CN100436309C - Decoloring and purifying process for coke over gas desulfurized by-product coarse sulfur - Google Patents
Decoloring and purifying process for coke over gas desulfurized by-product coarse sulfur Download PDFInfo
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- CN100436309C CN100436309C CNB2003101146271A CN200310114627A CN100436309C CN 100436309 C CN100436309 C CN 100436309C CN B2003101146271 A CNB2003101146271 A CN B2003101146271A CN 200310114627 A CN200310114627 A CN 200310114627A CN 100436309 C CN100436309 C CN 100436309C
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Abstract
The present invention relates to a process for discoloring and purifying coarse sulfur as desulphurization byproducts of coke oven gas. The present invention is characterized in that water is used for eliminating inorganic salt impurities in the coarse sulphur; then, organic solvents are used for dissolving the sulphur; undissolved organic substance impurities are removed, and high-quality sulphur products with 95 to 99% of carbon are obtained after filter liquor is cooled and crystallized.
Description
Technical field
The invention belongs to the coke chemicals manufacture field, specifically the sulphur that removes in the coke(oven)gas is carried out the processing method of decolorizing purification.
Background technology
Produce a large amount of hydrogen sulfide in refining of petroleum and gas purifying process, industrial old this method of gram that generally adopts is handled the sour gas that contains hydrogen sulfide, and this method has only the H of working as
2S: SO
2Be 2: 1 o'clock, could obtain peak rate of conversion.
Be alkali source at present with ammonia, HPF is that the coke-oven gas wet desulphurization production technique of catalyzer is: after precooling, enter the absorption tower from the bottom, absorption tower, with the top-down ammonia sweetening agent counter current contact mass transfer that contains by the pretreated coal gas of electrically trapped tar oil.The desulfurization rich solution goes out to enter reactive tank from tower bottom flow, sends into regenerator column by recycle pump.Pressurized air is sent into from the regenerator column bottom, carries out oxidation regeneration in regenerator column.
Sulfuric acid liquid after the regeneration returns sulfuric acid tower and recycles.The stream sulphur foam that regeneration generates in the regenerator column is from flowing into the sulphur foam chute, and after stirring clarification, clear liquid returns reactive tank, and the sulphur foam is put into sulfur melting kettle, pack outward transport behind the molten sulfur cooling forming.
General coke-oven plant sulfur removal technology desulfuration efficiency has only about 40%, and the sulphur sulphur content is only between (30～50) %.Owing to contain impurity such as tar, naphthalene in the coke-oven gas, be difficult to remove with usual way, sulphur is because of containing plurality of impurities, and color is darker, and is second-rate, and influence is sold.
Summary of the invention
By analysis to desulfurization and regenerative process, can think and cause the darker major cause of sulphur color and luster to cause by two portions impurity, first inorganic salt impurity comprises by product sulphite, vitriol, sulfur hydrogen salt, prussiate of sweetening process and regenerative process etc.; Another part is an organic impurity, comprises by products such as tar and organosulfur.
For removing above-mentioned two classes impurity of different nature, the inventor proposes to remove inorganic salt impurity and use organic solvent dissolution sulphur with water dissolution, remove the technical scheme that two step of not dissolved organic impurity operation combines, with realization the thick sulphur of coke oven gas desulfurization by-product is pulverized with pulverizer, put into water-soluble groove, add warm water, under condition of normal pressure, stir, water miscible inorganic salt impurity is removed in dissolving, leave standstill and carry out solid-liquid separation, remove the aqueous solution, isolated solid sulfur is sent in the reactor, add the selected organic solvent that is fit to, sulphur is all dissolved, and the solid organic matters impurity that elimination is not dissolved is lowered the temperature filtrate again, be crystallizable sulfur product of separating out behind the decolorizing purification, its purity can reach 95～99%.
The described suitable organic solvent of aforementioned technology mainly is to select the non-polar organic solvent good to the sulphur solubility property for use, is generally C
1～C
4Substitutive derivative, preferred organic solvents is CS
2, C
2HCl
3, CCl
4Deng.
The processing parameter of above-mentioned technological process is as follows:
1. thick sulphur sulphur content (30～50) %,
2. water-soluble water temperature (70～90) in poor ℃
3. the consumption of water is 2～4 times of thick sulphur weight
4. stirring and dissolving time (1～2) hour
5. time of repose (3～5) hour
6. the consumption of organic solvent is thick sulphur weight (20～40) %
7. the pressure of dissolution of sulphur reactor (0.3～0.8) MP
a
8. the temperature (110～140) in the dissolution of sulphur reactor ℃
9. dissolution of sulphur time (5～10) hour
10. sulphur Tc (20～30) ℃
Embodiment
Embodiment one:
The thick sulphur 100k that will come out from desulfurization post sulfur melting kettle between coke-oven plant's recovery vehicle
g, sulphur content 30-50% pulverizes with crusher, puts into dissolving tank, adds 70 ℃ warm water 200k
g, under condition of normal pressure, to stir 1 hour, water-soluble big inorganic impurity is removed in dissolving, leaves standstill 3 hours, adopts common solid-liquid separation technique to separate, and sulphur enters in the reactor, adds CS then in reactor
2k
g, at 0.5MP
a, 120 ℃ of following dissolution of sulphur 8 hours, the undissolved organic impurity of elimination; Filtrate is cooled to 20 ℃ of decrease temperature crystallines again, can obtain purity and be 95～99% sulfur product.
-embodiment two:
The thick sulphur 100k that will come out from desulfurization post sulfur melting kettle between coke-oven plant's recovery vehicle
g, sulphur content 30-50% pulverizes with crusher, puts into dissolving tank, adds 80 ℃ warm water 400k
g, under condition of normal pressure, to stir 2 hours, water-soluble big inorganic impurity is removed in dissolving, leaves standstill 5 hours, adopts common solid-liquid separation technique to separate, and sulphur enters in the reactor, adds C then in reactor
2HCl
340k
g, at 0.6MP
a, 135 ℃ of following dissolution of sulphur 10 hours, the undissolved organic impurity of elimination; Filtrate is cooled to 25 ℃ of decrease temperature crystallines again, can obtain purity and be 95～99% sulfur product.
Claims (1)
1. the decolorizing purification technology of the thick sulphur of coke oven gas desulfurization by-product is characterized in that removing inorganic salt impurity and using organic solvent CS with water dissolution
2Or C
2HCl
3Dissolution of sulphur removes two step of not dissolved organic impurity process combined method;
The decolorizing purification processing step is: thick sulphur is pulverized put into water-soluble groove, add warm water, stir, inorganic salt impurity is removed in dissolving, isolates solid sulfur and puts into reactor, adds organic solvent, sulphur is dissolved, the organic impurities that elimination is not dissolved with the filtrate cooling, separates out the sulphur crystallization;
The decolorizing purification processing parameter is as follows:
Thick sulphur sulphur content 30～50%,
70～90 ℃ of water temperatures in the water-soluble groove,
The consumption of water is 2～4 times of thick sulphur weight,
1～2 hour stirring and dissolving time,
Time of repose 3～5 hours,
The consumption of organic solvent is 20～40% of a thick sulphur weight,
Pressure 0.3～the 0.8MPa of dissolution of sulphur reactor,
110～140 ℃ of temperature in the dissolution of sulphur reactor,
5～10 hours dissolution of sulphur time,
20～30 ℃ of dissolution of sulphur temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101146271A CN100436309C (en) | 2003-12-22 | 2003-12-22 | Decoloring and purifying process for coke over gas desulfurized by-product coarse sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101146271A CN100436309C (en) | 2003-12-22 | 2003-12-22 | Decoloring and purifying process for coke over gas desulfurized by-product coarse sulfur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554572A CN1554572A (en) | 2004-12-15 |
| CN100436309C true CN100436309C (en) | 2008-11-26 |
Family
ID=34337170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101146271A Expired - Fee Related CN100436309C (en) | 2003-12-22 | 2003-12-22 | Decoloring and purifying process for coke over gas desulfurized by-product coarse sulfur |
Country Status (1)
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|---|---|
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112093778A (en) * | 2020-10-15 | 2020-12-18 | 中冶焦耐(大连)工程技术有限公司 | Treatment process for by-product low-quality sulfur in coke oven gas desulfurization process |
| CN114477098A (en) * | 2021-12-17 | 2022-05-13 | 湖南道安环保科技有限公司 | Purification process of byproduct sulfur in HPF (high pressure fluidized bed) desulfurization |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2189234A (en) * | 1986-04-17 | 1987-10-21 | Elf Aquitaine | Process for the production of elementary sulphur from an iron sulphide mineral |
| US5049370A (en) * | 1989-09-26 | 1991-09-17 | Ultraclean Incorporated | Process and apparatus for purifying elemental sulfur carried in an aqueous cake |
| CN1073657A (en) * | 1991-12-22 | 1993-06-30 | 山西大学 | The method of purification of sulphur |
| CN1260321A (en) * | 1999-11-10 | 2000-07-19 | 安泰科技股份有限公司 | Decontamination method for liquid sulphur in acid production with sulphur |
| US20020081261A1 (en) * | 2000-12-21 | 2002-06-27 | Institut Francais Du Petrole | Process for the purification of sulfur |
-
2003
- 2003-12-22 CN CNB2003101146271A patent/CN100436309C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2189234A (en) * | 1986-04-17 | 1987-10-21 | Elf Aquitaine | Process for the production of elementary sulphur from an iron sulphide mineral |
| US5049370A (en) * | 1989-09-26 | 1991-09-17 | Ultraclean Incorporated | Process and apparatus for purifying elemental sulfur carried in an aqueous cake |
| CN1073657A (en) * | 1991-12-22 | 1993-06-30 | 山西大学 | The method of purification of sulphur |
| CN1260321A (en) * | 1999-11-10 | 2000-07-19 | 安泰科技股份有限公司 | Decontamination method for liquid sulphur in acid production with sulphur |
| US20020081261A1 (en) * | 2000-12-21 | 2002-06-27 | Institut Francais Du Petrole | Process for the purification of sulfur |
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|---|---|
| CN1554572A (en) | 2004-12-15 |
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Granted publication date: 20081126 Termination date: 20131222 |