother liquor or the volatile residual liquid obtained in the step one at a molar ratio of 1, stirring for 0.5-2.5 h at a temperature of 25-105 ℃, and forcing SO in the second crystallization mother liquor or the volatile residual liquid 4 2- Precipitating in the form of calcium sulfate, filtering, washing and drying to obtain the calcium sulfate dihydrate product.
The invention relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate 2+ /NH 4 + Adding calcium oxide or/and calcium hydroxide into the solution after precipitation at a molar ratio of not less than 0.5, maintaining the pH of the solution at not less than 10.5, preferably at a pH of 11-13, stirring at 85-115 ℃ for 1.5-3.5 h to force NH in the solution 3 And volatilizing.
The invention relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate, wherein in the technological process of comprehensive utilization of sodium sulfate, ammonium bicarbonate and CO 2 And NH 3 The effective utilization rates of the calcium oxide or/and the calcium hydroxide are respectively more than or equal to 96.5 percent, the purity of the obtained calcium sulfate dihydrate product is more than or equal to 99 percent, and the product quality reaches the quality standard of calcium sulfate, a food additive, specified in GB 1892-2007; the purity of the sodium bicarbonate product is more than or equal to 99.5 percent, and the product quality reaches the quality standard of industrial sodium bicarbonate specified in GB/T1606-2008.
The invention relates to a method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate, which has the following basic principle:
Na 2 SO 4 +2NH 4 HCO 3 ＝2NaHCO 3 ↓+(NH 4 ) 2 SO 4 (1)
(NH 4 ) 2 SO 4 +CaCl 2 +2H 2 O＝CaSO·2H 2 O↓+2NH 4 Cl (2)
2NH 4 Cl+CaO＝CaCl 2 +2NH 3 ↑+H 2 O (3)
(NH 4 ) 2 SO 4 +Ca(NO 3 ) 2 +2H 2 O＝CaSO·2H 2 O↓+2NH 4 NO 3 (4)
2NH 4 NO 3 +CaO＝Ca(NO 3 ) 2 +2NH 3 ↑+H 2 O (5)
NH 3 +H 2 O+CO 2 ＝NH 4 HCO 3 (6)
compared with the prior art, the invention has the following advantages and effects:
the invention takes sodium sulfate as raw material, and uses ammonium bicarbonate and CO 2 And NH 3 The method comprises the steps of preparing sodium sulfate, calcium oxide or/and calcium hydroxide, ammonium salt, ammonium bicarbonate, ammonium sulfate, ammonium chloride or ammonium nitrate, and performing interconversion between the ammonium bicarbonate, the ammonium sulfate and the ammonium chloride or the ammonium nitrate.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate the invention but not to limit it further.
Example 1
Dissolving industrial Natrii sulfas in water, adding sodium carbonate to adjust pH to 9, purifying to remove impurities such as calcium, magnesium, ferrum, etc., to obtain Na 2 SO 4 460g/L of solution 5m 3 As a raw material for comprehensive utilization as Na + /NH 4 + The mol ratio is 1.15, ammonium bicarbonate is added as a double decomposition reactant by stirring, the solution is cooled to 20 ℃ after reacting for 1h at 38 ℃, and Na is utilized + The same ion effect generated by the ions forces the sodium bicarbonate to crystallize out, and sodium bicarbonate crystals and the first crystallization mother liquor are obtained by filtration. And washing and drying the obtained sodium bicarbonate crystals to obtain a sodium bicarbonate product with the purity of 99.6 percent and the quality reaching the standard specified in GB/T1606-2008. And adding mirabilite seed crystals into the obtained first crystallization mother liquor, crystallizing for 6 hours at the temperature of-10 ℃, filtering to obtain mirabilite and second crystallization mother liquor, and returning the obtained mirabilite to be continuously used as a raw material for comprehensive utilization. Then according to Ca 2+ /SO 4 2- Adding calcium chloride dihydrate as precipitant and SO into the second crystallization mother liquor at a molar ratio of 1 4 2- With Ca 2+ After calcium sulfate precipitation is formed by combination, filtering to obtain a calcium sulfate dihydrate filter cake and a precipitation solution. The obtained calcium sulfate dihydrate filter cakeAfter washing and drying, the calcium sulfate dihydrate product with the purity of 99.5 percent and the product quantity reaching the standard specified in GB1892-2007 is obtained. The obtained precipitated solution is mixed with Ca 2+ /NH 4 + Adding quicklime into the mixture with the molar ratio of 0.6, stirring and heating at 98 ℃ to remove ammonia, wherein the pH of ammonia removing final solution is 12.5, and volatilized NH 3 Collected for use as metathesis reactant. Finally, introducing CO into the ammonia removing final solution 2 Adjusting pH to 7.6, filtering to obtain CaCl 2 485.1 g/L solution 3.61m 3 The whole process comprises sodium sulfate, ammonium bicarbonate, quicklime and CO 2 The effective utilization rates of the active carbon are all more than or equal to 96.7 percent.
Example 2
Dissolving sodium sulfate in water, adding sodium carbonate to adjust pH to 9, purifying to remove impurities such as calcium, magnesium, and ferrum 2 SO 4 471g/L of solution 3m 3 As a raw material for comprehensive utilization, using CO 2 And NH 3 The mixed gas is used as a secondary decomposition reactant according to NH 3 NH is added into the solution under pressure with a molar ratio of Na/Na of 1.2 3 And CO 2 And using CO in combination 2 Acidifying until the pH of the solution is 5.5, stirring at 25 deg.C for 3h, and adding HCO 3 - The ion produces the same ion effect to force the sodium bicarbonate to crystallize and separate out, and sodium bicarbonate crystals and acidified liquid are obtained by filtration. The obtained sodium bicarbonate crystals are washed and dried to obtain a sodium bicarbonate product with the purity of 99.8% and the quality reaching the standard specified in GB/T1606-2008. Then decompressing the obtained acidified liquid to 0.03Mpa, stirring at 55 ℃ for 2.5h to force CO in the acidified liquid 2 And NH 3 Volatilized CO 2 And NH 3 Collected and used as metathesis reactant. Followed by addition of Ca 2+ /SO 4 2- The molar ratio is 1, and the CaCl obtained in example 1 is added to the volatilized residue 2 The solution being a precipitating agent, SO 4 2- With Ca 2+ After calcium sulfate precipitation is formed by combination, filtering to obtain a calcium sulfate dihydrate filter cake and a precipitation solution. The obtained calcium sulfate dihydrate filter cake is washed and dried to obtain a calcium sulfate dihydrate product with the purity of 99.6 percent and the product quantity reaching the standard specified in GB 1892-2007. The obtained post-precipitation solution is Ca 2+ /NH 4 + Adding cooked materials in a molar ratio of 0.55Lime, stirring and heating at 105 ℃ to remove ammonia, wherein the pH of ammonia removing final solution is 12.1, and volatilized NH 3 Collected for use as metathesis reactant. Finally, introducing CO into the ammonia removing final solution 2 Adjusting pH to 7.8, filtering to obtain CaCl 2 426.5g/L solution 2.50m 3 Sodium sulfate and CO in the whole process 2 、NH 3 And the effective utilization rate of the hydrated lime is more than or equal to 96.5 percent.
Example 3
Dissolving solid sodium sulfate containing 3.8% of ammonium sulfate in water, adding sodium carbonate, purifying and transforming to completely convert ammonium sulfate into sodium sulfate to obtain Na-containing product 2 SO 4 483g/L solution 2.5m 3 As a raw material for comprehensive utilization as Na + /NH 4 + The mol ratio is 1.11, ammonium bicarbonate is added as a double decomposition reactant by stirring, the solution is cooled to 17 ℃ after 1 hour of reaction at the temperature of 41 ℃, and Na is utilized + The ion produces the same ion effect to force the sodium bicarbonate to crystallize out, and sodium bicarbonate crystal and the first crystallization mother liquid are obtained through filtration. And washing, drying and calcining the obtained sodium bicarbonate crystals to obtain an industrial sodium carbonate product with the purity of 99.5 percent and the quality reaching the standard specified in GB 210-92. And adding mirabilite seed crystals into the obtained first crystallization mother liquor, crystallizing for 6 hours at the temperature of-12 ℃, filtering to obtain mirabilite and second crystallization mother liquor, and returning the obtained mirabilite to be continuously used as a raw material for comprehensive utilization. Then according to Ca 2+ /SO 4 2- Adding calcium nitrate as a precipitator and SO into the second crystallization mother liquor according to the molar ratio of 1 4 2- With Ca 2+ After calcium sulfate precipitation is formed by combination, filtering to obtain a calcium sulfate dihydrate filter cake and a precipitation solution. The obtained calcium sulfate dihydrate filter cake is washed and dried to obtain a calcium sulfate dihydrate product with the purity of 99.7 percent and the product quantity reaching the standard specified in GB 1892-2007. The obtained post-precipitation solution is Ca 2+ /NH 4 + Adding quicklime into the mixture with a molar ratio of 0.6, stirring and heating at 102 ℃ to remove ammonia, wherein the pH of ammonia removing final solution is 12.7, and volatilized NH 3 Collected for use as a metathesis reactant. Finally, introducing CO into the ammonia removing final solution 2 Adjusting pH to 7.4, and filtering to obtain Ca (NO) 3 ) 2 683.7g/L solution 1.96m 3 The whole process comprises the steps of sodium sulfate, ammonium bicarbonate,Quicklime and CO 2 The effective utilization rates of the active carbon are all more than or equal to 96.6 percent.
Claims (9)
1. A method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate is characterized by comprising the following steps:
the method comprises the following steps: production of sodium bicarbonate by sodium ion
The purified sodium sulfate solution is used as a raw material for comprehensive utilization, ammonium bicarbonate is used as a secondary decomposition reactant, and Na is controlled + /NH 4 + Molar ratio of>1, using Na + Forcing sodium bicarbonate to crystallize and separate out under the same ion effect generated by ions, filtering to obtain sodium bicarbonate crystals and first crystallization mother liquor, directly crystallizing the obtained first crystallization mother liquor or adding mirabilite seed crystals at the temperature of-14 ℃ for 2-12 hours, filtering to obtain mirabilite and second crystallization mother liquor, returning the obtained mirabilite to be continuously used as a raw material for comprehensive utilization, and using the obtained second crystallization mother liquor for producing calcium sulfate dihydrate or producing calcium sulfate dihydrate
With CO 2 And NH 3 The mixed gas is used as a secondary decomposition reactant to control NH 3 Molar ratio of Na>1, and introducing CO 2 Acidifying under pressure until the pH is 3.5-6.9, and using HCO 3 - The ion-producing uniionic effect forces sodium bicarbonate to crystallize and separate out, the liquid-solid separation obtains sodium bicarbonate crystal and acidified liquid, the acidified liquid is decompressed to force dissolved CO therein 2 And NH 3 Volatilized and volatilized CO 2 And NH 3 Returning to be continuously used as a double decomposition reaction agent, and using the obtained volatile residual liquid for producing calcium sulfate dihydrate;
step two: production of calcium sulfate dihydrate from sulfate radical
According to Ca 2+ /SO 4 2- Adding soluble calcium salt as precipitant and SO into the second crystallization mother liquor or volatile residual liquid obtained in step one at a molar ratio of 1 4 2- With Ca 2+ Combining to form calcium sulfate precipitate, filtering to obtain calcium sulfate dihydrate product and precipitated solution, adding calcium oxide or/and calcium hydroxide into the precipitated solution, heating to remove ammonia, controlling the final pH of the solution to be not less than 10.5, and volatilizing NH 3 Return toStep one, continuously using the reaction solution as a double decomposition reaction agent, and introducing CO into final liquid obtained by ammonia removal 2 And adjusting the pH value to 7-9, filtering to obtain a calcium salt solution, and returning the obtained calcium salt solution to be continuously used as a precipitator.
2. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to claim 1, which is characterized in that: in the first step, the purified sodium sulfate solution is obtained by adding sodium carbonate or/and sodium hydroxide into a sodium sulfate solution, adjusting the pH value to 8.5-9.5, purifying, transforming or removing impurities, and filtering to obtain a solution containing Na 2 SO 4 80-480 g/L of solution.
3. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to claim 1, which is characterized in that: in the first step, the process for preparing the sodium bicarbonate by using the ammonium bicarbonate as the repeated decomposition reactant comprises the following step of controlling Na + /NH 4 + Molar ratio of>1, adjusting the pH value of the solution to 7-9, stirring for 1-4 h at 15-45 ℃, and utilizing Na + The ion produces the same ion effect, forces the sodium bicarbonate to crystallize out.
4. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to claim 1, which is characterized in that: in step one, the CO is used 2 And NH 3 The technological process of preparing sodium bicarbonate with mixed gas as re-decomposing reactant includes controlling NH 3 Molar ratio of Na>1, with CO 2 Adjusting the pH value of the solution to 3.5-6.9, stirring for 1-4 h at 15-45 ℃, and using HCO 3 - The ion produces the same ion effect, forces the sodium bicarbonate to crystallize out.
5. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to claim 1, which is characterized in that: in the first step, the pressure reduction of the acidified liquid refers to stirring for 1-4 hours at 25-65 ℃ under the condition that the liquid surface pressure is less than or equal to 0.1Mpa to force CO in the acidified liquid 2 And NH 3 And volatilizing.
6. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to claim 1, which is characterized in that: in the second step, the soluble calcium salt is selected from at least one of calcium chloride, calcium bromide, calcium nitrate, calcium nitrite, calcium chlorate, calcium bromate, calcium acetate and calcium perchlorate.
7. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to claim 1, which is characterized in that: in the second step, the precipitation of calcium sulfate refers to Ca 2+ /SO 4 2- Adding soluble calcium salt as a precipitator into the second crystallization mother liquor or the volatile residual liquid obtained in the step one at a molar ratio of 1, stirring for 0.5-2.5 h at a temperature of 25-105 ℃, and forcing SO in the second crystallization mother liquor or the volatile residual liquid 4 2- Precipitating in the form of calcium sulfate, filtering, washing and drying to obtain the calcium sulfate dihydrate product.
8. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to claim 1, which is characterized in that: in the second step, the heating for removing ammonia is Ca 2+ /NH 4 + The mol ratio is more than or equal to 0.5, calcium oxide or/and calcium hydroxide is added into the solution after precipitation, the pH value of the solution is maintained to be more than or equal to 10.5, the solution is stirred for 1.5 to 3.5 hours at the temperature of 85 to 115 ℃, and NH in the solution is forced 3 And volatilizing.
9. The method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensive utilization of sodium sulfate according to any one of claims 1-8, characterized in that: in the process of comprehensive utilization of sodium sulfate, ammonium bicarbonate and CO 2 And NH 3 The effective utilization rates of the calcium oxide or/and the calcium hydroxide are respectively more than or equal to 96.5 percent, and the purity of the obtained calcium sulfate dihydrate product is more than or equal to 99 percent; the purity of the sodium bicarbonate product is more than or equal to 99.5 percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110294221.4A CN112875726B (en) | 2021-03-19 | 2021-03-19 | Method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110294221.4A CN112875726B (en) | 2021-03-19 | 2021-03-19 | Method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112875726A CN112875726A (en) | 2021-06-01 |
| CN112875726B true CN112875726B (en) | 2022-08-26 |
Family
ID=76041274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110294221.4A Active CN112875726B (en) | 2021-03-19 | 2021-03-19 | Method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112875726B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114014348B (en) * | 2021-12-10 | 2024-02-23 | 郑州中科新兴产业技术研究院 | Treatment method of sulfur-containing waste salt |
| CN114538471B (en) * | 2022-01-13 | 2023-08-01 | 宁波弗镁瑞环保科技有限公司 | Comprehensive utilization method of sodium sulfate-sodium chloride mixed salt |
| CN114455612B (en) * | 2022-03-07 | 2023-11-28 | 贵州东华工程股份有限公司 | Process for preparing sodium carbonate byproduct gypsum by using sodium sulfate and carbon dioxide as raw materials |
| CN115403059B (en) * | 2022-09-02 | 2023-07-07 | 东方电气集团东方锅炉股份有限公司 | Method and system for recycling baking soda dry desulfurization ash |
| CN115321575A (en) * | 2022-09-05 | 2022-11-11 | 宁波弗镁瑞环保科技有限公司 | Method for transforming and comprehensively utilizing industrial gypsum |
| CN117228694B (en) * | 2023-11-13 | 2024-01-26 | 北京康仑循环科技有限公司 | Method for preparing baking soda by using desulfurized fly ash |
| CN117682539B (en) * | 2024-02-04 | 2024-04-19 | 北京康仑循环科技有限公司 | Method for producing sodium carbonate and high-strength gypsum by using calcium carbonate and sodium sulfate as raw materials |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712382A (en) * | 2016-04-14 | 2016-06-29 | 中国中轻国际工程有限公司 | Technology for producing sodium bicarbonate from mirabilite |
| CN111039310B (en) * | 2018-10-12 | 2021-07-23 | 中国科学院过程工程研究所 | Method for preparing sodium bicarbonate and co-producing ammonium sulfate from sodium sulfate |
| CN109052434B (en) * | 2018-10-19 | 2021-06-04 | 四川金象赛瑞化工股份有限公司 | Method for jointly producing soda ash and composite nitrogen fertilizer by taking mirabilite and ammonium bicarbonate as raw materials |
| CN112225235A (en) * | 2020-10-14 | 2021-01-15 | 中国科学院过程工程研究所 | Method for preparing sodium bicarbonate and sodium bisulfate from sodium sulfate |
-
2021
- 2021-03-19 CN CN202110294221.4A patent/CN112875726B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112875726A (en) | 2021-06-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112875726B (en) | Method for preparing sodium bicarbonate and calcium sulfate dihydrate by comprehensively utilizing sodium sulfate | |
| CN106830012B (en) | Method for producing high-quality sodium fluoride by using fluorine-containing wastewater as raw material | |
| CN113460989B (en) | Battery-grade iron phosphate and preparation method thereof | |
| CN101259968A (en) | Method for preparing trihydrated magnesium carbonate from magnesium chloride-containing bittern by using ammonium carbonate | |
| CN104003443A (en) | Method for preparing ammonium metavanadate by adding seed crystals | |
| JP6926010B2 (en) | Method for producing lithium hydroxide | |
| CN110642282A (en) | Method for preparing calcium fluoride and potassium bicarbonate by using carbon dioxide | |
| CN112225235A (en) | Method for preparing sodium bicarbonate and sodium bisulfate from sodium sulfate | |
| CN113184820A (en) | Method for preparing iron phosphate by using titanium dioxide byproduct ferrous sulfate | |
| CN114436297B (en) | Method for preparing sodium carbonate from mirabilite | |
| KR20170101225A (en) | Method of producing lithium metal phosphates | |
| CN1736870A (en) | Method for preparing potassium nitrate using nitric acid conversion methdo | |
| WO2006111057A1 (en) | A method for comprehensively using of the raw material in wet-processing phosphorite and producing nano calcium carbonate with high purity and microsphere shape at the same time | |
| CN115676788B (en) | High-purity potassium dihydrogen phosphate and preparation method thereof | |
| CN110803714A (en) | Method for producing vanadium pentoxide by vanadium-containing solution | |
| CN113896214B (en) | Method for preparing high-purity lithium carbonate by adsorbing and carbonizing lithium sulfate solution | |
| CN115893749A (en) | Resource utilization method for lithium battery anode ternary precursor production wastewater | |
| CN111410215A (en) | Method for extracting lithium sulfate from brine with high magnesium-lithium ratio | |
| CN113072047A (en) | Production process for continuously preparing monopotassium phosphate | |
| CN109835924A (en) | A kind of method of efficient production high-purity potassium nitrate | |
| CN110627094A (en) | Method for utilizing associated fluorine and potassium of phosphorite | |
| CN1706748A (en) | Potassium chloride and calcium nitrate double decomposing-freezing process of producing potassium nitrate | |
| CN110436520A (en) | The method for preparing vanadium product using sodium vanadate cleaning | |
| CN115535979B (en) | Potassium dihydrogen phosphate and method for preparing potassium dihydrogen phosphate by using calcium hydrogen phosphate | |
| CN114873614B (en) | Method for preparing potassium nitrate byproduct potassium carnallite and magnesium chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |