CN102234535B - Method for processing low-quality heavy oil and simultaneously producing synthetic gas - Google Patents
Method for processing low-quality heavy oil and simultaneously producing synthetic gas Download PDFInfo
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Abstract
The invention relates to a method for processing low-quality heavy oil and simultaneously producing a synthetic gas. The method comprises the following steps: reacting heavy oil raw materials with a contact agent in a reactor to obtain a coked catalyst, and carrying out gasification reaction on the coked catalyst in a gasifier to generate a gas product containing the synthetic gas and to convert the coked catalyst into a semi-regenerative agent; and delivering the semi-regenerative agent to a regenerator, carrying out complete regeneration under the regeneration reaction conditions to obtain regenerated flue gas and a regenerated agent, returning the regenerated flue gas to the gasifier and returning the regenerated agent to the reactor. The method provided by the invention integrates the deep processing of low-quality heavy oil and the reasonable utilization of excess carbonaceous residues, gasifies surplus coke in the gasifier to generate the synthetic gas from the low-quality heavy oil used as the raw material on the premise of maximally producing light oil, and rationally utilizes the heavy oil processing residues to produce the products with high economic values.
Description
Technical field
The present invention relates to a kind of in the situation that not there is not hydrogen, the contact cracking of heavy oil, and the combined method of producing synthetic gas with solid carbonaceous material.
Background technology
Crude oil heaviness, the development trend of in poor quality and the increasingly stringent of relevant environmental regulation in world wide, proposed many new problems to refining of petroleum industry.For example, the reduction of the increase of foreign matter content and H/C atomic ratio in stock oil, requires in stock oil first being processed, and in order to improve product quality, all need through adding hydrogen pretreatment or unifining process, therefore, hydrogenation process has become a kind of requisite processing means.Although the highly purified hydrogen of catforming process energy by-product, this part amounts of hydrogen can not meet the demand of hydrogenation technique far away.Prior art can provide multiple other the hydrogen production process such as steam methane cracking hydrogen production, heavy oil hydrogen manufacturing, coal hydrogen manufacturing, but these method hydrogen manufacturing costs are higher.Therefore, development focus in hydrogenation technique hydrogen particularly the exploitation of cheap hydrogen be a matter of great account feelings.
Cracking-gasification integral process of heavy, inferior feedstock oil, takes into account oil refining, gas making hydrogen manufacturing, in processing inferior heavy oil, improve aspect efficiently the utilizing of low-quality carbonaceous and have obvious advance.Poor quality oil fluidized coking process and the flexicoking technique of the exploitation of U.S. Mobil Corp. are exactly the beginning of cracking-gasification integral process.The two all usings burnt core as fluidizing medium, as the carrier of coke and heat, still exists the size distribution of coke granule inhomogeneous simultaneously, easily produces compared with problems such as megalump and finely-ground cokes, affects fluid effect.3D and the MSCC technique of the ART technique of Engelhard Corp, the FTC technique of Japanese fuji oil company, the U.S., and the ROP technique of China all by limit react, limit decarburization carries out shallow degree processing to residual oil, the coke of the thermal barrier adopting or catalyst entrainment deposition is by burning heat release energy supply, complete regeneration simultaneously, but all have the problems such as capacity usage ratio is not high, bottoms conversion is low.
Due to the gasification technology of coal, biomass etc. comparative maturity, in view of with coke physicochemical property on similarity, can be used as the reference of coke gasification preparing synthetic gas.But existing gasification technology operational condition is harsh, especially shows that gasification temperature is too high, is generally 1000-2200 ℃.High gasification temperature is conducive to carbonaceous and is converted into synthetic gas, but equipment and operating process have all been proposed to very high requirement.More inapplicablely contact cracking-coke gasification integral process with inferior heavy oil, because heat energy efficiency, catalyst stability etc. are all subject to great restriction.
US 5597474 discloses the combined method of a kind of fluidized coking process and steam reformation production hydrogen, the method comprises fluid coking reactor, well heater and gasifier, from fluidized-bed reactor solid coke powder out, between reactor and well heater, and circulate between well heater and gasifier.Part coke in gasifier with steam reaction, produce the product gas be rich in hydrogen.
US 5362380 discloses a kind of fluidized catalytic cracking method that produces hydrogen, the method first by fluid catalytic cracking spent agent under the state of anaerobic, at 537～649 ℃ with steam reaction to generate synthetic gas, next under the state of aerobic, is regenerated gained half regenerator at 537～815 ℃.In 537～649 ℃ of temperature ranges, the speed of reaction of carbon deposit and water vapor is very slow, thereby has affected its economy, and can accelerate the aging inactivation of catalytic cracking catalyst.
CN1169707C discloses a kind of method of utilizing regeneration fume from catalytic cracking hydrogen manufacturing, the method is delivered to the first revivifier by the catalyzer of carbon deposit after catalytic cracking reaction, after contacting at the temperature of 500-660 ℃ with oxygen-containing gas, CO in gained regenerated flue gas and water vapor carry out transformationreation, obtain hydrogen-rich gas.Half regenerator that the first revivifier obtains enters Second reactivator, contacts, and regenerate under the catalytic cracked regenerated condition of routine with oxygen-containing gas, and the catalyzer Returning reactor after regeneration recycles.The conventional catalytically cracked material of the method processing treatment, used is also conventional catalytic cracking catalyst.
CN101457152A discloses a kind of conversion method for hydrocarbon oil, the method is included under cracking conditions, hydrocarbon ils is contacted in reactor with cracking catalyst, obtain reaction product and reclaimable catalyst, reaction product is separated with reclaimable catalyst, reclaimable catalyst contacts with oxygen-containing gas with water vapor in vapourizing furnace, obtains synthetic gas and half regenerated catalyst, the temperature of reaction of vapourizing furnace be 500 ℃ to being less than 800 ℃; This synthesis gas is separated with half regenerated catalyst, at least part of half regenerated catalyst is sent in reactor and recycled.
Summary of the invention
The object of the invention is on the basis of existing technology, a kind of inferior heavy oil method of production of synthetic gas of holding concurrently of processing is provided, can solve the thermo-efficiency that prior art exists low, and the problem such as catalyzer hydrothermal deactivation is fast.
Method provided by the invention comprises:
(1) heavy oil feedstock and contact substance, in reactor, react under contact reacts condition, and the product oil gas that reaction obtains carries out separated with spent agent;
(2) the product oil gas of step (1) gained, through fractionation, obtains gas, gasoline fraction, diesel oil distillate and wax oil cut;
(3) spent agent of step (1) gained is sent to gasifier after stripping, gasifier arranges Liang Ge district, part spent agent and vaporized chemical I enter gasifier Yi district from gasifier bottom, remaining spent agent and vaporized chemical II enter gasifier Er district from gasifier middle part, carbon deposit on spent agent is generating gasification reaction under gasification reaction conditions, the gaseous product that generation contains synthetic gas, spent agent becomes half regenerator;
(4) half regenerator of step (3) gained is sent to revivifier, in regenerative response condition, regenerates, and obtains regenerated flue gas and regenerator, and gained regenerator returns in the reactor of step (1).
The carbon residue of heavy oil feedstock of the present invention is 10-40 % by weight, and metal content is 25-1000 μ g/g.Described heavy oil feedstock is selected from one or more in oil at the bottom of heavy crude, acid-containing raw oil, shale oil, long residuum, vacuum residuum, decompressed wax oil, wax tailings, deasphalted oil, hydrocracking tail oil, tank, coal tar, coal liquefaction residue oil or other secondary processing distillate.Inferior heavy oil in reactor with contact substance contact reacts, can realize the lighting of the larger degree of depth, and decarburization, demetalization.The product oil gas of gained, through fractionation, obtains gas, gasoline fraction, diesel oil distillate and wax oil cut.The wax oil cut of gained can be used as the raw material of catalytic cracking or hydrocracking, also can utilize at this reactive system internal recycle.
The described reactor types of step (1) is selected from riser reactor, fluidized-bed reactor, moving-burden bed reactor or downer reactor, or is two or more reactor combining in them.Wherein riser reactor and downer reactor can be isodiametricly also can straighten footpath.
In described step (1), contact reacts condition is: temperature of reaction 300-700 ℃, reaction times 0.8-180 second, the weight ratio of contact substance and heavy oil feedstock is 4-20: 1, and the weight ratio of water vapor and heavy oil feedstock is 0.02-0.40: 1, reaction pressure is 130-450kPa (gauge pressure).Preferred reaction conditions is: temperature of reaction 450-650 ℃, more preferably 500-600 ℃, reaction times 1.0-4.5 second, the weight ratio 5-15 of contact substance and heavy oil feedstock: 1, the weight ratio 0.03-0.30 of water vapor and heavy oil feedstock: 1, reaction pressure 140-350kPa (gauge pressure).
Described contact substance contains silica-alumina material, and micro-activity (is measured by standard A STMD3907-87) between 5-50, and particle size range is between 20-1000 μ m, and median size is between 70-150 μ m.Described silica-alumina material is selected from one or more in molecular sieve, amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, aluminum oxide, quartz sand, silicon sol.Described contact substance is a kind of good hydrothermal stability, has the spheroidal particle of certain catalytic cracking activity.Can prepare by the dry or method of agglomeration of spraying.On the spent agent of described carbon deposit, coke content is 0.8 % by weight-25.0 % by weight.Contact substance of the present invention has three Main Functions: the one, and pressure fuel, the 2nd, carbonaceous resistates carrier, the 3rd, heat energy carrier.
Described step (1) can maintain certain hydrogen flowing quantity to reduce the coking of wall, tube wall in reaction process, improve transportation performance, can also promote as metallic nickel, vanadium the inhibitor of heavy oil dehydrogenation reaction, improve cracking performance, to reduce the selectivity of the dry gas such as hydrogen, the weight ratio of hydrogen and raw material is 0.001-0.20: 1.
The process of gas-oil separation described in the present invention, stripping process, product oil gas fractionation process all with conventional catalytic cracking (FCC) in sepn process, stripping process, product oil gas fractionation process similar.
In described step (3), gasifier is selected from riser tube gasifier, fluidized-bed gasifier or moving-bed gasification device, or is the two or more gasifiers that combine in them.
In method provided by the invention, described step (3) gasifier at least arranges Liang Ge district.From the spent agent sectional feeding of step (1), enter respectively the not same district of gasifier with the vaporized chemical of different oxygen.Part spent agent and the high vaporized chemical I of oxygen level enter gasifier Yi district, and combustion reactions mainly occurs, and the gasification reaction conditions in a described district is: temperature 800-1100 ℃, bed layer pressure 130-450kPa (gauge pressure), duration of contact 0.5-10 second; Low or the oxygen-free vaporized chemical II of remaining spent agent and oxygen level enters gasifier Er district, main generating gasification reaction, the gasification reaction conditions in described 2nd district is: temperature 740-1000 ℃, bed layer pressure 130-450kPa (gauge pressure), duration of contact 5-60 second.On spent agent, the gasification of carbon deposit is also half regenerative process of contact substance to be generated, the available gas (CO+H that gasification forms
2) content is greater than 50 volume % (butt).In described step (3), on half regenerator, coke content is 0.3-1.0 % by weight.
Gasification reaction in described gasifier carries out at 740-1000 ℃ of temperature, and this temperature is apparently higher than conventional FCC regeneration temperature, so gasification reaction speed is fast.In addition, gasifier mainly generates synthetic gas, CO+H in its gaseous product
2the content of (butt) is greater than 50 volume %, in this and FCC regenerative process, needs to reduce CO concentration, to prevent tail combustion, has obvious difference.
Step (1) the gained spent agent integral body of take is benchmark, and in mass, the spent agent that enters gasifier from bottom is 30%-90%, preferred 35%-70%, and the spent agent that enters gasifier from middle part is 10%-70%, preferably 30%-65%.
Oxygen content in vaporized chemical I is 15 volume %-50 volume %.Vaporized chemical I is selected from the mixed gas of one or more formation in oxygen-containing gas, water vapor, carbonic acid gas, and described oxygen-containing gas is oxygen and/or air, and wherein oxygen-containing gas is necessary component, and water vapor and carbonic acid gas are selectable components.Oxygen content in vaporized chemical II is 0 volume %-15 volume %.Vaporized chemical II is selected from one or more the mixed gas in oxygen, air, water vapor, carbonic acid gas.
Preferred gasifier be vertically followed successively by from bottom to up pre-fluidisation section, burning zone, enlarged-diameter gasification section, reduced outlet section.The pre-fluidisation section that in described step (3), a part of spent agent and vaporized chemical I enter gasifier from gasifier bottom, remaining spent agent and vaporized chemical II enter gasifier from the junction of gasifier burning zone and gasification section.
While adopting preferred gasifier, a part of spent agent and vaporized chemical I, through pre-fluidisation section, enter burning zone.The operating method that adopts turbulent bed or riser tube to carry at burning zone, spent agent carries out oxygen-enriched combusting within the shorter residence time, and the heat energy fast lifting spent agent of generation arrives very high temperature, and consumes most oxygen, produces a considerable amount of CO
2gas.The logistics of burning zone rises and enters gasification section, due to the increase of gasification section interior diameter, the flow velocity of logistics is minimized, and in the kinestate of gasification section, is bubbling bed or dispersion fluidized bed.Because the speed of coke gasification on spent agent is reacted far below its oxygen-enriched combusting, therefore, adopt the gasification section of enlarged-diameter, can extend the gasification reaction time, improve gasifyin g yield.Remaining spent agent and vaporized chemical II enter gasifier from the junction of gasifier burning zone and gasification section.The oxygen content of vaporized chemical II is low, and gasification section is Hypoxic habitats, with the synthetic gas of avoiding being generated as far as possible, is oxidized to carbonic acid gas and water.Described gasifier can be by the rapid combustion reaction of coke gasification reaction coupling slow with it, and again by the vaporized chemical sectional feeding of different oxygen, secondary reaction to the burning of coke on spent agent, gasification, product is optimized control, realize the autothermal equilibrium of system, and obtain the synthetic gas of high yield.
The gaseous product that step (3) gained is contained to synthetic gas with from the spent agent of step (1) reactor, carry out heat exchange, be about to the gaseous product that contains synthetic gas that gasifier draws and carry out heat exchange with the spent agent entering before gasifier; Spent agent initial temperature is 450-550 ℃, the gaseous product initial temperature 750-950 ℃ of gasifier, and through heat exchange, spent agent temperature is 600-700 ℃, is rich in the gas stream temperature 700-750 ℃ of synthetic gas.
The described gas stream that is rich in synthetic gas is delivered in follow-up water vapor conversion process hydrogen manufacturing or is prepared C-1 chemistry synthetic gas after desulfurization, dedusting, can also partly return in the reactor of step (1) and suppress gas for coke.
In the revivifier of step (4), the mixed gas contact reacts that half regenerator and oxygen-containing gas and water vapor form, carries out holomorphosis, and on gained regenerator, carbon deposit content is less than or equal to 0.05 % by weight, obtains regenerated flue gas simultaneously.In regenerative process, be also thermal exchange process, half regenerator initial temperature is 740-950 ℃, and in revivifier, with the coke of oxygen reaction burn off remnants, the heat that half regenerator carries and the heat that burns release heat up steam heating.Burning with heat-exchange time is 2-300 second, preferably 5-150 second.After holomorphosis, regenerator and regenerated flue gas temperature are 650-750 ℃, bed layer pressure 130-450kPa (gauge pressure) in regenerative process.In revivifier, the oxygen content 20 volume %-40 volume % in initial mixing gas, in the regenerated flue gas at revivifier top, oxygen content is 0 volume %-10 volume %.The regenerated flue gas of step (4), as vaporized chemical II, enters gasifier from gasifier middle part.
Advantage of the present invention:
(1) method provided by the present invention is integrated, and inferior heavy oil deep processing and superfluous carbonaceous resistates rationally utilize two aspects, take inferior heavy oil as raw material, maximize under the prerequisite of producing light oil, the coke of having more than needed gasifies and generates synthesis gas in vapourizing furnace, rationally utilize the resistates of heavy oil upgrading, produce the product of high economic worth.
(2) the present invention has adopted the method that subregion charging in gasifier, subregion react.The vaporized chemical I of part spent agent and high oxygen content enters gasifier from vapourizing furnace bottom, mainly carry out combustion reactions, provide gasification reaction required temperature, remainder spent agent with compared with the vaporized chemical II of low oxygen content, from gasifier middle part, enter gasifier, main generating gasification reaction, generates and is rich in CO+H
2gaseous product.By the vaporized chemical sectional feeding of different oxygen, making gasification section is Hypoxic habitats, with the secondary reaction (being oxidized to carbonic acid gas and water) of the synthetic gas avoiding being generated as far as possible.The secondary reaction of the burning by coke on spent agent, gasification, product is optimized control, obtains the synthetic gas of high yield.
(3) the present invention takes full advantage of temperature head between reactor and gasifier, and the temperature head between gasifier and revivifier, carry out on the one hand thermal exchange, reach the thermal equilibrium of device, make revivifier without outside heat removing, on the other hand regenerated flue gas is returned to gasifier as vaporized chemical II, reduce the Carbon emission of device integral body.
(4) the present invention takes full advantage of the carbon deposit of spent agent, and the one, as gasification reaction raw material, generate heat supply and generate synthetic gas; The 2nd, as the protective layer of contact substance, reduce the direct contact of water vapor to contact substance lattice in gasifier, improve the ability of heat-resisting, the water-fast thermal environment of contact substance; The 3rd, in gasifier, the carbon deposit on spent agent can consume object product C O+H
2the oxygen of periphery, protection object product is not consumed, thus the synthetic gas ratio obtaining in gaseous product is high.
Accompanying drawing explanation
Fig. 1 is the hold concurrently method flow schematic diagram of production of synthetic gas of processing inferior heavy oil provided by the present invention.
Fig. 2 is the schematic diagram of preferred gasifier provided by the present invention.
Embodiment
Below in conjunction with accompanying drawing, method provided by the present invention is further described, but not thereby limiting the invention.As shown in Figure 1, the hold concurrently method flow of production of synthetic gas of processing inferior heavy oil provided by the invention is described below:
From the heavy oil feedstock of pipeline 1, with fresh contact substance from pipeline 2 with from the regenerator of pipeline 13, and from the steam of pipeline 3 in the interior contact of reactor 4, reaction, heavy feed stock can decarburization and demetalization in lighting.The inactivation contact substance (spent agent) of the reaction oil gas of gained and carbon deposit is separated at reactor 4 tops, and separated oil gas is sent into subsequent separation system 8 through pipeline 5, is separated into distillate and gaseous product and extracts out through pipeline 11.
The spent agent of reactor 4 gained enters steam stripping unit 10 through pipeline 6, use from pipeline 7 water vapors and carry out stripping, stripping gained oil gas is sent into separation system 8 through pipeline 9, spent agent after stripping enters heat exchange unit 14 through pipeline 12, carry out heat exchange with the gaseous product of extracting out from gasifier 24 from pipeline 18, at the top of heat exchange unit gas, solid separated, the separating obtained gas stream that contains synthetic gas is extracted out through pipeline 23, and the high temperature spent agent of gained is extracted out through pipeline 19.Gas-solid heat exchange unit 14 can be adverse current, also stream, cross-current type operation.
High temperature spent agent from pipeline 19 is divided into two strands, and a stock-traders' know-how pipeline 22 and the bottom that enters gasifier 24 from the high vaporized chemical I of pipeline 25 oxygen levels, carry out combustion reactions in gasifier 24 mono-district; Another stock-traders' know-how pipeline 21 with from the low vaporized chemical II of pipeline 15 oxygen levels, from the middle part of gasifier 24, enter, in gasifier 24 2nd district, carry out gasification reaction.Gas-solid two-phase mixture is separated at gasifier 24 tops, and gained half regenerator is sent into revivifier 16 through pipeline 20, and gained is rich in the gaseous product of synthetic gas through 18 extractions, sends into heat exchange unit 14.Gaseous product after heat exchange enters desulfurization, cleaning apparatus 26 through pipeline 23, removes H
2s, and the solid dust carrying, be then sent to water vapor converter unit 27 for hydrogen manufacturing or as C-1 chemistry synthesis material gas, further at CO
2the interior separation of separating unit 28, gained CO
2gas is extracted out through pipeline 29, and gained synthetic gas or hydrogen are extracted out through pipeline 30.
Half regenerator of gasifier 24 gained is sent into revivifier 16 through pipeline 20, the mixed gas reaction forming with oxygen from pipeline 17 and water vapor, make half regeneration contact substance holomorphosis, gas solid separation is carried out at top at revivifier 16, gained regenerator is through pipeline 13 Returning reactors 4, and gained regenerated flue gas enters gasifier 24 through pipeline 15 as vaporized chemical II.
Fig. 2 is the schematic diagram of preferred gasifier provided by the present invention.As shown in Figure 2, gasifier is vertically followed successively by pre-fluidisation section 2, burning zone 4, the gasification section 6 of enlarged-diameter, the outlet section 7 of reduced identical with pre-fluidisation section diameter from bottom to up.
The vaporized chemical I that oxygen level is higher enters from pre-fluidisation section 2 through pipeline 1, part spent agent enters pre-fluidisation section 2 through reinforced inclined tube 3, by vaporized chemical I, carry and move upward and accelerate to enter burning zone 4, carry out under certain conditions oxygen-enriched combusting, improve the temperature of spent agent and vaporized chemical, and produce new vaporized chemical CO
2.Combining site by burning zone and gasification section after the vaporized chemical II that another part spent agent is lower with oxygen level from pipeline 5 mixes enters gasifier, carries out gasification reaction.Vaporized chemical II is the vaporized chemical that oxygen level is lower, and its effect is in order to improve or maintain the temperature of gasification section 6, is conducive to be beneficial to water vapor, CO
2gasification reaction with spent agent.The gaseous product that is rich in synthetic gas forming in gasifier and half regenerator, after the outlet section 7 of reduced, are extracted out by pipeline 8.
With embodiment, describe the present invention in detail below, but not thereby limiting the invention.The residual oil raw material main character adopting in embodiment and comparative example is in Table 1.
USY molecular sieve, sial matrix, silica-based binding agent are mixed to making beating according to the mass ratio of 10: 55: 35 with a small amount of deionization, spray drying forming, roasting, makes contact substance A.The initial micro-activity of contact substance A is 16.Residual oil raw material contacts, reacts with contact substance A in fluidized-bed reactor, and it is separated that inactivation contact substance and product oil gas carry out, and product oil gas obtains dry gas, cut wet goods product after fractionation, and catalytic reaction conditions and products distribution are as shown in table 2.
The content of the upper coke of spent agent A is 2.83 % by weight.By spent agent A water steam stripped 30 minutes, the temperature that obtains spent agent A was 470 ℃.Spent agent A after stripping and gasifier product gas are at heat exchange unit countercurrent flow, and revolving a minute rear spent agent A temperature is 610 ℃.Spent agent A is divided into two strands, sends in gasifier from vaporized chemical I and the vaporized chemical II segmentation of different oxygen level respectively, generating gasification reaction.Concrete gasification reaction conditions is as shown in table 2.In gasifier, after gas solid separation, obtain half regenerator A and gaseous product.Gaseous product distribution is as shown in table 2, as can be seen from Table 2, and gained object product C O+H
2volume fraction be 52.3%.
The upper coke content of half regenerator A of gasifier gained is 0.60 % by weight.This half regenerator A sends in revivifier and contains the mixed gas reaction of the oxygen+water vapor of oxygen volume fraction 23%.In revivifier, after gas solid separation, obtain regenerated flue gas and regenerator A.Regenerator A coke content is down to < 0.05 % by weight, and direct Returning reactor.Regenerated flue gas mixes with the spent agent of heat exchange after stripping, then as vaporized chemical II, sends into gasifier.In revivifier, reaction conditions is as shown in table 2.The present embodiment can reach thermal equilibrium, and revivifier does not need to establish external warmer.
By contact substance A continuous operation 10 times in said process, measure its micro-activity, numerical value is 12, and method provided by the invention is described, can guarantee the hydrothermal stability that contact substance is high.
Comparative example 1
This comparative example adopts contact substance A and stock oil in the same manner as in Example 1 in reactor, and the content of the upper coke of gained spent agent A is 2.89 % by weight.Catalytic reaction conditions and products distribution are as shown in table 2.Through overwinding divide, after stripping, all spent agent A send in gasifier with the vaporized chemical that oxygen+water vapor forms, generating gasification is reacted, and is different from gasifier subregion charging in embodiment 1.In gasifier, reaction conditions and gaseous product distribution are as shown in table 2.In table 2, can find out gained object product C O+H
2volume fraction be only 43.5%.Than embodiment 1 few nearly 10 percentage point.
The upper coke content of half regenerator A of gasifier gained is 0.75 % by weight, and half regenerator is sent in revivifier and reacted with the mixed gas that contains the oxygen+water vapor of oxygen volume fraction 23%.Revivifier carries out gas solid separation, and the coke content on gained regenerator is < 0.05 % by weight, and direct Returning reactor, and regenerated flue gas is discharged separately system.In revivifier, reaction conditions is as shown in table 2.This comparative example fails to reach thermal equilibrium, and revivifier need to be established external warmer.
By contact substance A continuous operation 10 times in said process, measure its micro-activity, numerical value reduces to 5, compares with embodiment 1, and 7 points have declined.
By the acidic white earth of pickling, roasting, screening processing, get the screening of 20-100 μ m particle size range, as contact substance B.The initial micro-activity of contact substance B is 8.Residual oil raw material contacts, reacts with contact substance B in fluidized-bed reactor, and it is separated that inactivation contact substance and product oil gas carry out, and product oil gas obtains dry gas, cut wet goods product after fractionation, and catalytic reaction conditions and products distribution are as shown in table 2.
The content of the upper coke of spent agent B is 2.31 % by weight.By spent agent B water steam stripped 30 minutes, the temperature that obtains spent agent B was 475 ℃.Spent agent B after stripping and gasifier product gas are at heat exchange unit countercurrent flow, and revolving a minute rear spent agent B temperature is 615 ℃.Spent agent B is divided into two strands, sends in gasifier from vaporized chemical I and the vaporized chemical II segmentation of different oxygen level respectively, generating gasification reaction.Concrete gasification reaction conditions is as shown in table 2.In gasifier, after gas solid separation, obtain half regenerator B and gaseous product.Gaseous product distribution is as shown in table 2, as can be seen from Table 2, and gained object product C O+H
2volume fraction be 54.8%.
The upper coke content of half regenerator B of gasifier gained is 0.40 % by weight.This half regenerator B sends in revivifier and contains the mixed gas reaction of the oxygen+water vapor of oxygen volume fraction 23%.In revivifier, after gas solid separation, obtain regenerated flue gas and regenerator B.Regenerator B coke content is down to and is less than 0.1 % by weight, and direct Returning reactor.Regenerated flue gas mixes with the spent agent of heat exchange after stripping, then as vaporized chemical II, sends into gasifier.In revivifier, reaction conditions is as shown in table 2.The present embodiment can reach thermal equilibrium, and revivifier does not need to establish external warmer.
By contact substance B continuous operation 10 times in said process, measure its micro-activity, numerical value is 6, and method provided by the invention is described, can guarantee the hydrothermal stability that contact substance is high.
Comparative example 2
This comparative example adopts contact substance B and stock oil in the same manner as in Example 2 in reactor, and the content of the upper coke of gained spent agent B is 2.32 % by weight.Catalytic reaction conditions and products distribution are as shown in table 2.Through overwinding divide, after stripping, all spent agent B send in gasifier with the vaporized chemical that oxygen+water vapor forms, generating gasification is reacted, and is different from gasifier subregion charging in embodiment 1.In gasifier, reaction conditions and gaseous product distribution are as shown in table 2.In table 2, can find out gained object product C O+H
2volume fraction be only 44.0%.Than embodiment 2 few nearly 10 percentage point.
The upper coke content of half regenerator B of gasifier gained is 0.60 % by weight, and half regenerator B sends in revivifier and reacts with the mixed gas that contains the oxygen+water vapor of oxygen volume fraction 23%.Regenerator B carries out gas solid separation, and the coke content on gained regenerator B is for being less than 0.1% % by weight, and direct Returning reactor, and regenerated flue gas is discharged separately system.In revivifier, reaction conditions is as shown in table 2.This comparative example fails to reach thermal equilibrium, and revivifier need to be established external warmer.By contact substance B continuous operation 10 times in said process, measure its micro-activity, numerical value reduces to 2, compares with embodiment 2, and 4 points have declined.
Table 1
Table 2
Claims (14)
1. process the inferior heavy oil method for production of synthetic gas of holding concurrently, comprising:
(1) heavy oil feedstock and contact substance, in reactor, react under contact reacts condition, and the product oil gas that reaction obtains carries out separated with spent agent;
(2) the product oil gas of step (1) gained, through fractionation, obtains gas, gasoline fraction, diesel oil distillate and wax oil cut;
(3) spent agent of step (1) gained is sent to gasifier after stripping, gasifier arranges Liang Ge district, part spent agent and vaporized chemical I enter gasifier Yi district from gasifier bottom, remaining spent agent and vaporized chemical II enter gasifier Er district from gasifier middle part, carbon deposit on spent agent is generating gasification reaction under gasification reaction conditions, the gaseous product that generation contains synthetic gas, spent agent becomes half regenerator; Described gasifier Yi district gasification reaction conditions is: temperature 800-1100 ℃, pressure 130-450kPa, reaction times 0.5-10 second; Gasifier Er district gasification reaction conditions is: temperature 740-1000 ℃, pressure 130-450kPa, reaction times 5-60 second;
Oxygen content in described vaporized chemical I is 15 volume %-50 volume %, and vaporized chemical I is selected from one or more the mixed gas in oxygen-containing gas, water vapor, carbonic acid gas, and described oxygen-containing gas is oxygen and/or air; Oxygen content in described vaporized chemical II is 0 volume %-15 volume %, and vaporized chemical II is selected from one or more the mixed gas in oxygen, air, water vapor, carbonic acid gas;
(4) half regenerator of step (3) gained is sent to revivifier, in regenerative response condition, regenerates, and obtains regenerated flue gas and regenerator, and gained regenerator returns in the reactor of step (1).
2. according to the method for claim 1, it is characterized in that, the carbon residue of described heavy oil feedstock is 10-40 % by weight, and metal content is 25-1000 μ g/g.
3. according to the method for claim 1, it is characterized in that, described heavy oil feedstock is selected from one or more in oil at the bottom of heavy crude, acid-containing raw oil, shale oil, long residuum, vacuum residuum, decompressed wax oil, wax tailings, deasphalted oil, hydrocracking tail oil, tank, coal tar, coal liquefaction residue oil or other secondary processing distillate.
4. according to the method for claim 1, it is characterized in that, in described step (1), contact reacts condition is: temperature of reaction 300-700 ℃, reaction times 0.8-180 second, the weight ratio of contact substance and heavy oil feedstock is 4-20:1, the weight ratio of water vapor and heavy oil feedstock is 0.02-0.40:1, and reaction pressure is 130-450kPa.
5. according to the method for claim 1, it is characterized in that described contact substance contains silica-alumina material, micro-activity is between 5-50, and particle size range is between 20-1000 μ m, and median size is between 70-150 μ m.
6. according to the method for claim 5, it is characterized in that described silica-alumina material is selected from one or more in molecular sieve, amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, aluminum oxide, quartz sand, silicon sol.
7. according to the method for claim 1, it is characterized in that, in described step (3), gasifier is selected from riser tube gasifier, fluidized-bed gasifier or moving-bed gasification device, or is the two or more gasifiers that combine in them.
8. according to the method for claim 1, it is characterized in that, gasifier be vertically followed successively by from bottom to up pre-fluidisation section, burning zone, enlarged-diameter gasification section, reduced outlet section.
9. according to the method for claim 8, it is characterized in that, the pre-fluidisation section that in described step (3), a part of spent agent and vaporized chemical I enter gasifier from gasifier bottom, remaining spent agent and vaporized chemical II enter gasifier from the junction of gasifier burning zone and gasification section.
10. according to the method for claim 1, it is characterized in that, step (1) the gained spent agent integral body of take is benchmark, and in mass, the spent agent that enters gasifier from bottom is 30%-90%, and the spent agent that enters gasifier from middle part is 10%-70%.
11. according to the method for claim 1, it is characterized in that, in described step (3), on half regenerator, coke content is 0.3-1.0 % by weight.
12. according to the method for claim 1, it is characterized in that, the gaseous product that step (3) gained is contained to synthetic gas carries out heat exchange with the spent agent from step (1) reactor.
13. according to the method for claim 1, it is characterized in that, step (4) half regenerator initial temperatures are 740-950 ℃, and after regeneration, regenerator and regenerated flue gas temperature are 650-750 ℃, bed layer pressure 130-450kPa in regenerative process, reaction times 2-300 second.
14. according to the method for claim 1, it is characterized in that, the regenerated flue gas of step (4), as vaporized chemical II, enters gasifier from gasifier middle part.
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| CN108774547B (en) * | 2018-05-02 | 2021-05-11 | 国家能源投资集团有限责任公司 | System and method for preparing synthesis gas from coal liquefaction residues |
| CN112538373B (en) * | 2019-09-23 | 2022-02-25 | 中国石油大学(北京) | Method and device for co-production of heavy oil deep lightening-synthesis gas |
| CN112538378B (en) * | 2019-09-23 | 2022-02-25 | 中国石油大学(北京) | Method and device for co-production of heavy oil lightening and synthesis gas |
| CN112538379B (en) * | 2019-09-23 | 2022-02-25 | 中国石油大学(北京) | Processing method and device for heavy oil lightening-coproduction synthesis gas |
| CN112538375B (en) * | 2019-09-23 | 2022-02-22 | 中国石油大学(北京) | Processing method and device for heavy oil lightening/synthesis gas co-production |
| CN112538380B (en) * | 2019-09-23 | 2022-02-22 | 中国石油大学(北京) | Method and device for integrating heavy oil contact cracking and coke gasification |
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| CN1504404A (en) * | 2002-11-29 | 2004-06-16 | 中国石油化工股份有限公司 | Process combined oil refining and gasification |
| CN101451073A (en) * | 2007-12-06 | 2009-06-10 | 中国石油化工股份有限公司 | Method for combination processing heavy oil by pyrolysis and gasification |
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