CN109705903A - Inferior heavy oil processing-coke gasification combined method - Google Patents
Inferior heavy oil processing-coke gasification combined method Download PDFInfo
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- 238000002309 gasification Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 58
- 239000000295 fuel oil Substances 0.000 title claims abstract description 44
- 239000000571 coke Substances 0.000 title claims abstract description 35
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000007789 gas Substances 0.000 claims abstract description 73
- 238000005336 cracking Methods 0.000 claims abstract description 46
- 239000003921 oil Substances 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 8
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012492 regenerant Substances 0.000 claims abstract description 4
- 238000006722 reduction reaction Methods 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 8
- -1 heavy crude Substances 0.000 claims description 4
- 230000008929 regeneration Effects 0.000 claims description 4
- 238000011069 regeneration method Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000001172 regenerating effect Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 20
- 230000008569 process Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004523 catalytic cracking Methods 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 239000008246 gaseous mixture Substances 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000003209 petroleum derivative Substances 0.000 description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- 238000004227 thermal cracking Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 229910001919 chlorite Inorganic materials 0.000 description 1
- 229910052619 chlorite group Inorganic materials 0.000 description 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910052900 illite Inorganic materials 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Abstract
The present invention relates to inferior heavy oil manufacture fields, disclose inferior heavy oil processing-coke gasification combined method, comprising: heavy oil feedstock and contact agent are carried out contact cracking reaction, and the material after contact cracking reaction is separated, obtains oil gas product and spent agent；Spent agent and oxygen-containing gas are subjected to gasification reaction, and the product obtained after gasification reaction is separated to obtain the contact agent after synthesis gas and gasification；Contact agent after the gasification is restored with the regenerative agent after being restored, and the regenerant recycle after reduction is gone back into step (1) and carries out contact cracking reaction.Method of the invention is able to suppress the generation of side effect caused by metal, especially vanadium metal are accumulated in heavy oil feedstock on the contact agent after contacting cracking reaction.
Description
Technical field
The present invention relates to inferior heavy oil manufacture fields, and in particular to a kind of combination side of inferior heavy oil processing-coke gasification
Method.
Background technique
With the development of world economy, the mankind are to lightweight, the demand of clean fuel oil also rapid growth.However, world's model
Enclose interior crude oil heaviness, the aggravation of in poor quality degree (is mainly shown as that the density of crude oil is big, viscosity is high, carbon residue is high, content of beary metal
High and sulphur nitrogen content height etc.), meanwhile, the environmental protection standard of countries in the world is increasingly stringent, these factors propose perhaps to petroleum refining industry
Mostly new problem.
Currently, processing of heavy oil is broadly divided into decarburization and plus two class of hydrogen from the point of view of in mechanism.
To add hydrogen mainly include hydrofinishing and is hydrocracked.Hydrogenation process is produced for improving the working depth of crude oil, improving
The quality of product and the yield for improving light-end products are of great significance；But not only operation temperature is high for heavy oil hydrogenation process, pressure
Power is also high, and conversion ratio is lower, usually 30~50 weight % or so.Meanwhile crude oil is carried out hydrogen is added also to need largely
Hydrogen, and the source of hydrogen is then always the problem for perplexing oil refining industry.
Decarbonization process is the main method of current processing of heavy oil, mainly includes heavy oil catalytic cracking, solvent deasphalting and prolonging
Slow coking.Heavy oil catalytic cracking is a kind of catalytic process, therefore not all raw material is not preprocessed directly to carry out
Catalytic cracking, the carbon residue general control that the country carries out the feedstock oil of heavy oil catalytic cracking is 4~6 weight %, tenor control
For no more than 10 μ g/g.Delayed coking is a kind of highest processing of heavy oil method of conversion level, now the slag of 60% or more foreign countries
Oil is all in this way, the disadvantage is that liquid product yield is lower；And sulfur-bearing is being processed using delay coking process
When residual oil, the sulfur content of coke is high, and there are problems for outlet.
Therefore, new Heavy oil conversion method is developed to be of great practical significance.
CN1504404A discloses a kind of oil refining with the process that combines of gasifying, this method comprises: (1) is by petroleum hydrocarbon
It is contacted in reactor with coke transfer agent；(2) coke transfer agent of carbon deposit after separating reaction oil gas generated and reacting, instead
Oil gas is answered to be sent into subsequent hydrocarbon products separation system, the coke transfer agent of carbon deposit is sent after stripping to gasification furnace；(3) in gasification furnace
Interior, the coke transfer agent of carbon deposit is contacted with vapor and oxygen-containing gas, to produce synthetic gas, while shifts the coke of carbon deposit
Agent is regenerated；(4) it is recycled in reactor described in the coke transfer agent return step (1) after step (3) regeneration.From
From the point of view of the prior art disclosed embodiment, the carbon residue of the petroleum hydrocarbon for processing is only up to 10 weight %.
CN102031140A discloses a kind of combined method of inferior heavy oil processing coke gasification, mainly includes heavy oil feedstock
It is contacted with catalyst, separation product oil gas and spent agent, oil gas enters subsequent separation system, and spent agent is sent to gasification after stripping
Furnace, the synthesis gas obtained after gasification reaction and the semi regeneration agent for removing part of coke separate, and synthesis gas carries out hydrogen manufacturing or work
For C-1 chemistry synthesis material gas；And the semi regeneration agent for removing part of coke is sent to regenerator and is regenerated completely, then weighs
It is new to import reactor.
In addition, a large amount of charcoal metallic substances and metal in petroleum hydrocarbon are heavy when the carbon residue of petroleum hydrocarbon and higher tenor
Product leads to the activity decline of coke transfer agent, selectivity is deteriorated, so that dry gas and coke in product on coke transfer agent
Content increase.Although addition matal deactivator can inhibit the side effect of metal on certain depth, effect is limited.
To sum up, the heavy oil conversion of high liquid component yield can be obtained while improve the method for quality of gasoline by developing one kind
It is a technical problem urgently to be resolved.
Summary of the invention
The present invention be directed to metal, especially vanadium metals to be accumulated in heavy oil feedstock on the contact agent after contacting cracking reaction
Caused by liquid yield is low etc. that side effects provide a kind of new inferior heavy oil processing-coke gasification combined method.
To achieve the goals above, the present invention provides a kind of combined method of inferior heavy oil processing-coke gasification, this method
Include:
(1) in the presence of fluidizing gas, heavy oil feedstock and contact agent are subjected to contact cracking reaction, and it is anti-to contact cracking
Material after answering, which is introduced in separation system, to be separated, and oil gas product and spent agent are obtained；
(2) spent agent is introduced in gasification reaction unit and carries out gasification reaction with oxygen-containing gas, and by gasified reverse
Should after obtained product separated to obtain the contact agent after synthesis gas and gasification；
(3) contact agent after at least partly described gasification is introduced to after restoring in reduction unit to be restored
Regenerative agent, and the regenerant recycle after the reduction is returned in step (1) as the contact agent to carry out contact cracking reaction.
The present invention relates to heavy oil feedstock contact cracking reaction and cracking generate coke through gasify synthetic gas production process,
It more specifically, is a kind of to produce a certain amount of lightweight using catalytic cracking or thermal cracking process working process heavy charge and fire
Oil, while hydrogen or synthesis gas are produced, the method that the residue carbon of mink cell focus is converted to the higher product of added value.
Method of the invention is able to suppress metal, especially vanadium metal and is accumulated in heavy oil feedstock after contacting cracking reaction
The generation of side effect caused by contact agent.So as to improve product distribution, raising liquid yield is specifically, of the invention
Method can reduce the yield of dry gas and coke in crackate, while gasoline fraction yield is significantly increased.
Detailed description of the invention
Fig. 1 is a kind of preferred embodiment of the combined method of inferior heavy oil processing-coke gasification of the invention
Process flow chart.
Description of symbols
1, Cracking Unit is contacted
2, gasification reaction unit
3, reduction unit
4, heavy oil feedstock
5, fluidizing gas
6, oil gas product
8, synthesis gas
7,9,10,11,12,13,14 be pipeline.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
As previously mentioned, the present invention provides a kind of combined methods of inferior heavy oil processing-coke gasification, this method comprises:
(1) in the presence of fluidizing gas, heavy oil feedstock and contact agent are subjected to contact cracking reaction, and it is anti-to contact cracking
Material after answering, which is introduced in separation system, to be separated, and oil gas product and spent agent are obtained；
(2) spent agent is introduced in gasification reaction unit and carries out gasification reaction with oxygen-containing gas, and by gasified reverse
Should after obtained product separated to obtain the contact agent after synthesis gas and gasification；
(3) contact agent after at least partly described gasification is introduced to after restoring in reduction unit to be restored
Regenerative agent, and the regenerant recycle after the reduction is returned in step (1) as the contact agent to carry out contact cracking reaction.
According to a kind of preferred embodiment, in step (1), the hydrogen volume score in the fluidizing gas is
5~100%.It was found by the inventors of the present invention that when containing hydrogen in the fluidizing gas, the production that can further increase
The content of liquid component in product.
According to above-mentioned preferred embodiment, in step (1), the condition packet of the preferably described contact cracking reaction
Include: reaction temperature is 300~700 DEG C；Reaction pressure is 0.045~5MPa.
According to another preferred embodiment, in step (1), hydrogen is contained in the fluidizing gas, and also
Containing vapor, the reaction temperature of the contact cracking reaction is 450~520 DEG C；Volume space velocity is 0.8~8h-1；Heavy oil feedstock
Weight ratio with contact agent is 1:(4~15).In the preferred embodiment, it is substantially carried out the catalysis of conventional or either shallow
Cracking.
Contain hydrogen in the fluidizing gas in step (1) according to there are also a kind of preferred embodiment, and
Also contain vapor, the reaction temperature of the contact cracking reaction is 520~700 DEG C；Volume space velocity is 0.8~8h-1；Heavy oil is former
The weight ratio of material and contact agent is 1:(4~15).In the preferred embodiment, it is substantially carried out thermal cracking or thermal cracking
With catalytic cracking.
The reactor for carrying out contact cracking reaction in step (1) of the invention can be anti-for riser reactor or bed
Device is answered, or adds bed reactor (variable diameter reactor) for riser.
FCC feedstock or hydrocracking raw material can be used for by the heavy constituent that separation system obtains in step (1) of the invention,
It can be recycled in system.
Under preferable case, in step (2), the condition of the gasification reaction includes: that temperature is 500~1000 DEG C, empty bed
Gas velocity is 0.05~1.5m/s, pressure is 0.045~5MPa, and the time is 0.5~150s.
Preferably, in step (2), the condition of the gasification reaction is controlled, so that described in obtaining after gasification reaction
CO and H in synthesis gas2The sum of content is greater than 50 volume %, and oxygen content is less than 0.2 volume %.
Under preferable case, in step (2), the condition of the gasification reaction is controlled, so that obtained after gasification reaction
The coke content on contact agent after the gasification is 0.1~0.6 weight %.
According to a kind of preferred embodiment, in step (2), the contact agent after the gasification of part is recycled back to
As the contact agent to carry out contact cracking reaction in step (1).It is connect described in conduct it is highly preferred that being recycled back in step (1)
The mass flowrate of contact agent after touching the gasification of agent account for the mass flowrate of the spent agent flowed out in step (1) 20~
90%.
According to another preferred embodiment, in step (2), all the contact agent after the gasification is introduced to
It is restored in reduction unit with the regenerative agent after being restored.
Preferably, in step (2), the oxygen content in the oxygen-containing gas is 10~30 volume %.
The gasification reaction of the invention can carry out in fluidized bed or moving-burden bed reactor.
The oxygen-containing gas of the invention can be oxygen and vapor gaseous mixture, be also possible to oxygen, vapor with
And the gaseous mixture of carbon dioxide.
Method of the invention can also include first stripping the spent agent that step (1) obtains, and then be re-introduced into step
Suddenly gasification reaction is carried out in the gasification reaction unit of (2).The stripping process can be with the stripping process phase in conventional FCC operation
Together.
The synthesis gas of the invention can be sent to water vapour converter unit and carry out hydrogen manufacturing or be used as C-1 chemistry synthesis
Unstrpped gas.
Preferably, in step (3), the condition of the reduction reaction includes: that temperature is 300~800 DEG C, pressure 0.1
~3MPa.
Under preferable case, in step (3), the reduction reaction is being selected from H2、CO、C1~C4Hydro carbons at least one
It is carried out in the presence of kind gas.
The present invention carry out reduction reaction after gas can a part enter step in (1), remainder is sent to subsequent system
It unites or is recycled.
Preferably, the carbon residue content in the heavy oil feedstock is 10~45, total metal content based on the element is 25~
1000 μ g/g, metal content of vanadium based on the element are 20~800 μ g/g, and the carbon residue content in GB/T 17144 according to providing
Method measurement, the total metal content and metal content of vanadium are measured according to method specified in RIPP124-90.
Preferably, the heavy oil feedstock be selected from normal pressure wax oil, reduced crude, decompressed wax oil, decompression residuum, wax tailings,
At least one of deasphalted oil, hydrocracking tail oil, heavy crude, acid-containing raw oil and tank bottom oil.
Preferably, the micro-activity of the contact agent is greater than 0 and less than or equal to 80, and average grain diameter is 10~200 μm, and
The micro-activity is measured according to standard ASTM D3907-87；More preferable average grain diameter is 60~95 μm；The more preferable contact
The micro-activity of agent is 20~50.
Under preferable case, the contact agent is porous mass, and the average pore size of the contact agent is 1~200nm, more excellent
It is selected as 10~100nm.
The contact agent of the invention can be for good hydrothermal stability and with the catalyst of certain catalytic cracking activity, institute
On the one hand cracking can be carried out to heavy oil by stating contact agent；On the other hand during residual oil cracking, carbonaceous is inevitably generated
Residue (that is, carbon residue) namely the contact agent can be as the carriers of the carbonaceous residue generated in cracking process, will be described
Carbonaceous residue is delivered to outside reactor；In addition, the contact agent can also be as the carrier of thermal energy.For example, the contact agent
For the substance containing silicon and/or aluminium.
The contact agent of the invention is generally spherical shape, can be prepared by spray drying or method of agglomeration.
The example of the contact agent of the invention can be but be not limited to: amorphous silica-alumina, carclazyte, kaolin, montmorillonite,
One of rectorite, illite, chlorite, aluminium oxide and quartz sand are a variety of.
The oil gas product that step (1) of the present invention obtains can obtain gas, gasoline fraction, diesel oil distillate and wax after being fractionated
Oil distillate etc..
A kind of preferred tool of the combined method of inferior heavy oil processing-coke gasification of the invention is provided below in conjunction with Fig. 1
The process flow of body embodiment:
Heavy oil feedstock 4 and fluidizing gas 5, which enter in contact Cracking Unit 1, to be contacted with the contact agent from pipeline 14 to carry out
Cracking reaction is contacted, the material obtained after contact cracking reaction, which is introduced in separation system, to be separated, and 6 He of oil gas product is obtained
Spent agent, spent agent are introduced in gasification reaction unit 2 by pipeline 7 and carry out gasification reaction with the oxygen-containing gas from pipeline 9,
And the product obtained after gasification reaction is separated to obtain the contact agent after synthesis gas 8 and gasification；Contact agent after gasification
Enter in reduction unit 3 through pipeline 10 and is restored with the reducing gas from pipeline 11 with the regenerative agent after being restored；Also
Regenerative agent after original returns in contact Cracking Unit 1 through pipeline 14, and the gas a part obtained after reduction enters through pipeline 12 to be connect
It touches in Cracking Unit 1, remainder is drawn through pipeline 13.
The present invention will be described in detail by way of examples below.
Embodiment 1-1 and embodiment 1-2
Embodiment is carried out using process flow shown in FIG. 1.
In the fluidized-bed reactor of laboratory, using the silicon aluminium microsphere particle of spray drying technology production as contact agent
(micro-activity 35, average grain diameter be 85 μm, average pore size 68nm), make its respectively with feedstock oil 1 shown in table 1 and original
Material oil 2 contacts and carries out contact cracking reaction, and the condition for contacting cracking reaction is as shown in table 2, and reaction pressure is 0.2MPa.
Reducing gas is hydrogen, and hydrogen volume content is 60% in fluidizing gas, the condition of reduction reaction and treated product point
Cloth is shown in Table 2, according to the difference of feedstock oil type, is respectively provided with embodiment 1-1 and embodiment 1-2.
Wherein, the condition in gasification reaction includes: the gaseous mixture that oxygen-containing gas is vapor and oxygen, and the content of oxygen
For 15 volume %；Temperature is 650 DEG C, gas empty bed speed 0.6m/s, pressure 0.2MPa, time 15s.
Comparative example 1-1 and comparative example 1-2
Comparative example is carried out using technique similar with previous embodiment 1-1 and embodiment 1-2, except that:
Contact agent after the gasification obtained after gasification reaction, is directly recycled back to by the step of reduction is not provided in this comparative example
It contacts in cracking reaction unit.
And it is directed to different raw materials, is respectively provided with comparative example 1-1 and comparative example 1-2, concrete outcome is referring to table 2.
Embodiment 2
The present embodiment is carried out using process flow shown in FIG. 1.
In the fluidized-bed reactor of laboratory, using the silicon aluminium microsphere particle of spray drying technology production as contact agent
(micro-activity 30, average grain diameter are 76 μm, average pore size 80nm), contacts it with feedstock oil 1 shown in table 1 and goes forward side by side
Row contact cracking reaction, cracking reaction condition is as shown in table 3, and reaction pressure is 0.8MPa.Reducing gas is that volume ratio is
The hydrogen of 1:1 and the gaseous mixture of methane, hydrogen volume content is 50% in fluidizing gas, after the condition and processing of reduction reaction
Product distribution be shown in Table 3, and according to the difference of reducing condition, be respectively provided with embodiment 2-1, embodiment 2-2, embodiment 2-
3 and embodiment 2-4.
Wherein, the condition in gasification reaction includes: the gaseous mixture that oxygen-containing gas is vapor and oxygen, and the content of oxygen
For 20 volume %；Temperature is 700 DEG C, gas empty bed speed 0.8m/s, pressure 0.6MPa, time 20s.
Comparative example 2
This comparative example is carried out using technique similar to Example 2, except that:
Contact agent after the gasification obtained after gasification reaction, is directly recycled back to by the step of reduction is not provided in this comparative example
It contacts in cracking reaction unit.Remaining is in the same manner as in Example 2.
Concrete outcome is referring to table 3.
Embodiment 3
The present embodiment is carried out using method similar with embodiment 1-1, except that:
Contact after 30% gasification of the mass flowrate of the spent agent flowed out in step (1) will be accounted in the present embodiment
Agent is recycled back in step (1) as the contact agent to carry out contact cracking reaction, remainder be introduced in reduction unit into
Row reduction.
Remaining is identical as embodiment 1-1, and the present embodiment the results are shown in Table 4.
Table 1
| Project | Feedstock oil 1 | Feedstock oil 2 |
| Density (20 DEG C)/(g/cm3) | 0.9908 | 0.9643 |
| Kinematic viscosity/(mm2/s) | ||
| 80℃ | 867.0 | 231 |
| 100℃ | 252.9 | 54 |
| Carbon residue/weight % | 16.8 | 10.2 |
| Average molecular weight/(g/mol) | 548 | 524 |
| Four components/weight % | ||
| Saturated hydrocarbons | 29.0 | 32.0 |
| Aromatic hydrocarbon | 32.5 | 48.3 |
| Colloid | 23.8 | 12.6 |
| Asphalitine | 14.7 | 3.4 |
| Element composition, weight % | ||
| C | 85.68 | 84.38 |
| H | 10.64 | 10.99 |
| S | 2.5 | 4.04 |
| N | 0.35 | 0.11 |
| Tenor/(μ g/g) | ||
| Ni | 30.9 | 15.3 |
| V | 223 | 55.0 |
Table 2
Table 3
Table 4
| Feedstock oil | Feedstock oil 1 |
| Temperature, DEG C | 500 |
| Air speed, h-1 | 4 |
| Agent oil weight ratio | 7 |
| Water oil weight ratio | 0.2 |
| Reducing condition | |
| Temperature, DEG C | 650 |
| Pressure, MPa | 0.2 |
| Product yield, weight % | |
| Dry gas | 3.03 |
| Liquefied gas | 8.22 |
| C5~gasoline | 18.15 |
| Diesel oil | 24.31 |
| Heavy oil | 25.49 |
| Coke | 20.80 |
| It amounts to | 100.00 |
By the result of comparative example 1-1 and embodiment 1-1 in table 2 it can be seen that after reduction, the cracking of feedstock oil
Dry gas and coke are greatly lowered in product, and especially coke reduces about 2 percentage points, meanwhile, the yield of gasoline increases.
By the result of comparative example 1-2 and embodiment 1-2 in table 2 it can be seen that after reduction, the cracking of feedstock oil
Dry gas and coke are greatly lowered in product, and especially coke reduces by 1 percentage point or more, while gasoline yield significantly increases
Add.
By in table 3 comparative example 2 and embodiment 2-1, embodiment 2-2, embodiment 2-3 and embodiment 2-4 result can be with
Find out: method of the invention can be substantially reduced dry gas and coke yield in crackate, while improve gasoline yield；Also,
This can be seen that by different reducing conditions, and dry gas and coke yield are different in crackate, can be made by optimum condition
Dry gas and coke yield in crackate is obtained to be greatly lowered.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (13)
1. a kind of combined method of inferior heavy oil processing-coke gasification, this method comprises:
(1) in the presence of fluidizing gas, heavy oil feedstock and contact agent are subjected to contact cracking reaction, and will be after contact cracking reaction
Material be introduced in separation system and separated, obtain oil gas product and spent agent；
(2) spent agent is introduced in gasification reaction unit and carries out gasification reaction with oxygen-containing gas, and will be after gasification reaction
Obtained product is separated to obtain the contact agent after synthesis gas and gasification；
(3) contact agent after at least partly described gasification is introduced to the regeneration restored in reduction unit with after being restored
Agent, and the regenerant recycle after the reduction is returned in step (1) as the contact agent to carry out contact cracking reaction.
2. according to the method described in claim 1, wherein, in step (1), the hydrogen volume score in the fluidizing gas is
5~100%.
3. method according to claim 1 or 2, wherein in step (1), the condition of the contact cracking reaction includes:
Reaction temperature is 300~700 DEG C；Reaction pressure is 0.045~5MPa.
4. the contact cracking is anti-according to the method described in claim 3, wherein, vapor is also contained in the fluidizing gas
The reaction temperature answered is 450~520 DEG C；Volume space velocity is 0.8~8h-1；The weight ratio of heavy oil feedstock and contact agent be 1:(4~
15)。
5. the contact cracking is anti-according to the method described in claim 3, wherein, vapor is also contained in the fluidizing gas
The reaction temperature answered is 520~700 DEG C；Volume space velocity is 0.8~8h-1；The weight ratio of heavy oil feedstock and contact agent be 1:(4~
15)。
6. according to the method described in claim 1, wherein, in step (2), the condition of the gasification reaction includes: that temperature is
500~1000 DEG C, gas empty bed speed is 0.05~1.5m/s, pressure is 0.045~5MPa, and the time is 0.5~150s；Preferably,
In step (2), the condition of the gasification reaction is controlled, so that CO and H in the synthesis gas obtained after gasification reaction2
The sum of content is greater than 50 volume %, and oxygen content is less than 0.2 volume %.
7. method according to claim 1 or 6, wherein in step (2), the condition of the gasification reaction is controlled, so that
The coke content on contact agent after the gasification obtained after gasification reaction is 0.1~0.6 weight %.
8. method according to claim 1 or claim 7, wherein in step (2), the contact agent after the gasification of part is followed
As the contact agent to carry out contact cracking reaction in loopback step (1)；Preferably,
It is recycled back to the mass flowrate in step (1) as the contact agent after the gasification of the contact agent and accounts for stream in step (1)
The 20~90% of the mass flowrate of spent agent out.
9. according to the method described in claim 1, wherein, in step (2), the oxygen content in the oxygen-containing gas is 10~
30 volume %.
10. method described in any one of -5 according to claim 1, wherein in step (3), the item of the reduction reaction
Part includes: that temperature is 300~800 DEG C, and pressure is 0.1~3MPa；Preferably,
In step (3), the reduction reaction is being selected from H2、CO、C1~C4At least one of hydro carbons gas in the presence of into
Row.
11. according to the method described in claim 1, wherein, the carbon residue content in the heavy oil feedstock is 10~45, based on the element
Total metal content be 25~1000 μ g/g, metal content of vanadium based on the element is 20~800 μ g/g；Preferably,
The heavy oil feedstock is selected from normal pressure wax oil, reduced crude, decompressed wax oil, decompression residuum, wax tailings, deasphalted oil, adds
At least one of hydrogen cracking tail oil, heavy crude, acid-containing raw oil and tank bottom oil.
12. according to the method described in claim 1, wherein, the micro-activity of the contact agent is greater than 0 and to be less than or equal to 80,
Average grain diameter is 10~200 μm.
13. according to claim 1 or method described in 12, wherein the contact agent is porous mass, and the contact agent is flat
Equal aperture is 1~200nm, preferably 10~100nm.
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| CN116004279A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) |
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| US5358630A (en) * | 1980-11-17 | 1994-10-25 | Phillips Petroleum Company | Regenerating zeolitic cracking catalyst |
| 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 |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5358630A (en) * | 1980-11-17 | 1994-10-25 | Phillips Petroleum Company | Regenerating zeolitic cracking catalyst |
| CN86101895A (en) * | 1985-02-28 | 1986-08-27 | 富士标准研究株式会社 | Process for thermal cracking of heavy oil |
| 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 |
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| CN116004279A (en) * | 2021-10-22 | 2023-04-25 | 中国石油化工股份有限公司 | Hydrogen production and CO enrichment from hydrocarbon raw materials 2 Is a method of (2) |
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