CN104419468A - Method for gasifying coke on spent catalyst - Google Patents
Method for gasifying coke on spent catalyst Download PDFInfo
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- CN104419468A CN104419468A CN201310386653.3A CN201310386653A CN104419468A CN 104419468 A CN104419468 A CN 104419468A CN 201310386653 A CN201310386653 A CN 201310386653A CN 104419468 A CN104419468 A CN 104419468A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/02—Fixed-bed gasification of lump fuel
- C10J3/06—Continuous processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/721—Multistage gasification, e.g. plural parallel or serial gasification stages
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
- C10J3/72—Other features
- C10J3/723—Controlling or regulating the gasification process
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0956—Air or oxygen enriched air
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0973—Water
- C10J2300/0976—Water as steam
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0983—Additives
- C10J2300/0986—Catalysts
Abstract
The invention relates to a method for gasifying coke on a spent catalyst. Two gasification reaction zones are set, the spent catalyst is in contact with an oxygen-containing gasification agent to perform gasification reaction in the first gasification reaction zone to obtain gasified gas I and a semi-regeneration agent, and the obtained semi-regeneration agent is in contact with an oxygen-free gasification agent to perform re-gasification reaction in the second gasification reaction zone to obtain gasified gas II and a regeneration agent; the oxygen-containing gasification agent contains oxygen, and the oxygen content is 8%-35% by volume; and the oxygen-free gasification agent does not contain oxygen, but contains water vapor, and the content of the water vapor is 60%-85% by volume. By adopting the method, the catalytic effect of gasification active components on the catalyst can be fully realized, so that the coke on the spent catalyst can be fully gasified to produce syngas, the gasification temperature is mitigated and the yield of the syngas is improved.
Description
Technical field
The invention belongs to a kind of renovation process of reclaimable catalyst.More particularly, be a kind of method of the coke on spent agent being carried out two times of gasification.
Background technology
Crude oil heaviness, in poor quality increasingly within the scope of our times, its feature shows as high-sulfur, peracid, high metal, high carbon residue, conventional crude complete processing is subject to the very big restriction of stock oil in poor quality, and the product of processing generally needs could meet service requirements by hydrotreatment, therefore develops new heavy oil upgrading technique and cheap process for making hydrogen becomes an urgent demand.
In heavy oil deep-processing process, heavy hydrocarbon finally exists with the form of coke, by coke gasification producing synthesis gas (CO+H
2) and then by conversion high purity H
2become valuable hydrogen manufacturing approach.Current heavy oil deep processing technology has: heavy oil fluid catalytic cracking, delayed coking, fluid coking, flexicoking, solvent deasphalting etc.; A part of coke powder is utilized air, O by wherein flexicoking technique
2, CO
2, the gasification such as water vapour produces the combustible gas with certain calorific value, carbon distribution on catalyst for heavy oil catalytic cracking is completely burned, and provides reaction heat, and other technique all produces coke product, along with the increase of stock oil sulphur content, the Utilizing question of high sulfur petroleum coke is on the rise.
US4297202 proposes a kind of fluid coking and coke gasification process integration, utilizes coke powder as the thermal barrier of reaction, and a part of coke powder utilizes water vapour and oxygen-containing gas gasification to produce synthetic gas in gasifier.US4331529 proposes a kind of flexicoking and gasifying process, a part of coke is gasified in atmosphere produce hot gas and Re Jiao and loop back well heater and make thermal source, synthetic gas is produced in part gasification in water vapour, carries out heavy oil fluidized pyrogenic reaction after other coke powder is heated as thermal barrier.Above two kinds of techniques gasification process temperature is higher, and only has part of coke to obtain utilization.CN102234535A proposes a kind of inferior heavy oil of processing and to hold concurrently the method for production of synthetic gas, and adopt spent agent sectional feeding method at coke gasification unit, spent agent reacts with the vaporized chemical generating gasification of different oxygen respectively, and this process is comparatively complicated.
In the heavy-oil catalytic course of processing, catalyzer deposits a large amount of coke, this part coke gasification production of synthetic gas is utilized to have good prospect, the vaporized chemical that coke gasification adopts usually is pure oxygen, oxygen rich gas, air, carbonic acid gas, water vapour etc., and when utilizing oxygen-containing gas to gasify, first coke is oxidized heat supply, for gasification provides heat, can carry out at a lower temperature, generally just have good gasification rate at about 600 DEG C, gasification gas consists of CO, CO
2, H
2, CH
4, but the more difficult control of Hypoxic habitats, the synthetic gas of generation easily and oxygen occur to react further, synthetic gas productive rate is reduced.When utilizing water vapour and carbon dioxide gasification, synthetic gas is CO, H
2and CH
4, and productive rate is higher, but reaction is thermo-negative reaction, under low temperature, speed of reaction is comparatively slow, and needs just there is good gasification rate higher than 1000 DEG C, generally uses basic metal, alkaline-earth metal or transition metal salt as gasifying catalyst to relax gasification temperature.
Summary of the invention
To be solved by this invention is the problem that in prior art, synthesis gas yield is low, the present invention on the basis of existing technology, the method of coke gasification production of synthetic gas on a kind of spent agent is provided, coke on spent agent is made full use of, reduce the further reaction of synthetic gas and oxygen, improve synthesis gas yield.
Method provided by the invention is: arrange Liang Ge gasification reaction district, spent agent and oxygenous agent contact in the first gasification reaction district carries out gasification reaction, obtain gasification gas I and semi regeneration agent, the agent of gained semi regeneration and no oxygen agent contact in the second gasification reaction district carries out gasification reaction again, obtains gasification gas II and regenerator; Containing oxygen in described oxygenous agent, by volume, oxygen content is 8% ~ 35%; Not containing oxygen in described no oxygen agent, containing water vapor, by volume, water vapour content is 60% ~ 85%.
Wherein in a kind of preferred embodiment, arrange two gasifiers, two gasifiers are spent agent downstream operation, comprising:
(1) upper entrance of spent agent autopneumatolysis device I enters gasifier I, the lower entrances of oxygenous agent autopneumatolysis device I enters gasifier I, oxygenous agent fully contacts with descending spent agent after gas distribution dish is uniformly distributed, coke on spent agent carries out gasification reaction, obtain semi regeneration agent, semi regeneration agent falls to gasifier I outlet at bottom, and the cyclonic separator that in gasifier I, gas goes upward to gasifier I top is separated, and obtains gasification gas I and discharges.
(2) from gasifier I semi regeneration agent through heating tube heating after, the upper entrance of autopneumatolysis device II enters gasifier II, the lower entrances of no oxygen agent autopneumatolysis device II enters gasifier II, contact with descending semi regeneration agent, residual coke in semi regeneration agent carries out gasification reaction, obtains regenerator, and regenerator falls to gasifier II outlet at bottom and discharges, the cyclonic separator that in gasifier II, gas goes upward to gasifier II top is separated, and obtains gasification gas II and discharges.
In embodiments of the invention, be arranged in series gasifier I and gasifier II, spent agent is entered by gasifier I upper end, contact with up oxygenous agent and oxidizing reaction occurs, with the whereabouts of spent agent, gasifier I is divided into oxygen deprivation gasification zone and oxygen-enriched combusting district from top to bottom, stop oxidizing reaction until spent agent falls to below oxygenous agent import and discharge gasifier I, gasifier II is entered after heating, in semi regeneration agent, remaining coke is in gasifier II, under the effect of no oxygen agent, carry out rapid anaerobic catalytic gasification.Present method can give full play to the catalytic gasification effect of loaded metal on catalyzer, relaxes gasification temperature, improves synthesis gas yield.
Described oxygenous agent is the mixture of air and water vapor or the mixture for oxygen and water vapour, and by volume, oxygen content is 10% ~ 30%.
Described no oxygen agent is gasification gas I, or gasification gas I and CO
2and/or the mixture of water vapour, or be CO
2with the mixture of water vapour, by volume, water vapour content is 65% ~ 80%.
Described spent agent is the carbon distribution rear catalyst in heavy oil contact cracking process, coke content 1.5 ~ 8.0 % by weight on spent agent.Coke content in described semi regeneration agent is 0.3 ~ 2.0 % by weight; Coke content < 0.1 % by weight on regenerator.
Described catalyzer is silica-alumina material and gasifying catalyst, and described gasifying catalyst and silica-alumina material are mechanically mixing, or gasifying catalyst load is on silica-alumina material.Described catalyzer is mainly used in heavy oil contact cracking process.
Described silica-alumina material is selected from containing the catalyzer of molecular sieve and/or not containing the silica-alumina material catalyzer of molecular sieve.
Preferably the described catalyzer containing molecular sieve is be selected from the catalyzer containing one or more molecular sieves in X molecular sieve, Y molecular sieve, mordenite, ZSM-5, clay molecular sieve with layer structure, SAPO.
Silica-alumina material catalyzer not containing molecular sieve preferably refers to the catalyzer prepared for raw material with the mixture of one or more in amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, pseudo-boehmite, silicon-dioxide.Also one or more catalyzer prepared for raw material in pickling, roasting, the amorphous silicon aluminium of screening process, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite can be through.One or more and pseudo-boehmite in pickling, roasting, the amorphous silicon aluminium of screening process, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite can also be through and/or silicon-dioxide is catalyzer prepared by raw material.
Described gasifying catalyst is natural crystal containing metal single in basic metal, alkaline-earth metal and group VIII metal or various metals combination, synthetic materials, one or more in derivative compound.Such as, the mixture of one or more in the carbonate containing basic metal, alkaline-earth metal and group VIII metal, vitriol, oxide compound, muriate, oxyhydroxide.Can also be the synthetic materials containing basic metal, alkaline-earth metal, group VIII metal such as perovskite typed, spinel type, and natural ore powder, as Wingdale, rhombspar, peridotites etc.
Preferred described basic metal is potassium, and alkaline-earth metal is calcium, group VIII metal is iron.
Basic metal, alkaline-earth metal, transition metal energy catalytic coke gasification reaction, therefore effect catalyzer playing catalytic coke gasification can be loaded to, but because the coke on spent agent is mainly positioned at the surface of catalyzer, the gasifying catalyst of gasification initial stage spent agent top layer load, namely loaded metal is covered can not well play gasification catalysis effect by carbon-coating, so what realize in gasifier I is the reaction that most of coke has gasification generation synthetic gas, gasification required necessary temperature condition can be provided in gasifier I, simultaneously along with coke layer on spent agent is thinning, the active ingredient of gasifying catalyst plays catalytic activity gradually, in gasifier II, remaining coke in semi regeneration agent, under anaerobic, catalytic gasification reaction is carried out under the effect of gasifying catalyst, produce synthetic gas.
Arrange 2 ~ 4 cyclonic separators respectively on the top of gasifier I and gasifier II, by catalyzer and generation gas sharp separation, the generation gas in gasifier I can be used as a part for vaporized chemical in gasifier II.The mixture of gasification gas II or gasification gas I and gasification gas II can enter gas separation unit or enter water-gas shift device and obtain high concentration hydrogen, the CO after gas delivery
2gasifier II capable of circulation makes no oxygen agent.
Two gasifiers are downstream operation, arrange in height block form; By regulating the gas of oxygenous agent speed to control the residence time of spent agent in gasifier I, when guaranteeing that spent agent falls to oxygenous agent entrance location in gasifier I, on spent agent, coke content is 0.3 ~ 2.0 % by weight, to keep coke excessive; Same by regulating the no oxygen agent gas speed control semi regeneration agent residence time in gasifier II, and the regenerator coke content < 0.1 % by weight after making gasification complete.
The reaction conditions used in two gasifiers is: gasifier I temperature 600 ~ 800 DEG C, preferably 650 ~ 750 DEG C, spent agent residence time time 2 ~ 20s, preferably 5 ~ 15s, and gas speed is 0.02 ~ 0.25m/s, preferably 0.03 ~ 0.1m/s; Gasifier II temperature is 720 ~ 900 DEG C, preferably 730 ~ 850 DEG C, the semi regeneration agent residence time 10 ~ 60s, preferably 15 ~ 50s, and gas speed is 0.02 ~ 0.25m/s, preferably 0.06 ~ 0.15m/s.Reaction institute heat requirement in gasifier I mainly comes from the combustion heat release of spent agent upper part coke in gasifier I, heat in gasifier II is mainly semi regeneration agent and brings into, and the boosting of heating tube 4, gasifier II gained regenerator carries out heat exchange, obtain overheated steam through heat exchange and make vaporized chemical, after heat exchange, regenerator is down to 480 ~ 520 DEG C, and regenerator returns heavy oil cracking reactor cycles and uses.
The vaporized chemical that the gasification gas generated in gasifier I in this gasification process can be used as gasifier II uses, the synthetic gas (CO+H after two step gasifications
2) content is greater than 65 (v) %(butt).
The invention has the advantages that the regenerative response that to be gasified by spent agent arranges Liang Ge district, make coke in gasifier I excessive, there is not exclusively gasification, be easy to control Hypoxic habitats, reduce the further reaction of synthetic gas and oxygen, in gasifier II, carry out the gasification of catalysis anaerobic, play the katalysis of catalytic active component in gasifying catalyst, coke on spent agent is fully gasified production of synthetic gas, relaxes gasification temperature, improve synthetic gas productive rate.
Accompanying drawing explanation
Fig. 1 is coke gasification process schematic diagram on spent agent provided by the invention
Embodiment
Below by accompanying drawing to method of the present invention, illustrate further, but not thereby limiting the invention.
As shown in Figure 1, the upper entrance 1 of spent agent autopneumatolysis device I enters gasifier I, the lower entrances 2 of oxygenous agent autopneumatolysis device I enters gasifier I, oxygenous agent fully contacts with descending spent agent after gas distribution dish 3 is uniformly distributed, coke on spent agent carries out gasification reaction, obtains semi regeneration agent, and semi regeneration agent falls to gasifier I outlet at bottom 11, the cyclonic separator 8 that in gasifier I, gas goes upward to gasifier I top is separated, and obtains gasification gas I and discharges through pipeline 9.From gasifier I outlet at bottom 11 semi regeneration agent through heating tube 4 heat after, the upper entrance 5 of autopneumatolysis device II enters gasifier II, the lower entrances 6 of no oxygen agent autopneumatolysis device II enters gasifier II, contact with descending semi regeneration agent after gas distribution dish 13 is uniformly distributed, residual coke in semi regeneration agent carries out gasification reaction, obtain regenerator, regenerator falls to gasifier II outlet at bottom and discharges through pipeline 7, the cyclonic separator 12 that in gasifier II, gas goes upward to gasifier II top is separated, and obtains gasification gas II and discharges through pipeline 10.
The present invention is described in detail below by embodiment, but the use range that embodiment is not thereby limiting the invention.
Embodiment 1
Adopt amorphous alumina as the silica-alumina material not containing molecular sieve, gasifying catalyst is calcium naphthenate, iron naphthenate, by by calcium naphthenate, iron naphthenate dipping, after roasting, calcium, iron load are obtained catalyzer on silica-alumina material, wherein, with live catalyst weighing scale, calcium element content is 2.0 % by weight, iron content is 1.5 % by weight, and catalyst particle size is 100 ~ 200 orders.
Adopt Tahe long residuum to make raw material, above-mentioned catalyzer contacts cracking process through heavy oil, becomes spent agent.Contact cracking reaction condition is: temperature of reaction 500 DEG C, agent-oil ratio is 7.0, air speed 4h
-1, water-oil ratio 0.23, Tahe long residuum main character is in table 1.
Table 1
| Project | Data | Project | Data |
| Density (20 DEG C), g.cm -3 | 1.0021 | Simulation distil boiling range, DEG C | V/% |
| Carbon residue (Kang Shi), weight/% | 18.9 | Initial boiling point | 170 |
| Metal content, μ g.g -1 | 5% | 300 | |
| Ni | 46.0 | 10 | 353 |
| V | 301.0 | 30 | 482 |
| Fe | 19.5 | 50 | 605 |
| Ca | 1.5 | 70 | 706 |
The gasification that above-mentioned spent agent adopts is: spent agent is entered by end entrance 1 on gasifier I, generating gasification reaction under the oxygenous agent effect that certain oxygen level and water vapour mix, spent agent under gravity, fall to after below oxygenous agent entrance, spent agent stops aerobic gasification reaction, by controlling the residence time of spent agent in gasifier I, control spent agent to the coke content on spent agent during oxygenous agent entrance, the semi regeneration agent of gasifier I gained enters gasifier II and carries out anaerobic gasification, no oxygen agent selects the gasification gas I of gasifier I and the mixture of water vapour.Major gasification condition and gasification products distribution are listed in table 2.As shown in Table 2, adopt gasification process provided by the invention, gained synthetic gas volume fraction is 67.29%, and on regenerator, coke is residual is less than 0.1 % by weight.
Comparative example 1
Select the spent agent identical with embodiment 1, by upper end entrance 1 charging of gasifier I, the coke on spent agent is made to gasify completely in gasifier I, namely spent agent completes a step gasification regeneration under aerobic conditions, and gasification temperature adopts 780 DEG C, and vaporized chemical adopts the mixed gas of oxygen and water vapour, vaporization time is that embodiment 1 gasifies total time, major gasification condition and gasification products distribution list in table 2, and as shown in Table 2, gained gasification synthesis gas volume fraction is 60.15%.
A gasification temperature of this comparative example is higher than embodiment 1, under the condition that vaporization time is the same, synthesis gas yield in embodiment 1, higher than nearly 7.2 percentage points of this comparative example, illustrates a two step gasification process of the present invention comparatively step gasification process, and not only low the and synthetic gas productive rate of gasification temperature obviously increases.
Comparative example 2
Select the silica-alumina material identical with embodiment 1 to be catalyzer, but not containing gasifying catalyst, silica-alumina material catalyzer is done containing charcoal spent agent after heavy oil contact cracking, and contact cracking process is identical with embodiment 1.The gasification of the spent agent of this comparative example adopts two step gasification process, and gasification is with embodiment 1, and major gasification condition and gasification products distribution are in table 2.
As shown in Table 2, this comparative example gained gasification synthesis gas volume fraction is 65.11%, and on regenerator, coke remains is 0.58 % by weight, compared with embodiment 1, under the identical residence time and close gasification temperature, synthetic gas content reduce and on spent agent coke gasification incomplete.Therefore, the gasification process that embodiment 1 provides can play the katalysis of gasification reactivity component, improves synthetic gas productive rate and coke gasification speed.
Embodiment 2
Adopt kaolin as silica-alumina material, potassium metal load as gasifying catalyst, and is obtained catalyzer by potassium metal on silica-alumina material, take catalyzer as benchmark, and potassium content is 4.0 % by weight, and particle size range is 100 ~ 200 orders.Gained catalyzer obtains containing charcoal spent agent by heavy oil contact cracking process, and contact cracking process is identical with embodiment 1.Gained spent agent adopts method provided by the invention to carry out two step gasifications, and major gasification condition and gasification products distribution list in table 3.
As shown in Table 3, gained synthetic gas volume fraction is 69.12%.
Embodiment 3
Adopt containing Y molecular sieve as containing the silica-alumina material of molecular sieve, metallic iron as gasifying catalyst, and using metallic iron load on silica-alumina material as catalyzer, particle size range 100 ~ 200 order, is benchmark with catalyzer, consists of: Y molecular sieve 10 % by weight, Al
2o
3be 65.2 % by weight, SiO
2be 22.8 % by weight, iron is 2.0 % by weight.Gained catalyzer obtains containing charcoal spent agent by heavy oil contact cracking process, and contact cracking process is identical with embodiment 1.Gained spent agent adopts method provided by the invention to carry out two step gasifications, and major gasification condition and gasification product list in table 3.
As shown in Table 3, gained synthetic gas volume fraction is 66.50%.
Table 2
Table 3
Claims (14)
1. coke gasification process on a spent agent, it is characterized in that, Liang Ge gasification reaction district is set, spent agent and oxygenous agent contact in the first gasification reaction district carries out gasification reaction, obtain gasification gas I and semi regeneration agent, the agent of gained semi regeneration and no oxygen agent contact in the second gasification reaction district carries out gasification reaction again, obtains gasification gas II and regenerator; Containing oxygen in described oxygenous agent, by volume, oxygen content is 8% ~ 35%; Not containing oxygen in described no oxygen agent, containing water vapor, by volume, water vapour content is 60% ~ 85%.
2. in accordance with the method for claim 1, it is characterized in that, arrange two gasifiers, two gasifiers are spent agent downstream operation, comprising:
(1) upper entrance of spent agent autopneumatolysis device I enters gasifier I, the lower entrances of oxygenous agent autopneumatolysis device I enters gasifier I, oxygenous agent fully contacts with descending spent agent after gas distribution dish is uniformly distributed, coke on spent agent carries out gasification reaction, obtain semi regeneration agent, semi regeneration agent falls to gasifier I outlet at bottom, and the cyclonic separator that in gasifier I, gas goes upward to gasifier I top is separated, obtain gasification gas I to discharge
(2) from gasifier I semi regeneration agent through heating tube heating after, the upper entrance of autopneumatolysis device II enters gasifier II, the lower entrances of no oxygen agent autopneumatolysis device II enters gasifier II, contact with descending semi regeneration agent, residual coke in semi regeneration agent carries out gasification reaction, obtains regenerator, and regenerator falls to gasifier II outlet at bottom and discharges, the cyclonic separator that in gasifier II, gas goes upward to gasifier II top is separated, and obtains gasification gas II and discharges.
3. according to the method described in claim 1 or 2, it is characterized in that, described oxygenous agent is the mixture of air and water vapor or the mixture for oxygen and water vapour, and by volume, oxygen content is 10% ~ 30%.
4. according to the method described in claim 1 or 2, it is characterized in that, described no oxygen agent is gasification gas I, or gasification gas I and CO
2and/or the mixture of water vapour, or be CO
2with the mixture of water vapour, by volume, water vapour content is 65% ~ 80%.
5. according to the method described in claim 1 or 2, it is characterized in that, described spent agent is the carbon deposit rear catalyst in heavy oil contact cracking process, and on spent agent, coke content is 1.5 ~ 8.0 % by weight.
6. according to the method described in claim 1 or 2, it is characterized in that, the coke content in described semi regeneration agent is 0.3 ~ 2.0 % by weight; Coke content < 0.1 % by weight on regenerator.
7. according to the method described in claim 1 or 2, it is characterized in that, the reaction conditions in the first gasification reaction district is: gasification temperature 600 ~ 800 DEG C, the spent agent residence time 2 ~ 20s, and gas speed is 0.02 ~ 0.25m/s; The reaction conditions in the second gasification reaction district is: gasification temperature 720 ~ 900 DEG C, the semi regeneration agent residence time 10 ~ 60s, and gas speed is 0.02 ~ 0.25m/s.
8. in accordance with the method for claim 7, it is characterized in that, the reaction conditions in the first gasification reaction district is: gasification temperature 650 ~ 750 DEG C, the spent agent residence time 5 ~ 15s, gas speed is the reaction conditions in 0.03 ~ 0.1m/s second gasification reaction district: gasification temperature 730 ~ 850 DEG C, the semi regeneration agent residence time 15 ~ 50s, gas speed is 0.06 ~ 0.15m/s.
9., according to the method for claim 5, it is characterized in that described catalyzer is silica-alumina material and gasifying catalyst, described gasifying catalyst and silica-alumina material are mechanically mixing, or gasifying catalyst load is on silica-alumina material.
10., according to the method for claim 9, it is characterized in that described silica-alumina material is selected from containing the catalyzer of molecular sieve and/or not containing the silica-alumina material catalyzer of molecular sieve.
11. according to the method for claim 10, it is characterized in that the described catalyzer containing molecular sieve is be selected from the catalyzer containing one or more molecular sieves in X molecular sieve, Y molecular sieve, mordenite, ZSM-5, clay molecular sieve with layer structure, SAPO.
12. according to the method for claim 10, and the silica-alumina material catalyzer not containing molecular sieve described in it is characterized in that refers to the catalyzer prepared for raw material with the mixture of one or more in amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, pseudo-boehmite, silicon-dioxide.
13. according to the method for claim 9, it is characterized in that described gasifying catalyst is one or more in natural crystal containing metal single in basic metal, alkaline-earth metal and group VIII metal or various metals combination, synthetic materials, derivative compound.
14. according to the method for claim 13, and it is characterized in that described basic metal is potassium, alkaline-earth metal is calcium, group VIII metal is iron.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602626A (en) * | 2015-12-21 | 2016-05-25 | 郭凯 | Gasifier and household refuse harmless gasification energy process thereof |
| CN105838451A (en) * | 2016-04-26 | 2016-08-10 | 华陆工程科技有限责任公司 | Method for gasifying pulverized coal step by step in double beds connected in series |
| CN109722289A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Reduce the catalyst cracking method of dry gas and coke yield |
| WO2022077460A1 (en) * | 2020-10-16 | 2022-04-21 | 中国科学院大连化学物理研究所 | Fluidised bed regenerator, apparatus for preparing low carbon olefin, and application thereof |
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| US4224140A (en) * | 1979-01-30 | 1980-09-23 | Nippon Mining Co., Ltd. | Process for producing cracked distillate and hydrogen from heavy oil |
| US4336160A (en) * | 1980-07-15 | 1982-06-22 | Dean Robert R | Method and apparatus for cracking residual oils |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4224140A (en) * | 1979-01-30 | 1980-09-23 | Nippon Mining Co., Ltd. | Process for producing cracked distillate and hydrogen from heavy oil |
| US4336160A (en) * | 1980-07-15 | 1982-06-22 | Dean Robert R | Method and apparatus for cracking residual oils |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105602626A (en) * | 2015-12-21 | 2016-05-25 | 郭凯 | Gasifier and household refuse harmless gasification energy process thereof |
| CN105602626B (en) * | 2015-12-21 | 2018-03-06 | 郭凯 | Gasification furnace and its harmless gasification energy process of house refuse |
| CN105838451A (en) * | 2016-04-26 | 2016-08-10 | 华陆工程科技有限责任公司 | Method for gasifying pulverized coal step by step in double beds connected in series |
| CN109722289A (en) * | 2017-10-30 | 2019-05-07 | 中国石油化工股份有限公司 | Reduce the catalyst cracking method of dry gas and coke yield |
| CN109722289B (en) * | 2017-10-30 | 2021-05-14 | 中国石油化工股份有限公司 | Catalytic cracking process for reducing dry gas and coke yields |
| WO2022077460A1 (en) * | 2020-10-16 | 2022-04-21 | 中国科学院大连化学物理研究所 | Fluidised bed regenerator, apparatus for preparing low carbon olefin, and application thereof |
| JP7449415B2 (en) | 2020-10-16 | 2024-03-13 | 中国科学院大▲連▼化学物理研究所 | Fluidized bed regenerator, equipment for preparing light olefins and its applications |
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