CN1978034A - Improved vanadium-base wet-type oxidation desulfurizing method - Google Patents
Improved vanadium-base wet-type oxidation desulfurizing method Download PDFInfo
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- CN1978034A CN1978034A CN 200510122917 CN200510122917A CN1978034A CN 1978034 A CN1978034 A CN 1978034A CN 200510122917 CN200510122917 CN 200510122917 CN 200510122917 A CN200510122917 A CN 200510122917A CN 1978034 A CN1978034 A CN 1978034A
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Abstract
The present invention discloses an improved vanadium base wet oxidative desulfurization method, belonging to the field of gas purification technology. The desulfurizing agent is characterized by that an additive is added into the wet oxidative desulfurizing liquor, said additive can raise desulfurization speed and efficiency.
Description
Technical field
The invention belongs to the gas purification technique field, a kind of method that removes hydrogen sulfide from admixture of gas the present invention relates to a kind of improvement of vanadium-base wet-type oxidation deoxidized desulfurization method specifically.
Background technology
As everyone knows, sulfur-bearing raw material of industry gas can cause pipeline, equipment corrosion, catalyst poisoning; The discharging of sulphur-containing exhaust gas can cause serious environmental problem.
The method that removes hydrogen sulfide mainly contains: (1) dry desulfurization, and as iron oxide process, zinc oxide method and activated carbon method etc.(2) hydramine method.(3) wet oxidation process is as ADA method, tannin extract method, MSQ method, PDS method and complex iron etc.(4) physical solvent process such as low-temp methanol method, NHD method etc.
Wet oxidation process has advantages such as can directly hydrogen sulfide being changed into sulphur, thereby is widely used in China's coal chemical technology.Wherein use the most extensive with vanadium-base wet-type oxidation method ADA method, especially tannin extract method.
Along with the develop rapidly of modern chemical industry, require more and more higher to desulfurization in the production; In addition, production capacity improves on the one hand in order to strengthen competitiveness in many enterprises, uses sulphur coal (oil) on the other hand, thereby makes desulfurizer become bottleneck in the production.Existing wet oxidation process desulfur technology is difficult under the condition of not changing former desulfurizer, increases substantially the desulphurizing ability of device and improves desulfurization purifying degree simultaneously.
Summary of the invention
The objective of the invention is to improve the desulfurization and the regeneration efficiency of existing Wet-type oxidation sweetening technology (as ADA method, tannin extract method), reduce the side reaction production rate, improve sulfur recovery rate; Adopt present technique, only need in former doctor solution, to add a small amount of additive, do not change original device, just can increase substantially the desulphurizing ability of original device, improve desulfurization purifying degree simultaneously.
The technical solution used in the present invention is the method that adds additive in former desulfuration solution, to reach desulphurizing ability that improves device and the purpose that improves desulfurization purifying degree.
What this method adopted is to add additive in wet oxidation process (as ADA method, tannin extract method) doctor solution, and the doctor solution that adds additive has following feature: the speed of (1) solution absorbing hydrogen sulphide improves; (2) reproduction speed of solution obviously improves; (3) sulphur of analysing of solution is accelerated.
Additive is one or both a mixture of one or more and vanadium, ferriferous oxide or salt in citric acid, tartaric acid, ethylenediamine tetra-acetic acid, oxine sodium sulfonate, the p-methyl benzenesulfonic acid.
Additive can be that one or more are added in the former doctor solution, and its addition is 0.02 grams per liter～30 grams per liters why, and optimal addn is 0.3 grams per liter～15 grams per liters.
The absorption of doctor solution and regeneration temperature are 25 ℃～55 ℃, and the pH value of desulfuration solution is 6.5～9.5.
In ADA, tannin extract desulfurizing solution, add the said additive of the present invention, need not change original device, just can increase substantially the desulphurizing ability of original device, improve desulfurization purifying degree simultaneously.
The specific embodiment
Below in conjunction with example with further elaboration content of the present invention.
Example 1: join in the tannin extract desulfurizing solution with the said additive of the present invention, remove hydrogen sulfide in the conversion gas.
(1) additive is composed as follows:
Citric acid 3 grams per liters
Iron chloride 2 grams per liters
P-methyl benzenesulfonic acid 1 grams per liter
(2) process conditions
Air blow strength: 85 meters
3/ rice
2Hour
Recovery time: 25 minutes
Regeneration temperature: 25～45 ℃
(3) desulfurized effect
As seen from Table 1, when gas liquid ratio 257, the present technique desulfuration efficiency is better than tannin extract, under the identical condition, and H in the purified gas
2S content reduces about 50%.Therefore, use present technique can increase substantially the desulfurization purifying degree of tannin extract device.
Table 1
| Semiwater gas amount/1h -1 | Gas liquid ratio | Present technique | Tannin extract | ||
| Import H 2S /g·m -3 | Purified gas H 2S /mg·m -3 | Import H 2S /mg·m -3 | Purified gas H 2S /mg·m -3 | ||
| 1400 | 257 | 0.688 | 85 | 0.678 | 150 |
| 1400 | 257 | 0.465 | 23 | 0.477 | 75 |
Example 2: join in the ADA doctor solution with the said additive of the present invention, remove hydrogen sulfide in the conversion gas.
(1) additive is composed as follows:
Di-iron trioxide 2 grams per liters
Tartaric acid 1.5 grams per liters
Ethylenediamine tetra-acetic acid 1 grams per liter
Oxine sodium sulfonate 2 grams per liters
(2) process conditions
Air blow strength: 85 meters
3/ rice
2Hour
Recovery time: 25 minutes
Regeneration temperature: 25～45 ℃
(3) desulfurized effect
By table 2 as seen, it be～260 constant keeping gas liquid ratio,, the degree of purification of present technique is much better than ADA, illustrates that the use present technique can increase substantially the desulfurization purifying degree of ADA solution.
Table 2
| Semiwater gas amount/1/h | Present technique | ADA | ||
| Import H 2S /g·m -3 | Purified gas H 2S /mg·m -3 | Import H 2S /mg·m -3 | Purified gas H 2S /mg·m -3 | |
| 1480 | 0.654 | 67 | 0.648 | 143 |
| 1480 | 0.452 | 21 | 0.448 | 66 |
Example 3: join in the ADA doctor solution with the said additive of the present invention, remove hydrogen sulfide in the conversion gas.
(1) additive is composed as follows:
Sodium metavanadate 2 grams per liters
Tartaric acid 1.5 grams per liters
Ethylenediamine tetra-acetic acid 1 grams per liter
Oxine sodium sulfonate 2 grams per liters
(2) process conditions
Air blow strength: 85 meters
3/ rice
2Hour
Recovery time: 25 minutes
Regeneration temperature: 25～45 ℃
(3) desulfurized effect
By table 2 as seen, it be～260 constant keeping gas liquid ratio,, the degree of purification of present technique is much better than ADA, illustrates that the use present technique can increase substantially the desulfurization purifying degree of ADA solution.
Table 3
| Semiwater gas amount/1/h | Present technique | ADA | ||
| Import H 2S /g·m -3 | Purified gas H 2S /mg·m -3 | Import H 2S /mg·m -3 | Purified gas H 2S /mg·m -3 | |
| 1480 | 0.654 | 67 | 0.648 | 143 |
| 1480 | 0.452 | 21 | 0.448 | 66 |
Example 4: join in the ADA doctor solution with the said additive of the present invention, remove hydrogen sulfide in the conversion gas.
(1) additive is composed as follows:
Sodium metavanadate 2 grams per liters
Tartaric acid 1.5 grams per liters
Ethylenediamine tetra-acetic acid 1 grams per liter
Oxine sodium sulfonate 2 grams per liters
(2) process conditions
Air blow strength: 85 meters
3/ rice
2Hour
Recovery time: 25 minutes
Regeneration temperature: 25～45 ℃
(3) desulfurization regeneration effect
By table 4 as seen, additive joins in the tannin extract desulfurizing solution, and the conversion ratio that the tetravalence vanadium is oxidized to the pentavalent vanadium obviously improves.
Table 4
| Recovery time (minute) | Present technique | ADA |
| V 5+/V 4+ | V 5+/V 4+ | |
| 5 | 75％ | 50％ |
| 10 | 95％ | 80％ |
Example 5: join in the tannin extract desulfurizing solution with the said additive of the present invention, remove hydrogen sulfide in the conversion gas.
(1) additive is composed as follows:
Sodium metavanadate 2 grams per liters
Tartaric acid 1.5 grams per liters
Ethylenediamine tetra-acetic acid 1 grams per liter
Oxine sodium sulfonate 2 grams per liters
Iron chloride 0.5 grams per liter
(2) process conditions
Air blow strength: 85 meters
3/ rice
2Hour
Recovery time: 25 minutes
Regeneration temperature: 25～45 ℃
(3) desulfurized effect
By table 5 as seen, it be～260 constant keeping gas liquid ratio,, the degree of purification of present technique is much better than tannin extract, illustrates that the use present technique can increase substantially the desulfurization purifying degree of tannin extract solution.
Table 5
| Semiwater gas amount/l/h | Present technique | ADA | ||
| Import H 2S /g·m -3 | Purified gas H 2S /mg·m -3 | Import H 2S /mg·m -3 | Purified gas H 2S /mg·m -3 | |
| 1480 | 0.875 | 29 | 0.864 | 109 |
| 1480 | 0.438 | 12 | 0.433 | 60 |
Example 6: join in the tannin extract desulfurizing solution with the said additive of the present invention, remove hydrogen sulfide in the conversion gas, pass through six months the tannin extract solution and the consumption of its desulfurizing agent of tannin extract solution contrast desulfurization test that adds additive and seen Table 3, as can be seen from Table 3, the consumption of its desulfurizing agent obviously reduces behind the tannin extract solution of adding additive.
(1) additive is composed as follows:
Citric acid 3 grams per liters
Iron chloride 2 grams per liters
P-methyl benzenesulfonic acid 1 grams per liter
(3) process conditions
Air blow strength: 85 meters
3/ rice
2Hour
Recovery time: 25 minutes
Regeneration temperature: 25～45 ℃
(3) sorbent consumption
With in the conversion gas serve as the test source of the gas, in the conversion gas hydrogen sulfide content be controlled at～about 0.5, under the identical again process conditions and test period, sorbent consumption sees Table 3.
Table 6 sorbent consumption (Kg/Kg sulphur)
| Title | Na 2CO 3 | NaVO 3 | Tannin extract | Additive | The side reaction production rate |
| The tannin extract method | 0.49 | 0.09 | 0.18 | -- | 3.8％ |
| Present technique | 0.28 | 0.03 | 0.04 | 0.08 | 1.1％ |
By above-mentioned example as seen, this desulfur technology has advantages such as desulfurized effect is good, and side reaction is few, sorbent consumption is low.
Claims (4)
1. improved vanadium-base wet-type oxidation desulfurizing method, it is characterized in that adopting adding additive in doctor for wet oxidation process, this additive is one or both a mixture of one or more and vanadium, ferriferous oxide or salt in citric acid, tartaric acid, ethylenediamine tetra-acetic acid, oxine sodium sulfonate, the p-methyl benzenesulfonic acid; The additive addition is 0.02 grams per liter～30 grams per liters.
2. an improved according to claim 1 vanadium-base wet-type oxidation desulfurizing method is characterized in that the additive addition is 0.3 grams per liter～15 grams per liters.
3. an improved according to claim 1 vanadium-base wet-type oxidation desulfurizing method is characterized in that the absorption of doctor solution and regeneration temperature are 25 ℃～55 ℃, and the pH value of desulfuration solution is 6.5～9.5.
4. improved according to claim 1 vanadium-base wet-type oxidation desulfurizing method is characterized in that additive is added in tannin extract, the ADA doctor solution to use.
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| CN 200510122917 CN1978034A (en) | 2005-12-07 | 2005-12-07 | Improved vanadium-base wet-type oxidation desulfurizing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773783A (en) * | 2010-03-17 | 2010-07-14 | 南京碳环生物质科技有限公司 | Wet catalytic oxidative desulfurization method for biogas |
| CN114870571A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院大连化学物理研究所 | Hydrogen sulfide absorption liquid, preparation method thereof and method for absorbing hydrogen sulfide |
-
2005
- 2005-12-07 CN CN 200510122917 patent/CN1978034A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101773783A (en) * | 2010-03-17 | 2010-07-14 | 南京碳环生物质科技有限公司 | Wet catalytic oxidative desulfurization method for biogas |
| CN114870571A (en) * | 2022-06-06 | 2022-08-09 | 中国科学院大连化学物理研究所 | Hydrogen sulfide absorption liquid, preparation method thereof and method for absorbing hydrogen sulfide |
| CN114870571B (en) * | 2022-06-06 | 2024-02-13 | 中国科学院大连化学物理研究所 | Hydrogen sulfide absorption liquid, preparation method thereof and method for absorbing hydrogen sulfide |
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