CN103773425A - Processing method of heavy oil - Google Patents
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- CN103773425A CN103773425A CN201210409263.9A CN201210409263A CN103773425A CN 103773425 A CN103773425 A CN 103773425A CN 201210409263 A CN201210409263 A CN 201210409263A CN 103773425 A CN103773425 A CN 103773425A
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Abstract
A processing method of heavy oil comprises the following steps: carrying out a contact cracking treatment on inferior heavy oil, making cokes deposited on a contact agent carry out a gasification reaction at a low temperature in a gasification unit to convert the cokes into gasified gas which is rich in carbon monoxide and hydrogen gas, transporting the gasified gas rich in carbon monoxide and hydrogen gas into a converting unit to generate hydrogen gas and CO2, separating the hydrogen gas and CO2, and transporting CO2 to a dry reforming unit to carry out reaction with gas rich in methane in the presence of a regeneration contact agent so as to generate CO and hydrogen gas; wherein the contact agent can be recycled and returned to the contact cracking reactor after the contact agent has exerted a catalyzing function and then is discharged out from the dry reforming reactor. The processing method reasonably utilizes residues and metals of heavy oil processing to produce products with a high economic value, and is economic and environment-friendly.
Description
Technical field
The invention belongs to a kind of inferior heavy oil working method.More particularly, be a kind of combinational processing method that heavy oil is contacted to cracking and gasification regeneration, the whole combination of gas dry weight.
Background technology
The heaviness of crude oil and in poor quality become clear day by day in the world, and the object of oil refining processing from now on will turn to heavy oil or sulphur-bearing crude gradually, and the course of processing is by more and more difficult.The heaviness of crude oil and in poor quality are mainly reflected in that density is large, carbon residue is high, sulphur content is high, resin and asphalt content is high and the aspect such as heavy metal nickel and content of vanadium height, if the asphalt content of the heavy vacuum residuum of sand is up to 15%.Processing heavy oil can be divided into catalysis processing and on-catalytic processing.Catalysis complete processing comprises the technique such as heavy oil fluid catalytic cracking, heavy-oil hydrogenation.On-catalytic processing comprises the techniques such as viscosity breaking, coking and solvent deasphalting.Wherein coking process due to technology maturation, bottoms conversion is high, adaptability to raw material is strong, production cost is low, is widely used in heavy oil deep processing.Coking process (comprising delayed coking and fluid coking) is as one of Main Means of heavy oil upgrading, its working ability cumulative year after year, inevitably produce a large amount of refinery cokes, except a part of high-quality petroleum coke can be used as the field such as electrode, fuel of aluminium metallurgy steel-making, the high sulfur petroleum coke (if the refinery coke sulphur content of enterprise's production of domestic processing import high-sulfur crude oil is up to 5.9%) that increasing sulphur-bearing crude produces, and powder Jiao of producing of fluid coking, it utilizes problem urgently to be resolved hurrily.
Hydrotreatment is the important method of development green processes craft and the friendly oil product of production environment, no matter from the environmental requirement of increasingly stringent, or from the trend of crude oil heaviness, in poor quality, the hydrogen-consuming volume of refinery also can constantly increase, the amounts of hydrogen of original refinery reformer by-product can not satisfy the demands, China's hydrogen aggregate demand is up to approximately 45.8 ten thousand tons/year, and the demand of China's oil refining industry hydrogen is by the speed increment with annual 5% left and right.
Hydrogen is mainly by fossil energy Sweet natural gas (CH
4), the raw material such as oil refinery dry gas, petroleum naphtha, heavy oil, pitch, coke or coal, at high temperature generate through the technique such as vapour reforming or partial oxidation process with water vapor.Wherein comparatively conventional is lighter hydrocarbons Steam Reforming method, it has that technical process is short, simple to operate, technology maturation and the feature such as investment is lower, and still, lighter hydrocarbons are valuable fuel, industrial chemicals, and these cost of material are higher, make the cost of hydrogen manufacturing high.In addition, refinery and some chemical processes also can some hydrogen of by-product, but can provide the gas production rate of cheap hydrogen technological process often limited, as catalytic reforming hydrogen supply and dry gas hydrogen manufacturing, conventionally cannot meet the demand of refinery to hydrogen, therefore find new production hydrogen approach and keep rational economy just to become one of subject matter that modern refinery will consider.
Oil refining industry is high energy consumption, high carbon dioxide discharge industry.Carbonic acid gas is as the main component of greenhouse gases and the global climate problem causing has badly influenced the mankind's existence.The requirement of carbon dioxide discharge-reduction and the needs of energy sustainable development are how to realize new carbon cycle problem after all.According to China's energy structure and the strategy of sustainable development, the development trend of energy technology will be from high-carbon to low-carbon (LC) and even Non-carbonized utilization development, realizes making full use of and minimum discharge of carbon resource, reaches resources effective utilization and eco-friendly win-win.
Petroleum resources shortage, international oil price are high, petroleum resources are inferior, heaviness and environmental requirement increasingly stringent are that oil Refining Technologies has proposed new challenge: the efficient green refining technology of development China mink cell focus.The efficient green of mink cell focus transforms, requires on the one hand stock oil " to eat dry squeezing clean " as much as possible, and be exactly to want environmental protection on the other hand.
The fluid coking of Exxon Neftegas Limited exploitation and flexicoking technique coke yield are carbon residue 1.1 ~ 1.3 times, the coke part burning producing provides system thermal, and remainder adopts air or oxygen, water vapour etc. to produce and have certain low-heat value gas in high temperature (900 ℃ of left and right) gasification.This technique adopts high-temperature gasification on the one hand, and energy consumption is higher, on the other hand CO and H in institute's producing coal gas
2content lower, calorific value is lower, its added value is very low fluid coking and flexicoking technique also.The two as the carrier of coke and heat, exists the size distribution of coke granule inhomogeneous all using burnt core as fluidizing medium simultaneously, easily produces compared with the problem such as megalump and finely-ground coke, affects fluid effect.
US3542532 discloses the technique of a kind of fluid coking and gasification combinations produce hydrogen, this technique in the fluid coking stage using coke particle as deposition of carbon carrier, coke particle after reaction finishes is after elutriator, particle size enters in moving-bed gasification reactor at the coke particle of 3.17 ~ 6.35 millimeters, vaporized chemical is air and water vapour, and gasification temperature is at 649 ~ 1316 ℃.After gasification, particle size is less than the coke particle of 3.17 millimeters and returns in fluid coking reactor.This technique, using coke particle as thermal barrier, therefore only has thermally splitting to produce in coking reactor, and easily produces fine powder Jiao in technological process, and gasification temperature is higher simultaneously.
US4269696 discloses a kind of process integration of fluid coking and the gasification of adding cracking catalyst, coke and hydrogen-containing gas solid in this technological process after this part heating of vaporizer reacts generating portion gasification with water vapor and oxygen-containing gas after, the service temperature of gasifier is 538 ~ 1537 ℃, preferably 760 ~ 1093 ℃.Change that in technological process, in raw material, to add 0.1 ~ 10%(heavy) catalyzer of (take raw material as basis), catalyzer is carclazyte cracking catalyst, crystalline aluminium-silicon zeolite, inorganic oxide and their mixture.This process combination exists that gasification temperature is high, gasification causes the cracking catalyst skeleton problems such as inactivation of caving in using water and oxygen as vaporized chemical.
US4331529 discloses the technique of a kind of fluid coking and gasification combination, this technique is using coke as thermal barrier, in this technique, a part of coke exists in the first gasifier of oxygen-containing gas and produces hot gas and hot coke one, and a part produces hot coke and has one the gas that produces H2 and CO composition in the second gasifier of steam.Temperature in first and second gasifier is 825 ~ 1093 ℃, and the effective rate of utilization that this technique generates coke is not high, and in air gasification device, burning generates approximately 69% of coke, and in steam gasification device, gasification generates approximately 28% of coke.
Can see from a large amount of disclosed relating to coke gasification prior art, all higher in gasification section temperature after deposit coke on contact substance, more than 900 ℃, this is mainly the restriction that charcoal gasification is subject to thermodynamic(al)equilibrium, and high temperature is conducive to generate CO and H
2, the conversion efficiency of raising charcoal.And under so high thermal and hydric environment, contact substance especially silica-alumina material is difficult to guarantee the hydrothermal stability recycling in process, and the physico-chemical property of contact substance is destroyed, impact reaction and fluidizing stability.Meanwhile, although can see in disclosed patent that coke gasification is utilized refinery coke inferior, generate a large amount of CO simultaneously
2greenhouse gases.
CO
2transformed and utilized the target that becomes scientific worker's effort for many years as carbon resource.Methane is the main composition of Sweet natural gas, and it is widely used as clean energy.The maximum purposes of Sweet natural gas is the huge heat energy that utilizes methyl hydride combustion to produce at present, and the CO generating in combustion processes
2inevitably enter atmosphere.Therefore need to set up a new carbon cycle theory: methane-carbon dioxide-methane.
Synthesizing gas by reforming methane with co 2 is the loaded catalyst that precious metal or Ni are main active component mostly at present, and wherein the catalyst based price of Ni is lower, has good development prospect.But the catalyticreactor of the pellet type catalyst of load filling is generally fixed-bed reactor, bed pressure drop is larger under normal conditions, between bed, there is larger thermograde, and thermal conductivity is poor, thermal resistance is larger, very easily cause beds local superheating, thereby active ingredient Ni is compared with easy-sintering in reaction process, the activity of catalyzer declines very fast.In CN1234366A invention, disclosed catalyzer is with ZrO
2for the CO of carrier loaded Ni
2reforming methane catalyzer, reactor is fixed-bed reactor, needs catalyzer prereduction 3 ~ 13 hours before use.In CN101112692A invention disclosed catalyzer be a kind of add magnesium with ZrO
2for the CO of carrier loaded Ni
2reforming methane catalyzer, reactor is fixed-bed reactor, needs catalyzer prereduction before use.
Summary of the invention
The object of the invention is to provide a kind of heavy oil upgrading method.
Method provided by the invention, comprise: (1) is in contact cracking unit, heavy oil enters contact cracking case, under the existence of contact substance, contact cracking reaction, the effluent of contact cracking case comprises dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil cut and band charcoal contact substance, and described band charcoal contact substance enters gasification unit;
(2) in gasification unit, react with the charcoal on charcoal contact substance and vaporized chemical, generate and be rich in CO and H
2gasification gas, and obtain the contact substance of regenerating;
(3) step (2) gained gasification gas separates and obtains hydrogen and CO through water-gas shift
2, hydrogen and CO
2after separation, CO
2enter dry reformer unit; Step (2) gained regeneration contact substance enters dry reformer unit;
(4) CO
2at dry reformer unit, under the effect of regeneration contact substance, react together with methane-rich gas, generate containing CO and H
2synthetic gas, the contact substance occurring after katalysis returns to step (1) contact cracking unit again.
The carbon residue of described heavy oil is in 5 % by weight ~ 40 % by weight, and metal content is at 1 ~ 1000 μ g/g, and wherein Ni content is greater than 5 μ g/g.Described heavy oil can be one or more the mixture in oil at the bottom of heavy crude, acid-containing raw oil, super viscous crude, long residuum, vacuum residuum, decompressed wax oil, wax tailings, deasphalted oil, oil sands bitumen, hydrocracking tail oil, coal tar, shale oil, tank, coal liquefaction residue oil or other secondary processing distillate.
The processing condition of the contact cracking unit in described step (1) are: 450 ~ 650 ℃ of temperature of reaction, weight hourly space velocity 1 ~ 100h
-1, the mass ratio of contact substance and heavy oil feedstock is 1 ~ 30:1, the mass ratio of water vapour and heavy oil feedstock is 0.05 ~ 1:1.
Contact substance in described step (1) is silica-alumina material and/or gasifying catalyst.
In one of them embodiment of the present invention, the contact substance in described step (1) is silica-alumina material and gasifying catalyst, and gasifying catalyst and silica-alumina material are mechanically mixing, or gasifying catalyst loads on silica-alumina material.
Described silica-alumina material is selected from containing the catalyzer of molecular sieve and/or not containing the silica-alumina material catalyzer of molecular sieve.
Preferably the described catalyzer containing molecular sieve is the catalyzer being selected from containing one or more molecular sieves in X molecular sieve, Y molecular sieve, mordenite, ZSM-5, clay molecular sieve with layer structure, SAPO.
The described catalyzer containing molecular sieve can also be catalytic cracking spent catalyst.
Describedly do not refer to containing the silica-alumina material catalyzer of molecular sieve the catalyzer of preparing as raw material take one or more the mixture in amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, pseudo-boehmite, silicon-dioxide.Also can be one or more catalyzer prepared for raw material in the amorphous silicon aluminium of overpickling, roasting, screening processing, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite.Can also be that one or more and pseudo-boehmite and/or silicon-dioxide in the amorphous silicon aluminium of overpickling, roasting, screening processing, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite is catalyzer prepared by raw material.
Described gasifying catalyst is one or more in the natural crystal that contains single metal in basic metal, alkaline-earth metal and VIII family metal or various metals combination, synthetic materials, derivative compound.The mixture of for example, in the carbonate that, contains basic metal, alkaline-earth metal and VIII family metal, vitriol, oxide compound, muriate, oxyhydroxide one or more.Can also be the synthetic materials that perovskite typed, spinel type etc. contain basic metal, alkaline-earth metal, VIII family metal, and natural ore powder, as Wingdale, rhombspar, peridotites etc.
In one of them embodiment of the present invention, in described gasifying catalyst, contain containing potassium active ingredient, be wherein respectively 21 °, 29 °, 35 ° containing principal phase peak 2 θ in the XRD thing phasor of potassium active ingredient.The described potassium active ingredient that contains comprises potassium oxide, alkaline earth metal oxide and sial component, and to contain potassium active ingredient weighing scale, potassium oxide is 10 ~ 40 heavy %, and the mol ratio of alkaline earth metal oxide and potassium oxide is 1:9 ~ 1:0.5, and all the other are sial component.Described is to be beaten into wet feed by potassium-containing compound, alkaline earth metal compound and sial component containing potassium active ingredient, is then dried into siccative, then obtain after roasting, maturing temperature is 900 ~ 1100 ℃, roasting time 1 ~ 10h; Described potassium-containing compound is one or more that are selected from potassium oxide, potassium hydroxide and salt of wormwood, and described alkaline earth metal compound is one or more that are selected from alkaline earth metal oxide, alkaline earth metal carbonate.Preferably described is kaolin containing the sial component in potassium active ingredient.
The operational condition of described step (2) gasification unit: gasification temperature is 600 ~ 800 ℃.
Described step (2) vaporized chemical refers to oxygen and water vapour and/or CO
2gas, take vaporized chemical as benchmark, the molar fraction of oxygen is 5% ~ 30%, water vapour and/or CO
2the molar fraction of gas is 70% ~ 95%.Described CO
2gas is from water-gas shift unit.
Separate the rich CO obtaining from water-gas change unit
2gas enters dry reformer unit as one of raw material, reacts together with methane-rich gas at dry reformer unit, generates containing CO and H
2synthetic gas.The processing condition of dry reformer unit are 600 ~ 850 ℃ of temperature of reaction, and air speed is 1000 ~ 100000h
-1.Enter on the regeneration contact substance of dry reformer unit and contain active ingredient Ni, by the quality of contact substance, active component nickel content is 0.5% ~ 5%.
Described methane-rich gas is selected from one or more the mixture in methane, Sweet natural gas, oil field gas.Also can be the methane-rich gas that is mixed with one or more mixtures in a certain amount of dry gas that is selected from catalytic cracked dry gas, coking dry gas, step of the present invention (1) contact cracking generation in above-mentioned gas.
The reactor of described dry reformer unit is fluidized-bed.
Compared with prior art, beneficial effect of the present invention is mainly reflected in the following aspects:
First, the present invention is intended to process inferior heavy oil, the rich CO of integrated inferior heavy oil deep processing and the hydrogen manufacturing of residue carbon resistates, generation
2whole three aspects of gas and methane dry weight, take inferior heavy oil as raw material, maximize under the prerequisite of producing light oil, and the coke of having more than needed gasifies to generate and is rich in H in vapourizing furnace
2with the gas of CO, enter the rich CO that converter unit produces after utilizing the nickel metal that is deposited in inferior heavy oil on contact substance and gasification simultaneously
2gas and methane dry weight are whole, produce CO and H
2, therefore, the processing that the method is inferior heavy oil provides a kind of economy, effective approach.
Secondly, because the gasification temperature in step of the present invention (2) is at 600 ~ 800 ℃, compared with prior art, greatly reduce gasification temperature, can not destroy structure and the character of contact substance simultaneously.
The 3rd, the dry reforming reaction in step of the present invention (3) enters the rich CO that converter unit produces after having utilized the nickel metal that is deposited in inferior heavy oil on contact substance and gasification
2gas and methane dry weight are whole, have reduced on the one hand the discharge of greenhouse gases, also take full advantage of on the other hand the metal in heavy oil, greatly reduce process costs.
The 4th, owing to having made the metallic reducing on contact substance in gasifying reactor, contact substance does not need reduction to process entering before dry reforming reactor.
Accompanying drawing explanation
Accompanying drawing is the schematic process flow diagram of heavy oil upgrading method provided by the invention.
Embodiment
, illustrate further method of the present invention below by accompanying drawing, but not thereby limiting the invention.
1 is contact cracking unit, and 2 is coke gasification unit on spent agent, and 3 is converter unit, and 4 is dry reformer unit.Inferior heavy oil is entered and is contacted cracking case by pipeline 5 with atomizing steam, fresh contact substance is entered and is contacted cracking case by pipeline 7 with the contact substance the regeneration coming from 16 pipelines, after inferior heavy oil contacts cracking with contact substance in cracking case, the oil gas producing enters subsequent separation system by pipeline 10, and band charcoal contact substance enters gasifier by pipeline 8.In gasifier, with the charcoal on charcoal contact substance with water vapour and oxygen from pipeline 6 and/or react from the carbonic acid gas generating gasification of converter unit, the gasification gas generating is drawn and is entered subsequent conversion unit from pipeline 11, and after conversion, isolated hydrogen is drawn by pipeline 12, isolated CO
2gas is introduced dry reforming reactor by pipeline 13 and under the katalysis of the contact substance of drawing by pipeline 9 from gasifying reactor 2, reforming reaction is occurred with the methane-rich gas of introducing from pipeline 14, and the hydrogen of generation and CO draw by pipeline 15.The CO and the hydrogen that generate can return to converter unit hydrogen manufacturing, also can be used as downstream synthesis material.
Describe the present invention in detail with embodiment below, but embodiment use range not thereby limiting the invention.
The silica-alumina material adopting in embodiment is for by weight, and the silica-alumina material catalyzer that does not contain molecular sieve making containing 10% aluminum oxide, 80% kaolinic spraying dry roasting, is designated as MFC-1.Silica-alumina material adopts containing 5% rectorite clay molecular sieve with layer structure and 5%ZSM-5 molecular sieve, and all the other are 90% kaolin, and the spray-dried catalyzer making is designated as MFC-2.The trade names of the catalytic cracking catalyst containing Y molecular sieve that silica-alumina material adopts are CRC-1.
The gasifying catalyst that embodiment adopts is for containing 85 % by weight K
2cO
3catalyzer, be designated as GC-1; Gasifying catalyst is through pulverizing the natural rhombspar of median size at 65 μ m, being designated as GC-2.Gasifying catalyst GC-3 be synthetic containing potassium active ingredient, its preparation process is: take 3.5 kilograms of kaolin, 0.42 kilogram of K
2o and 0.028 kilogram of CaO, mix three, adds appropriate amount of deionized water, makes slurry solid content 15 ~ 50%, stirs at least 20 minutes, and spraying is dry, and at 950 ℃, roasting 4 hours, makes containing potassium active ingredient.Should it be respectively 21 °, 29 °, 35 ° containing principal phase peak 2 θ in potassium active ingredient XRD thing phasor.
Embodiment 1
The catalytic cracking catalyst that is CRC-1 by trade names is that 15.10 % by weight, metal are that 50 μ g/g, sulphur content are 1.12%(quality with carbon residue) heavy oil come in contact cracking reaction contacting cracking unit, the processing condition of contact cracking reaction are: 460 ℃ of cracking temperature, air speed 10h
-1, agent-oil ratio 10, water-oil ratio 0.1, the coke content of gained spent agent is 1.8 % by weight.
By spent agent water steam stripped 30 minutes, contact substance mixed heat transfer the spent agent after stripping and the regeneration coming from revivifier, spent agent temperature reaches 610 ℃, pass in molar fraction, the vaporized chemical of oxygen 15%, water 85%, generating gasification reaction, gained object product C O+H
2volume fraction (butt) be 71.5%.
The object product C O+H that gasification unit is obtained
2introduce converter unit, product separates hydrogen and CO after separating
2, by CO
2introduce dry reformer unit, CO
2and CH
4mol ratio be 1:1, catalyzer is the nickel-base catalyst containing Ni 1.5 % by weight, temperature of reaction is 750 ℃, air speed is 5000h
-1, after reforming, the transformation efficiency of methane reaches 82.1%, CO
2transformation efficiency reach 79.6%.
The catalytic cracking catalyst that is CRC-1 by trade names and gasifying catalyst GC-1 carry out mechanically mixing, both mass ratios are 9:1, then be that 18.10 % by weight, metal are that 200 μ g/g, sulphur content are 1.12%(quality with carbon residue) heavy oil come in contact cracking reaction contacting cracking unit, the processing condition of contact cracking reaction are: 500 ℃ of cracking temperature, air speed 20h
-1, agent-oil ratio 7, water-oil ratio 0.2, the coke content of gained spent agent is 2.5 % by weight.
By spent agent water steam stripped 30 minutes, contact substance mixed heat transfer the spent agent after stripping and the regeneration coming from revivifier, spent agent temperature reaches 700 ℃, passes in molar fraction oxygen 10%, water 80%, the part CO coming from converter unit
210% vaporized chemical, generating gasification reaction, gained object product C O+H
2volume fraction (butt) be 65.20%.
The object product C O+H that gasification unit is obtained
2introduce converter unit, product separates hydrogen and CO after separating
2, by part CO
2introduce dry reformer unit, CO
2and CH
4mol ratio be 1:1, catalyzer is the nickel-base catalyst containing Ni 3.0 % by weight, temperature of reaction is 700 ℃, air speed is 30000h
-1, after reforming, the transformation efficiency of methane reaches 84.6%, CO
2transformation efficiency reach 86.1%.
Be that 35.0 % by weight, metal 425 μ g/g, sulphur content are 3.12%(quality by silica-alumina material MFC-1 and carbon residue) heavy oil come in contact cracking reaction contacting cracking unit, the processing condition of contact cracking reaction are: 520 ℃ of cracking temperature, air speed 50h
-1, agent-oil ratio 20, water-oil ratio 0.5, the coke content of gained spent agent is 2.8 % by weight.
By spent agent water steam stripped 30 minutes, contact substance mixed heat transfer the spent agent after stripping and the regeneration coming from revivifier, spent agent temperature reaches 800 ℃, pass in molar fraction, the vaporized chemical of oxygen 5%, water 95%, generating gasification reaction, gained object product C O+H
2volume fraction (butt) be 83.5%.
The object product C O+H that gasification unit is obtained
2introduce converter unit, product separates hydrogen and CO after separating
2, by CO
2introduce dry reformer unit, CO
2and CH
4mol ratio be 1:1, catalyzer is the nickel-base catalyst containing Ni 5 % by weight, temperature of reaction is 800 ℃, air speed is 10000h
-1, after reforming, the transformation efficiency of methane reaches 88.2%, CO
2transformation efficiency reach 84.8%.
By silica-alumina material MFC-2 and gasifying catalyst GC-2,1:1 mechanically mixing is even in mass ratio, be that 25.0 % by weight, metal content are that 100.1 μ g/g, sulphur content are 3.12%(quality with carbon residue) heavy oil come in contact cracking reaction contacting cracking unit, the processing condition of contact cracking reaction are: 580 ℃ of cracking temperature, air speed 30h
-1, agent-oil ratio 15, water-oil ratio 0.3, the coke content of gained spent agent is 4.2 % by weight.
By spent agent water steam stripped 30 minutes, contact substance mixed heat transfer the spent agent after stripping and the regeneration coming from revivifier, spent agent temperature reaches 750 ℃, passes in molar fraction oxygen 12%, the CO coming from converter unit
288% vaporized chemical, generating gasification reaction, gained object product C O+H
2volume fraction be 5.5%.
The object product C O+H that gasification unit is obtained
2introduce converter unit, product separates hydrogen and CO after separating
2, by CO
2introduce dry reformer unit, CO
2and CH
4mol ratio be 1:1, catalyzer is the nickel-base catalyst containing Ni 2.4 % by weight, temperature of reaction is 650 ℃, air speed is 1500h
-1, after reforming, the transformation efficiency of methane reaches 76.2%, CO
2transformation efficiency reach 75.8%.
Embodiment 5
Gasifying catalyst GC-3 is that 18.1 % by weight, metal content are that 200 μ g/g, sulphur content are 3.12%(quality with carbon residue) heavy oil come in contact cracking reaction contacting cracking unit, the processing condition of contact cracking reaction are: 530 ℃ of cracking temperature, air speed 60h
-1, agent-oil ratio 2, water-oil ratio 0.8, the coke content of gained spent agent is 6.4 % by weight.
By spent agent water steam stripped 30 minutes, contact substance mixed heat transfer the spent agent after stripping and the regeneration coming from revivifier, spent agent temperature reaches 650 ℃, passes in molar fraction oxygen 25%, the CO coming from converter unit
275% vaporized chemical, generating gasification reaction, gained object product C O+H
2volume fraction be 7.2%.
The object product C O+H that gasification unit is obtained
2introduce converter unit, product separates hydrogen and CO after separating
2, by CO
2introduce dry reformer unit, CO
2and CH
4mol ratio be 1:1, catalyzer is the nickel-base catalyst containing Ni 2.4 % by weight, temperature of reaction is 650 ℃, air speed is 1500h
-1, after reforming, the transformation efficiency of methane reaches 76.2%, CO
2transformation efficiency reach 75.8%.
Claims (17)
1. a working method for heavy oil, the method comprises:
(1) in contact cracking unit, heavy oil enters contact cracking case, under the existence of contact substance, contact cracking reaction, the effluent of contact cracking case comprises dry gas, liquefied gas, gasoline fraction, diesel oil distillate, wax oil cut and band charcoal contact substance, and described band charcoal contact substance enters gasification unit;
(2) in gasification unit, react with the charcoal on charcoal contact substance and vaporized chemical, generate and be rich in CO and H
2gasification gas, and obtain the contact substance of regenerating;
(3) step (2) gained gasification gas separates and obtains hydrogen and CO through water-gas shift
2, hydrogen and CO
2after separation, CO
2enter dry reformer unit; Step (2) gained regeneration contact substance enters dry reformer unit;
(4) CO
2at dry reformer unit, under the effect of regeneration contact substance, react together with methane-rich gas, generate containing CO and H
2synthetic gas, the contact substance occurring after katalysis returns to step (1) contact cracking unit again.
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, and metal content is at 1 ~ 1000 μ g/g, and wherein Ni content is greater than 5 μ g/g.
3. according to the method for claim 1, it is characterized in that the processing condition of the contact cracking unit in described step (1) are: 450 ~ 650 ℃ of temperature of reaction, weight hourly space velocity 1 ~ 100h
-1, the mass ratio of contact substance and heavy oil feedstock is 1 ~ 30:1, the mass ratio of water vapour and heavy oil feedstock is 0.05 ~ 1:1.
4. according to the method for claim 1, it is characterized in that the contact substance in described step (1) is silica-alumina material and/or gasifying catalyst.
5. according to the method for claim 4, it is characterized in that the contact substance in described step (1) is silica-alumina material and gasifying catalyst, gasifying catalyst and silica-alumina material are mechanically mixing, or gasifying catalyst loads on silica-alumina material.
6. according to the method for claim 4 or 5, it is characterized in that described silica-alumina material is selected from containing the catalyzer of molecular sieve and/or not containing the silica-alumina material catalyzer of molecular sieve.
7. according to the method for claim 6, it is characterized in that the described catalyzer containing molecular sieve is the catalyzer being selected from containing one or more molecular sieves in X molecular sieve, Y molecular sieve, mordenite, ZSM-5, clay molecular sieve with layer structure, SAPO.
8. according to the method for claim 6, described in it is characterized in that, the silica-alumina material catalyzer containing molecular sieve does not refer to the catalyzer of preparing as raw material take one or more the mixture in amorphous silicon aluminium, carclazyte, kaolin, montmorillonite, rectorite leng, illite, chlorite, pseudo-boehmite, silicon-dioxide.
9. according to the method for claim 4 or 5, it is characterized in that described gasifying catalyst is one or more in the natural crystal that contains single metal in basic metal, alkaline-earth metal and VIII family metal or various metals combination, synthetic materials, derivative compound.
10. according to the method for claim 4 or 5, it is characterized in that containing containing potassium active ingredient in described gasifying catalyst, is wherein respectively 21 °, 29 °, 35 ° containing principal phase peak 2 θ in the XRD thing phasor of potassium active ingredient.
11. according to the method for claim 1, it is characterized in that band charcoal contact substance carbon content that described step (1) obtains is in 0.5 % by weight ~ 7.0 % by weight.
12. according to the method for claim 1, it is characterized in that the operational condition of described step (2) gasification unit: gasification temperature is 600 ~ 800 ℃.
13. according to the method for claim 1 or 12, it is characterized in that described step (2) vaporized chemical refers to oxygen and water vapour and/or CO
2gas, take vaporized chemical as benchmark, the molar fraction of oxygen is 5% ~ 30%, described CO
2gas is from water-gas shift unit.
14. according to the method for claim 1, it is characterized in that the carbon content of described step (2) gained regeneration contact substance is lower than 0.5 % by weight.
15. according to the method for claim 1, and the processing condition that it is characterized in that the dry reformer unit of described step (3) are 600 ~ 850 ℃ of temperature of reaction, and air speed is 1000 ~ 100000h
-1, enter on the regeneration contact substance of dry reformer unit and contain active ingredient Ni, by the quality of contact substance, active ingredient Ni content is 0.5% ~ 5%.
16. according to the method for claim 1, it is characterized in that described step (3) methane-rich gas is selected from one or more the mixture in methane, Sweet natural gas, oil field gas, or in above-mentioned gas, be mixed with the methane-rich gas of one or more mixtures in a certain amount of dry gas that is selected from catalytic cracked dry gas, coking dry gas, step (1) gained contact cracking.
17. according to the method for claim 1, it is characterized in that the reactor of the dry reformer unit of described step (3) is fluidized-bed reactor.
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