CN102344831B - Petroleum hydrocarbon catalytic conversion method - Google Patents
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Abstract
The invention discloses a petroleum hydrocarbon catalytic conversion method. The petroleum hydrocarbon catalytic conversion method comprises the following steps that raw oil contacts a mesoporous zeolite-rich catalyst in a first reaction zone of a reactor and undergo a cracking reaction; a reactant flow and a part of the raw oil are fed into a second reaction zone of the reactor and further undergo a cracking reaction; reaction oil gas and a catalyst needing to be regenerated are separated out, wherein the catalyst needing to be regenerated is subjected to steam stripping and burning regeneration and then is fed back to the reactor; the reaction oil gas is subjected to separation to form a desired ethane product, propylene and aromatic hydrocarbon-rich catalytic gasoline; the aromatic hydrocarbon-rich catalytic gasoline is subjected to selective hydrogenation and then is fed into a aromatic hydrocarbon extraction device to produce a desired light aromatic hydrocarbon product by separation; and the extract oil obtained by the previous step is fed back to the first reaction zone of the reactor. Through petroleum hydrocarbon catalytic conversion method, an ethene yield is 22.43 wt%; a propylene yield is 33.22 wt%; and a benzene-toluene-xylene mixture yield is 25.28 wt%.
Description
Technical field
The present invention provides a kind of petroleum hydrocarbon catalytic conversion method on the basis of existing technology, particularly heavy feed stock is converted into the low-carbon alkene such as ethene and propylene, produces light aromatic hydrocarbons simultaneously, thereby realizes the efficient method of utilizing of petroleum resources.
Background technology
Ethene is one of most important basic material of petrochemical industry, by vinyl polymerization, with the alkylation of benzene and with the addition reaction of water, oxygen, halogen, can obtain a series of extremely valuable derivatives.World Ethylene Industry continues keeping the situation of stable development.Estimate 2007～2012 years, the world will increase 3,878 ten thousand tons/year of ethene abilities newly, and average growth rate per annum reaches 5.6%, will reach 162,670,000 tons/year to world Ethylene throughput in 2012.At present, approximately 98% ethene comes from tube furnace steam cracking technology in the world, and in ethylene production raw material, petroleum naphtha accounts for 46%, and ethane accounts for 34%.
Propylene is one of most important alkene, and consumption is only second to ethene.Approximately 8,348 ten thousand tons of World Propylene throughput in 2007, within 2006～2011 years, global propylene demand growth speed will reach 4.9%, and by 2011, global propylene demand will reach 8,834 ten thousand tons.The derivative of propylene research on maximum utilized quantity is polypropylene, accounts for 61% of global propylene consumption.2005, about 62% propylene in the whole world was from the coproduction of preparing ethylene by steam cracking, and 34% propylene, from plant catalytic cracking unit by-product, also has 4% propylene from dehydrogenating propane and ethene-butylene metathesis reaction.
Adopt traditional preparing ethylene by steam cracking, propylene route, larger to the chemical industry such as lighter hydrocarbons, petroleum naphtha lighter hydrocarbons demand, estimate to need for 2010 530000 tons/year of chemical industry light oils, the year two thousand twenty needs 700,000 tons/year of chemical industry light oils, and domestic crude oil is generally laid particular stress on, chemical industry light oil is difficult to meet the demand of ethene, propylene feedstocks, the in the situation that of petroleum resources deficiency, the variation of ethene, propylene feedstocks and heaviness have become ethene, propylene industrial development trend, and the exploitation of mink cell focus ethene processed and propylene technology also will open up a new raw material approach to ethene, propylene industry.
EP305720A2 discloses a kind of hydrocarbon conversion processes of preparing low-carbon olefins, and petroleum fractions, residual oil or crude oil that raw material is different boiling ranges use solid acid catalyst in fluidized-bed or moving-burden bed reactor, at 500～650 ℃ of temperature, pressure 1.5 × 10
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 after coke burning regeneration Returning reactor internal recycle use.The overall yield of the method propylene and butylene can reach 40 heavy % left and right, and wherein productivity of propylene is up to 26.34 heavy %.
WO00/31215A1 discloses a kind of catalyst cracking method of producing alkene, the method adopts ZSM-5 and/or ZSM-11 zeolite to do active ingredient, catalyzer take a large amount of inert substances as matrix, take vacuum gas oil (VGO) as raw material, productivity of propylene is lower than 20 heavy %.
US 2002/0003103A1 discloses a kind of catalytic cracking process that increases productivity of propylene.Gasoline product is introduced in second riser tube and is carried out cracking reaction more at least partly, and in the catalyst composition adopting except containing macropore USY zeolite, also contain the mesopore zeolites such as ZSM-5 and there is the mineral binder bond component of cracking performance, phosphorous in mineral binder bond component wherein, its P/Al ratio is 0.1～10.
US 5009769 discloses a kind of cracking hydrocarbon method and has adopted duo-lift tube reactor cracking hydrocarbon raw material of different nature.Wax oil and residual oil inject first riser tube, cracking under agent-oil ratio 5～10, the condition of 1～4 second residence time; Straight-run spirit, straight run intermediate oil and catalysis heavy petrol inject second riser tube, cracking under agent-oil ratio 3～12, the condition of 1～5 second residence time, and two riser tube ends enter in same settling vessel, and share follow-up fractionating system.
US 4422925 discloses the method that the multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, hydro carbons described in the method at least contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material, the method has different cracking performances according to different hydrocarbon molecules, adopt multiple reaction zones to carry out cracking reaction, with voluminous low-molecular olefine.
Light aromatic hydrocarbons (benzene, toluene and dimethylbenzene are called for short BTX) is also a kind of important Organic Chemicals, and output and scale are inferior to ethene and propylene, and its derivative is widely used in Chemicals and fine chemicals such as producing chemical fibre, plastics and rubber.Light aromatic hydrocarbons is produced and is mainly come from reformed gasoline and cracking of ethylene gasoline apparatus.It is predicted, meet following demand growth, between 2006～2015 years, the whole world need to newly increase the purified petroleum benzin production capacity of about 1,600 ten thousand tons/year of p-Xylol and 1,400 ten thousand tons/year, and future possibly cannot meet the market growth demand of purified petroleum benzin and p-Xylol as source using the by-product of these devices.
CN101362963A discloses a kind of catalysis conversion method of preparing aromatic hydrocarbons and light olefins, and the hydrocarbon raw material of different cracking performances contacts with catalytic cracking catalyst, at 450～750 ℃, weight hourly space velocity 0.1～800h
-1, reaction pressure 0.1～1.0MPa, catalytic cracking catalyst and raw material weight ratio 1～150, the weight ratio of water vapor and raw material is under 0.05～1.0 condition, in fluidized-bed reactor, carry out cracking reaction, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regeneration, separating reaction oil gas, obtain object product low-carbon alkene, aromatic hydrocarbons and the raw material of cracking again, the method is produced the low-carbon alkenes such as propylene to greatest extent from heavy feed stock, wherein productivity of propylene is more than 40 heavy %, the aromatic hydrocarbons such as while coproduction toluene and dimethylbenzene.
CN100487080C discloses a kind of chemical industry type oil refining method of producing low-carbon alkene and aromatic hydrocarbons, stock oil with through regeneration catalytic cracking catalyst, water vapor in catalytic cracking reaction device, contact, under weight ratio 0.05～0.6 condition of the weight ratio 5～50 of 500～700 ℃ of temperature of reaction, pressure 0.15～0.4MPa, catalytic cracking catalyst and stock oil, water vapor and stock oil, react, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regeneration; Separating reaction oil gas obtains object product low-carbon alkene and aromatic hydrocarbons.The method is produced the low-carbon alkene such as propylene, ethene to greatest extent from heavy feed stock, and wherein the productive rate of propylene exceedes 30 heavy %, the light aromatic hydrocarbons such as the BTX of coproduction simultaneously.
CN101362669A discloses the catalysis conversion method of a kind of preparing ethylene, propylene and aromatic hydrocarbons, contacts, at temperature 550-800 ℃, weight hourly space velocity 0.1～800h at the hydro carbons of different cracking performances with raw material with catalytic cracking catalyst
-1, reaction pressure 0.10～1.0MPa, catalytic cracking catalyst and raw material weight ratio 10～150, the weight ratio of water vapor and raw material is under 0.15～1.0 condition, in fluidized-bed reactor, carry out cracking reaction, separate reclaimable catalyst and reaction oil gas, reclaimable catalyst is Returning reactor after regeneration, separating reaction oil gas is isolated to object product low-carbon alkene and aromatic hydrocarbons, wherein 160～260 ℃ of cuts return to catalytic pyrolysis as recycle stock, and ethane, propane, butane enter steam cracking and further produce ethene, propylene.Ethene and productivity of propylene more than 20 heavy %, the aromatic hydrocarbons such as coproduction toluene and dimethylbenzene simultaneously.
Above-mentioned prior art is deposited not enough both ways: the one, in producing low-carbon alkene, underuse Aromatic Hydrocarbon in Gasoline potential content; The 2nd, the technology of producing low-carbon alkene and light aromatic hydrocarbons, fails to make full use of hydrocarbon resources, and especially light aromatics yield and quality also exist larger room for promotion.In order to meet the demand of the growing industrial chemicals such as low-carbon alkene and aromatic hydrocarbons, be necessary to develop a kind of catalysis conversion method that heavy feed stock is converted into greatest extent to ethene, propylene and light aromatic hydrocarbons, thereby realize the efficient utilization of petroleum resources.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of catalysis conversion method that heavy feed stock is converted into ethene, propylene and BTX.
The technical scheme of petroleum hydrocarbon catalytic conversion method provided by the invention is as follows: the method is carried out in the reactor that comprises two reaction zones.
Stock oil contacts with the catalyzer that is rich in mesopore zeolite in the first reaction zone of reactor, is 600～750 ℃, weight hourly space velocity 100～200h in temperature of reaction
-1, pressure 0.10～1.0MPa, catalyzer and stock oil the weight ratio of weight ratio 30～150 (hereinafter to be referred as agent-oil ratio), water vapor and the raw material condition that is 0.05～1.0 under carry out cracking reaction, reactant flow and part material oil enter the second reaction zone of reactor, at 450～600 ℃ of temperature of reaction, weight hourly space velocity 0.1～100h
-1, pressure 0.10～1.0MPa, catalyzer and stock oil weight ratio 1～30, the weight ratio of water vapor and stock oil is that cracking reaction further occurs under 0.05～1.0 condition, separate reclaimable catalyst and reaction oil gas, wherein reclaimable catalyst Returning reactor after stripping, coke burning regeneration, reaction oil gas is isolated to the product that comprises object product ethene, propylene and be rich in the catalytic gasoline of aromatic hydrocarbons, catalytic gasoline is after selective hydrogenation, enter aromatic extraction unit separation and obtain the light aromatic hydrocarbons of object product, and first reaction zone of extracting oily Returning reactor out.
Described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, its Petroleum Hydrocarbon is selected from one or more in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, and other mineral oil is selected from one or more in liquefied coal coil, tar sand oil, shale oil.
Described catalyzer comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight: the heavy % of zeolite 1～50, the heavy % of inorganic oxide 5～99, the heavy % of clay 0～70.Its mesolite, as active ingredient, is selected from mesopore zeolite and optional large pore zeolite, and mesopore zeolite accounts for 50～100 heavy % of zeolite gross weight, preferably 70～100 heavy %, and large pore zeolite accounts for 0～50 heavy % of zeolite gross weight, preferably 0～30 heavy %.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification to the transition metal such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel for above-mentioned mesopore zeolite, about the more detailed description of ZRP is referring to US5,232,675, ZSM series zeolite is selected from one or more among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, about the more detailed description of ZSM-5 is referring to US3,702,886.Large pore zeolite selects one or more in this group zeolite that super steady Y, high silicon Y that free Rare Earth Y (REY), rare earth hydrogen Y (REHY), different methods obtain form.
Inorganic oxide, as caking agent, is selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).
Clay, as matrix (being carrier), is selected from kaolin and/or halloysite.
Described reactor be selected from riser tube, etc. the combination of one or more in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the two or more combinations of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.Wherein the gas speed of fluidized-bed is 0.1～2 meter per second, and the gas speed of riser tube is 2～30 meter per seconds (disregarding catalyzer).
Preferred forms of the present invention is to carry out in a kind of reducing riser reactor, about the more detailed description of this reactor referring to CN1237477A.
In order to increase the agent-oil ratio of second reaction zone, improve the catalytic activity of catalyzer, can pass through supplemental heat or cold regenerated catalyst, half regenerated catalyst, reclaimable catalyst, live catalyst.Cooling regenerated catalyst and half cooling regenerated catalyst are reclaimable catalyst cooling obtaining after two-stage regeneration and one section of regeneration respectively, regenerated catalyst carbon content is below 0.1 heavy %, be preferably below 0.05 heavy %, half regenerated catalyst carbon content is 0.1～0.9 heavy %, and preferably carbon content is 0.15～0.7 heavy %; Reclaimable catalyst carbon content is more than 0.9 heavy %, and preferably carbon content is 0.9～1.2 heavy %.
Reaction oil gas is isolated to the product that comprises object product ethene, propylene and be rich in the catalytic gasoline of aromatic hydrocarbons, also comprises dry gas, C3-4 alkane (being propane and butane), C4 alkene, diesel oil, slurry oil etc. in product.The first reaction zone that wherein C4 alkene can Returning reactor is or/and the further cracking in second reaction zone.
Catalytic gasoline selective hydrogenation is under hydrogen exists situation, contacts, at hydrogen dividing potential drop 1.2～8.0MPa (absolute pressure), 150～400 ℃ of temperature of reaction, hydrogen to oil volume ratio 150～600Nm with selective hydrogenation catalyst
3/ m
3, volume space velocity 1～20h
-1under condition, react, the selective hydrogenation gasoline obtaining is as the raw material of aromatic extraction unit.Described selective hydrogenation catalyst be take Ni-W, Co-Ni-W, Ni-Mo or Co-Mo as active ingredient, activated alumina is the non-precious metal catalyst of carrier, requires this catalyzer to possess high de-diene active and desulphurizing activated.
Aromatic extraction unit extraction solvent used is selected from one or more in tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether.Extractive process solvent recovery cycle is used.Extraction temperature is 40～120 ℃, and the volume ratio between solvent and the raw material of aromatic extraction unit is 0.5～5.0.Extracting oil out is object product B TX, and raffinating oil is non-aromatics as one of raw material of catalytic pyrolysis.
The method that the method such as separating ethene, propylene is known with those of ordinary skills from reaction product is identical; From the catalytic gasoline of reaction oil gas, separating the method for aromatics separation from steam cracking or reformed gasoline that the method for light aromatic hydrocarbons knows with those of ordinary skills is that solvent extraction is identical.
This technical scheme organically combines the techniques such as catalytic pyrolysis, catalytic gasoline selective hydrogenation and catalytic gasoline Aromatics Extractive Project, produces to greatest extent the low-carbon alkene such as ethene, propylene and light aromatic hydrocarbons from the lower heavy feed stock of hydrogen richness.The present invention compared with prior art has following technique effect:
1, ethene, productivity of propylene and selectivity increase, and wherein ethylene yield can be up to 22.43 heavy %, and productivity of propylene is up to 33.22 heavy %.
2, BTX productive rate is up to approximately 25.28 heavy %, and wherein benzene productive rate is 4.46 heavy %, and toluene productive rate is 12.82 heavy %, and dimethylbenzene productive rate is 8.00 heavy %.
3, C4 alkene and/or aromatic hydrocarbons are raffinated oil and are mixed with stock oil, have improved stock oil atomizing effect, and in the situation that reaction severity reduces, heavy oil yield reduces significantly.
4, in dry gas, other component productive rate reduces significantly.
Adopt method provided by the invention, refinery can produce ethene, propylene and light aromatic hydrocarbons to greatest extent from heavy feed stock, thereby realize the technological breakthrough of refinery's concept, change to chemical industry type from traditional fuel type and fuel-Lube Type refinery production model, make refinery from single oil refining to industrial chemicals and the production development of high added value derived product and extension, both the problem that had solved petrochemical material shortage, has improved again the economic benefit of refinery.
Accompanying drawing explanation
Accompanying drawing is and the basic procedure schematic diagram of catalysis conversion method of the present invention.
Embodiment
Further illustrate method provided by the present invention below in conjunction with accompanying drawing, but the present invention is not therefore subject to any restriction.
Accompanying drawing is and the basic procedure schematic diagram of catalysis conversion method of the present invention.
Its technical process is as follows:
Pre-lift medium is entered by reducing riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 16 under the castering action of pre-lift medium along upwards accelerated motion of riser tube, C4 alkene and/or aromatic hydrocarbons raffinate oil and mix with raw material after through pipeline 3 bottom with the first reaction zone I of injecting lift pipe 2 together with atomizing steam from pipeline 4, mix with the existing logistics of riser reactor, on hot catalyzer, there is cracking reaction in stock oil, and upwards accelerated motion, with be mixed into second reaction zone II through pipeline 5 and the part material oil injecting together with atomizing steam from pipeline 6 cracking reaction occur.The reaction product oil gas generating and the reclaimable catalyst of inactivation enter the cyclonic separator in settling vessel 8 through pipeline 7, realize separating of reclaimable catalyst and reaction product oil gas, and reaction product oil gas enters collection chamber 9, and catalyst fines returns to settling vessel by dipleg.In settling vessel, reclaimable catalyst flows to stripping stage 10, and contacts from the steam of pipeline 11.The reaction product oil gas going out from stripping reclaimable catalyst enters collection chamber 9 after cyclonic separator.Reclaimable catalyst after stripping enters revivifier 13 through inclined tube 12, and main air enters revivifier through pipeline 14, and the coke on burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters cigarette machine through pipeline 15.Catalyzer after regeneration enters riser tube through inclined tube 16.
Reaction product oil gas in collection chamber 9, through main oil gas piping 17, enters follow-up separation system 18, and separation obtains catalytic pyrolysis dry gas and draws through pipeline 19, through further separating and obtain one of object product-ethene; The propane that separation obtains and butane are drawn through pipeline 20, and propylene is drawn the two-propylene that obtains object product through pipeline 21; The C 4 olefin that separation obtains is drawn through pipeline 3 and/or pipeline 5 and is returned to riser tube cracking again through pipeline 22; Diesel oil is drawn and is returned to riser tube 2 through pipeline 24; Slurry oil is drawn through pipeline 25; The aromatic type gasoline that is rich in of catalytic pyrolysis C5～180 ℃ is drawn out to selective hydrogenation unit 26 through pipeline 23, isolating light constituent draws through pipeline 27, after hydrogenation, gasoline enters Aromatics Extractive Project unit 29 through pipeline 28, aromatic hydrocarbons is raffinated oil and is drawn through pipeline 30, mix with heavy feed stock through pipeline 3 and the first reaction zone I that returns to riser reactor 2, extraction oil is that three-aromatic hydrocarbons pipeline 31 of object product is drawn as object product B TX.
The following examples will be further described present method, but therefore not limit present method.
In embodiment, raw material used is VGO, and its character is as shown in table 1.In embodiment, extraction solvent used is tetramethylene sulfone.In embodiment, the selective hydrogenation catalyst trade mark used is RSDS-1, and by Sinopec catalyzer, branch office produces.
Catalytic cracking catalyst preparation method used in embodiment is summarized as follows:
1) by 20gNH
4cl is dissolved in 1000g water, in this solution, adds 100g (butt) crystallization product ZRP-1 zeolite (Qilu Petrochemical Company's catalyst plant production, SiO
2/ Al
2o
3=30, content of rare earth RE
2o
3=2.0 heavy %), after 90 ℃ of exchange 0.5h, filter to obtain filter cake; Add 4.0gH
3pO
4(concentration 85%) and 4.5gFe (NO
3)
3be dissolved in 90g water, dry with filter cake hybrid infusion; Then process and within 2 hours, obtain phosphorous and MFI structure mesopore zeolite iron at 550 ℃ of roasting temperatures, its elementary analytical chemistry consists of
0.1Na
2O·5.1Al
2O
3·2.4P
2O
5·1.5Fe
2O
3·3.8RE
2O
3·88.1SiO
2。
2) use 250kg decationized Y sieve water by 75.4kg halloysite (Suzhou china clay company Industrial products, the heavy % of solid content 71.6) making beating, add again 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, the heavy % of solid content 63), its PH is adjusted to 2～4 with hydrochloric acid, stir, at 60～70 ℃, leave standstill aging 1 hour, keeping PH is 2～4, cools the temperature to below 60 ℃, add 41.5kg aluminium colloidal sol (Qilu Petrochemical Company's catalyst plant product, Al
2o
3content is 21.7 heavy %), stir 40 minutes, obtain mixed serum.
3) by step 1) MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (Qilu Petrochemical Company's catalyst plant Industrial products of the phosphorous and iron prepared, lattice constant is 2.445～2.448nm, butt is 2.0kg) join step 2) in the mixed serum that obtains, stir, spray drying forming, with ammonium dihydrogen phosphate (phosphorus content is 1 heavy %) washing, wash away free Na
+, being drying to obtain catalytic cracking catalyst sample, consist of 18 heavy % MFI structure mesopore zeolite, 2 heavy %DASY zeolites, the 28 heavy % pseudo-boehmites, 7 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Embodiment
This embodiment tests according to the flow process of accompanying drawing, stock oil A is directly as the raw material of catalytic pyrolysis, on the middle-scale device by riser reactor, test, aromatic hydrocarbons is raffinated oil and is mixed into the first reaction zone I bottom with stock oil, at 640 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, the weight ratio 60 of catalytic cracking catalyst and stock oil, the weight ratio of water vapor and stock oil is under 0.20 condition, to carry out cracking reaction; At second reaction zone II, after reactant flow oil gas mixes with C 4 olefin at 540 ℃ of temperature of reaction, weight hourly space velocity 30h
-1the weight ratio 30 of catalytic cracking catalyst and stock oil, water vapor and stock oil weight ratio are that cracking reaction further occurs under 0.15 condition, reaction product oil gas separates at settling vessel with catalyzer to be generated, product cuts by boiling range in separation system, thereby obtain ethene, propylene and be rich in the products such as aromatic type gasoline, the gasoline that is rich in aromatic hydrocarbons enters selective hydrogenation unit, at hydrogen dividing potential drop 1.6MPa, 270 ℃ of temperature of reaction, hydrogen to oil volume ratio 350, volume space velocity 4.0h
-1reaction conditions under carry out hydrogenation, gasoline after hydrogenation enters extracting unit through Sulfolane Extraction, extraction temperature is 100 ℃, the volume ratio of the gasoline after solvent and hydrogenation is 3.0, separate and raffinate oil (being mainly stable hydrocarbon) and extract oil (light aromatic hydrocarbons BTX) out, raffinate oil and return to the first bottom, reaction zone and mixes further production ethene and propylene with stock oil.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, ethylene yield can reach 22.43 heavy %, and productivity of propylene can reach 33.22 heavy %; Benzene productive rate is 4.46 heavy %; Toluene productive rate is 12.82 heavy %, and dimethylbenzene productive rate is 8.00 heavy %, and coke yield is only 5.67 heavy %, and slurry oil productive rate is 4.78 heavy %.
Table 1
| Stock oil numbering | A |
| Stock oil character | |
| Density (20 ℃), g/cm 3 | 0.9083 |
| Sulphur content, ppm | 3700 |
| Nitrogen content, ppm | 2600 |
| Aromatic hydrocarbons, heavy % | 24.7 |
| C, heavy % | 87.25 |
| H, heavy % | 12.75 |
| Boiling range (ASTM D-1160), ℃ | |
| IBP | 251 |
| 10％ | 362 |
| 30％ | 408 |
| 50％ | 437 |
| 70％ | 464 |
| 90％ | 510 |
| 95％ | 529 |
Table 2
| Catalytic pyrolysis unit | |
| Outlet temperature of riser, ℃ | 530 |
| Riser reaction zone II | |
| Temperature of reaction, ℃ | 540 |
| Weight hourly space velocity, |
30 |
| Agent- |
30 |
| The weight ratio of water vapor/raw material | 0.15 |
| Riser reaction zone I | |
| Temperature of reaction, ℃ | 640 |
| Agent-oil ratio | 60 |
| Weight hourly space velocity, h -1 | 180 |
| The weight ratio of water vapor/raw material | 0.20 |
| Aromatics Extractive Project unit | |
| Temperature, ℃ | 100 |
| Solvent volume ratio | 3.0 |
| Selective hydrogenation unit | |
| Hydrogen dividing potential drop, MPa | 1.6 |
| Temperature of reaction, ℃ | 270 |
| Hydrogen to oil volume ratio | 350 |
| Volume space velocity, h -1 | 4.0 |
| Product distributes, heavy % | |
| Hydrogen+methane | 3.71 |
| Ethene | 22.43 |
| Propylene | 33.22 |
| Propane+butane | 4.91 |
| Benzene | 4.46 |
| Toluene | 12.82 |
| Dimethylbenzene | 8.00 |
| Slurry oil | 4.78 |
| Coke | 5.67 |
Claims (8)
1. a petroleum hydrocarbon catalytic conversion method, is characterized in that stock oil contacts with the catalyzer that is rich in mesopore zeolite in the first reaction zone of reactor, is 600～750 ℃, weight hourly space velocity 100～200h in temperature of reaction
-1, pressure 0.10～1.0MPa, catalyzer and stock oil the weight ratio of weight ratio 30～150, water vapor and the raw material condition that is 0.05～1.0 under carry out cracking reaction, reactant flow and part material oil enter the second reaction zone of reactor, at 450～600 ℃ of temperature of reaction, weight hourly space velocity 0.1～100h
-1, pressure 0.10～1.0MPa, catalyzer and stock oil weight ratio 1～30, the weight ratio of water vapor and stock oil is that cracking reaction further occurs under 0.05～1.0 condition, separate reclaimable catalyst and reaction oil gas, wherein reclaimable catalyst Returning reactor after stripping, coke burning regeneration, reaction oil gas is isolated to the product that comprises ethene, propylene and be rich in the catalytic gasoline of aromatic hydrocarbons, catalytic gasoline is after selective hydrogenation, enter aromatic extraction unit separation and obtain the light aromatic hydrocarbons of object product, and first reaction zone of extracting oily Returning reactor out; Described catalyzer comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight: the heavy % of zeolite 1～50, the heavy % of inorganic oxide 5～99, the heavy % of clay 0～70; Described zeolite, as active ingredient, is selected from mesopore zeolite and optional large pore zeolite, and mesopore zeolite accounts for 50～100 heavy % of zeolite gross weight, and large pore zeolite accounts for 0～50 heavy % of zeolite gross weight.
2. according to the method for claim 1, it is characterized in that described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, its Petroleum Hydrocarbon is selected from one or more in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, and other mineral oil is selected from one or more in liquefied coal coil, tar sand oil, shale oil.
3. according to the method for claim 1, it is characterized in that described reactor be selected from riser tube, etc. the combination of one or more in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or the two or more combinations of same reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
4. according to the method for claim 1, it is characterized in that also comprising C4 alkene in product, the first reaction zone of C4 alkene Returning reactor is or/and the further cracking in second reaction zone.
5. according to the method for claim 1, it is characterized in that catalytic gasoline selective hydrogenation is under hydrogen exists situation, contact with selecting raw hydrogenation catalyst, at hydrogen dividing potential drop 1.2～8.0MPa, 150～400 ℃ of temperature of reaction, hydrogen to oil volume ratio 150～600Nm
3/ m
3, volume space velocity 1～20h
-1under condition, react.
6. according to the method for claim 5, it is characterized in that described selective hydrogenation catalyst be take Ni-W, Co-Ni-W, Ni-Mo or Co-Mo as active ingredient, activated alumina is the non-precious metal catalyst of carrier.
7. according to the method for claim 1, it is characterized in that aromatic extraction unit extraction solvent used is selected from one or more in tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether.
8. according to the method for claim 1, it is characterized in that Aromatics Extractive Project temperature is 40～120 ℃, the volume ratio between solvent and aromatics extraction raw material is 0.5～5.0.
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| CN109679686B (en) * | 2017-10-18 | 2021-07-09 | 中国石油化工股份有限公司 | Hydrocarbon catalytic cracking method for increasing yield of ethylene and light aromatic hydrocarbon |
| CN109678634B (en) * | 2017-10-18 | 2022-03-11 | 中国石油化工股份有限公司 | Catalytic cracking method for increasing yield of ethylene and propylene |
| CN109722306B (en) * | 2017-10-27 | 2021-04-06 | 中国石油化工股份有限公司 | Processing method of inferior heavy oil |
| CN110857397B (en) * | 2018-08-24 | 2021-11-12 | 中国石油化工股份有限公司 | Method and system for processing coker gasoline by using variable-diameter riser |
| CN110857401B (en) * | 2018-08-24 | 2021-11-16 | 中国石油化工股份有限公司 | Processing method and system of coking gasoline |
| CN112536003B (en) * | 2019-09-20 | 2022-09-06 | 中国石油化工股份有限公司 | Catalytic conversion reactor and system suitable for preparing olefin and aromatic hydrocarbon |
| CN111484875B (en) * | 2020-04-16 | 2021-11-19 | 中国石油化工股份有限公司 | Catalytic cracking method and reaction system |
| CN115028507A (en) * | 2021-03-05 | 2022-09-09 | 中国石油化工股份有限公司 | Catalytic conversion method for maximally producing ethylene and simultaneously producing propylene |
| CN113244861B (en) * | 2021-06-03 | 2021-09-24 | 山东胜星新能源有限公司 | Multistage fluidized catalytic reactor for petroleum hydrocarbon |
| CN114686252B (en) * | 2021-12-26 | 2024-02-09 | 中海油天津化工研究设计院有限公司 | Method for preparing chemicals from crude oil |
| CN116515524A (en) * | 2022-07-25 | 2023-08-01 | 中国石油化工股份有限公司 | Method for producing light aromatic hydrocarbon by secondary hydrogenation of inferior diesel oil |
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| CN101191081A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Catalytic conversion method for hydrocarbon oil raw material |
| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
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| CN101531924A (en) * | 2008-03-13 | 2009-09-16 | 中国石油化工股份有限公司 | Method for preparing light fuel oil and propylene from poor-quality raw oil |
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