CN100487080C - Chemical oil-refining method for preparing low carbon olefin and arene - Google Patents

Chemical oil-refining method for preparing low carbon olefin and arene Download PDF

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CN100487080C
CN100487080C CNB2004100061891A CN200410006189A CN100487080C CN 100487080 C CN100487080 C CN 100487080C CN B2004100061891 A CNB2004100061891 A CN B2004100061891A CN 200410006189 A CN200410006189 A CN 200410006189A CN 100487080 C CN100487080 C CN 100487080C
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China
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oil
reaction
stock
catalyst
catalytic
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CN1667089A (en
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李大东
汪燮卿
龙军
达志坚
舒兴田
谢朝钢
聂红
张久顺
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CNB2005800013693A priority patent/CN100465250C/en
Priority to US10/592,166 priority patent/US8778170B2/en
Priority to KR1020067018080A priority patent/KR101147469B1/en
Priority to EP05714812A priority patent/EP1734098A4/en
Priority to ES17151967T priority patent/ES2913654T3/en
Priority to JP2007502171A priority patent/JP4808209B2/en
Priority to EP17151967.1A priority patent/EP3225678B1/en
Priority to BRPI0508591-8A priority patent/BRPI0508591B1/en
Priority to PCT/CN2005/000281 priority patent/WO2005085391A1/en
Priority to SA05260089A priority patent/SA05260089B1/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

This invention is a chemical oil refining method of generating low carbon alkene and arene. Material oil, regenerated catalytic cracking catalyst and vapor are contact to each other in cracking device. On condition of 500~7000C, pressure 0.15~0.4MPa, weight ratio of catalytic cracking catalyst and material oil is 5~50, weight ratio of vapor and material oil is 0.05~0.6, catalyst and reaction oil gas are separated, the catalyst go back to reaction device after regenerated, then the low carbon alkene and arene are got after separating the reaction oil gas. Propylene, ethane and other low carbon alkene is got from heavy feed stock at maximum limit, yield of propylene exceed 30%, and toluene, xylene and other arene are generated at the same time.

Description

A kind of chemical industry type oil refining method of producing low-carbon alkene and aromatic hydrocarbons
Technical field
The invention belongs to the catalysis conversion method of hydrocarbon ils under the situation that does not have hydrogen, more particularly, is a kind of chemical industry type oil refining method that heavy feed stock is converted into the low-carbon alkene that is rich in propylene, ethene and is rich in the aromatic hydrocarbons of toluene, dimethylbenzene.
Background technology
Low-carbon alkene such as ethene, propylene etc. are important Organic Chemicals, and wherein propylene is the synthon of products such as polypropylene, vinyl cyanide.Along with increasing rapidly of derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in propylene market, the world is 1,520 ten thousand tons of 5,120 ten thousand tons of being increased to 2000 before 20 years, and average growth rate per annum reaches 6.3%.The demand that expects propylene in 2010 will reach 8,600 ten thousand tons, and average growth rate per annum is about 5.6% therebetween.
The method of producing propylene mainly is steam cracking and catalytic cracking (FCC), wherein steam cracking is that raw material is produced ethene, propylene by thermo-cracking with lightweight oils such as petroleum naphthas, but the productive rate of propylene only is that FCC is a raw material with decompressed wax oil mink cell focuses such as (VGO) then about 15 heavy %.At present, 66% propylene is produced the byproduct of ethene from steam cracking in the world, and 32% produces the byproduct of vapour, diesel oil from refinery FCC, and a small amount of (about 2%) is obtained by dehydrogenating propane and ethene-butylene metathesis reaction.
If petrochemical complex is walked traditional preparing ethylene by steam cracking, propylene route, will face the shortage of lightweight material oil, inefficiency of production and cost and cross high several big restraining factors.
FCC is owing to advantages such as its adaptability to raw material is wide, flexible operation come into one's own day by day.In the U.S., almost 50% of the propylene market demand all derive from FCC apparatus.It is very fast that the catalytic cracking of propylene enhancing improves technical development.
US4,980,053 disclose a kind of hydrocarbon conversion processes of producing low-carbon alkene, and raw material is petroleum fractions, residual oil or the crude oil of different boiling ranges, uses solid acid catalyst in fluidized-bed or moving-burden bed reactor, temperature 500-650 ℃, pressure 1.5-3 * 10 5Pa, weight hourly space velocity 0.2-2.0h -1, agent-oil ratio 2-12 condition under carry out catalytic conversion reaction, reacted catalyzer Returning reactor internal recycle behind coke burning regeneration uses.The overall yield of this method propylene and butylene can reach about 40%, and wherein productivity of propylene is up to 26.34%.
WO00/31215A1 discloses a kind of catalyst cracking method of producing alkene, and this method adopts ZSM-5 and/or ZSM-11 zeolite to do active component, is the catalyzer of matrix with a large amount of inert substances, is raw material with VGO, and the productive rate of propylene also is no more than 20 heavy %.
US6,123,830 disclose the combined technical method of a kind of two-stage catalytic cracking and two hydrotreatments, and the purpose of this method is that maximum is produced alkene, improves the quality of distillate and the octane value of gasoline.Stock oil obtains first hydrogenation tail oil through first hydrotreater earlier; First hydrogenation tail oil enters first catalytic cracking unit, the catalyst activity component of this catalytic cracking unit is mainly large pore zeolite, obtain petroleum naphtha, diesel oil and heavy oil, wherein heavy oil enters second hydrotreater and carries out hydrogenation, obtain second hydrogenation tail oil, second hydrogenation tail oil to the second catalytic cracking unit carried out cracking, and the catalyst activity component of this catalytic cracking unit is mainly mesopore zeolite.The productivity of propylene of this method is lower.
Aromatic hydrocarbons also is a kind of important chemical material, and especially light aromatic hydrocarbons BTX (benzene,toluene,xylene) is mainly used in synthetic materialss such as producing chemical fibre, plastics.The main method of producing aromatic hydrocarbons at present is a catalytic reforming, because the active ingredient of reforming catalyst is a precious metal, therefore must carry out strict pre-treatment to raw material.In addition, also more complicated of the moving of reforming catalyst, regeneration flow process.
The just by-product propylene when producing gasoline, diesel oil that above-mentioned prior art has, the productive rate of propylene is on the low side, all is no more than 30 heavy %, has plenty of and can only produce aromatic hydrocarbons, but all can not produce low-carbon alkene and aromatic hydrocarbons simultaneously.In order to satisfy the demand of industrial chemicals such as growing propylene, ethene and aromatic hydrocarbons, be necessary to develop a kind of special chemical industry type oil refining method from heavy feed stock while mass production propylene, ethene and aromatic hydrocarbons.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of and produce the chemical industry type oil refining method of low-carbon alkene and aromatic hydrocarbons simultaneously, and the productive rate of propylene will be greater than 30 heavy % from heavy feed stock.
Method provided by the invention comprises: stock oil is introduced into catalytic hydrogenation unit with the partially liq recycle stock of choosing wantonly, contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, the generation of catalytic hydrogenation unit oil with contact in the catalytic cracking reaction device through regenerated catalytic cracking catalyst, water vapor, under the condition of the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the stock oil of 500～700 ℃ of temperature, pressure 0.15～0.4MPa, catalytic cracking catalyst and stock oil, react, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regenerating; Separating reaction oil gas obtains purpose product low-carbon alkene and aromatic hydrocarbons.
Described low-carbon alkene is ethene, propylene and optional butylene.
Remove purpose product, H in the reaction oil gas 2, CH 4Outer remaining gas and/or liquid is as recycle stock, all or part of catalytic cracking reaction device that returns.
Described stock oil is introduced into catalytic hydrogenation unit with the partially liq recycle stock of choosing wantonly, contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, the generation of catalytic hydrogenation unit spontaneously the back as the unitary raw material of catalytic pyrolysis.
Method of the present invention is produced low-carbon alkenes such as propylene, ethene to greatest extent from heavy feed stock, wherein the productive rate of propylene surpasses 30 heavy %, and aromatic hydrocarbons such as toluene, dimethylbenzene are rich in coproduction simultaneously.
Description of drawings
Fig. 1 is the total principle process synoptic diagram of the inventive method.
Fig. 2 is the methodological principle schematic flow sheet of stock oil behind shortening.
Fig. 3 is the principle process synoptic diagram of stock oil and the turning oil catalytic hydrogenation unit when handling respectively.
Fig. 4 is the process flow diagram of optimal technical scheme.
Embodiment
Method of the present invention is so concrete enforcement:
Method provided by the invention comprises: stock oil with contact in the catalytic cracking reaction device through regenerated catalytic cracking catalyst, water vapor, under the condition of the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the stock oil of 500～700 ℃ of temperature, pressure 0.15～0.4MPa, catalytic cracking catalyst and stock oil, react, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regenerating; Separating reaction oil gas obtains purpose product low-carbon alkene and aromatic hydrocarbons.
To divide six parts that this method is described in detail below.
One, stock oil
Described stock oil is oil hydrocarbon ils and/or other mineral oil, the mixture of one or more in this group material of constituting of the free decompressed wax oil of petroleum hydrocarbon grease separation (VGO), wax tailings (CGO), deasphalted oil (DAO), gasoline, diesel oil and residual oil wherein, other mineral oil is liquefied coal coil, tar sand oil or shale oil.Preferred stock oil is VGO.
For the lower stock oil of hydrogen richness, preferably be introduced into catalytic hydrogenation unit, contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, the generation of catalytic hydrogenation unit spontaneously the back as the raw material of catalytic pyrolysis.This hydrogenated oil is compared with stock oil, and hydrogen richness increases, and sulphur, nitrogen, aromaticity content reduce, and as the unitary raw material of catalytic pyrolysis, help to improve productivity of propylene.
Two, catalytic cracking catalyst
Catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, and each components contents is respectively: zeolite 10～50 heavy %, inorganic oxide 5～90 heavy %, clay 0～70 heavy %.
Its mesolite is selected from mesopore zeolite and optional large pore zeolite as active ingredient, and mesopore zeolite accounts for 25～100 heavy % preferred 50～100 heavy % of active ingredient, and large pore zeolite accounts for 0～75 heavy % preferred 0～50 heavy % of active ingredient.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as non-metallic elements such as phosphorus and/or iron, cobalt, nickel to above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, the ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.Large pore zeolite is selected from one or more the mixture in this group zeolite that the super steady Y that is obtained by Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods, high silicon Y constitute.
Inorganic oxide is selected from silicon-dioxide (SiO as caking agent 2) and/or aluminium sesquioxide (Al 2O 3).
Clay is selected from kaolin and/or halloysite as matrix (being carrier).
Three, catalytic cracking reaction device
The used reactor in catalytic pyrolysis unit is selected from riser tube, fluidized-bed, downstriker transfer limes reactor, moving-bed, the compound reactor that constitutes by riser tube and fluidized-bed, the compound reactor that constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, compound reactor that is made of two or more downstriker transfer limess or the compound reactor that is made of two or more moving-beds, preferred catalytic cracking reaction device are riser tube and the compound reactor of fluidized-bed formation.Above-mentioned reactor can use existing catalyst cracker, also can carry out necessary transformation to existing catalyst cracker, can also use and the similar reactor of existing catalyst cracker 26S Proteasome Structure and Function.Catalytic cracking catalyst in each reactor in the compound reactor can be identical, also can be different.
Four, reaction conditions
The riser tube in riser tube, downstriker transfer limes reactor, the compound reactor and/or the processing condition of downstriker transfer limes are: the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the catalytic pyrolysis stock oil of 500～700 ℃ preferred 550～650 ℃ of temperature, pressure (absolute pressure) 0.15～0.4MPa, 1～10 second residence time, catalytic cracking catalyst and catalytic pyrolysis stock oil.
The fluidized-bed in fluidized-bed, moving-bed, the compound reactor and/or the processing condition of moving-bed are: 500～700 ℃ preferred 550～650 ℃ of temperature, pressure (absolute pressure) 0.15～0.4MPa, weight hourly space velocity 0.5～20h -1, catalytic cracking catalyst and catalytic pyrolysis stock oil the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and catalytic pyrolysis stock oil.
Five, product separation
Described low-carbon alkene is ethene, propylene and optional butylene, and promptly low-carbon alkene is ethene, propylene, perhaps ethene, propylene and butylene.
The method of separating ethene is identical with the method for separating ethene from catalytic cracked dry gas that those of ordinary skills know from reaction oil gas, and the method for separation of propylene from the catalytic cracking liquefied gas that the method for separation of propylene and optional butylene and those of ordinary skills know from reaction oil gas and the butylene of choosing wantonly is identical.The method of aromatics separation is that the solvent extracting is identical with the method for aromatics separation from steam cracking gasoline that those of ordinary skills know from the pyrolysis gasoline cut fraction of reaction oil gas, before the pyrolysis gasoline aromatics separation, and can be with the C in the pyrolysis gasoline 5-C 6Separate as recycle stock earlier.
Six, material circulation
Remove purpose product, H in the reaction oil gas 2, CH 4Outer remaining gas and liquid are as recycle stock, and wherein the gas circulation material is ethane, propane and C 4, the liquid circulation material is C 5-C 6, pyrolysis gasoline raffinate oil, turning oil and slurry oil.The all or part of catalytic cracking reaction device that directly or indirectly returns of above-mentioned recycle stock, recycle stock return the catalytic cracking reaction device indirectly and mean that recycle stock earlier through catalytic hydrogenation unit, returns the catalytic cracking reaction device then.
Optimized technical scheme comprises the following steps:
(1), stock oil and optional recycle stock be introduced into catalytic hydrogenation unit, contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, the separating reaction effluent obtains hydrogenated oil;
(2), hydrogenated oil, water vapor enter the riser reaction zone in the composite catalyzing cracking reactor that is made of riser tube and fluidized-bed, with contact through the regenerated catalytic cracking catalyst, under the condition of the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the catalytic pyrolysis stock oil of 500～650 ℃ of temperature, pressure 0.15～0.4MPa, 1～10 second residence time, catalytic cracking catalyst and catalytic pyrolysis stock oil, react;
(3), the reaction effluent of riser reaction zone without finish separate enter fluidized bed reaction zone again with through regenerated catalytic cracking catalyst, water vapor, ethane, propane, C 4-C 6And/or the contact of pyrolysis gasoline raffinate oil, at 520～700 ℃ of temperature, pressure 0.15～0.4MPa, weight hourly space velocity 0.5～20h -1, catalytic cracking catalyst and catalytic pyrolysis stock oil the condition of weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and catalytic pyrolysis stock oil under react;
(4), the reclaimable catalyst and the reaction oil gas that separate fluidized bed reaction zone, wherein reclaimable catalyst returns riser reaction zone and fluidized bed reaction zone through entering revivifier behind the stripping behind coke burning regeneration, reaction oil gas goes to separate and obtains purpose product low-carbon alkene and aromatic hydrocarbons, wherein said aromatic hydrocarbons is that pyrolysis gasoline is separating obtained through solvent extraction, obtains the pyrolysis gasoline raffinate oil simultaneously;
(5), remove purpose product, H in the reaction oil gas 2, CH 4Outer remaining gas and liquid are as recycle stock, and wherein the gas circulation material is ethane, propane and C 4, the liquid circulation material is C 5-C 6, pyrolysis gasoline raffinate oil, turning oil and slurry oil, ethane, propane, C 4-C 6And/or the pyrolysis gasoline raffinate oil returns fluidized bed reaction zone, and slurry oil returns riser reaction zone, and turning oil returns catalytic hydrogenation unit.
Ethane, propane, C in the step (5) 4-C 6Be not limited to ethane, propane, C 4, C 5-C 6, also can be ethane, propane, C 4-C 6Perhaps C wherein 4-C 5
Stock oil in the step (1) and turning oil can be mixed and enter hydrotreating reactor, to reduce facility investment.Heavy feed stock, turning oil contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, reaction effluent successively through high pressure separate, low pressure is separated and the product fractionation obtains hydrogenated oil.
Preferably separate treatment heavy feed stock and turning oil are to obtain optimized reaction effect, but can common high voltage separate, low pressure separates and the product fractionating system, and two reactive systems can adopt identical pressure rating with shared make-up hydrogen compressor and circulating hydrogen compressor.The processing condition of stock oil hydrogenation are: hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1The processing condition of turning oil hydrogenation are: hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.2～2.0h -1The used hydrogenation catalyst of catalytic hydrogenation unit is VIB and the VIII family non-precious metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium carrier, require this catalyzer to possess high hydrogenation saturated activity and denitrification activity, but lytic activity is low, to keep the long linear alkane in the raw material as far as possible, reach the purpose of producing more propylene in catalytic pyrolysis process, preferred Hydrobon catalyst is by 0～10 heavy % additive, one or more group VIII metals of 1～9 heavy %, one or more group vib metals of 12～39 heavy % and surplus aluminum oxide and/or amorphous silicon aluminium carrier constitute, and wherein said additive is selected from fluorine, phosphorus, non-metallic element and metallic elements such as titanium.
This hydrogenated oil is compared with heavy feed stock, and sulphur, nitrogen, aromaticity content reduce, and hydrogen richness increases, and as the unitary raw material of catalytic pyrolysis, helps to improve productivity of propylene.
Optimized technical scheme organically combines shortening and two kinds of oil refining process of catalytic pyrolysis, produce low-carbon alkenes such as propylene, ethene to greatest extent from the heavy feed stock that hydrogen richness is lower, wherein the productive rate of propylene surpasses 30 heavy %, aromatic hydrocarbons such as the toluene of coproduction simultaneously, dimethylbenzene.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed, but does not therefore limit the present invention.
Fig. 1 is the total principle process synoptic diagram of the inventive method.
Total principle process is summarized as follows: stock oil through pipeline 1 with after recycle stock from pipeline 17 mixes, enter catalytic cracking reaction device 2 through pipeline 18, with catalytic cracking catalyst, the water vapor contact, 500～700 ℃ of temperature, pressure (absolute pressure) 0.15～0.4MPa, the weight ratio 5～50 of catalytic cracking catalyst and catalytic pyrolysis stock oil, react under the condition of the weight ratio 0.05～0.6 of water vapor and catalytic pyrolysis stock oil, the reclaimable catalyst of carbon deposit and reaction oil gas enter finish separating device 4 through pipeline 3, isolated reclaimable catalyst enters revivifier 6 through pipeline 5, the catalyzer of coke burning regeneration has higher activity and selectivity, through pipeline 7 Returning reactors 2, reaction oil gas then enters product separation device 9 through pipeline 8, separate the ethene that obtains, propylene is drawn through pipeline 12, removes C 5-C 6Pyrolysis gasoline enter solvent extraction device 19 through pipeline 14, gained aromatic hydrocarbons is drawn through pipeline 21, the gasoline raffinate oil is drawn through pipeline 20, hydrogen and methane are drawn through pipeline 10, ethane and propane are drawn through pipeline 11, C 4-C 6Draw through pipeline 13, turning oil is drawn through pipeline 15, and slurry oil is drawn through pipeline 16, ethane and propane, C 4-C 6, gasoline raffinate oil, turning oil, slurry oil be back to catalytic cracking reaction device 2 through pipeline 17,18 successively as recycle stock is all or part of.
Fig. 2 is the methodological principle schematic flow sheet of stock oil behind shortening.
Stock oil is as follows through the methodological principle process description behind the shortening: stock oil through pipeline 1 with after turning oil from pipeline 15 mixes, enter catalytic hydrogenation unit 23 through pipeline 22, contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, the generation oil of catalytic hydrogenation unit through pipeline 24 with after recycle stock from pipeline 17 mixes, enter catalytic cracking reaction device 2 through pipeline 18, with catalytic cracking catalyst, the water vapor contact, 500～700 ℃ of temperature, pressure (absolute pressure) 0.15～0.4MPa, the weight ratio 5～50 of catalytic cracking catalyst and catalytic pyrolysis stock oil, react under the condition of the weight ratio 0.05～0.6 of water vapor and catalytic pyrolysis stock oil, the reclaimable catalyst of carbon deposit and reaction oil gas enter finish separating device 4 through pipeline 3, isolated reclaimable catalyst enters revivifier 6 through pipeline 5, the catalyzer of coke burning regeneration has higher activity and selectivity, through pipeline 7 Returning reactors 2, reaction oil gas then enters product separation device 9 through pipeline 8, separate the ethene that obtains, propylene is drawn through pipeline 12, removes C 5-C 6Pyrolysis gasoline enter solvent extraction device 19 through pipeline 14, gained aromatic hydrocarbons is drawn through pipeline 21, the gasoline raffinate oil is drawn through pipeline 20, hydrogen and methane are drawn through pipeline 10, ethane and propane are drawn through pipeline 11, C 4-C 6Draw through pipeline 13, turning oil is drawn through pipeline 15, and slurry oil is drawn through pipeline 16, ethane and propane, C 4-C 6, the gasoline raffinate oil, slurry oil is all or part of is back to catalytic cracking reaction device 2 through pipeline 17,18 successively, turning oil then returns catalytic hydrogenation unit 23 through pipeline 15,22 successively.
Fig. 3 is the principle process synoptic diagram of stock oil and the turning oil catalytic hydrogenation unit when handling respectively.
The process description of catalytic hydrogenation unit is as follows: stock oil enters hydrotreating reactor 25 through pipeline 1, contact with hydrogenation catalyst, hydrogen (not marking among the figure), at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, reaction effluent enters high-pressure separator 30 through pipeline 26,29 successively; Turning oil then enters hydro-upgrading reactor 27 through pipeline 15, contacts with hydrogenation catalyst, hydrogen (not marking among the figure), at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.2～2.0h -1Condition under react, reaction effluent through pipeline 28 with after reaction effluent from pipeline 26 mixes, enter separation column 34 through pipeline 29, high-pressure separator 30, pipeline 31, light pressure separator 32, pipeline 33 successively, separate and obtain gas, petroleum naphtha and generation oil, wherein gas is through pipeline 35 caterpillars, petroleum naphtha is through pipeline 36 caterpillars, generate oil and then enter the catalytic pyrolysis unit through pipeline 24, the hydrogen recycle of recovery is returned hydrotreating reactor 25 and hydro-upgrading reactor 27 (not marking among the figure).
Fig. 4 is the process flow diagram of optimal technical scheme.
The technical process of optimized technical scheme is as follows:
The pre-steam that promotes enters through the riser reaction zone A bottom of pipeline 37 by compound reactor 38, from the regenerated catalyst of pipeline 53 in the accelerated motion that makes progress of the castering action lower edge of steam riser tube; Stock oil and optional turning oil or its shortening generate oil through pipeline 18 with from the atomizing steam of pipeline 39 from by nozzle 40 injecting lift tube reaction district A, contact with regenerated catalyst.From the regenerated catalyst of pipeline 54 after the steam from pipeline 55 promotes, and from the ethane of pipeline 17 and propane, C 4-C 6, all or part of among the pyrolysis gasoline raffinate oil enter together and carry standpipe 56 and move upward, finally the fluidized bed reaction zone B that enters compound reactor 38 with oil gas and catalyzer from riser reaction zone A reacts.Steam enters fluidized bed reaction zone B bottom to guarantee fluidization and the reaction of fluidized bed reaction zone B through pipeline 41.The oil gas that generates in the fluidized bed reaction zone B and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 43 through pipeline 42, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 44, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 47 in the settling vessel, contacts with steam from pipeline 48.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 44 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 50 through inclined tube 49, and main air enters revivifier through pipeline 51, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters the cigarette machine through pipeline 52.Catalyzer after the regeneration is divided into two portions, and wherein a part enters among the riser reaction zone A through inclined tube 53, and another part then enters fluidized bed reaction zone B and recycles through inclined tube 54, conveying standpipe 56 successively.Oil gas in the collection chamber 44 enters follow-up separation system 46 through main oil gas piping 45, separates the ethene, the propylene that obtain and draws through pipeline 12, removes C 5-C 6The pyrolysis gasoline aromatic hydrocarbons such as extraction plant separation of methylbenzene and dimethylbenzene that desolvate through pipeline 14, hydrogen and methane are drawn through pipeline 10, ethane and propane are drawn through pipeline 11, C 4-C 6Draw through pipeline 13, turning oil is drawn through pipeline 15, and slurry oil is drawn through pipeline 16, ethane and propane, C 4-C 6, pyrolysis gasoline raffinate oil, slurry oil all or part of successively through pipeline 17, carry standpipe 56 to be back to fluidized bed reaction zone B, turning oil (or behind hydrogenation) and/or slurry oil then return riser reaction zone A through pipeline 18.
Adopt method provided by the invention, the refinery can produce low-carbon alkenes such as propylene, ethene to greatest extent from heavy feed stock, and wherein the productive rate of propylene surpasses 30 heavy %, and aromatic hydrocarbons such as toluene, dimethylbenzene are rich in coproduction simultaneously.Thereby realize the technological breakthrough of refinery's notion, change to chemical refinery from traditional fuel type and fuel-lubricated oil type refinery production model, make the refinery from single oil refining to industrial chemicals and production development of high added value derived product and extension, both solve the petrochemical material problem of shortage, improved the economic benefit of refinery again.
The following examples will give further instruction to present method, but therefore not limit present method.
Raw material used among the embodiment is VGO, and its character is as shown in table 1.
Catalytic cracking catalyst preparation method used among the embodiment is summarized as follows:
1) with 20gNH 4Cl is dissolved in the 1000g water, and (Qilu Petrochemical company catalyst plant is produced, SiO to add 100g (butt) crystallization product ZRP-1 zeolite in this solution 2/ Al 2O 3=30, content of rare earth RE 2O 3=4.0 heavy %), behind 90 ℃ of exchange 0.5h, filter filter cake; Add 4.0gH 3PO 4(concentration 85%) and 4.5gFe (NO 3) 3Be dissolved in the 90g water, dry with the filter cake hybrid infusion; Then handle at 550 ℃ of roasting temperatures and obtained phosphorous and MFI structure mesopore zeolite iron in 2 hours, its elementary analytical chemistry consists of 0.1Na 2O5.1Al 2O 32.4P 2O 51.5Fe 2O 33.8RE 2O 388.1SiO 2
2) use 250kg decationized Y sieve water with 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%) again, its PH is transferred to 2-4 with hydrochloric acid, stir, left standstill under 60-70 ℃ aging 1 hour, maintenance PH is 2-4, cools the temperature to below 60 ℃, add 41.5Kg aluminium colloidal sol (Qilu Petrochemical company catalyst plant product, Al 2O 3Content is 21.7m%), stirred 40 minutes, obtain mixed serum.
3) (Qilu Petrochemical company catalyst plant Industrial products, lattice constant is 2.445-2.448nm, contains RE for the MFI structure mesopore zeolite (butt is 45kg) of the phosphorous and iron that step 1) is prepared and DASY zeolite 2O 3Be 2.0%, butt is 7.5kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1m%) washing, the flush away Na that dissociates +, being drying to obtain the catalytic cracking catalyst sample, consist of 30 heavy % MFI structure mesopore zeolite, 5 heavy % DASY zeolites, the 23 heavy % pseudo-boehmites, 6 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Hydrobon catalyst preparation method used among the embodiment is summarized as follows: take by weighing ammonium metawolframate ((NH 4) 2W 4O 1318H 2O, chemical pure) and nickelous nitrate (Ni (NO 3) 26H 2O, chemical pure), water is made into 200mL solution.Solution is joined in alumina supporter 50 grams, at room temperature flooded 3 hours, use ultrasonic instrument to handle steeping fluid 30 minutes in steeping process, cooling is filtered, and puts into microwave oven (trade mark Galanz WD900B) dry about 15 minutes.Consisting of of this catalyzer: 30.0 heavy % WO 3, 3.1 heavy % NiO and surplus aluminum oxide.
Embodiment 1
Stock oil A is earlier after hydrotreatment, (hydrogen richness increases to 13.54 heavy % from 12.40 heavy % to the gained hydrogenated oil, aromaticity content drops to 20.0 heavy % from 44.1 heavy %) as the raw material of catalytic pyrolysis, in medium-sized riser tube+fluidized-bed reactor, test, at last product is separated, wherein have only slurry oil to be circulated to riser tube, other recycle stock is circulation not.The operational condition of hydrotreatment, catalytic pyrolysis and product distribute as shown in table 2.
As can be seen from Table 2, propylene, yield of ethene are respectively up to 32.97 heavy %, 12.63 heavy %, and toluene and dimethylbenzene yield are respectively 1.93 heavy % and 4.05 heavy %.
Embodiment 2
Stock oil B directly as the raw material of catalytic pyrolysis, tests in medium-sized riser tube+fluidized-bed reactor, at last product is separated, and wherein has only slurry oil to be circulated to riser tube, C 4-C 6Be circulated to fluidized-bed, other recycle stock is circulation not.The operational condition of catalytic pyrolysis and product distribute as shown in table 2.
As can be seen from Table 2, propylene, yield of ethene are respectively up to 30.46 heavy %, 18.31 heavy %, and toluene and dimethylbenzene yield are respectively 2.45 heavy % and 7.38 heavy %.
Embodiment 3
Through hydrotreatment after, as the raw material of catalytic pyrolysis in medium-sized riser tube+fluidized-bed reactor test, at last product separated earlier by the gained hydrogenated oil for stock oil C, and recycle stock all circulates, wherein ethane and propane, C 4-C 6, the pyrolysis gasoline raffinate oil is circulated to fluidized-bed, slurry oil is circulated to riser tube, turning oil is back to hydrotreating reactor.The operational condition of hydrotreatment, catalytic pyrolysis and product distribute as shown in table 2.
As can be seen from Table 2, propylene, yield of ethene are respectively up to 36.86 heavy %, 12.89 heavy %, and toluene and dimethylbenzene yield are respectively 3.89 heavy % and 10.56 heavy %.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3
The stock oil numbering A B C
Stock oil character
Density (20 ℃), g/cm 3 0.9087 0.8886 0.9134
Sulphur content, ppm 18000 4700 5800
Nitrogen content, ppm 847 1600 2900
Aromatic hydrocarbons, m% 44.1 26.3 32.6
C，m％ 85.85 86.46 86.23
H，m％ 12.40 12.86 12.69
Boiling range (ASTM D-1160), ℃
IBP 267 312 327
10％ 399 361 363
30％ 429 412 409
50％ 449 452 450
70％ 464 478 482
90％ 493 506 504
95％ 501 532 526
EP 538 546 542
Table 2
Embodiment 1 Embodiment 2 Embodiment 3
The stock oil numbering A B C
The hydrotreatment unit
Operational condition
Temperature of reaction, ℃ 370 - 360
The hydrogen dividing potential drop, MPa 14.0 - 10.0
Volume space velocity, h -1 0.6 - 0.5
Hydrogen-oil ratio, v/v 800 - 600
Product distributes, m%
Gas 2.55 - 2.21
Petroleum naphtha 1.80 - 1.60
Generate oil 96.90 - 97.32
The catalytic pyrolysis unit
Operational condition
Riser tube
The riser tube temperature out, ℃ 580 650 540
Agent-oil ratio, m/m 12 20 8
The residence time, s 1.6 1.0 5
Water filling (accounting for raw material), m% 15 10 20
Fluidized-bed
The bed medial temperature, ℃ 620 680 580
Agent-oil ratio, m/m 25 45 32
Weight hourly space velocity, h -1 4 0.5 8
Water filling (accounting for raw material), m% 30 60 40
Product distributes, m%
H 2+CH 4 4.36 6.47 4.34
Ethene 12.63 18.31 12.89
Propylene 32.97 30.46 36.86
Ethane+propane 4.73 5.17 3.56
C 4 18.68 0 6.65
C 5-C 6 1.86 0 0.56
Toluene 1.93 2.45 3.89
Dimethylbenzene 4.05 7.38 10.56
Other mononuclear aromatics 3.86 9.76 10.17
The pyrolysis gasoline raffinate oil 1.09 1.84 0
Turning oil 3.50 8.68 0
Slurry oil 2.28 0 0
Coke 8.06 9.48 10.52

Claims (15)

1, a kind of chemical industry type oil refining method of producing low-carbon alkene and aromatic hydrocarbons, it is characterized in that stock oil and the partially liq recycle stock of choosing wantonly are introduced into catalytic hydrogenation unit, contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, the generation of catalytic hydrogenation unit oil with contact in the catalytic cracking reaction device through regenerated catalytic cracking catalyst, water vapor, under the condition of the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the stock oil of 500～700 ℃ of temperature, pressure 0.15～0.4MPa, catalytic cracking catalyst and stock oil, react, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regenerating; Separating reaction oil gas obtains purpose product low-carbon alkene and aromatic hydrocarbons, removes purpose product, H in the reaction oil gas 2, CH 4Outer remaining gas and liquid is as recycle stock, all or part of catalytic cracking reaction device that returns of recycle stock.
2,, it is characterized in that described low-carbon alkene is ethene, propylene and optional butylene according to the method for claim 1.
3,, it is characterized in that described hydrogenation catalyst is VIB and the VIII family non-precious metal catalyst that loads on aluminum oxide and/or the amorphous aluminum silicide according to the method for claim 1.
4,, it is characterized in that removing in the reaction oil gas purpose product, H according to the method for claim 1 or 3 2, CH 4Outer remaining gas and liquid is as recycle stock, all or part of catalytic cracking reaction device that directly or indirectly returns of recycle stock.
5, according to the method for claim 1, it is characterized in that described stock oil is oil hydrocarbon ils and/or other mineral oil, the mixture of one or more in this group hydrocarbon ils of constituting of the free decompressed wax oil of petroleum hydrocarbon grease separation, wax tailings, deasphalted oil, residual oil, gasoline, diesel oil wherein, other mineral oil is liquefied coal coil, tar sand oil or shale oil.
6, according to the method for claim 1, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each components contents is respectively: zeolite 10～50 heavy %, inorganic oxide 5～90 heavy %, clay 0～70 heavy %.
7, according to the method for claim 6, it is characterized in that described zeolite is selected from the mixture of mesopore zeolite or mesopore zeolite and large pore zeolite, mesopore zeolite accounts for 25～100 heavy % of active ingredient, large pore zeolite accounts for 0～75 heavy % of active ingredient, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and the ZSM series zeolite is selected from one or more the mixture among ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, the ZSM-48; Large pore zeolite is selected from this group of being made of Rare Earth Y, rare earth hydrogen Y, super steady Y, high silicon Y one or more mixture in zeolite.
8,, it is characterized in that described inorganic oxide is selected from SiO according to the method for claim 6 2And/or Al 2O 3Clay is selected from kaolin and/or halloysite.
9, according to the method for claim 1, the compound reactor that it is characterized in that compound reactor that the catalytic cracking reaction device is selected from riser tube, fluidized-bed, downstriker transfer limes reactor, moving-bed, is made of riser tube and fluidized-bed, constitutes by riser tube and downstriker transfer limes, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, the compound reactor that constitutes by two or more downstriker transfer limess or the compound reactor that constitutes by two or more moving-beds.
10,, it is characterized in that the catalytic cracking catalyst in each reactor in the described compound reactor is identical or different according to the method for claim 9.
11,, it is characterized in that the riser tube in described riser tube, downstriker transfer limes reactor, the compound reactor and/or the processing condition of downstriker transfer limes are: the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the catalytic pyrolysis stock oil of 500～700 ℃ of temperature, pressure 0.15～0.4MPa, 1～10 second residence time, catalytic cracking catalyst and catalytic pyrolysis stock oil according to the method for claim 9.
12,, it is characterized in that the fluidized-bed in described fluidized-bed, moving-bed, the compound reactor and/or the processing condition of moving-bed are: 500～700 ℃ of temperature, pressure 0.15～0.4MPa, weight hourly space velocity 0.5～20h according to the method for claim 9 -1, catalytic cracking catalyst and catalytic pyrolysis stock oil the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and catalytic pyrolysis stock oil.
13, according to claim 1,11 or 12 method, it is characterized in that cracking temperature is 550～650 ℃.
14,, it is characterized in that this method comprises the following steps: according to the method for claim 1
(1), stock oil and optional recycle stock be introduced into catalytic hydrogenation unit, contact with hydrogenation catalyst, hydrogen, at hydrogen dividing potential drop 3.0～20.0MPa, 300～450 ℃ of temperature of reaction, hydrogen to oil volume ratio 300～2000v/v, volume space velocity 0.1～3.0h -1Condition under react, the separating reaction effluent obtains hydrogenated oil;
(2), hydrogenated oil, water vapor enter the riser reaction zone in the composite catalyzing cracking reactor that is made of riser tube and fluidized-bed, with contact through the regenerated catalytic cracking catalyst, under the condition of the weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and the catalytic pyrolysis stock oil of 500～650 ℃ of temperature, pressure 0.15～0.4MPa, 1～10 second residence time, catalytic cracking catalyst and catalytic pyrolysis stock oil, react;
(3), the reaction effluent of riser reaction zone without finish separate enter fluidized bed reaction zone again with regenerated catalyst, water vapor, ethane, propane, C 4-C 6And/or the contact of pyrolysis gasoline raffinate oil, at 520～700 ℃ of temperature, pressure 0.15～0.4MPa, weight hourly space velocity 0.5～20h -1, catalytic cracking catalyst and catalytic pyrolysis stock oil the condition of weight ratio 0.05～0.6 of weight ratio 5～50, water vapor and catalytic pyrolysis stock oil under react;
(4), the reclaimable catalyst and the reaction oil gas that separate fluidized bed reaction zone, wherein reclaimable catalyst returns riser reaction zone and fluidized bed reaction zone through entering revivifier behind the stripping behind coke burning regeneration, reaction oil gas goes to separate and obtains purpose product low-carbon alkene and aromatic hydrocarbons, wherein said aromatic hydrocarbons is that pyrolysis gasoline is separating obtained through solvent extraction, obtains the pyrolysis gasoline raffinate oil simultaneously;
(5), remove purpose product, H in the reaction oil gas 2, CH 4Outer remaining gas and liquid are as recycle stock, and wherein the gas circulation material is ethane, propane and C 4, the liquid circulation material is C 5-C 6, pyrolysis gasoline raffinate oil, turning oil and slurry oil, ethane, propane, C 4-C 6And/or the pyrolysis gasoline raffinate oil returns fluidized bed reaction zone, and slurry oil returns riser reaction zone, and turning oil returns catalytic hydrogenation unit.
15, according to the method for claim 14, the temperature that it is characterized in that riser reaction zone is 520～600 ℃, and the residence time is 2～5 seconds; The temperature of fluidized bed reaction zone is 550～650 ℃, and weight hourly space velocity is 1～10h -1The weight ratio of the water vapor of riser reaction zone and fluidized bed reaction zone and catalytic pyrolysis stock oil is 0.1～0.3.
CNB2004100061891A 2004-03-08 2004-03-08 Chemical oil-refining method for preparing low carbon olefin and arene Expired - Lifetime CN100487080C (en)

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BRPI0508591-8A BRPI0508591B1 (en) 2004-03-08 2005-03-08 processes for the production of light and aromatic olefins
KR1020067018080A KR101147469B1 (en) 2004-03-08 2005-03-08 A process of production of lower olefins and aromatics
EP05714812A EP1734098A4 (en) 2004-03-08 2005-03-08 A process of production of lower olefins and aromaticas
ES17151967T ES2913654T3 (en) 2004-03-08 2005-03-08 FCC procedure with two reaction zones
JP2007502171A JP4808209B2 (en) 2004-03-08 2005-03-08 Process for producing lower olefins and aromatic hydrocarbons
CNB2005800013693A CN100465250C (en) 2004-03-08 2005-03-08 Production of low-carbon olefine and arene
US10/592,166 US8778170B2 (en) 2004-03-08 2005-03-08 Process for producing light olefins and aromatics
PCT/CN2005/000281 WO2005085391A1 (en) 2004-03-08 2005-03-08 A process of production of lower olefins and aromaticas
EP17151967.1A EP3225678B1 (en) 2004-03-08 2005-03-08 Am fcc process with two reaction zones
SA05260089A SA05260089B1 (en) 2004-03-08 2005-04-12 A process for producing light olefins and aromatics
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