CN100595264C - Coupling method between making hydrogen and desulfurizing petroleum coking gas - Google Patents
Coupling method between making hydrogen and desulfurizing petroleum coking gas Download PDFInfo
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- CN100595264C CN100595264C CN200710064514A CN200710064514A CN100595264C CN 100595264 C CN100595264 C CN 100595264C CN 200710064514 A CN200710064514 A CN 200710064514A CN 200710064514 A CN200710064514 A CN 200710064514A CN 100595264 C CN100595264 C CN 100595264C
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Abstract
The present invention discloses method of coupling the hydrogen making reaction and desulfurizing reaction of gasifying petroleum coke. The present invention features that the mixture of petroleum coke and sodium carbonate or potassium carbonate is added into the reactor and gasified with the introduced water vapor to obtain synthesized gas with high hydrogen content, and of the synthesized gas, part is returned to the reactor through the water vapor inlet for hydrogenating and desulfurizing while the rest is further purified. After some time of gasification reaction, the rest solid product isexhausted for acid pickling, water washing and drying to obtain petroleum coke with low sulfur content.
Description
Technical field
The present invention relates to smelt, electric power and chemical industry be to the utilization of refinery coke, by adopting effective processing method the sulphur content in the refinery coke reduced, to improve postorder workshop section quality product, reduce to pollute.
Background technology
Because environment and healthy requirement reduce the top priority that sulphur content has become the refinery coke deep processing from the source.High-temperature calcination is desulfurizing petrol coke means commonly used, surpasses 1000 ℃ high temperature, not only needs to expend higher energy, and needs to adopt expensive high temperature material to provide closed environment for the processing of refinery coke.In addition, the flue gas that produces in the calcining can not reuse as the energy, also must consider it is handled, and prevents the pollution of the environment.In order to strengthen sweetening effectiveness, U.S. Pat 3598528A proposes refinery coke is carried out preheating, preoxidation earlier, make it to take place partial gasification, its internal structure is also changed, and then pretreated refinery coke sent in the hydrogenator, introduce the synthetic gas that gasifying reactor produces and carry out hydrogenating desulfurization.US3595965A is carrying out metal carbonyl with the refinery coke of preheating, preoxidation on the basis of said process.The processing method of these two kinds of desulfurizing petrol cokes comprises several operations such as preheating, preoxidation, metal carbonyl, hydrogenating desulfurization and refinery coke gasification, and reactor also needs 4-5, has increased the complicacy of flow process greatly.English Patent GB2143844A improves the refinery coke gasification process, thinks that alkaline carbonate has good katalysis.Characteristics of the present invention are to make the gasification reaction of refinery coke and hydrodesulfurization reaction to carry out in same reactor, and the katalysis that utilizes alkaline carbonate strengthens refinery coke internal structure strength at break, make the easier fracture of carbon-sulfide linkage, to obtain the more refinery coke of low sulfur content.
Summary of the invention
The objective of the invention is to gasification hydrogen-producing and desulfurization are combined, thereby provide one to overlap the sulphur that can remove at a lower temperature in the refinery coke, and can produce the processing method of high value added product-hydrogen.
This method is: refinery coke and yellow soda ash or salt of wormwood were mixed by 1: 1 add in the reactor, feed water vapor and be heated to 500～800 ℃ of gasifications, the synthetic gas that produces goes out behind the device one the tunnel and turns back to the water vapor import and enter reactor, and another road is gone to separate and obtained High Purity Hydrogen; Behind the gasification reaction 0.5～8 hour, the solid materials in the reactor is discharged from pickling, washing, and dry, obtains the refinery coke of low sulfur content.Synthetic gas also contains methane, carbonic acid gas, carbon monoxide based on hydrogen.The used acid of pickling is hydrochloric acid, and pickling temperature is 80 ℃.Refinery coke and other solid materialss washing separation temperature are 80 ℃.The refinery coke drying temperature is greater than 100 ℃.
Specific implementation process is as follows: in high sulfur petroleum coke and yellow soda ash or salt of wormwood mixing adding reactor 1, feed water vapor in 500～800 ℃ of gasifications down of temperature, the synthetic gas that obtains goes out reactor 1, enters storage tank 3 after condenser 2 is sloughed water.The synthetic gas that took off behind the water divides two-way, and a pass returns in the reactor 1 and contact with refinery coke, infiltrates removing of the inner promotion of refinery coke sulphur, generation H
2Product such as S and COS; Another road enters hydrogen purification apparatus 4 and obtains highly purified hydrogen.And yellow soda ash or salt of wormwood can play fixedly H on the one hand
2The effect of product such as S and COS; Because its alkalescence effect promotes the generation of tar, destroy the structure of refinery coke on the other hand, help removing of organosulfur.Behind the gasification reaction 0.5～8 hour, remaining solid product is entered a large amount of yellow soda ash (or potassium) of washing separator 5 first flush awaies, enter the remaining alkali of pickling separator 6 further flush awaies then, and be soluble salt, the reduction ash content original insoluble impurity conversion.In addition, yellow soda ash or salt of wormwood institute fixed sulphur also is converted into H
2S discharges, and separates with solid product.Enter the acid of washing separator 7 flush away refinery coke surface attachment and the soluble salt of formation again, enter moisture eliminator 8 at last and obtain petroleum coke with low sulfur content carrying out drying more than 100 ℃.
Description of drawings
Fig. 1 is refinery coke gasification hydrogen-producing provided by the invention and desulfurization coupling technique schematic flow sheet.
Each numbering is described as follows in the accompanying drawing:
1 gasification hydrogen-producing and desulfurization coupled reactor; 2 condensers; 3 synthetic gas storage tanks; 4 hydrogen purification apparatus; 5 washing separators; 6 pickling separators; 7 washing separators; 8 moisture eliminators.
Specific implementation method
The present invention illustrates with following example, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Get certain refinery refinery coke 5g, its ultimate analysis is C 89.08%, and H 3.25%, and N 1.86%, and S 3.6%.Be milled to below 100 orders, mix by 1: 1 with sodium carbonate particle, add in the reactor 1, feed water vapour, flow is 200ml/min, and temperature of reactor is 750 ℃, and the reaction times is 6 hours.Reactor outlet gas cooling back sampling is analyzed generating gas, and gas composition is by removing H
2O and N
2Calculate H
248%, CH
422%, CO 12%, CO
213%, C
2H
43%, C
2H
62%, H
2S 5ppm and NH
3100ppm.After reaction finished, the solid product in the reactor 1 was sloughed most of yellow soda ash with 80 ℃ of washings earlier half an hour, is 80 ℃ of following pickling 1 hour with hydrochloric acid in temperature then, washed 2 hours flush away hydrochloric acid with 80 ℃ again, at last drying 2 hours under 120 ℃.The desulfurizing petrol coke rate is 65.3%.
Basic identical with example 1, the flow that difference is to feed water vapour is 160ml/min, simultaneously, mixes the hydrogen of example 1 flow 20%, and promptly flow is 40ml/min.The desulfurizing petrol coke rate is 72.5%.
Basic identical with example 1, the flow that difference is to feed water vapour is 120ml/min, simultaneously, mixes the hydrogen of example 1 flow 40%, and promptly flow is 80ml/min.The desulfurizing petrol coke rate is 82.8%.
Basic identical with example 1, the flow that difference is to feed water vapour is 40ml/min, simultaneously, mixes the hydrogen of example 1 flow 80%, and promptly flow is 160ml/min.The desulfurizing petrol coke rate is 92.7%.
Basic identical with example 1, the flow that difference is to feed hydrogen is 200ml/min.The desulfurizing petrol coke rate is 96.4%.
Claims (5)
1. refinery coke gasification reaction hydrogen manufacturing and desulphurization reaction coupled method, concrete step is: refinery coke and yellow soda ash or salt of wormwood were mixed by 1: 1 add in the reactor, feed water vapor and be heated to 500～800 ℃ of gasifications, the synthetic gas that produces goes out behind the device one the tunnel and turns back to the water vapor import and enter reactor, and another road is gone to separate and obtained High Purity Hydrogen; Behind the gasification reaction 0.5～8 hour, the solid materials in the reactor is discharged from pickling, washing, and dry, obtains the refinery coke of low sulfur content.
2. according to claim 1 described refinery coke gasification reaction hydrogen manufacturing and desulphurization reaction coupled method, it is characterized in that synthetic gas also contains methane, carbonic acid gas, carbon monoxide based on hydrogen.
3. according to claim 1 described refinery coke gasification reaction hydrogen manufacturing and desulphurization reaction coupled method, it is characterized in that the used acid of pickling is hydrochloric acid, pickling temperature is 80 ℃.
4. according to claim 1 described refinery coke gasification reaction hydrogen manufacturing and desulphurization reaction coupled method, it is characterized in that refinery coke and other solid materialss washing separation temperature are 80 ℃.
5. according to claim 1 described refinery coke gasification reaction hydrogen manufacturing and desulphurization reaction coupled method, it is characterized in that the refinery coke drying temperature is greater than 100 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710064514A CN100595264C (en) | 2007-03-16 | 2007-03-16 | Coupling method between making hydrogen and desulfurizing petroleum coking gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710064514A CN100595264C (en) | 2007-03-16 | 2007-03-16 | Coupling method between making hydrogen and desulfurizing petroleum coking gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101020854A CN101020854A (en) | 2007-08-22 |
| CN100595264C true CN100595264C (en) | 2010-03-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200710064514A Expired - Fee Related CN100595264C (en) | 2007-03-16 | 2007-03-16 | Coupling method between making hydrogen and desulfurizing petroleum coking gas |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2716135C (en) * | 2008-02-29 | 2013-05-28 | Greatpoint Energy, Inc. | Particulate composition for gasification, preparation and continuous conversion thereof |
| CN102417835A (en) * | 2011-10-13 | 2012-04-18 | 华东理工大学 | Method for preparing hydrogen-rich gas by performing catalytic gasification on petroleum coke |
| CN104651011A (en) * | 2015-02-05 | 2015-05-27 | 昆明理工大学 | Method for catalyzing deep desulfurization of high sulfur petroleum coke by using alkali carbonate |
| CN105060270A (en) * | 2015-07-29 | 2015-11-18 | 中南大学 | Technology for improving petroleum coke desulfurization efficiency in ammonia gas atmosphere |
| CN107384503A (en) * | 2017-08-09 | 2017-11-24 | 昆明理工大学 | A kind of sulfur method of petroleum coke |
| CN114606016A (en) * | 2022-03-18 | 2022-06-10 | 昆明理工大学 | Method for directional separation and desulfurization of high-sulfur petroleum coke by calcination and conversion |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3598528A (en) * | 1969-06-27 | 1971-08-10 | Texaco Inc | Purification of petroleum coke |
| GB2143844A (en) * | 1983-07-23 | 1985-02-20 | Metallgesellschaft Ag | Process for operating a plant for gasifying solid fuels |
| CN1923975A (en) * | 2005-09-03 | 2007-03-07 | 未来能源有限公司 | Gasification method and device for producing synthesis gas |
-
2007
- 2007-03-16 CN CN200710064514A patent/CN100595264C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3598528A (en) * | 1969-06-27 | 1971-08-10 | Texaco Inc | Purification of petroleum coke |
| GB2143844A (en) * | 1983-07-23 | 1985-02-20 | Metallgesellschaft Ag | Process for operating a plant for gasifying solid fuels |
| CN1923975A (en) * | 2005-09-03 | 2007-03-07 | 未来能源有限公司 | Gasification method and device for producing synthesis gas |
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| CN101020854A (en) | 2007-08-22 |
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Granted publication date: 20100324 Termination date: 20160316 |