CN117486237A - Sodium sulfate and calcium sulfate combined alkali process - Google Patents
Sodium sulfate and calcium sulfate combined alkali process Download PDFInfo
- Publication number
- CN117486237A CN117486237A CN202311457440.5A CN202311457440A CN117486237A CN 117486237 A CN117486237 A CN 117486237A CN 202311457440 A CN202311457440 A CN 202311457440A CN 117486237 A CN117486237 A CN 117486237A
- Authority
- CN
- China
- Prior art keywords
- sodium
- ammonia
- chloride solution
- calcium
- carbon dioxide
- 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.)
- Pending
Links
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 20
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 15
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 15
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000003513 alkali Substances 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 43
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 38
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 34
- 239000011780 sodium chloride Substances 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 18
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- 238000009621 Solvay process Methods 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 235000019738 Limestone Nutrition 0.000 claims abstract description 5
- 239000006028 limestone Substances 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000002351 wastewater Substances 0.000 claims abstract description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 3
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 28
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- 239000001569 carbon dioxide Substances 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 11
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 8
- 235000012255 calcium oxide Nutrition 0.000 claims description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 5
- 238000009993 causticizing Methods 0.000 claims description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 4
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 4
- 239000004571 lime Substances 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000006071 cream Substances 0.000 claims description 2
- 230000009615 deamination Effects 0.000 claims description 2
- 238000006481 deamination reaction Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C01D7/18—Preparation by the ammonia-soda process
-
- 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 belongs to the technical field of sodium carbonate preparation, and based on an ammonia-soda process, limestone and sodium sulfate are used as raw materials, sodium chloride and ammonia are used as circulating media to prepare sodium carbonate and co-produce calcium sulfate, so that high-salt wastewater generated in the process of producing sodium carbonate by the ammonia-soda process is fundamentally prevented, and meanwhile, the utilization rate of sodium is improved.
Description
Technical Field
The invention belongs to the technical field of sodium carbonate preparation, and in particular relates to a method for preparing sodium carbonate and co-producing calcium sulfate by taking limestone and sodium sulfate as raw materials and sodium chloride and ammonia as circulating media.
Background
Sodium carbonate is a large amount of chemical raw materials, and is generally prepared by an ammonia alkaline method (Soy-Vietnam alkaline method) or a combined alkaline method (House alkaline method) at present, and most of sodium chloride is obtained by airing seawater, refining or obtaining the sodium chloride through a salt well. The ammonia-soda process produces a large amount of high-salt wastewater containing calcium chloride and sodium chloride.
The production amount of sodium sulfate in China is large, a large amount of sodium sulfate is excessive, and the sodium sulfate is stored in a storage yard, so that the environmental risk and the resource waste are serious. If sodium sulfate is used to replace sodium chloride as raw material to prepare sodium carbonate, the economic benefit and the environmental benefit are very remarkable.
Disclosure of Invention
The invention provides a method for preparing sodium carbonate and co-producing calcium sulfate by taking limestone and sodium sulfate as raw materials and sodium chloride and ammonia as circulating media on the basis of an ammonia-soda process, which radically eliminates high-salt wastewater generated in the process of producing sodium carbonate by the ammonia-soda process and improves the utilization rate of sodium.
The invention is realized by adopting the following technical scheme, and the specific steps are as follows:
preparation of S1 sodium bicarbonate: absorbing ammonia gas by the sodium chloride solution to prepare ammonia water, introducing carbon dioxide into the ammonia water, carbonating the sodium chloride into sodium bicarbonate, and carrying out solid-liquid separation to obtain sodium bicarbonate and ammonium chloride solution;
s2, preparing sodium carbonate: calcining the sodium bicarbonate obtained in the step S1 to obtain sodium carbonate and carbon dioxide; returning the carbon dioxide to the step S1;
s3, deamination of an ammonium chloride solution: adding lime cream into the ammonium chloride solution obtained in the step S1 for causticizing, converting the combined ammonium into free ammonia and volatilizing the free ammonia to obtain ammonia gas, and returning the ammonia gas to the step S1 for preparing ammonia brine; removing ammonium, and then carrying out solid-liquid separation to obtain a calcium chloride solution;
s4, adding sodium sulfate into the calcium chloride solution obtained in the step S3, and carrying out solid-liquid separation to obtain a sodium chloride solution and calcium sulfate dihydrate; the sodium chloride solution is refined and then returns to the step S1 to prepare ammonia brine;
s5, calcining calcium carbonate to obtain carbon dioxide and quicklime; carbon dioxide is used for step S1; quicklime is used for step S3.
S6 principle:
s61 metathesis reaction to prepare sodium bicarbonate: 2CO 2 +2NH 3 +2NaCl+2H 2 O＝2NaHCO 3 ↓+2NH 4 Cl
S62, sodium bicarbonate is calcined to prepare sodium carbonate: 2NaHCO 3 ＝Na 2 CO 3 +CO 2 ↑+H 2 O
S63, causticizing ammonia distillation: 2NH 4 Cl+Ca(OH) 2 ＝CaCl 2 +2NH 3 ↑+2H 2 O
S64 double decomposition reaction to prepare calcium sulfate dihydrate: caCl (CaCl) 2 +Na 2 SO 4 +2H 2 O＝CaSO 4 ·2H 2 O↓+2NaCl
S65, limestone calcination: caCO (CaCO) 3 ＝CaO+CO 2 ↑
S66, quicklime digestion: caO+H 2 O＝Ca(OH) 2
S67 total reaction: caCO (CaCO) 3 +Na 2 SO 4 +2H 2 O—→Na 2 CO 3 +CaSO 4 ·2H 2 O
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The following description of the embodiments of the present invention refers to the accompanying drawings.
1, absorbing ammonia gas by sodium chloride solution to prepare ammonia water;
introducing carbon dioxide into the ammonia water to prepare sodium bicarbonate, and separating solid from liquid to obtain an ammonium chloride solution;
3, calcining sodium bicarbonate to prepare sodium carbonate, wherein carbon dioxide generated by calcining is reused for preparing sodium bicarbonate;
4, adding lime milk into the ammonium chloride solution for causticizing, distilling ammonia, and separating solid from liquid after ammonia distillation to obtain a calcium chloride solution;
5 adding sodium sulfate into the calcium chloride solution, and separating solid and liquid to obtain sodium chloride solution and calcium sulfate dihydrate, wherein the sodium chloride solution is reused for preparing ammonia brine;
6, calcining calcium carbonate to obtain carbon dioxide and quicklime, wherein the carbon dioxide is used for preparing sodium bicarbonate; lime milk prepared from quicklime is used for causticizing and distilling ammonia of an ammonium chloride solution;
and 7, washing and drying the calcium sulfate.
Claims (3)
1. On the basis of the ammonia-soda process, limestone and sodium sulfate are used as raw materials, sodium chloride and ammonia are used as circulating media to prepare sodium carbonate and co-produce calcium sulfate, so that high-salt wastewater generated in the process of producing sodium carbonate by the ammonia-soda process is fundamentally prevented, and meanwhile, the utilization rate of sodium is improved. The method is characterized by comprising the following steps of:
preparation of S1 sodium bicarbonate: absorbing ammonia gas by the sodium chloride solution to prepare ammonia water, introducing carbon dioxide into the ammonia water, carbonating the sodium chloride into sodium bicarbonate, and carrying out solid-liquid separation to obtain sodium bicarbonate and ammonium chloride solution;
s2, preparing sodium carbonate: calcining the sodium bicarbonate obtained in the step S1 to obtain sodium carbonate and carbon dioxide; returning the carbon dioxide to the step S1;
s3, deamination of an ammonium chloride solution: causticizing the ammonium chloride solution obtained in the step S1 by lime cream, converting the combined ammonium into free ammonia and volatilizing the free ammonia to obtain ammonia gas, and returning the ammonia gas to the step S1 to prepare ammonia brine; removing ammonium, and then carrying out solid-liquid separation to obtain a calcium chloride solution;
s4, adding sodium sulfate into the calcium chloride solution obtained in the step S3, and carrying out solid-liquid separation to obtain a sodium chloride solution and calcium sulfate dihydrate; the sodium chloride solution is refined and then returns to the step S1 to prepare ammonia brine;
s5, calcining calcium carbonate to obtain carbon dioxide and quicklime; carbon dioxide is used for step S1; quicklime is used for step S3.
2. The sodium sulfate according to step S4 of claim 1, wherein the sodium sulfate mass fraction is greater than 98%.
3. The calcium sulfate dihydrate according to step S4 of claim 1, wherein the mass fraction of the calcium sulfate dihydrate is greater than 98%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311457440.5A CN117486237A (en) | 2023-11-03 | 2023-11-03 | Sodium sulfate and calcium sulfate combined alkali process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311457440.5A CN117486237A (en) | 2023-11-03 | 2023-11-03 | Sodium sulfate and calcium sulfate combined alkali process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117486237A true CN117486237A (en) | 2024-02-02 |
Family
ID=89677631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311457440.5A Pending CN117486237A (en) | 2023-11-03 | 2023-11-03 | Sodium sulfate and calcium sulfate combined alkali process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117486237A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117682539A (en) * | 2024-02-04 | 2024-03-12 | 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 |
-
2023
- 2023-11-03 CN CN202311457440.5A patent/CN117486237A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117682539A (en) * | 2024-02-04 | 2024-03-12 | 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 |
| 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 |
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| PB01 | Publication | ||
| PB01 | Publication |