CN101372628B - Method for producing clean fuel oil and high-purity chemical products from calcium carbide tail gas - Google Patents
Method for producing clean fuel oil and high-purity chemical products from calcium carbide tail gas Download PDFInfo
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- CN101372628B CN101372628B CN2008102316484A CN200810231648A CN101372628B CN 101372628 B CN101372628 B CN 101372628B CN 2008102316484 A CN2008102316484 A CN 2008102316484A CN 200810231648 A CN200810231648 A CN 200810231648A CN 101372628 B CN101372628 B CN 101372628B
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- gas
- oil
- calcium carbide
- tail gas
- carbide tail
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method which takes calcium carbide tail gas as raw material to prepare clean fuel oil; gas is integrated to ensure that H2: CO in the gas is equal to 1-2.1; meanwhile, after the gas is purified, qualified synthetic gas is used for synthesizing clean fuel oil under certain temperature and pressure. The method has the advantages: (1) by adopting the method, environmental pollution caused by emission of calcium carbide tail gas, and the like, can be reduced; (2) the method can be adopted for producing diesel oil and high-purity wax; (3) the waste water and tail gas generated in the invention can be both utilized, and dead catalyst is recycled by manufacturers, thus causing no environmental pollution.
Description
Technical field
The invention belongs to technical field of chemical synthesis, discarded gas ratio of the pollution that particularly a kind of utilization it has been generally acknowledged that such as coking coke(oven)gas, calcium carbide tail gas, coal-seam gas etc. are the method for producing clean fuel oil and high-purity chemical products.
Background technology
At present, utilize calcium carbide tail gas etc. to produce methyl alcohol, synthetic ammonia and other Chemicals both at home and abroad.Contain a large amount of carbon monoxide in the calcium carbide tail gas, gas is obtained qualified synthetic gas after integrating (conversion), purification and tonifying Qi, not only help to reduce and pollute, and can increase economic efficiency greatly.
Summary of the invention
The object of the present invention is to provide a kind of is the method that raw material is produced clean fuel oil and high-purity chemical products with the calcium carbide tail gas.
A kind of is the method that raw material is produced clean fuel oil and high-purity chemical products with the calcium carbide tail gas; Comprise gas integration operation, cleaning section, Fischer-Tropsch synthesis procedure; Calcium carbide tail gas is incorporated into makes H2:CO=1-2.1 in the gas, through after purifying, obtain qualified synthetic gas simultaneously; Qualified synthetic gas carries out building-up reactions and generates alkane, alkene under suitable temperature and pressure, obtain oil fuel and high-purity chemical products through after the refrigerated separation.
It is that the ratio of regulating hydrogen and carbon monoxide makes H2:CO=1-2.1 in the gas to calcium carbide tail gas process gas conversion, decarburization that gas is integrated operation.
Cleaning section is: integrating back gas employing organic sulfur hydrolyst is inorganic sulfur with tempreture organic sulphur hydrolysis; Gas is through desulfurization; Total sulfur in the gas is taken off to 0.1ppm; Remove carbonic acid gas wherein through decarbonization device again, gas purifies through deep desulfuration again, makes wherein total sulfur less than 0.02ppm.
Synthesis procedure be synthetic gas with qualified H2:CO=1～2.1 under suitable temperature and pressure, get into synthesis reactor, under catalyst action; Generate alkane, alkene; Through after the refrigerated separation, obtain wax, light oil and heavy oil, and adopt three reactors in series; Reacted gas does not circulate, and usefulness acts as a fuel; After the reaction water treatment as boiler water-filling; Wax, light oil and heavy oil obtain high purity wax and diesel oil again after refining.
Adopt fixed bed multiple reactor series and parallel form, reaction back gas is the round-robin Technology not, and synthesis pressure is 2.5～3.5MPa, and service temperature is used Fe and Co series catalysts at 200～300 ℃.
Qualified synthetic gas is preheated to reacting initial temperature, gets into synthesis reactor then and reacts; The synthetic tower exit gas is the paraffin in paraffin separator separates gas at first, then after heavy oil water cooler cooling to heavy fuel separator, isolate the heavy oil in the gas; Gas again through light oil water cooler cooling back to the light oil separator, isolate wherein light oil and water, unreacted gas to next reactor drum continues to react; The oil-water mixture of each reactor drum is after separator separates; Oil is to medial launder, and reaction water is handled the back reuse to reacting tank.
The present invention is to be the method that raw material is produced clean fuel oil with the calcium carbide tail gas, be with gas through integration, make H in the gas
2: CO=1～2.1, through after purifying, qualified synthetic gas is at synthetic fuel oil under certain temperature and pressure, under catalyst action simultaneously.Calcium carbide tail gas is changed into oil fuel, reduce the various pollutions that these gases directly burn and bring; Institute's synthetic liquid fuel belongs to clean fuel; Be characterized in low-sulfur; Do not contain any beavy metal impurity, use the mover of this fuel, its total hydrocarbon discharge index, carbon monoxide emission index, sulfide and discharged nitrous oxides index all are superior to the traditional refining and the reformation liquid fuel of existing market.The wax that is generated is claimed F-T wax, and its purity is high, and foreign matter content is low, belongs to high-purity wax, can be applicable to height, pointed collar territory, fills up the domestic production blank.The exhaust emissions of automobile also is the important source of present China topsoil.Adopting clean fuel liquid, reduce the pollution that vehicle exhaust causes, also is the inevitable outlet of liquid fuel development.The utilization of above-mentioned clean fuel oil can bring huge environmental protection effect.The present invention utilizes these gases, and oil fuel and high-purity wax product that the production existing market is good are turned waste into wealth, and meets the industry policy of country, the requirement of environmental protection policy.
Beneficial effect of the present invention:
(1) adopt the present invention can reduce the environmental pollution caused by discharge of calcium carbide tail gas etc.;
(2) adopt the present invention can produce diesel oil and high purity wax;
(3) waste water that the present invention produced and tail gas all obtain utilizing, and spent catalyst manufacturer reclaims, and can not pollute environment.
Description of drawings
Figure is a process flow sheet of the present invention.
Embodiment
Be illustrated as practical implementation technology of the present invention.With the calcium carbide tail gas is producing clean fuel oil, and this technology comprises following operation: the compression of gas, the conversion of gas, desulfurization and decarburization, smart desulfurization and deep purifying, synthetic, the oil purification of F-T.
Overall technical process is:
Calcium carbide tail gas is after overdraft; Make the ratio of hydrogen and carbon monoxide reach the desired ratio of synthetic oil through conversion, remove wherein hydrogen sulfide and carbonic acid gas to decarbonization device, remove organosulfur and inorganic sulfur in the gas through dry desulfurization; Make sulphur content in the gas less than 0.01ppm through the degree of depth again; Qualified synthetic gas is synthetic to F-T, and the synthetic product obtains light oil, heavy oil and wax through refrigerated separation, after refining, obtains diesel oil and elaboration wax.
Detailed process flow of the present invention is following:
(1) the part conversion of calcium carbide tail gas
Through purifying the calcium carbide tail gas of compression, after preheating to shift converter, after the gas cooling after the conversion to lower procedure.
(2) gas cleaning
The existence of small amount of sulfur will influence the normal use and the life-span of synthetic catalyst in the gas, before advancing to synthesize, must remove clean.
The form of sulphur is mainly H2S and a spot of COS in the gas; Therefore adopt and use organic sulfur hydrolyst that tempreture organic sulphur hydrolysis is inorganic sulfur, gas takes off to 0.1ppm the total sulfur in the gas through desulfurization; Remove carbonic acid gas wherein through decarbonization device again; Gas purifies through deep desulfuration again, makes wherein total sulfur less than 0.02ppm, satisfies the synthetic requirement of oil.
(3) Fischer-Tropsch (F-T) synthesis technique
This process using fixed bed multiple reactor series and parallel form, reaction back gas is the round-robin Technology not, and synthesis pressure is 2.5～3.5MPa, and service temperature is used Fe and Co series catalysts at 200～300 ℃.Have the quality product height, equipment is prone to the characteristics of manufacturing.
Qualified synthetic gas is preheated to reacting initial temperature, gets into synthesis reactor then and reacts.The synthetic tower exit gas is the paraffin in paraffin separator separates gas at first, then after heavy oil water cooler cooling to heavy fuel separator, isolate the heavy oil in the gas; Gas again through light oil water cooler cooling back to the light oil separator, isolate wherein light oil and water, unreacted gas to next reactor drum continues to react; The oil-water mixture of each reactor drum is after separator separates; Oil is to medial launder, and reaction water is handled the back reuse to reacting tank.Wax, heavy oil and light oil are to refining step.
The oil synthesizing process difference mainly is the reaction water that it generated with the methyl alcohol reaction, and the amount of reaction water is bigger, is generally about 1.3 times of oil, and this part water only contains a spot of oils etc., can be used as BW after handling.
The reacted tail gas staple is unreacted CO, H2, CO2, hydro carbons etc., and use acts as a fuel.
It is pointed out that following technology is a known technology among the present invention, the present invention does not do qualification, is not specifically describing simultaneously yet.
1, the tempreture organic sulphur hydrolysis agent is one type of catalyzer, and the COS hydrolyst is applied to water-gas, semi-water gas, synthetic ammonia, methyl alcohol and Fischer-Tropsch synthetic raw gas etc.Staple is: activated alumina market; Universal models has EH-2, RH101, A911, T504 etc.
Chemical reaction general formula: COS+H
2O=H
2S+CO
2CS
2+ 2H
2O=2H
2S+CO
2
2, Fischer-Tropsch synthesis process is a common processes, and fixed-bed reactor are general-purpose equipment.
3,, iron is fischer-tropsch synthetic catalyst, staple is that oxidation state is Fe
2O
3, going back ortho states is Fe
3O
4, Fe
3C; Cobalt is a fischer-tropsch synthetic catalyst, and staple is that oxidation state is Co
3O
4, going back ortho states is Co.
4, calcium carbide tail gas is integrated gas conversion, decarburization in the operation, at first is that the reaction of carbon monoxide and water vapour generates hydrogen and carbonic acid gas, removes carbonic acid gas then.This technology is the fertilizer industry common processes.
Claims (1)
1. one kind is the method that raw material is produced clean fuel oil and high-purity chemical products with the calcium carbide tail gas; Comprise gas integration operation, cleaning section, Fischer-Tropsch synthesis procedure; It is characterized in that: calcium carbide tail gas is incorporated into makes H2 in the gas: CO=1-2.1, through after purifying, obtain qualified synthetic gas simultaneously; Qualified synthetic gas carries out building-up reactions and generates alkane, alkene under suitable temperature and pressure, obtain oil fuel and high-purity chemical products through after the refrigerated separation; And it is that the ratio of regulating hydrogen and carbon monoxide makes H2 in the gas: CO=1-2.1 to calcium carbide tail gas process gas conversion, decarburization that gas is integrated operation; Cleaning section is: integrating back gas employing organic sulfur hydrolyst is inorganic sulfur with tempreture organic sulphur hydrolysis; Gas is through desulfurization; Total sulfur in the gas is taken off to 0.1ppm; Remove carbonic acid gas wherein through decarbonization device again, gas purifies through deep desulfuration again, makes wherein total sulfur less than 0.02ppm; Synthesis procedure be synthetic gas with qualified H2: CO=1～2.1 under suitable temperature and pressure, get into synthesis reactor, under catalyst action; Generate alkane, alkene; Through after the refrigerated separation, obtain wax, light oil and heavy oil, and adopt three reactors in series; Reacted gas does not circulate, and usefulness acts as a fuel; After the reaction water treatment as boiler water-filling; Wax, light oil and heavy oil obtain high purity wax and diesel oil again after refining.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102316484A CN101372628B (en) | 2008-09-28 | 2008-09-28 | Method for producing clean fuel oil and high-purity chemical products from calcium carbide tail gas |
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|---|---|---|---|
| CN2008102316484A CN101372628B (en) | 2008-09-28 | 2008-09-28 | Method for producing clean fuel oil and high-purity chemical products from calcium carbide tail gas |
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| Publication Number | Publication Date |
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| CN101372628A CN101372628A (en) | 2009-02-25 |
| CN101372628B true CN101372628B (en) | 2012-05-23 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845319B (en) * | 2010-05-26 | 2013-07-03 | 陕西金巢投资有限公司 | Process for producing wax and clean fuel oil by using biomass as raw material |
| CN103467232B (en) * | 2013-08-23 | 2015-09-02 | 宁夏宝塔石化科技实业发展有限公司 | A kind of method utilizing calcium carbide stove exhaust to prepare alkene |
| CN103483120B (en) * | 2013-08-23 | 2015-01-07 | 宁夏宝塔石化科技实业发展有限公司 | Method for preparing olefin by utilizing coke-oven gas and calcium carbide furnace tail gas |
| CN106554824B (en) * | 2015-09-29 | 2019-04-05 | 亚申科技研发中心（上海）有限公司 | A kind of processing method of Fischer-Tropsch synthetic |
| CN105692550B (en) * | 2016-02-04 | 2017-11-24 | 中国五环工程有限公司 | Calcium carbide tail gas detests sulfur type depth conversion technique |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6282900B1 (en) * | 2000-06-27 | 2001-09-04 | Ealious D. Bell | Calcium carbide power system with waste energy recovery |
| CN1417291A (en) * | 2001-11-05 | 2003-05-14 | 中国科学院大连化学物理研究所 | Technological process of preparing diesel oil fraction selectively with Fischer-tropsch synthetic gas |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6282900B1 (en) * | 2000-06-27 | 2001-09-04 | Ealious D. Bell | Calcium carbide power system with waste energy recovery |
| CN1417291A (en) * | 2001-11-05 | 2003-05-14 | 中国科学院大连化学物理研究所 | Technological process of preparing diesel oil fraction selectively with Fischer-tropsch synthetic gas |
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Effective date of registration: 20120213 Address after: 721000 No. 18, Dorset Road, Shaanxi, Baoji Applicant after: Shaanxi Jinchao Energy Chemical Technology Co., Ltd. Co-applicant after: Shanghai Huanqiu Petrochemistry Engineering Co., Ltd. Address before: 710016 Oceanic Building, No. 17, two road, Xi'an economic and Technological Development Zone, Shaanxi, Fengcheng 11-1103 Applicant before: Shaanxi Jinchao Investment Co., Ltd. Co-applicant before: Shanghai Chemical Industry Design Institute Co., Ltd. |
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