CN103571529B - A kind of methanogenic processing of heavy oil method of holding concurrently - Google Patents
A kind of methanogenic processing of heavy oil method of holding concurrently Download PDFInfo
- Publication number
- CN103571529B CN103571529B CN201210253853.7A CN201210253853A CN103571529B CN 103571529 B CN103571529 B CN 103571529B CN 201210253853 A CN201210253853 A CN 201210253853A CN 103571529 B CN103571529 B CN 103571529B
- Authority
- CN
- China
- Prior art keywords
- gas
- gasification
- contact
- agent
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A kind of methanogenic processing of heavy oil method of holding concurrently, when inferior heavy oil comes in contact and produces light oil after cracking, the spent agent of gained enters gasification unit, and in gasifier, the coke on spent agent and gasifying agent generating gasification and methanation reaction, generate and comprise CH4、CO、H2、CO2Gasification gas, the sulphur of gasification in gas is mainly H2S. Gasification gas enters sulphur and removes device and remove after sulphur, gas is further separated to gained CH4Extract isolated CO and H out2Return to gasifier. The contact agent of partly regenerating of gained is at regeneration unit, and under the condition that has oxygen to exist, on contact agent, residual charcoal generation completing combustion, obtains holomorphosis contact agent and flue gas, and the sulphur in flue gas is mainly SOX, flue gas is arranged outward after reaching discharge standard by alkaline cleaner or sulfur transfer additive, and regeneration contact agent returns to contact cracker. This invention can be efficiently, green is utilized petroleum resources.
Description
Technical field
The invention belongs to a kind of inferior heavy oil processing method. More particularly, be that one contacts heavy oilThe combinational processing method that cracking and gasification regeneration organically combine.
Background technology
In recent years, it is heavy that petroleum resources become day by day, and carbon residue, sulphur and tenor increase. And residual oil catalysisCracked stock requires (Ni+V) < 25 μ gg-1, be generally 10 μ gg-1Left and right, also has sulfur contentRestriction, as sulphur in the feedstock oil of residual oil fluid catalytic cracking (RFCC) technological requirement of pyrrosia lingua company containsAmount is in 0.2 ~ 2.4%(quality), therefore inferior heavy oil or residual oil processing problems become increasingly conspicuous. Petroleum resourcesShortage, international oil price is high, petroleum resources are inferior, heaviness and environmental requirement increasingly stringent areOil Refining Technologies proposed new challenge, is badly in need of the especially inferior heavy oil of poor oil of development efficient greenNovel refining technology. The efficient green of mink cell focus transforms, and requires on the one hand feedstock oil " to eat as much as possibleDry squeezing only ", be exactly to want environmental protection on the other hand.
Inferior heavy oil is brought many problems to processing. First, the density of inferior heavy oil is large, hydrogenCarbon ratio is low, and colloid, asphalt content are high, and carbon residue is high, causes light oil yield low, and coke yield is high.When catalyzed cracking processing heavy, inferior feedstock oil, a large amount of green cokes cause whole device heat surplus, withTime also cause great amount of carbon dioxide discharge. When delay coking process processing inferior heavy oil, liquid is received lower,Coke yield is very high, is approximately 1.5 times of raw material carbon residue. The heavy oil that how will account for crude oil 40% ~ 60% is (normalPress residual oil and decompression residuum) be more converted into light-end products, this is Jiao that the World Refining industry is paid close attention toPoint and worldwide technological puzzle are also that the significant problem solving is badly in need of in domestic petroleum refining industry. Secondly,The sulfur content of inferior heavy oil is high, concerning catalytic cracking process, has increased regenerating section de-SOx, NOxCost. Coking process (comprising delayed coking and fluid coking) is as the Main Means of processing of heavy oilOne of, its working ability cumulative year after year, inevitably produces a large amount of petroleum cokes, except a partHigh-quality petroleum coke can be used as outside the fields such as the electrode of aluminium metallurgy steel-making, and increasing sour crude oil producesHigh sulfur petroleum coke, for example, as the petroleum coke sulfur content of enterprise's production of domestic processing import sour crudeUp to 5.9 % by weight, use if set it as fuel, certainly will produce again new atmosphere SOx, NOxEmission problem. Therefore sulphur conversion and sulphur emissions problem while, processing inferior heavy oil are urgently to be resolved hurrily.
In order efficiently to utilize petroleum resources, the coke that inferior heavy oil process produces will be converted at presentHigh value-added product, as US3542532 discloses a kind of fluid coking and gasification combinations produce hydrogenTechnique, this technique in the fluid coking stage using coke particle as carbon deposit carrier, reaction finish afterCoke particle after elutriator, particle size enters movement at the coke particle of 3.17 ~ 6.35 millimetersIn bed gasification reactor, gasifying agent is air and steam, and gasification temperature is at 649 ~ 1316 DEG C. GasificationRear particle size is less than the coke particle of 3.17 millimeters and returns in fluid coking reactor. This technique is with JiaoCarbon granule, as heat carrier, therefore only has thermal cracking to produce in coking reactor, and in technique mistakeIn journey, easily produce fine powder Jiao, gasification temperature is higher simultaneously.
US4269696 discloses a kind of associating work of fluid coking and the gasification of adding Cracking catalystSkill, the solid in this technical process after this part heating of vaporizer and water vapour and oxygen-containing gas carry outCoke and hydrogen-containing gas after the gasification of reaction generating portion, the operating temperature of gasifier is 538 ~ 1537 DEG C,Preferably 760 ~ 1093 DEG C. Change that in technical process, in raw material, to add 0.1 ~ 10%(heavy) (taking raw material asBasis) catalyst, catalyst is carclazyte Cracking catalyst, crystalline aluminium-silicon zeolite, inorganic oxideWith their mixture. This process combination exists that gasification temperature is high, gasification is using water and oxygen as gasAgent causes the Cracking catalyst skeleton problems such as inactivation of caving in.
US4331529 discloses the technique of a kind of fluid coking and gasification combination, and this technique is done with cokeFor heat carrier, in this technique, a part of coke exists and in the first gasifier of oxygen-containing gas, is producing heatGas and hot coke, a part produce hot coke in the second gasifier that has steam, produce H2Gas with CO composition. Temperature in first and second gasifier is 825 ~ 1093 DEG C, and this technique generatesThe effective rate of utilization of coke is not high, and in air gasification device, burning generates approximately 69% of coke, steam gasificationIn device, gasification generates approximately 28% of coke.
From relate to coke gasification hydrogen manufacturing prior art, can see, on contact agent after deposit coke at gasChange section temperature all higher, this is mainly the restriction that charcoal gasification is subject to thermodynamical equilibrium, and high temperature is conducive to rawBecome CO and H2, the conversion efficiency of raising charcoal. And under so high thermal and hydric environment, contact agent is outstandingIt is that silica-alumina material is difficult to ensure the hydrothermal stability recycling in process, makes the materialization of contact agentCharacter is destroyed, impact reaction and fluidizing stability.
Natural gas is a kind of safety, clean energy resource that calorific value is high of using, and its main component is methane. My godSo gas is widely used in the industries such as generating, chemical industry, gas, motor vehicle fuel, is to lead in the worldOne of clean energy resource of wanting. But, the natural gas resource rareness of China, along with China's national economyDevelop rapidly, the demand of natural gas resource is also continued to increase, will reach to Eleventh Five-Year Plan end breach20000000000 m3. The disparities between supply and demand problem that solves Natural Gas In China will be by all kinds of means, multimode expands resourceSupply with, meet the growing market demand.
CN200680037989 discloses a kind of catalytic steam gasification process of petroleum coke to methane, shouldMethod is that petroleum coke and the catalyst with steam gasification activity are mixed in aqueous medium, with shapeBecome feed slurry to carry out vaporizing system methane. A kind of urging by carbonaceous material disclosed in CN200880122933Change in the coke obtaining that gasifies and extract and reclaim alkali-metal method.
In current disclosed prior art, be all by petroleum coke and gasifying catalyst machine with petroleum coke methane processedTool mixes or petroleum coke is flooded with the aqueous solution of catalyst, or two kinds of method combinations, asCN200980137381, CN200680031251. In addition showing from coal and coke gasification methane processed,Have in technology and can see, all exist gasifying catalyst regeneration to reclaim, prepare gasification feed complexity etc. and askTopic.
Summary of the invention
The object of the invention is to overcome in existing contact cracking-gasification synthetic gas production process and exists tail to fireSafety problem, and sulfur recovery and the sulphur emissions problem of processing when inferior heavy oil.
Method provided by the invention, comprising:
(1) in contact cracking unit, heavy oil enters contact cracker, under the existence of contact agentContact cracking reaction, the effluent of contact cracker comprises that dry gas, liquefied gas, gasoline heat up in a steamerPoint, diesel oil distillate, wax oil cut and band charcoal contact agent, described band charcoal contact agent enters gasification unit;
(2), in gasification unit, the band charcoal contact agent of step (1) gained enters gasifier after strippingIn, react with gasifying agent generating gasification with the coke on charcoal contact agent, generate and comprise CH4、CO、H2、CO2Gasification gas and the contact agent of partly regenerating, the sulphur of gasification in gas is with H2S form exists;
(3), at air processing unit, step (2) gained gasification gas enters sulphur and removes device and remove sulphurAfter, respectively by the CO in gasification gas2And CH4Separate separately isolated CO and H2MixGas returns to gasifier;
(4), at regeneration unit, the contact agent of partly regenerating of step (2) gained, is having oxygen to existUnder condition, on contact agent, residual charcoal generation completing combustion, obtains holomorphosis contact agent and flue gas, cigaretteSulphur in gas is with SOXForm exists, and holomorphosis contact agent returns to contact cracker.
The carbon residue of described heavy oil is in 5 % by weight ~ 40 % by weight, and tenor is at 1 ~ 1000 μ g/g. InstituteThe heavy oil of stating can be heavy crude, acid-containing raw oil, super viscous crude, reduced crude, decompression residuum, subtractPress wax oil, wax tailings, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shaleThe mixing of one or more at the bottom of oil, tank in oil, coal liquefaction residue oil or other secondary operations distillateThing.
The process conditions of the contact cracking unit in described step (1) are: 450 ~ 650 DEG C of reaction temperatures,Weight (hourly) space velocity (WHSV) 1 ~ 100h-1, the mass ratio of contact agent and heavy oil feedstock is 1 ~ 30:1, steam and heavy oilThe mass ratio of raw material is 0.05～1:1.
Contact agent in described step (1) is silica-alumina material and gasifying catalyst, wherein gasifying catalystAccount for 50% ~ 100% of contact agent gross weight.
Described gasifying catalyst and silica-alumina material can be mechanical mixture, or gasifying catalyst loadOn silica-alumina material.
Described silica-alumina material is selected from containing the catalyst of molecular sieve and/or not containing the silica-alumina material of molecular sieveCatalyst.
Preferably the described catalyst containing molecular sieve for be selected from containing X molecular sieve, Y molecular sieve, modenite,The catalyst of one or more molecular sieves in ZSM-5, clay molecular sieve with layer structure, SAPO.
Described not containing the silica-alumina material catalyst of molecular sieve refer to amorphous silicon aluminium, carclazyte, kaolin,One in montmorillonite, rectorite, illite, chlorite, boehmite, silica or severalThe mixture of planting is catalyst prepared by raw material. Also can be through overpickling, roasting, screening processingOne in amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite, illite, chloriteOr several catalyst of preparing for raw material. Can also be through overpickling, roasting, screening processing without fixedOne in type sial, carclazyte, kaolin, montmorillonite, rectorite, illite, chlorite or severalPlanting with boehmite and/or silica is catalyst prepared by raw material.
Described gasifying catalyst is for containing single metal in alkali metal, alkaline-earth metal and VIII family metalOr one or more in the natural crystal of various metals combination, synthetic material, derivative compound. ExampleAs, the carbonate that contains alkali metal, alkaline-earth metal and VIII family metal, sulfate, oxide,The mixture of one or more in chloride, hydroxide. Can also be Ca-Ti ore type, spinelleThe synthetic material that type etc. contain alkali metal, alkaline-earth metal, VIII family metal, and natural ore powder,As lime stone, dolomite, olivine etc.
In one of them embodiment of the present invention, in described gasifying catalyst, contain containing the active group of potassiumPoint, wherein containing principal phase peak 2 θ in the XRD thing phasor of potassium active component be respectively 21 °, 29 °,35 °. The described potassium active component that contains comprises potassium oxide, alkaline earth oxide and sial component, to containPotassium active component weighing scale, potassium oxide is 10 ~ 40 heavy %, the rubbing of alkaline earth oxide and potassium oxideYou are than being 1:9 ~ 1:0.5, and all the other are sial component. Described containing potassium active component be by potassium-containing compound,Alkaline earth metal compound and sial component are beaten into wet feed, are then dried into siccative, then obtain after roasting, sintering temperature is 900 ~ 1100 DEG C, roasting time 1 ~ 10h; Described potassium-containing compound is for being selected from oxygenChange one or more in potassium, potassium hydroxide and potash, described alkaline earth metal compound is for being selected from alkaliOne or more in soil metal oxide, alkaline earth metal carbonate. Preferably described containing potassium active componentIn sial component be kaolin.
In step (2), the band charcoal contact agent (spent agent) of step (1) gained is laggard through strippingEnter in gasifier, react with gasifying agent generating gasification with the coke on charcoal contact agent, generate and comprise CH4、CO、H2、CO2Gasification gas and the contact agent of partly regenerating. The band charcoal contact that described step (1) obtainsAgent carbon content is in 0.5 % by weight ~ 7.0 % by weight. The contact agent of partly regenerating that step (2) obtains containing charcoalAmount is less than 1.0 % by weight.
In described step (2), gasifying agent is steam; Reaction condition in gasifier is: gasification temperatureBe 500 ~ 700 DEG C, gas line speed 0.05 ~ 0.6m/s, pressure 1Mpa ~ 10MPa.
Coke on spent agent vaporizing system methane process in gasification unit relates to three key reactions:
C＋H2O(g)→CO＋H2，+131.4kJ/mol（1）
CO＋H2O(g)→CO2＋H2，-41.2kJ/mol（2）
C＋2H2→CH4，-74.7kJ/mol（3）
Overall reaction is: 2C+2H2O(g)→CO2＋CH4，+15.5kJ/mol
The present invention is incorporated into three reactions in a gasification reactor and carries out, and whole process substantially canEnough maintain autothermal equilibrium, need outer to seldom hot, so gasification temperature is not high.
CH in the gasification gas generating in described step (2)4Molar content at least 20%. GasificationH in gas2S accounts for 70 volume % ~ 99.9 volume % of total sulfur in gasification gas.
At the air processing unit of step (3), described sulfur recovery unit refer to be widely used in coal,The device of the industry gas sweetenings such as oil refining and sulfur recovery, as wet oxidation process, dry oxidation iron processes, gramLouth method etc. The gasification gas of step (2) gained enters sulphur and removes device and remove after sulphur, and gas will gasifyIn CO2After separating, CO2Can trap, isolated containing CO, H2、CH4Gas enter oneStep is isolated CH4，CH4Can be used as gas utilization, isolated CO and H2Return to gasifier.
In the regeneration unit of step (4), holomorphosis temperature is 600 ~ 800 DEG C, passes into gas for containingThe gas of oxygen 10 volume % ~ 50 volume %. Obtain holomorphosis contact agent and flue gas, the sulphur in flue gasBe mainly SOX, flue gas is arranged outward after reaching discharge standard by alkaline cleaner or sulfur transfer additive.
In one of them embodiment of the present invention, holomorphosis contact agent partly or entirely enters step(2) in gasifier, be the band charcoal contact agent heat exchange coming from step (1), then holomorphosis connectsStep (1) contact cracker is returned in tactile agent.
Advantage of the present invention:
(1) rationally profit of heavy oil deep processing and superfluous carbonaceous residue that method provided by the present invention is integratedBy two aspects, when producing light oil, the coke of having more than needed gasifies and methanation in gasifier, gasChange gas after separating, make and be rich in CH4Synthetic natural gas, simultaneously CO2Can reclaim a sideFace rationally utilizes the residue of processing of heavy oil, produces the product of high economic worth, can subtract on the other handFew carbon emission.
(2) H in the gasification gas that gasification reaction of the present invention generates2S accounts for total sulfur in gasification gas70% ~ 99.9%(volume), be easy to reclaim sulphur, whole technical process environmental protection.
(3) that the coke on spent agent is related to three key reactions in vaporizing system methane process is whole in the present inventionBe combined in a gasification reactor and carry out, whole process can maintain autothermal equilibrium substantially, outside needingGive heat seldom, so gasification temperature is not high.
Brief description of the drawings
Accompanying drawing is the schematic process flow diagram of the methanogenic processing of heavy oil method of holding concurrently provided by the invention.
Detailed description of the invention
, illustrate further method of the present invention below by accompanying drawing, but therefore do not limitThe present invention processed.
As shown in the figure, heavy oil is entered and is contacted cracking unit 1 by pipeline 4 with atomizing steam, from pipeline14 fresh contact agent with from holomorphosis contact agent from pipeline 15 mixes, split with entering to contactChange unit 1, heavy oil comes in contact after cracking reaction with contact agent in cracker, the oil of generationGas enters subsequent separation system by pipeline 10, and band charcoal contact agent (spent agent) enters by pipeline 5Gasification unit 2. From the steam of pipeline 7 and through pipeline 20, pipeline 6 containing H2With CO gasBody enters gasification reactor after mixing. React with gasifying agent generating gasification with the coke on charcoal contact agent,Generation comprises CH4、CO、H2、CO2Gasification gas and the contact agent of partly regenerating, the gasification gas of generation fromPipeline 8 is drawn and is entered sulphur and remove device 16, the gasification gas after desulfurization by pipeline 17 enter separate singleUnit 18, by the CO in gasification gas2After separating, extract out through pipeline 19, isolated containing CO, H2、CH4Gas further isolate CH4，CH4Extract isolated CO and H out through pipeline 212Enter gasifier through pipeline 20, pipeline 6. At the contact agent of partly regenerating of gasification unit 2 gained through pipeline9 enter regeneration unit 3, in regeneration unit, the remaining coke on contact agent with from pipeline 10Air and the oxygen generation completing combustion reaction of pipeline 11, obtain flue gas and holomorphosis contact agent.The flue gas generating is entered after flue gas desulfur device reaches discharge standard and can directly be discharged by pipeline 13Atmosphere, obtain holomorphosis contact agent by pipeline 13 enter gasification unit 2 with from contacting cracking listAfter the spent agent heat exchange of unit, extract out and return to contact cracking unit 1 through pipeline 15.
Describe the present invention in detail with embodiment below, but embodiment is not thereby limiting the inventionThe scope of application.
The silica-alumina material adopting in embodiment is for by weight, containing 10% aluminium oxide, 80% kaolinSpraying dry roasting make not containing the silica-alumina material catalyst of molecular sieve, be designated as MFC-1. SiliconAluminum is not urging containing the silica-alumina material of molecular sieve of making containing the spraying dry roasting of 90% aluminium oxideAgent, is designated as MFC-2. Silica-alumina material adopts containing 5% rectorite clay molecular sieve with layer structure and 5%ZSM-5Molecular sieve, all the other are 90% kaolin, the spray-dried catalyst making is designated as MFC-3. SialThe trade names of the catalytic cracking catalyst containing Y molecular sieve that material adopts are CRC-1.
The gasifying catalyst that embodiment adopts is for containing 85 % by weight K2CO3Catalyst, be designated as GC-1;Gasifying catalyst is through pulverizing the natural dolomite of average grain diameter at 65 μ m, being designated as GC-2. GasificationCatalyst GC-3 is artificial synthetic containing potassium active component, and its preparation process is: take 3.5 kilograms highRidge soil, 0.42 kilogram of K2O and 0.028 kilogram of CaO, mix three, adds appropriate amount of deionized water,Make slurry solid content 15 ~ 50%, stir at least 20 minutes, spraying is dry, roasting 4 at 950 DEG CHour, make containing potassium active component. Should be containing 2 θ of principal phase peak in potassium active component XRD thing phasor respectivelyIt is 21 °, 29 °, 35 °.
Embodiment 1
The catalytic cracking catalyst that is CRC-1 by trade names and gasifying catalyst GC-3 are in mass ratio1:1 mechanical mixture, with carbon residue be that 15.10 % by weight, metal are that 50 μ g/g, sulfur content are 1.12%The heavy oil of (quality) comes in contact cracking reaction in contact cracking unit, the technique of contact cracking reactionCondition is: 460 DEG C of cracking temperature, air speed 10h-1, oil ratio 10, water-oil factor 0.1, gained is to be generatedThe coke content of agent is 1.8 % by weight.
Spent agent through stripping laggard enter fluidized-bed gasifier. The gas line speed of gasifier is0.25m/s, 620 DEG C of gasification temperatures, pressure 1.2Mpa, passes into steam as gasifying agent, and gas occursChange and methanation reaction. In gasifier, after gas solid separation, obtain the half regeneration contact containing charcoal 0.61 % by weightAgent and gasification gas, CH after gasification qi exhaustion water4Molar content 45%, H2S accounts for total sulfur in gasification gas99.1%(volume), gasification gas enters sulphur and removes device and remove after sulphur, by the CO in gasification gas2SeparateAfter, CO2Can trap, isolated containing CO, H2、CH4Gas further isolate CH4，CH4Can be used as gas utilization, isolated CO and H2Return to gasifier.
The contact agent of partly regenerating is sent into regeneration unit and is carried out holomorphosis, and reaction temperature is 701 DEG C, and containing oxygenThe gas reaction of volume fraction 21%. In regenerator, after gas solid separation, obtain regenerated flue gas and holomorphosisContact agent, the sulphur in flue gas is mainly SOX, flue gas reaches discharge by alkaline cleaner or sulfur transfer additiveOuter row after standard, the coke content of holomorphosis contact agent is 0.06 % by weight, returns to contact cracking listUnit.
Embodiment 2
The catalytic cracking catalyst that is CRC-1 by trade names and gasifying catalyst GC-1 carry out machineryMix, both mass ratios are 3:7, then with carbon residue be 18.10 % by weight, metal be 200 μ g/g,Sulfur content is 1.12%(quality) heavy oil contact cracking unit come in contact cracking reaction, contactThe process conditions of cracking reaction are: 500 DEG C of cracking temperature, air speed 20h-1, oil ratio 7, water-oil factor0.2, the coke content of gained spent agent is 2.5 % by weight.
Spent agent through stripping laggard enter fluidized-bed gasifier. The gas line speed of gasifier is0.12m/s, 520 DEG C of gasification temperatures, pressure 5Mpa, passes into steam as gasifying agent, generating gasificationAnd methanation reaction. In gasifier, after gas solid separation, obtain the contact agent of partly regenerating of carbon content 0.6 % by weightWith gasification gas, CH after gasification qi exhaustion water4Molar content 32%, H2S accounts for total sulfur in gasification gas99.5%(volume), gasification gas enters sulphur and removes device and remove after sulphur, by the CO in gasification gas2SeparateAfter, CO2Can trap, isolated containing CO, H2、CH4Gas further isolate CH4，CH4Can be used as gas utilization, isolated CO and H2Return to gasifier.
The contact agent of partly regenerating is sent into regeneration unit and is carried out holomorphosis, and reaction temperature is 680 DEG C, and containing oxygenThe gas reaction of volume fraction 18%. In regenerator, after gas solid separation, obtain regenerated flue gas and holomorphosisContact agent, the sulphur in flue gas is mainly SOX, flue gas is arranged outward after reaching discharge standard by alkaline cleaner,The coke content of holomorphosis contact agent is 0.02 % by weight, returns to contact cracking unit.
Embodiment 3
Be that 35.0 % by weight, metal 425 μ g/g, sulfur content are by silica-alumina material MFC-1 and carbon residue3.12%(quality) heavy oil come in contact cracking reaction in contact cracking unit, contact cracking reactionProcess conditions are: 520 DEG C of cracking temperature, air speed 50h-1, oil ratio 20, water-oil factor 0.5, gainedThe coke content of spent agent is 2.8 % by weight.
Spent agent through stripping laggard enter fluidized-bed gasifier. The gas line speed of gasifier is 0.4m/s,650 DEG C of gasification temperatures, pressure 9Mpa, passes into steam as gasifying agent, generating gasification and methanationReaction. In gasifier, after gas solid separation, obtain half regenerative agent and the gasification gas of carbon content 0.92 % by weight,CH after gasification qi exhaustion water4Molar content 50.6%, H2S accounts for the 95.5%(volume of total sulfur in gasification gas),Gasification gas enters sulphur and removes device and remove after sulphur, by the CO in gasification gas2After separating, CO2Can catchCollection, isolated containing CO, H2、CH4Gas further isolate CH4，CH4Can be used as skySo gas utilization, isolated CO and H2Return to gasifier.
Half regenerative agent is sent into regeneration unit and is carried out holomorphosis, and reaction temperature is 730 DEG C, with long-pending containing oxysomeThe gas reaction of mark 10%. In regenerator, after gas solid separation, obtaining regenerated flue gas contacts with holomorphosisAgent, the sulphur in flue gas is mainly SOX, flue gas is arranged outward after reaching discharge standard by alkaline cleaner, completeThe coke content of full regeneration contact agent is 0.06 % by weight, returns to contact cracking unit.
Embodiment 4
By silica-alumina material MFC-2, silica-alumina material MFC-3, gasifying catalyst GC-1 in mass ratio 1:After 1:3 mixes, be that 20.0 % by weight, tenor are that 120 μ g/g, sulfur content are with containing with carbon residue3.12%(quality) heavy oil come in contact cracking reaction in contact cracking unit, contact cracking reactionProcess conditions are: 550 DEG C of cracking temperature, air speed 80h-1, oil ratio 28, water-oil factor 0.1, gainedThe coke content of spent agent is 2.0 % by weight.
Spent agent through stripping laggard enter fluidized-bed gasifier. The gas line speed of gasifier is 0.6m/s,700 DEG C of gasification temperatures, pressure 8Mpa, passes into steam as gasifying agent, generating gasification and methanationReaction. In gasification unit, after gas solid separation, obtain half regenerative agent and the gasification gas of carbon content 1.0 % by weight,CH after gasification qi exhaustion water4Molar content 62%, H2S accounts for the 99.2%(volume of total sulfur in gasification gas),Gasification gas enters sulphur and removes device and remove after sulphur, by the CO in gasification gas2After separating, CO2Can catchCollection, isolated containing CO, H2、CH4Gas further isolate CH4，CH4Can be used as skySo gas utilization, isolated CO and H2Return to gasifier.
Half regenerative agent is sent into regeneration unit and is carried out holomorphosis reaction, and reaction temperature is 730 DEG C, and containing oxygenThe gas reaction of volume fraction 10%. In regenerator, after gas solid separation, obtain regenerated flue gas and holomorphosisContact agent, the sulphur in flue gas is mainly SOX, flue gas is arranged outward after reaching discharge standard by alkaline cleaner,The coke content of holomorphosis contact agent is that 0.05 % by weight is returned to contact cracking unit.
Embodiment 5
By silica-alumina material MFC-2 and gasifying catalyst GC-2,1:1 mechanical mixture is even in mass ratio,With carbon residue be that 25.0 % by weight, tenor are that 100.1 μ g/g, sulfur content are 3.12%(quality)Heavy oil contact cracking unit come in contact cracking reaction, contact cracking reaction process conditions be:580 DEG C of cracking temperature, air speed 30h-1, oil ratio 15, water-oil factor 0.3, the coke of gained spent agentContent is 4.2 % by weight.
Spent agent through stripping laggard enter fluidized-bed gasifier. The gas line speed of gasifier is0.32m/s, 500 DEG C of gasification temperatures, pressure 10Mpa, passes into steam as gasifying agent, and gas occursChange and methanation reaction. In gasifier, after gas solid separation, obtain carbon content 0.8 % by weight half regenerative agent andGasification gas, CH after gasification qi exhaustion water4Molar content 70%, H2S account for gasification gas in total sulfur 99.2%(volume), gasification gas enters sulphur and removes device and remove after sulphur, by the CO in gasification gas2After separating,CO2Can trap, isolated containing CO, H2、CH4Gas further isolate CH4，CH4Can be used as gas utilization, isolated CO and H2Return to gasifier.
Half regenerative agent is sent into regeneration unit and is carried out holomorphosis reaction, and reaction temperature is 650 DEG C, and containing oxygenThe gas reaction of volume fraction 15%. In regenerator, after gas solid separation, obtain regenerated flue gas and holomorphosisContact agent, the sulphur in flue gas is mainly SOX, flue gas is arranged outward after reaching discharge standard by alkaline cleaner,The coke content of holomorphosis contact agent is 0.04 % by weight, returns to contact cracking unit.
Embodiment 6
Gasifying catalyst GC-3 and carbon residue are that 18.1 % by weight, tenor are that 200 μ g/g, sulphur containAmount is for 3.12%(quality) heavy oil come in contact cracking reaction in contact cracking unit, contact crackingThe process conditions of reaction are: 530 DEG C of cracking temperature, air speed 60h-1, oil ratio 2, water-oil factor 0.8,The coke content of gained spent agent is 6.4 % by weight.
Spent agent through stripping laggard enter fluidized-bed gasifier. The gas line speed of gasifier is0.51m/s, 680 DEG C of gasification temperatures, pressure 3.1Mpa, passes into steam as gasifying agent, and gas occursChange and methanation reaction. In gasifier, after gas solid separation, obtain carbon content 0.8 % by weight half regenerative agent andGasification gas, CH after gasification qi exhaustion water4Molar content 55.2%, H2S account for gasification gas in total sulfur 99.2%(volume), gasification gas enters sulphur and removes device and remove after sulphur, by the CO in gasification gas2After separating,CO2Can trap, isolated containing CO, H2、CH4Gas further isolate CH4，CH4Can be used as gas utilization, isolated CO and H2Return to gasifier.
Half regenerative agent is sent into regeneration unit and is carried out holomorphosis, and reaction temperature is 690 DEG C, with long-pending containing oxysomeThe gas reaction of mark 38%. In regenerator, after gas solid separation, obtaining regenerated flue gas contacts with holomorphosisAgent, the sulphur in flue gas is mainly SOX, flue gas is arranged outward after reaching discharge standard by alkaline cleaner, completeThe coke content of full regeneration contact agent is 0.05 % by weight, returns to contact cracking unit.
Can find out by embodiment, by the present invention, can utilize efficiently petroleum resources on the one hand,Make the coke producing generate the coke of high added value, make again gasification temperature not higher than 700 DEG C, the opposing partyWhen face method provided by the invention does not exist petroleum coke vaporizing system methane, gasifying catalyst regeneration is reclaimed, is madeThe problems such as standby gasification feed complexity.
Claims (12)
1. a double methanogenic processing of heavy oil method, the method comprises:
(1) in contact cracking unit, heavy oil enters contact cracker, under the existence of contact agentContact cracking reaction, the effluent of contact cracker comprises that dry gas, liquefied gas, gasoline heat up in a steamerPoint, diesel oil distillate, wax oil cut and band charcoal contact agent, described band charcoal contact agent enters gasification unit;Described contact agent is silica-alumina material and gasifying catalyst, and gasifying catalyst accounts for contact agent gross weight50%～100%, in described gasifying catalyst, contain containing potassium active component, wherein containing potassium active componentIn XRD thing phasor, principal phase peak 2 θ are respectively 21 °, 29 °, 35 °;
(2), in gasification unit, the band charcoal contact agent of step (1) gained enters gasifier after strippingIn, react with gasifying agent generating gasification with the coke on charcoal contact agent, generate and comprise CH4、CO、H2、CO2Gasification gas and the contact agent of partly regenerating, the sulphur of gasification in gas is with H2S form exists; Gasifying agent isSteam; Reaction condition in gasifier is: gasification temperature is 500～700 DEG C, gas line speed0.05～0.6m/s, pressure 1Mpa～10MPa;
(3), at air processing unit, step (2) gained gasification gas enters sulphur and removes device and remove sulphurAfter, respectively by the CO in gasification gas2And CH4Separate separately isolated CO and H2MixGas returns to gasifier;
(4), at regeneration unit, the contact agent of partly regenerating of step (2) gained, is having oxygen to existUnder condition, on contact agent, residual charcoal generation completing combustion, obtains holomorphosis contact agent and flue gas, cigaretteSulphur in gas is with SOXForm exists, and holomorphosis contact agent partly or entirely enters step (2)In gasifier, be the band charcoal contact agent heat exchange coming from step (1), then holomorphosis contact agent returnsStep (1) contact cracker.
2. according to the method for claim 1, the carbon residue that it is characterized in that described heavy oil is 5 % by weight～40% by weight, tenor is at 1～1000 μ g/g.
3. according to the method for claim 1, it is characterized in that the contact cracking in described step (1)The process conditions of unit are: 450～650 DEG C of reaction temperatures, weight (hourly) space velocity (WHSV) 1～100h-1, contact agent is with heavyThe mass ratio of oil raw material is 1～30:1, and the mass ratio of steam and heavy oil feedstock is 0.05～1:1.
4. according to the method for claim 1, it is characterized in that described gasifying catalyst and silica-alumina material areMechanical mixture, or gasifying catalyst loads on silica-alumina material.
5. according to the method for claim 1 or 4, it is characterized in that described silica-alumina material is selected from containing dividingThe catalyst of son sieve and/or not containing the silica-alumina material catalyst of molecular sieve.
6. according to the method for claim 5, it is characterized in that the described catalyst containing molecular sieve is for choosingSelf-contained X molecular sieve, Y molecular sieve, modenite, ZSM-5, clay molecular sieve with layer structure, SAPOIn the catalyst of one or more molecular sieves.
7. according to the method for claim 5, described in it is characterized in that, the silica-alumina material containing molecular sieve is not urgedAgent refers to amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite, illite, green mudThe mixture of one or more in stone, boehmite, silica is catalyst prepared by raw material.
8. according to the method for claim 1 or 4, it is characterized in that described gasifying catalyst is for containing alkaliThe natural crystal of single metal or various metals combination in metal, alkaline-earth metal and VIII family metal,One or more in synthetic material, derivative compound.
9. according to the method for claim 1, it is characterized in that the band charcoal that described step (1) obtains connectsTouch the carbon content of agent in 0.5 % by weight～7.0 % by weight.
10. according to the method for claim 1, it is characterized in that half regeneration contact in described step (2)The carbon content of agent is lower than 1.0 % by weight.
11. according to the method for claim 1, it is characterized in that in described step (2) gasification gasH2S accounts for 70 volume %～99.9 volume % of total sulfur in gasification gas.
12. in accordance with the method for claim 1, it is characterized in that, described step (4) regeneration is singleThe holomorphosis temperature of unit is 600～800 DEG C, and passing into gas is containing oxygen 10 volume %～50 volume %'sGas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210253853.7A CN103571529B (en) | 2012-07-20 | 2012-07-20 | A kind of methanogenic processing of heavy oil method of holding concurrently |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210253853.7A CN103571529B (en) | 2012-07-20 | 2012-07-20 | A kind of methanogenic processing of heavy oil method of holding concurrently |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103571529A CN103571529A (en) | 2014-02-12 |
| CN103571529B true CN103571529B (en) | 2016-05-25 |
Family
ID=50044250
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210253853.7A Active CN103571529B (en) | 2012-07-20 | 2012-07-20 | A kind of methanogenic processing of heavy oil method of holding concurrently |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103571529B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113025357B (en) * | 2021-05-28 | 2021-08-20 | 中国农业科学院农业环境与可持续发展研究所 | Biomass pyrolysis co-production method for recycling pyrolysis oil |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362380A (en) * | 1993-08-16 | 1994-11-08 | Texaco Inc. | Fluid catalytic cracking process yielding hydrogen |
| CN102031140A (en) * | 2009-09-29 | 2011-04-27 | 中国石油化工股份有限公司 | Combination method of gasification and coke processing from inferior heavy oil |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4077869A (en) * | 1975-10-21 | 1978-03-07 | Exxon Research & Engineering Co. | Integrated coking and gasification process |
| CN102234534B (en) * | 2010-04-28 | 2014-01-15 | 中国石油化工股份有限公司 | Method for processing inferior heavy oil |
-
2012
- 2012-07-20 CN CN201210253853.7A patent/CN103571529B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5362380A (en) * | 1993-08-16 | 1994-11-08 | Texaco Inc. | Fluid catalytic cracking process yielding hydrogen |
| CN102031140A (en) * | 2009-09-29 | 2011-04-27 | 中国石油化工股份有限公司 | Combination method of gasification and coke processing from inferior heavy oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103571529A (en) | 2014-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102031140B (en) | Combination method of gasification and coke processing from inferior heavy oil | |
| CN103773425B (en) | A kind of working method of heavy oil | |
| CN100584928C (en) | Technology of preparing synthetic gas using non agglomerating or weak agglomerating coal fluidized destructive distillation | |
| CN104232147B (en) | A kind of heavy oil lightweight treatment technique | |
| CN104803819B (en) | A kind of method and system utilizing fine coal preparing ethylene | |
| CN102477312B (en) | Method for gasifying carbon-containing substance by using supercritical water | |
| CN102234534B (en) | Method for processing inferior heavy oil | |
| CN102260529A (en) | Combined method for processing inferior heavy oil | |
| CN104974799A (en) | Method and system used for preparing high methane gas via co-gasifying of coal and biomass | |
| CN102703107A (en) | Method for manufacturing liquid hydrocarbon product with synthetic gas produced by biomass | |
| CN102453518B (en) | Inferior heavy oil contact cracking-gasification combined treatment method | |
| CN102234535B (en) | Method for processing low-quality heavy oil and simultaneously producing synthetic gas | |
| CN102234545B (en) | Preparation method of synthesis gas by gasifying carbonaceous materials | |
| CN102698817B (en) | Pure oxygen regeneration process for fluid catalytic cracking catalyst and hydrogen preparation method | |
| CN100441663C (en) | Fluidization hydrogenation liquefaction method for coal | |
| CN104945215B (en) | Method and system for preparing ethylene from powdered coal | |
| CN103571529B (en) | A kind of methanogenic processing of heavy oil method of holding concurrently | |
| CN101767801B (en) | Process for preparing synthetic ammonia by furnace gas generated when producing phosphoric acid in blast furnace | |
| CN103896209A (en) | Method for producing synthesis gas by catalytically reforming coal, natural gas and carbon dioxide | |
| CN101781576A (en) | Method for preparing liquid fuel by carbon dioxide | |
| CN103506106B (en) | A kind of for contact agent processing inferior heavy oil and its preparation method and application | |
| CN103773449B (en) | A kind of method of inferior heavy oil efficiency utilization | |
| CN103571528B (en) | A kind of methanogenic heavy oil combinational processing method of holding concurrently | |
| CN103509586B (en) | A kind of working method of inferior heavy oil | |
| CN103571519B (en) | A kind of combinational processing method of heavy oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |