CN102874770B - Method for producing sulfuric acid from calcium sulfate - Google Patents
Method for producing sulfuric acid from calcium sulfate Download PDFInfo
- Publication number
- CN102874770B CN102874770B CN201210406759.0A CN201210406759A CN102874770B CN 102874770 B CN102874770 B CN 102874770B CN 201210406759 A CN201210406759 A CN 201210406759A CN 102874770 B CN102874770 B CN 102874770B
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- calcium sulfate
- water
- temperature
- gas
- 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 70
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000012153 distilled water Substances 0.000 claims abstract description 5
- 235000011132 calcium sulphate Nutrition 0.000 claims description 30
- 239000001175 calcium sulphate Substances 0.000 claims description 12
- 241000605739 Desulfovibrio desulfuricans Species 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 16
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000037 hydrogen sulfide Inorganic materials 0.000 abstract description 8
- 239000012535 impurity Substances 0.000 abstract description 5
- 239000011261 inert gas Substances 0.000 abstract description 3
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 abstract 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to a method for producing sulfuric acid from calcium sulfate, which comprises the following steps: (1) adding calcium sulfate powder into a closed oxygen-free container in which distilled water is filled, ensuring that the calcium sulfate powder is immersed, and controlling the water temperature to be 28-85 DEG C; (2) adding a high-temperature sulfate reducing bacterium into the water, controlling the pH value of the water to be 6.4-7.5, and enabling the high-temperature sulfate reducing bacterium and SO4<2-> dissolved in the water to react to form H2S; (3) introducing inert gas into the water to continuously take out the H2S gas, thus reducing the H2S content in the solution; (4) introducing the H2S gas taken out into 98wt% concentrated sulfuric acid, wherein H2S is absorbed and converted into H2SO3; and (5) introducing oxygen gas into H2SO3, wherein H2SO3 is converted into H2SO4. According to the invention, the high-temperature sulfate reducing bacterium is used as the bridge, and calcium sulfate slightly soluble in water is converted into sulfuric acid; and no impurity is introduced in the whole process, and the generated hydrogen sulfide is absorbed 100%, thereby achieving the purposes of energy saving and environmental protection.
Description
Technical field
The present invention relates to a kind of method of producing sulfuric acid, especially relate to a kind of method utilizing calcium sulfate to produce sulfuric acid.
Background technology
Current China gas washing in SA production mostly is acid production with sulphur and pyrite-based sulfuric acid production, and along with the increasing price of raw materials of sulphur and sulfurous iron ore, sulphuric acid cost raises gradually, and the explained hereafter sulfuric acid finding new raw material new is imperative.
Chinese invention patent application 200910019882.5 discloses a kind of technology utilizing magnesium sulphate to produce sulphuric acid, adopts suspension calcining and sulfur dioxide flue gas reuse to preheat magnesium sulfate raw material, adopts " double conversion and double absorption " technique simultaneously, improve SO
3the specific absorption of gas, but have also been introduced new fuel in its process, introduce possible tramp material.
Chinese invention patent application 200910265076.6 discloses a kind of novel method of producing sulfuric acid, and the method adds the modified step of mixed gas on the basis of conventional production methods, thus improves the specific absorption of sulfuric acid, but whole process is wayward.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes the rare valency of prior art raw material high, introduces new impurity and the too high deficiency of energy consumption, provide a kind of cost low, do not introduce impurity because of solid-fuelled use, and what energy consumption was low utilizes calcium sulfate to produce the method for sulfuric acid.
The technical scheme that the present invention solves the employing of its technical problem is: a kind of method utilizing calcium sulfate to produce sulfuric acid, comprises the following steps:
(1) be that the calcium sulphate powders of 100-3000 order (preferred 800-1200 order) joins in the container of airtight anaerobic by particle diameter, hold distilled water in container, ensure calcium sulphate powders to flood, control water temperature at 28-85 DEG C (preferred 30-40 DEG C);
The calcium sulphate powders that the preferred whiteness of described calcium sulphate powders is greater than 99%, purity is greater than 99wt%;
(2) Xiang Shuizhong add high-temperature sulfuric acid salt reducing bacteria (
desulfovibrio desulf uricans), and the pH controlling water is 6.4-7.5, regulates the acid used during pH to be hydrochloric acid, makes the SO dissolved in itself and water
4 2-react and generate H
2s;
Its reaction principle is: high-temperature sulfuric acid salt reducing bacteria (
desulfovibrio desulf uricans) under anaerobic state, using organism as electronics donor, sulfate radical is reduced to S
2-, a part is for the synthesis of microorganism cells, and major part is then with S
2-form be released to cells in vitro and H is produced in water effect
2s;
(3) Xiang Shuizhong passes into rare gas element, constantly by H
2s gas is taken out of, reduces H in solution
2the content of S;
Described rare gas element preferred nitrogen or argon gas;
(4) H will taken out of
2s gas passes in the 98wt% vitriol oil, by H
2s absorbs and changes into H
2sO
3;
(5) to H
2sO
3in pass into the oxygen of volumetric concentration>=99%, H
2sO
3be converted into H
2sO
4.
The high-temperature sulfuric acid salt reducing bacteria of the present invention's use (
desulfovibrio desulf uricans) be a kind of natural bacterial classification, be distributed widely in soil, fresh water and suitable terrestrial environment.
In the present invention, calcium sulfate can be slightly soluble in water, by controlling temperature, the pH value of whole system, the biological activity of high-temperature sulfuric acid salt reducing bacteria can be brought up to optimum value, along with the carrying out of reaction, and SO in water
4 2-the concentration of ion reduces, and calcium sulfate can constantly dissolve, and maintains continuing of reacting and carries out.High-temperature sulfuric acid salt reducing bacteria can by SO by chemical reaction
4 2-be converted into H
2s, H
2s is slightly soluble in water, then can by H by passing into inert gas flow wherein
2s constantly takes out of, also reduces H simultaneously
2the meltage of S in water, ensures the activity of high-temperature sulfuric acid salt reducing bacteria.The H be drawn out of
2s is H by vitriol oil sorption enhanced
2sO
3, it is further oxidized to sulfuric acid by high-concentration oxygen.
Present invention employs high-temperature sulfuric acid salt reducing bacteria (
desulfovibrio desulf uricans) as bridge, the calcium sulfate being slightly soluble in water being converted into sulfuric acid, whole process does not introduce secondary impurities, and the hydrogen sulfide 100% of generation absorbs, energy-conserving and environment-protective.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
High-temperature sulfuric acid salt reducing bacteria described in following embodiment (
desulfovibrio desulf uricans) all take from Salt Lake In Yuncheng Region of Shanxi.
Embodiment 1
The present embodiment comprises the following steps:
(1) be that 1000 object calcium sulphate powders join in the container of airtight anaerobic by particle diameter, hold distilled water in container, ensure calcium sulphate powders to flood, control water temperature at 65 DEG C;
Described calcium sulfate is the calcium sulfate of whiteness 99.1%, purity 99.2wt%;
(2) Xiang Shuizhong adds high-temperature sulfuric acid salt reducing bacteria, and is 6.8 ± 0.2 with the pH of hydrochloric acid control water, makes the SO dissolved in itself and water
4 2-react and generate H
2s;
(3) Xiang Shuizhong passes into nitrogen, constantly by H
2s gas is taken out of, reduces H in solution
2the content of S;
(4) H will taken out of
2pass in S in the vitriol oil of 98wt%, by H
2s absorbs and changes into H
2sO
3;
(5) to H
2sO
3in pass into the oxygen that volumetric concentration is 99%, H
2sO
3be converted into H
2sO
4.
In the present embodiment, by controlling temperature, the pH value of whole system, can by high-temperature sulfuric acid salt reducing bacteria (
desulfovibrio desulf uricans) biological activity bring up to optimum value, along with reaction carry out SO in water
4 2-the concentration of ion reduces, and calcium sulfate can constantly dissolve, and maintains continuing of reacting and carries out.High-temperature sulfuric acid salt reducing bacteria (
desulfovibrio desulf uricans) can by SO by chemical reaction
4 2-be converted into H
2s, H
2s is slightly soluble in water, then can by H by passing into inert gas flow wherein
2s constantly takes out of, also reduces H simultaneously
2the meltage of S in water, guarantee high-temperature sulfuric acid salt reducing bacteria (
desulfovibrio desulf uricans) activity.The H be drawn out of
2s is H by vitriol oil sorption enhanced
2sO
3, it is further oxidized to sulfuric acid by high-concentration oxygen.
The whole process of the present embodiment does not introduce any secondary impurities, and the hydrogen sulfide 100% of generation absorbs, energy-conserving and environment-protective.
Embodiment 2
The present embodiment comprises the following steps:
(1) be that 2500 object calcium sulphate powders join in the container of airtight anaerobic by particle diameter, hold distilled water in container, ensure calcium sulphate powders to flood, control water temperature at 36 DEG C;
Described calcium sulfate is the calcium sulfate of whiteness 99.1%, purity 99.2wt%;
(2) Xiang Shuizhong add high-temperature sulfuric acid salt reducing bacteria (
desulfovibrio desulf uricans), and be 6.8 ± 0.2 with the pH of hydrochloric acid control water, make the SO dissolved in itself and water
4 2-react and generate H
2s;
(3) Xiang Shuizhong passes into nitrogen, constantly by H
2s gas is taken out of, reduces H in solution
2the content of S;
(4) H will taken out of
2pass in S in the vitriol oil of 98wt%, by H
2s absorbs and changes into H
2sO
3;
(5) to H
2sO
3in pass into the oxygen that volumetric concentration is 99%, H
2sO
3be converted into H
2sO
4.
Claims (5)
1. utilize calcium sulfate to produce a method for sulfuric acid, it is characterized in that, comprise the following steps:
(1) be that 100-3000 object calcium sulphate powders joins in the container of airtight anaerobic by particle diameter, hold distilled water in container, ensure calcium sulphate powders to flood, control water temperature at 28-85 DEG C;
(2) Xiang Shuizhong adds high-temperature sulfuric acid salt reducing bacteria
desulfovibrio desulf uricans, and the pH controlling water is 6.4-7.5, regulates the acid used during pH to be hydrochloric acid, makes the SO in itself and water
4 2-react and generate H
2s;
(3) Xiang Shuizhong passes into rare gas element, constantly by H
2s gas is taken out of, reduces H in solution
2the content of S;
(4) H will taken out of
2s gas passes in the 98wt% vitriol oil, by H
2s absorbs and changes into H
2sO
3;
(5) to H
2sO
3in pass into the oxygen of volumetric concentration>=99%, H
2sO
3be converted into H
2sO
4.
2. calcium sulfate according to claim 1 produces the method for sulfuric acid, it is characterized in that, in step (1), described calcium sulphate powders is the calcium sulfate that whiteness is greater than 99%, purity is greater than 99wt%.
3. calcium sulfate according to claim 1 and 2 produces the method for sulfuric acid, and it is characterized in that, in step (1), the order number of described calcium sulphate powders is 800-1200 order.
4. calcium sulfate according to claim 1 and 2 produces the method for sulfuric acid, and it is characterized in that, in step (1), described water temperature is 30-40 DEG C.
5. calcium sulfate according to claim 1 and 2 produces the method for sulfuric acid, and it is characterized in that, in step (3), described rare gas element is nitrogen or argon gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210406759.0A CN102874770B (en) | 2012-10-23 | 2012-10-23 | Method for producing sulfuric acid from calcium sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210406759.0A CN102874770B (en) | 2012-10-23 | 2012-10-23 | Method for producing sulfuric acid from calcium sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102874770A CN102874770A (en) | 2013-01-16 |
| CN102874770B true CN102874770B (en) | 2015-05-06 |
Family
ID=47476335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210406759.0A Active CN102874770B (en) | 2012-10-23 | 2012-10-23 | Method for producing sulfuric acid from calcium sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102874770B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113957273B (en) * | 2021-10-24 | 2022-12-20 | 崇义章源钨业股份有限公司 | Method for efficiently decomposing calcium sulfate by hydrochloric acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1245759A (en) * | 1967-11-08 | 1971-09-08 | Douglas Coghill | Production of sulphur from calcium and/or sodium sulphate |
| NL9301000A (en) * | 1993-06-10 | 1995-01-02 | Pacques Bv | Method for the purification of waste water containing sulphide. |
| CN101003364A (en) * | 2007-01-22 | 2007-07-25 | 桂林工学院 | Process for recovering elemental sulfur from molasses alcohol wastewater |
-
2012
- 2012-10-23 CN CN201210406759.0A patent/CN102874770B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102874770A (en) | 2013-01-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107445209B (en) | Method for preparing saturated manganese sulfate slurry and manganese sulfate by removing manganese dithionate in pyrolusite slurry leaching solution | |
| CN106400049B (en) | A kind of method of sulfide ore tailings recycling | |
| CN105176614A (en) | Microbial electrochemical in-situ biogas desulfurization method | |
| US20220135425A1 (en) | Method for Co-Producing Synthetical Rutile and Polymeric Ferric Sulfate with Waste Sulfuric Acid | |
| CN107586951B (en) | A kind of method that manganese, iron isochronous resources utilize in low-grade manganese carbonate ore | |
| CN107804861A (en) | A kind of method that battery-level lithium carbonate is manufactured using industrial level lithium carbonate | |
| CN101717956A (en) | Method for preparing electrolytic manganese metal electrolytic solution by pyrolusite water law | |
| CN103579608A (en) | Preparation method of electrolytic manganese dioxide for positive material-lithium manganate of lithium battery | |
| CN109761251A (en) | A method of lithium hydroxide is prepared using waste and old lithium ion battery | |
| CN102815730B (en) | Oxidation sweetening-the magnetization of a kind of high-sulfur bauxite removes ferrum preprocess method | |
| CN110052099A (en) | A kind of method of sulfur-containing smoke gas biochemical de-sulfur and sulphur recovery | |
| CN104152943B (en) | Device and method for preparing ammonium persulphate with ammonia and urea solution flue gas purified absorption solution | |
| CN102874770B (en) | Method for producing sulfuric acid from calcium sulfate | |
| CN110331284A (en) | A method of electrolytic manganese is prepared using pyrolusite | |
| CN104313055B (en) | Microbial preparation method of strontium carbonate | |
| CN106241889B (en) | A kind of preparation method of solid sulphuric acid iron | |
| CN109326836A (en) | Enhance CO using saltcake2The method and its battery of mineralising battery electricity generation performance | |
| CN110358936A (en) | A method of electrolytic manganese dioxide is prepared using pyrolusite | |
| CN110183682A (en) | A kind of method that lignite thermal oxide improves Humic Acid Production Rate | |
| CN100497680C (en) | New method for extracting nickel from enriched ore of nickel sulfide | |
| Pan et al. | Cleaner production of ammonium poly-vanadate by membrane electrolysis of sodium vanadate solution: The effect of membrane materials and electrode arrangements | |
| CN112569754B (en) | Bioelectrochemical reaction device and gas purification method | |
| CN107381646B (en) | The method for preparing mangano-manganic oxide using acid-soluble manganese ore recycled based on sulphur, ammonia | |
| CN103539207B (en) | A kind of preparation method of red iron oxide | |
| CN106757119A (en) | One kind is for realizing CO2The electro-chemical systems that capture is sealed up for safekeeping with mineralising |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160728 Address after: An Industrial Park Economic Development Zone, Changde City, Hunan province Linli County 415200 Patentee after: Hunan Fu Xiang new type building material Co., Ltd. Address before: 410005, 12 floor, Haidong mansion, Furong Road, Changsha, Hunan Patentee before: Liu Liwen |