CN104371756A - Method for simultaneously treating inferior heavy oil and producing synthetic gas - Google Patents
Method for simultaneously treating inferior heavy oil and producing synthetic gas Download PDFInfo
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- CN104371756A CN104371756A CN201410642390.2A CN201410642390A CN104371756A CN 104371756 A CN104371756 A CN 104371756A CN 201410642390 A CN201410642390 A CN 201410642390A CN 104371756 A CN104371756 A CN 104371756A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
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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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/48—Apparatus; Plants
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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
- C10J3/46—Gasification of granular or pulverulent flues in suspension
- C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
- C10J3/56—Apparatus; Plants
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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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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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
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
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- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a method for simultaneously treating inferior heavy oil and producing synthetic gas. The method comprises the following steps: contacting the inferior heavy oil raw material with a catalyst for reacting and separating oil and gas generated in the reaction from the spent catalyst, putting the spent catalyst in countercurrent contact with oxygen-containing gas to have a charcoaling reaction so as to a semi-regenerative catalyst until the temperature of the spent catalyst rises to the temperature required by a gasification reaction, and finally, contacting the semi-regenerative catalyst with water vapor to have the gasification reaction, thereby generating the synthetic gas and the regenerated catalyst. The method for simultaneously treating the inferior heavy oil and producing the synthetic gas is capable of effectively utilizing coke generated in the treatment process while performing efficient treatment of conversion to light fraction on the inferior heavy oil, and the generated synthetic gas yield is increased.
Description
Technical field
The present invention relates to the method for the double production of synthetic gas of a kind of inferior heavy oil processing, belong to Petroleum Processing Technology field.
Background technology
Along with world economy is fast-developing and continuous growth to petroleum demand, conventional oil reserves reduce day by day, and inferior heavy oil will become one of 21 century important Energy resources as a kind of non-conventional oil resource.But, the restriction that inferior heavy oil is subject to self property and environmental regulation on the one hand directly can not be used as oil fuel and road bitumen, on the other hand because carbon residue is large, metal content is high, the traditional techniques such as such as residual hydrogenation technology, delayed coking, solvent deasphalting are adopted to there is many problems.Therefore, need to carry out decarburization, removing heavy-metal upgrading to inferior heavy oil, thus provide the raw material of relative clean for downstream process.
In the modifying low-quality heavy oil course of processing, because inferior heavy oil carbon residue is high, cause coke yield in upgrading processes high, can consider to be have synthetic gas (CO and H compared with high added value by coke more than needed
2), to make full use of coke more than needed, produce synthetic gas at an easy rate simultaneously.
Exxon company of the U.S. discloses a kind of flexicoking technique in patent USP 4213848, in production of synthetic gas is held concurrently in inferior heavy oil processing, made initiative work.Using coke granule as carrier in this technique, bear the mass-and heat-transfer effect between reactor and gasifier.Be specially: heavy oil feedstock and coke granule are in reactor, react under contact reacts condition, the oil gas be obtained by reacting is separated with coke granule, the coke granule generated in reactor enters in gasifier, and air and coke granule at high temperature (760-1093 DEG C) react and produce air gas.Although this process solves the Utilizing question of coke, air is adopted to carry out burning a large amount of low-calorie air gas of generation; Simultaneously because in fact coke granule does not exist cracking activity, just circulate between reactor and gasifier as mass transfer, heat transfer carrier, in above-mentioned coking process, mainly there is heat cracking reaction on the coke particles in inferior heavy oil, therefore dry gas amount is larger in product, coke yield is higher, and coke granule is easily united into bulk coke-like thing and is broken into finely-ground coke, causes the possibility of the improper shut-down of device to increase.
Use for reference fluidized coking process technology, utilize that cheap inert solid catalytic microspheres particle replaces coke granule to carry out the decarburization of heavy oil, the technology of removing heavy-metal and diasphaltene upgrading is suggested.Patent application CN1504404A discloses a kind of oil refining and the processing method combined that gasifies, and the method comprises the following steps: (1) petroleum hydrocarbon contacts with coke transfer agent, reacts in reactor; (2) be separated the coke transfer agent of the reaction oil gas generated and the rear carbon deposit of reaction, reaction oil gas sends into follow-up hydrocarbon products separation system, and the coke transfer agent of carbon deposit delivers to vapourizing furnace after stripping; (3) in vapourizing furnace, coke contacts with oxygen-containing gas with water vapour under gasification condition, to produce synthesis gas, makes the coke transfer agent of carbon deposit be regenerated simultaneously; (4) the reactor thermal cycling that the coke transfer agent after step (3) regeneration returns described in step (1) uses.But in the method, the synthetic gas that partial gasification generates may react with the oxygen in reactant and be consumed, thus makes the synthetic gas productive rate of acquisition reduce.
Summary of the invention
The invention provides the method for the double production of synthetic gas of a kind of inferior heavy oil processing, while efficient light processing is carried out to inferior heavy oil raw material, effectively utilize the coke that the course of processing generates, and improve the productive rate generating synthetic gas.
The invention provides the method for the double production of synthetic gas of a kind of inferior heavy oil processing, wherein,
Inferior heavy oil raw material contacts with contact substance and reacts, and is separated with spent agent by the oil gas that reaction generates;
Described spent agent and oxygen-containing gas counter current contact are made charcoal react, and it is temperature required to make the temperature of described spent agent rise to gasification reaction, obtains semi regeneration agent;
Make described semi regeneration agent contact generating gasification with water vapour to react, collect gasification product and regenerator.
Further, described inferior heavy oil raw material is vacuum residuum, heavy oil residue, de-oiled asphalt, one or more of oil sands bitumen, tar, shale oil, coal liquefaction residue oil.
Further, described inferior heavy oil raw material contacts the weight hourly space velocity of carrying out reacting with contact substance is 5-40h
-1, agent-oil ratio is 4-12.
Further, described contact substance is the microballoon of silicon-aluminum containing material composition, and micro anti-active index is 5-40, and specific surface area is at 40-220m
2g
-1, aperture 5-60nm, bulk density 0.7-1.50gcm
-3, skeletal density 1.8-2.8gcm
-3, abrasion index is less than 2.0%.
Further, described in make charcoal reaction reaction times be 10-600s, carrier of oxygen volume concentrations is 2-30%.
Further, described in make charcoal reaction reaction times be 60-900s, the linear velocity of water vapour is 0.2-1m/s.
Further, described inferior heavy oil raw material contacts the reactor carrying out reacting with contact substance be fluidization combined reactor, and described fluidization combined reactor bottom is riser tube, top series connection fast fluidized bed reactor.
Further, described riser reactor length is less than 60% of described fluidization combined reactor total length.
Further, make charcoal described in reaction or the reactor of gasification reaction is selected from riser reactor, fluidized-bed reactor, moving-burden bed reactor or the two or more reactors combined wherein.
Further, the regenerator obtained through gasification reaction is reacted with inferior heavy oil contact raw again as contact substance.
The enforcement of the present invention program, at least has following advantage:
1, the processing of methods combining provided by the present invention inferior heavy oil and process coke efficiency utilization two aspects, one side is raw material with inferior heavy oil, higher liquid yield can be kept after processing, the index of metal removal rate, asphaltene removal and carbon residue decreasing ratio is advanced, can provide more lighting raw materials for downstream process; On the other hand, in spent agent regenerative process, making on it coke of deposition is effectively the synthetic gas that added value is higher, whole process economy, efficient.
2, present invention employs the method for two step regeneration, avoiding the oxygen in the synthetic gas of gasification generation and reactant react and be consumed, thus improve the synthetic gas productive rate of acquisition.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the method for the double production of synthetic gas of inferior heavy oil processing in the embodiment of the present invention.
Description of reference numerals
| 1-process furnace | 2-interchanger | 3-gasifier |
| 4-riser reactor | 5-fast fluidized bed reactor | 6-cyclonic separator |
| 7-gas pipeline | 8-settling vessel | 9-stripping stage |
| 10-regenerator sloped tube | 11-inclined tube to be generated | 12-guiding valve to be generated |
| 13-burns device | 14-synthetic gas pipeline | 15-regenerates guiding valve |
| 16-makes charcoal and reacts flue gas pipeline | 17-surge tank | 18-semi regeneration agent pipeline |
| 19-regenerator pipeline | A-inferior heavy oil raw material | B-water vapour |
| C-oxygen-containing gas | The fresh contact substance of D- |
Embodiment
The method of the double production of synthetic gas of a kind of inferior heavy oil of embodiment of the present invention processing, comprising following steps:
(1) inferior heavy oil raw material contacts with contact substance and reacts, and is separated with spent agent by the oil gas that reaction generates;
(2) make spent agent and oxygen-containing gas counter current contact make charcoal to react, and it is temperature required to make the temperature of described spent agent rise to gasification reaction, obtains semi regeneration agent;
(3) make described semi regeneration agent contact generating gasification with water vapour to react, collect gasification product and regenerator.
The present invention is by spraying into fluidization combined reactor by after inferior heavy oil preheating, with there is excellent surface structure, fluidizing performance and pore passage structure and the adjustable solid particle catalyst hybrid reaction of heavy oil cracking activity, make inferior heavy oil, at catalyst surface, de-carbon residue, removing heavy-metal, diasphaltene reaction occur, by regulating suitable reaction conditions in reaction process, make liquid product yield remain on higher level, reduce gas yield and coke yield simultaneously as far as possible; On the other hand, after isolated spent agent enters the reactor of reaction of making charcoal, spent agent upper part coke and oxygen combustion, release large calorimetric, spent agent particle is made to be warming up to coke gasification temperature required, form semi regeneration agent thereupon, then, semi regeneration agent is transferred to gasifier, there is the gasification reaction absorbed heat in coke in gasifier in the semi regeneration agent coke of unburn remainder (on the spent agent) and water vapour, generate and be rich in the gaseous product of synthetic gas, thus realize inferior heavy oil efficient light and to hold concurrently the object of production of synthetic gas.
In the present invention, contact substance particle with the rear surface coking of inferior heavy oil contact reacts is called " spent agent ", it can by burning and/or the method manipulation of regeneration such as gasification and re-using, for being different from the contact substance (also claiming " fresh contact substance ") used first, the contact substance Gong recycling after regeneration is also called " regenerator " by the present invention.
The heavy oil residue that in step (1), inferior heavy oil raw material comprises vacuum residuum, be separated through pentane equal solvent and de-oiled asphalt, and oil sands bitumen, tar, shale oil, one or more in coal liquefaction residue oil.The carbon residue massfraction of raw material can be 10-40%, and containing metal massfraction is 100-1000 μ g/g.1.0g/cm is greater than for density
3inferior heavy oil, can suitably add light hydrocarbons dilute after again with contact substance contact reacts.Inferior heavy oil raw material can realize deep removal carbon residue and heavy metal with contact substance contact reacts in the reactor, obtains the lighting oil product that quality significantly promotes, can be used as the raw material of catalytic cracking or hydrocracking.
In step (1), reactor can use fluidized combined reactor, and it can be combined by the fast fluidized bed reactor on the riser reactor of bottom and top usually, and riser reactor length is less than 60% of whole reactor length.
In step (1), the condition of reaction can be: weight hourly space velocity 5-40h
-1, agent-oil ratio 4-12.Temperature under this reaction conditions in reactor can reach about 430-530 DEG C usually.Described agent-oil ratio is the mass ratio of contact substance and inferior heavy oil raw material, selects above-mentioned reaction conditions to be more conducive to inferior heavy oil raw material and fully reacts at short notice.
Contact substance can select the contact substance for carrying out inferior heavy oil processing conventional in this area, such as can select the microballoon of silicon-aluminum containing material composition, its Main Function removes carbon residue in inferior heavy oil and heavy metal, promote oil quality, for subsequent process steps creates conditions, and can be used as heat carrier.For being conducive to the carrying out reacted, micro anti-active index can be selected to be 5-40, and specific surface area is at 40-220m
2g
-1, aperture 5-60nm, bulk density 0.7-1.50gcm
-3, skeletal density 1.8-2.8gcm
-3, the contact substance that abrasion index is less than 2.0%.Preferred contact substance molecular sieve content is less than 20wt%, keep stronger structural stability under being conducive to high temperature in subsequent step and water vapour existence condition, such as, can use the contact substance prepared through the method for spraying and drying by mineral materials such as montmorillonite, halloysite or kaolin.Adopt particle that above-mentioned activity is lower as contact substance, without the need to holomorphosis, can be able to reuse, be conducive to the processing requirement reducing spent agent gasification regeneration step.
Or the reaction in step (1) method can be carried out disclosed in referenced patent CN201310455197.3.After step (1) reaction terminates, the oil gas that the ordinary methods such as stripping can be used to generate is separated with spent agent, and the product oil gas of gained can use ordinary method to carry out fractionation, thus obtains the light-end products such as gasoline fraction, diesel oil distillate and wax oil cut.
The reactor (also claiming " burning device " in the present invention) of the reaction of making charcoal in step (2) can use riser reactor, fluidized-bed reactor, moving-burden bed reactor or the two or more reactors combined wherein.In the specific embodiment of the present invention, use fluidized-bed reactor, be more conducive to fully contacting of spent agent and oxygen, promote reaction efficiency.
In step (2), spent agent is transferred to burn device and oxygen reverse contact to make charcoal react, the coke content on spent agent surface is reduced, and releases a large amount of heat, make spent agent particle temperature rise to temperature needed for gasification reaction, obtain semi regeneration agent.
For the benefit of the carrying out of follow-up gasification reaction, namely in order to improve the temperature of overall spent agent to 740-860 DEG C, thus the reaction of next step gasifier is at high temperature carried out, reaction of making charcoal should consume the 20-50wt% of spent agent total surface coke content usually, the 20-50wt% consuming spent agent total surface coke content is conducive to making spent agent to be warmed up to temperature needed for gasification reaction, is more conducive to the productive rate ensureing synthetic gas.Therefore the condition of reaction of making charcoal such as controlledly is made as: reaction times 10-600s, the volumetric concentration of oxygen can be 2-30%, preferred 15-27%.The temperature of burning under above-mentioned reaction conditions in device can reach about 740-860 DEG C usually, reaches the temperature needed for gasification reaction.
The reactor (also claiming " gasifier " in the present invention) of the gasification reaction in step (3) can be selected from riser reactor, fluidized-bed reactor, moving-burden bed reactor or the two or more reactors combined wherein.In the specific embodiment of the present invention, gasifier also can use fluidized-bed reactor, is more conducive to fully contacting of semi regeneration agent and water vapour, promotes reaction efficiency.
In step (3), under the condition ensureing gasification temperature, the amount of coke that gasification reaction consumes is The more the better, gasification reaction should consume the 50-70wt% of spent agent total surface coke content usually, therefore the condition of gasification reaction is such as controlled is made as: reaction times 60-900s, the linear velocity of water vapour is 0.2-1m/s, preferred 0.4-1m/s.Temperature in above-mentioned reaction conditions gasified device can reach about 740-860 DEG C usually.
Due to the gasification reaction that coke and water vapour occur main in gasifier, therefore synthetic gas (CO+H in gasification product
2) content is generally greater than 85%.This gasification product being rich in synthetic gas can deliver to CO and H in the hydrogen manufacturing of water-gas shift device or adjustments of gas composition after desulfurization, dedusting
2ratio as the raw material of C-1 chemistry.
After above-mentioned steps, the regenerator surface char content usually obtained is less than 2% of spent agent total surface coke content, and regenerator can be made to maintain the activity of process inferior heavy oil.The regenerator obtained can re-start contact reacts with inferior heavy oil raw material, because gasification reaction is a strong endothermic process, in reaction process, semi regeneration agent temperature in gasifier declines, the regenerator temperature obtained is 680-800 DEG C, but temperature is still higher, before reaction, can heat exchange be carried out, the temperature of regenerator be met and carries out catalytic requirement with inferior heavy oil raw material.
In above-mentioned steps (1)-(3), the pressure controllable of reaction is between 0.1-0.5MPa (absolute pressure), to ensure steadily carrying out of reaction.
Gas-oil separation process of the present invention, stripping process, product oil gas fractionation process are all similar with the sepn process in Conventional catalytic cracking process, stripping process, product oil gas fractionation process.
Accompanying drawing referring to the embodiment of the present invention describes the present invention more fully.But the present invention can embody in many different forms, should not be construed as the embodiment being limited to and stating herein.
First inferior heavy oil raw material A can be preheated to 260-350 DEG C through process furnace 1, is then sprayed into riser reactor 4 and is carried out contact reacts by steam atomizing with contact substance.Inferior heavy oil raw material A and contact substance after short stay, enter fast fluidized bed reactor 5 and continue reaction in riser reactor 4, and heavy oil cracking reaction mainly occurs in fast fluidized bed reactor 5.After reaction, the oil gas of generation is separated through cyclonic separator 6 in settling vessel 8 with spent agent mixture, and oil gas goes out stripping stage through gas pipeline 7, and spent agent falls into stripping stage 9 and carries out stripping by from the water vapour B bottom stripping stage 9.The oil gas that spent agent adsorbs and intergranular oil gas are displaced by the water vapour B from stripping 9 sections of bottoms and return to top.Spent agent after stripping, by inclined tube 11 to be generated, enters through guiding valve 12 to be generated and burns device 13.Device 13 is burnt for vulcanization bed reactor in the present embodiment.
Make charcoal after spent agent enters and burns device 13 and from the oxygen-containing gas C burnt bottom device 13 and react, the part of coke on removing spent agent, and it is temperature required to make spent agent be warming up to follow-up gasification, obtains semi regeneration agent.The flue gas that reaction of making charcoal generates is isolated after the contact substance wherein carried secretly through cyclonic separator 6 and is discharged through reaction flue gas pipeline 16 of making charcoal.
Semi regeneration agent is first transferred to surge tank 17, is transferred to gasifier 3 by semi regeneration agent pipeline 18.In the present embodiment, gasifier 3 is vulcanization bed reactor.Semi regeneration agent standing sedimentation in surge tank 17, the oxygen-containing gas making to carry secretly between particle effusion, and the pipeline through surge tank 17 top returns and burns device 13 and continue to participate in reaction.In gasifier 3, partly residual coke and water vapour B react in agent again, and semi regeneration agent is well regenerated.What generate is rich in synthetic gas (CO and H
2) gasification product isolate through entering following process flow process by synthetic gas pipeline 14 after the regenerator particle carried secretly through cyclonic separator 6, isolated regenerator particle can return gasifier 3.
Regenerator in gasifier 3 enters interchanger 2 through regenerator pipeline 19, is regulated the heat of regenerator by interchanger 2, with meet its in riser reactor 4 with the catalytic needs of inferior heavy oil.In interchanger 2, heat transferring medium is water vapor B, and the low-temp recovery agent after heat exchange returns riser reactor 4 by regenerator sloped tube 10 through regeneration guiding valve 15 and recycles.In order to maintain the activity of contact substance, can regularly by a part of regenerator by gasifier 3 bottom caterpillar, simultaneously can fill into fresh contact substance D at interchanger 2 top.
Embodiment
For verifying the effect of the inventive method, adopt the technical process shown in Fig. 1, committee Rui Neila vacuum residuum is as inferior heavy oil raw material A to be processed, and the character of this vacuum residuum is shown in Table 1.The contact substance character adopted is as shown in table 2.It is as shown in table 3 that inferior heavy oil raw material A and contact substance carry out catalytic condition, and the composition of product is as shown in table 4.
Inferior heavy oil raw material A is preheating to 300 DEG C, then introduces riser reactor 4, at weight hourly space velocity 5h
-1, carry out under the condition of agent-oil ratio 7-8 and contact substance contact reacts, reactor interior reaction temperature is 480 DEG C, liquid product yield is more than 70wt%, and coke yield is close to raw material carbon residue, and carbon residue decreasing ratio is close to 90%, asphaltene removal is greater than 95%, and metal removal rate is more than 99%.Use the index of the heavy metal removing rate of above-mentioned technique acquisition product, asphaltene removal, carbon residue decreasing ratio advanced, and inferior heavy oil raw material A can obtain higher liquid yield after processing, and reduce gas yield and coke yield.
After stripping, on isolated spent agent, the H/C atomic ratio of coke is 0.74, and coke content is 2.14wt%, and the temperature of spent agent is 430 DEG C.Being sent into by spent agent burns in device 13, makes charcoal react with oxygen.In burner 13, reaction product obtains semi regeneration agent after being separated, and temperature is 840 DEG C.Semi regeneration agent is transferred to gasifier 3, reacts with water vapour B contact substance generating gasification.Make charcoal reaction and the technological condition of gasification reaction and product slates in table 5.After gasification reaction, synthetic gas (CO+H in gained gaseous product
2) volume fraction reach 87.2%.
Table 1
Table 2
| Catalyst property | Numerical value |
| Micro-activity | 16.7 |
| Abrasion index, % by weight | 0.6 |
| Specific surface area, m 2·g -1 | 89.7 |
| Pore volume, mlg -1 | 0.215 |
| Tap density, gcm -3 | 1.045 |
| Skeletal density, gcm -3 | 2.895 |
Table 3
| Project | The present invention program |
| Temperature of reaction, DEG C | 480 |
| Raw material preheating temperature, DEG C | 300 |
| Weight hourly space velocity, hour -1 | 5 |
| Catalyst/feed oil, weight by weight | 7-8 |
Table 4
| Product slates and character | The present invention program |
| Gas yield, % by weight | 7.58 |
| Liquid yield, % by weight | 72.67 |
| Coke yield, % by weight | 19.75 |
| Product liquid metal removal rate, % | 99.60 |
| Product liquid carbon residue decreasing ratio, % | 89.16 |
| Product liquid asphaltene removal, | 95.28 |
Table 5
As can be seen from table 4 and table 5, adopt method provided by the invention not only obviously can improve the quality of inferior heavy oil raw material A, produce the lighting oil products such as a certain amount of gasoline, diesel oil simultaneously, the synthetic gas that can also simultaneously provide productive rate higher (account for gasification product overall more than 85%), can be used for follow-up hydrogen production process or the raw material as C-1 chemistry.
Last it is noted that above each embodiment is only in order to illustrate technical scheme of the present invention, be not intended to limit; Although with reference to foregoing embodiments to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein some or all of technical characteristic; And these amendments or replacement, do not make the essence of appropriate technical solution depart from the scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a method for the double production of synthetic gas of inferior heavy oil processing, wherein,
Inferior heavy oil raw material contacts with contact substance and reacts, and is separated with spent agent by the oil gas that reaction generates;
Described spent agent and oxygen-containing gas counter current contact are made charcoal react, and it is temperature required to make the temperature of described spent agent rise to gasification reaction, obtains semi regeneration agent;
Make described semi regeneration agent contact generating gasification with water vapour to react, collect gasification product and regenerator.
2. method according to claim 1, wherein, described inferior heavy oil raw material is vacuum residuum, heavy oil residue, de-oiled asphalt, one or more of oil sands bitumen, tar, shale oil, coal liquefaction residue oil.
3. method according to claim 1, wherein, described inferior heavy oil raw material contacts the weight hourly space velocity of carrying out reacting with contact substance be 5-40h
-1, agent-oil ratio is 4-12.
4. method according to claim 1, wherein, described contact substance is the microballoon of silicon-aluminum containing material composition, and micro anti-active index is 5-40, and specific surface area is at 40-220m
2g
-1, aperture 5-60nm, bulk density 0.7-1.50gcm
-3, skeletal density 1.8-2.8gcm
-3, abrasion index is less than 2.0%.
5. method according to claim 1, wherein, described in make charcoal reaction reaction times be 10-600s, carrier of oxygen volume concentrations is 2-30%.
6. method according to claim 1, wherein, described in make charcoal reaction reaction times be 60-900s, the linear velocity of water vapour is 0.2-1m/s.
7. method according to claim 1, wherein, described inferior heavy oil raw material contacts the reactor carrying out reacting with contact substance be fluidization combined reactor, and described fluidization combined reactor bottom is riser tube, top series connection fast fluidized bed reactor.
8. method according to claim 7, wherein, described riser reactor length is less than 60% of described fluidization combined reactor total length.
9. method according to claim 1, wherein, described in make charcoal reaction or the reactor of gasification reaction be selected from riser reactor, fluidized-bed reactor, moving-burden bed reactor or the two or more reactors combined wherein.
10. method according to claim 1, wherein, reacts with inferior heavy oil contact raw as contact substance again using the regenerator obtained through gasification reaction.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020015602A1 (en) * | 2018-07-16 | 2020-01-23 | 中国石油化工股份有限公司 | Method for catalytic cracking hydrocarbon oil and system therefor |
| CN109054903B (en) * | 2018-08-24 | 2021-04-16 | 新奥科技发展有限公司 | Coal hydro-gasification method and device |
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| US11891578B2 (en) | 2018-07-16 | 2024-02-06 | China Petroleum & Chemical Corporation | Process and system for catalytic cracking of hydrocarbon oils |
| CN109054903B (en) * | 2018-08-24 | 2021-04-16 | 新奥科技发展有限公司 | Coal hydro-gasification method and device |
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