CN101531558B - Catalytic conversion method for preparing propylene and aromatic hydrocarbons - Google Patents
Catalytic conversion method for preparing propylene and aromatic hydrocarbons Download PDFInfo
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Abstract
A catalytic conversion method for preparing propylene and aromatic hydrocarbons comprises the following steps: hydrocarbon raw materials with different cracking performances are contacted with a catalytic cracking catalyst to carry out cracking reaction in a fluidized-bed reactor under the conditions that the temperature is 450-750 DEG C, the weight hourly space velocity is 0.1-800h<-1>, the reaction pressure is 0.10-1.0MPa, the weight ratio of the catalytic cracking catalyst to the raw materials is 1-150 and the weight ratio of water vapor to the raw materials is 0.05-1.0, the spent catalyst and reaction oil and gas are separated, the spent catalyst returns to the reactor after the regeneration, the separated reaction oil and gas are separated to obtain target products of low-carbon olefins, aromatic hydrocarbons and the raw materials for re-cracking, wherein the raw materials for re-cracking are re-cracked after hydrotreating. The method can product the propylene and other low-carbon olefins from the heavy raw materials to the maximum extent, wherein the yield of the propylene is more than 40 percent by weight; meanwhile, the method can co-produce toluene, xylene and other aromatic hydrocarbons, and the yield of the dry gas is unexpectedly reduced by more than 80 percent by weight.
Description
Technical field
The invention belongs to the catalysis conversion method of hydrocarbon ils, more particularly, is by the combination of hydrocarbon oil catalytic cracking and hydroprocessing technique process heavy feed stock to be converted into the low-carbon alkene that is rich in propylene and the method for aromatic hydrocarbons.
Background technology
Low-carbon alkene such as ethene, propylene etc. are important Organic Chemicals, and wherein propylene is the synthon of the products such as polypropylene, vinyl cyanide.Along with increasing rapidly of the derivative demands such as polypropylene, the demand of propylene is also all being increased year by year.The demand in World Propylene market 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 produced ethene, propylene take lightweight oils such as petroleum naphthas as raw material by thermo-cracking, but the productive rate of propylene only is that FCC is then take mink cell focuses such as vacuum gas oils (VGO) as raw material 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 several large restraining factors such as the shortage of lightweight material oil, inefficiency of production and high cost.
FCC is owing to the 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 preparing low-carbon olefins, 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 the 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 the method adopts ZSM-5 and/or ZSM-11 zeolite to do active component, the catalyzer take a large amount of inert substances as matrix, and take VGO as raw material, the productive rate of propylene also is no more than 20 heavy %.
US4,422,925 disclose the method that multiple hydro carbons with different cracking performances contacts and transforms with hot regenerated catalyst, the described hydro carbons of the method contains a kind of gas alkane raw material and a kind of liquid hydrocarbon raw material at least, the method has different cracking performances according to different hydrocarbon molecules, reaction zone is divided into a plurality of reaction zones carries out cracking reaction, with voluminous low-molecular olefine.
CN1667089A 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 the catalytic cracking reaction device, contact, 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 regeneration; Separating reaction oil gas obtains purpose product low-carbon alkene and aromatic hydrocarbons.The method is produced the low-carbon alkenes such as propylene, ethene to greatest extent from heavy feed stock, wherein the productive rate of propylene surpasses 30 heavy %, the simultaneously aromatic hydrocarbons such as coproduction toluene and dimethylbenzene.
Although above-mentioned these methods can producing more propylene, but the increase along with liquefied gas yield or productivity of propylene, gasoline yield reduces, aromatic hydrocarbons in the gasoline and benzene content also increase considerably, if the gasoline of high benzene content without extracting or saturated, is not suitable for blended gasoline usually, except the high problem of Aromatic Hydrocarbon in Gasoline and benzene content, dry gas yied increases nearly 5 times, thereby causes the waste of heavy oil resources, the unrealized efficient utilization of petroleum resources.
At present the world is being faced with crude oil and becomes and heavily become bad trend, and the demand of heavy fuel oil (HFO) is gradually reduced, and the demand of light-weight fuel oil is then increased considerably, and therefore, residual hydrocracking is used widely as the technique of heavy oil catalytic cracking raw material oil.CN1382776A discloses the method for residual hydrocracking and catalytically cracking heavy oil, be that residual oil and slurry oil steam that thing, catalytic cracking heavily follow carburetion, optional distillate enters hydrotreater together, in the presence of hydrogen and hydrogenation catalyst, carry out hydrogenation reaction; After the generation oil of reaction gained steams petrol and diesel oil, hydrogenated residue enters catalytic cracking unit with optional vacuum gas oil, carry out cracking reaction in the presence of cracking catalyst, reaction gained heavy cycle oil enters residual hydrogenation equipment, and the distillation slurry oil obtains steaming thing and is back to hydrogenation unit.The method can be converted into light-end products with slurry oil and heavy cycle oil, has improved the yield of gasoline and diesel oil.Although heavy oil is by behind the hydroprocessing technique, catalytic cracking process can be produced more liquid product, and the foreign matter content of product is low, character makes moderate progress, but when the density of heavy oil large, viscosity is high, heavy metal, when resin and asphalt content is high, the operational condition of hydrotreater is very harsh, and working pressure is high, and temperature of reaction is high, air speed is low, on-stream time is short, and process cost is high, and the one-time investment of device is also high.In addition, when the method is processed heavy oil, also produce the small molecules hydro carbons, especially dry gas causes the reduction of the utilising efficiency of heavy oil resource, simultaneously, when hydrogenated residue enters the catalytic cracking unit processing, still produce the heavy oil of 8～10 heavy %, cause again the reduction of the utilising efficiency of heavy oil resource.This heavy oil can return residual hydrogenation equipment, but this heavy oil and residual oil character differ larger, and hydrogen richness is low, even through hydrotreatment, the character of this heavy oil is improved limited.
Above-mentioned prior art designs still Shortcomings to the alkane molecule cracking reaction in the stock oil, and it is excessive to other hydrocarbon molecules cracking reaction in the raw material, cause dry gas and coke yield to increase considerably, simultaneously, the product of prior art distributes and is that routinely FCC fractionating system is cut, arene underwater content in gasoline or the diesel oil and low-carbon alkene potential content are underused, and cause the productive rate of propylene and aromatic hydrocarbons on the low side.In order to satisfy the demand of the industrial chemicals such as growing propylene, ethene and aromatic hydrocarbons, be necessary to develop and a kind of heavy feed stock be converted into a large amount of propylene and the catalysis conversion method of aromatic hydrocarbons.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of by catalytic cracking process and hydroprocessing technique organic assembling, heavy feed stock is converted into the method for the lightweight oil of the low-carbon alkene that is rich in propylene and high yield, combined method is that catalytic cracking process is only processed alkane group in the heavy feed stock, and remaining aromatic hydrocarbon group is processed by hydroprocessing technique, thereby realizes that petroleum resources efficiently utilize.
Method provided by the invention comprises that three kinds of different cracking performance hydrocarbon raw materials contact with catalytic cracking catalyst, and step is as follows:
(1), the raw material of type three contacts with hot regeneration catalyzing catalyst for cracking first, at 650 ℃-800 ℃ of temperature of reaction, weight hourly space velocity 100h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(2), the reaction effluent of step (1) separates without finish, mixes with the raw material of type two, the raw material of type two is at 550 ℃-720 ℃ of temperature of reaction, weight hourly space velocity 10h
-1-300h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(3), the reaction effluent of step (2) mixes with the raw material of type one again, the stock oil of type one is at 450 ℃-620 ℃ of temperature of reaction, weight hourly space velocity 0.1h
-1-100h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 1.0-30, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(4), reclaimable catalyst and the reaction oil gas of separating step (3), reclaimable catalyst is Returning reactor after regeneration, separating reaction oil gas is isolated to purpose product propylene, aromatic hydrocarbons, again cracking stock and heavy oil feedstock.
(5), step (4) heavy oil feedstock under there is situation in hydrogen, contact with hydrotreating catalyst, 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
-1Reaction conditions under carry out hydrotreatment, resulting hydrogenation heavy oil can be used as the stock oil of step (3), also can be used as the stock oil of conventional catalytic cracking unit.
Described three kinds of different cracking performance hydrocarbon raw material classification: type of feed one is easy cracking stock, and type of feed two is more difficult cracking stock, type of feed three awkward cracking stocks.
The raw material of described type one is petroleum hydrocarbon and/or other mineral oil, and its Petroleum Hydrocarbon is selected from a kind of in vacuum gas oil (VGO), atmospheric gas oil (AGO), coker gas oil (CGO), deasphalted oil (DAO), vacuum residuum (VR), long residuum (AR), the hydrogenation heavy oil or more than one mixture wherein.Other mineral oil is one or more in liquefied coal coil, tar sand oil, the shale oil.Preferred raw material is selected from a kind of in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, the hydrogenation heavy oil or more than one mixture wherein.Wherein VGO, AGO, CGO, DAO, VR, AR are full cut or the part cut of not hydrogenation, or are full cut or part cut behind the hydrogenation.
The raw material of described type two is selected from a kind of in alkene that diesel oil, gasoline, carbonatoms are 4-8, the cut that boiling range is 160～260 ℃ or more than one mixture wherein, preferred boiling range is 160～260 ℃ cut, more preferably 170～250 ℃ cut, preferred cut installs from this, perhaps conventional catalytic cracking, coking, thermally splitting, hydrogenation unit.
Described gasoline is selected from a kind of in present method gained catalytic cracking gasoline, catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, the hydrogenated gasoline or more than one mixture wherein, and wherein catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, hydrogenated gasoline are from the outer gasoline of this device.
Described diesel oil is to be selected from a kind of in present method gained catalytic pyrolysis diesel oil, catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, the hydrogenated diesel oil or more than one mixture wherein, and wherein catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, hydrogenated diesel oil are from the outer diesel oil of this device.
Described carbonatoms is that 4～8 alkene can be from catalytic cracking method of the present invention, also can be from techniques such as conventional catalytic cracking, coking, thermally splitting, hydrogenation.
It is raffinate oil a kind of of 4～8 alkane, light aromatic hydrocarbons or more than one mixture wherein that the raw material of described type three is selected from carbonatoms, described carbonatoms is that 4～8 alkane can be from catalytic cracking method of the present invention, also can be from techniques such as conventional catalytic cracking, coking, thermally splitting, hydrogenation.
Described light aromatic hydrocarbons raffinate oil be the boiling range of the devices such as this device or external device such as conventional catalytic cracking, coking, thermally splitting, hydrogenation be C7～160 ℃ cut first after selective hydrogenation again through the solvent extraction gained; the solvent of light Aromatics Extractive Project is selected from by one or more the mixture in tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and the N-formyl morpholine ether; the temperature of solvent extraction is 40-120 ℃, and the volume ratio between solvent and the solvent extraction raw material is 2-6.
The raw material of described again cracking be selected from that boiling range is 160～260 ℃ cut, light aromatic hydrocarbons is raffinated oil and hydrogenation heavy oil in one or more mixture.
Described hydrogenation heavy oil is the boiling range produced of this device or external device such as conventional catalytic cracking greater than 260 ℃ heavy oil, heavy oil more preferably greater than 330 ℃, under there is situation in hydrogen, contact with hydrotreating catalyst, 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
-1Reaction conditions under to carry out hydrotreatment resulting.
Described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, and each component accounts for respectively total catalyst weight: the heavy % of zeolite 1 heavy %-50, the heavy % of inorganic oxide 5 heavy %-99, the heavy % of clay 0 heavy %-70.
Its mesolite is selected from mesopore zeolite and optional large pore zeolite as active ingredient, and mesopore zeolite accounts for the heavy % of 50 heavy %-100 of zeolite gross weight, and the heavy % of preferred 70 heavy %-100, large pore zeolite account for the heavy % of 0 heavy %-50 of zeolite gross weight, the heavy % of preferred 0 heavy %-30.Mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, also can carry out modification with transition metals such as the 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 consist of.
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).
Catalytic cracking catalyst in each reactor can be identical, also can be different.
The used reactor in catalytic pyrolysis of the present invention unit be selected from riser tube, etc. one or both series combinations in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed.Riser tube can be conventional isodiametric riser tube, also can be the riser tube of various forms reducing.Wherein the gas of fluidized-bed speed is the 0.1-2 meter per second, and the gas speed of riser tube is 2-30 meter per second (disregarding catalyzer).
In order to increase the agent-oil ratio of reaction catchment, improve the lytic activity of catalyzer, can be by supplemental heat or cold regenerated catalyst, half regenerated catalyst, catalyzer, live catalyst to be generated.The regenerated catalyst of cooling and half regenerated catalyst of cooling are that reclaimable catalyst cools off after two-stage regeneration and one section regeneration respectively and obtains, the regenerated catalyst carbon content is below the 0.1 heavy %, be preferably below the 0.05 heavy %, half regenerated catalyst carbon content is the heavy % in 0.1 heavy %～0.9, and preferably carbon content is the heavy % in 0.15 heavy %～0.7; The reclaimable catalyst carbon content is more than the 0.9 heavy %, and preferably carbon content is the heavy % in 0.9 heavy %～1.2.
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.
Described low-carbon alkene is ethene, propylene and butylene.
Described hydrotreating catalyst is group vib metal and/or the VIII family metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium carrier, preferred hydrotreating catalyst is that one or more group VIII metals, 12～39 one or more group vib metals of heavy % and surplus aluminum oxide and/or the amorphous silicon aluminium carrier by 0～10 heavy % additive, 1～9 heavy % consists of, and wherein said additive is selected from non-metallic element and the metallic elements such as fluorine, phosphorus, titanium, platinum.Described group vib metal is selected from Mo or/and W, and VIII family metal is selected from Co or/and Ni.
Separation of propylene is identical with the method that those of ordinary skills know with the method for the butylene of choosing wantonly from reaction oil gas; Out identical with the method that those of ordinary skills know as the recycle stock method from reaction oil gas separation of C 5-C8; The method of aromatics separation and non-aromatics is that the solvent extracting is identical with the method that those of ordinary skills know in the aroamtic hydrocarbon raw material oil on the lenient side; Separating described boiling range is that 160～260 ℃ of preferred cuts of 170～250 ℃ can separate in existing FCC separation column, boiling range can adopt the raw material of hydrotreater greater than the heavy oil of 250 ℃ or 260 ℃, perhaps greater than the heavy oil of 250 ℃ or the 260 ℃ raw material as conventional catalytic cracking unit.
Description of drawings
Fig. 1 is the process flow diagram of embodiments of the present invention one.
Fig. 2 is the process flow diagram of embodiments of the present invention two.
Embodiment
Embodiment one
The preferred technical scheme of present embodiment comprises the following steps:
(1) raw material of type three contacts with hot regenerated catalyst first, at 650 ℃-800 ℃ of temperature of reaction, weight hourly space velocity 100h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(2) reaction effluent separates without finish, mixes with the raw material of type two, and the raw material of type two is at 550 ℃-720 ℃ of temperature of reaction, weight hourly space velocity 10h
-1-300h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(3) reaction effluent mixes with the raw material of type one again, and the stock oil of type one is at 450 ℃-620 ℃ of temperature of reaction, weight hourly space velocity 0.1h
-1-100h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 1.0-30, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(4) reclaimable catalyst separates by cyclonic separator with reaction oil gas, and reclaimable catalyst enters stripper, Returning reactor behind the stripping coke burning regeneration, and reaction oil gas enters follow-up separation system.
(5) reaction oil gas is told purpose product propylene in separation system, and H
2, CH
4, ethene, ethane, propane, C4-C6 hydro carbons, C7-160 ℃ cut, 160～260 ℃ of cuts, be preferably greater than 330 ℃ of heavy oil greater than 260 ℃, wherein the C4-C6 hydro carbons returns step (1) and/or (2) again cracking;
(6) isolated C7-160 ℃ of cut obtains purpose product aromatic hydrocarbons and light aromatic hydrocarbons is raffinated oil through light Aromatics Extractive Project first again after selective hydrogenation, and light aromatic hydrocarbons is raffinated oil and returned again cracking of step (1).
(7) the isolated hydrogenation heavy oil that obtains through hydrotreater greater than 260 ℃ of heavy oil, hydrogenation heavy oil return again cracking or return the again cracking of another set of conventional catalytic cracking unit of step (3).
Embodiment two
The preferred technical scheme of present embodiment comprises the following steps:
(1) raw material of type three contacts with hot regenerated catalyst first, at 650 ℃-800 ℃ of temperature of reaction, weight hourly space velocity 100h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(2) reaction effluent separates without finish, mixes with the raw material of type two, and the raw material of type two is at 550 ℃-720 ℃ of temperature of reaction, weight hourly space velocity 10h
-1-300h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(3) reaction effluent mixes with the raw material of type one again, and the stock oil of type one is at 450 ℃-620 ℃ of temperature of reaction, weight hourly space velocity 0.1h
-1-100h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 1.0-30, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0;
(4) reclaimable catalyst separates by cyclonic separator with reaction oil gas, and reclaimable catalyst enters stripper, Returning reactor behind the stripping coke burning regeneration, and reaction oil gas enters follow-up separation system.
(5) reaction oil gas is told purpose product propylene in separation system, and H
2, CH
4, ethene, ethane, propane, C4-C6 hydrocarbon, C7-160 ℃ cut, 160～260 ℃ of cuts, be preferably greater than 330 ℃ of heavy oil greater than 260 ℃, wherein the C4-C6 hydrocarbon returns step (1) and/or (2) again cracking;
(6) isolated C7-160 ℃ of cut obtains purpose product aromatic hydrocarbons and light aromatic hydrocarbons is raffinated oil through light Aromatics Extractive Project first again after selective hydrogenation, and light aromatic hydrocarbons is raffinated oil and returned again cracking of step (1).
(7) the isolated hydrogenation heavy oil that obtains through hydrotreater greater than 260 ℃ of heavy oil, hydrogenation heavy oil return again cracking or return the again cracking of another set of conventional catalytic cracking unit of step (3);
(8) ethene of step (5) and butylene enter the olefin metathesis reactions device, and ethene and butylene are converted into purpose product propylene by metathesis reaction.
The solvent of light Aromatics Extractive Project is selected from one or more mixture of this group material of being made of tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and N-formyl morpholine ether.Recycle after the solvent recuperation.The temperature of solvent extraction is 40-120 ℃, and the volume ratio between solvent and the solvent extraction raw material is 2-6.The extraction oil of solvent extraction is one of purpose product aromatic hydrocarbons, and raffinating oil is non-aromatics as one of raw material of step (1) catalytic pyrolysis.
The catalyzer of metathesis reaction is selected from Mo, W and Re is compound loaded on molecular sieve carrier, and molecular sieve comprises Y, β, SAPO series, ZSM is serial and MCM is serial.Temperature of reaction 10-450 ℃, pressure 0.1-3.0MPa, butylene weight space velocity 0.01-3h
-1, ethylene/butylene is than being 0.2-10.The purpose product of metathesis reaction is propylene.
This technical scheme organically combines the techniques such as catalytic pyrolysis, metathesis reaction, oil gas fractionation, gas delivery, light aromatic solvent extracting and hydrotreatment, produce to greatest extent propylene from the heavy feed stock that hydrogen richness is lower, its productive rate can surpass 40 heavy %, the aromatic hydrocarbons such as simultaneously coproduction toluene, dimethylbenzene.
The operating unit that method provided by the invention relates to comprises cracking unit, hydrotreating unit, fractionation unit, selective hydrogenation unit, light Aromatics Extractive Project unit, gas separation unit, transposable element.Below respectively narration.
The catalytic pyrolysis unit:
The catalytic pyrolysis part is comprised of reactor and revivifier, three kinds of different cracking performance hydrocarbon raw materials contact in reactor with catalyst for cracking, under different reaction conditionss, carry out cracking reaction, reacted oil gas and catalyst separating, reclaimable catalyst is through stripping, Returning reactor after the regeneration, isolated oil gas send fractionation unit, gas separation unit and extracting unit, 160～260 ℃ cut of fractionation unit returns the catalytic pyrolysis unit, raffinating oil of extracting unit returned the catalytic pyrolysis unit, the ethane of gas separation unit, propane and butane go out device or return the catalytic pyrolysis unit as product.The C 4 olefin of gas separation unit returns the catalytic pyrolysis unit or advances transposable element or go out device as product.The C5-C6 hydro carbons returns the catalytic pyrolysis unit.
Hydrotreating unit:
The hydrotreatment part is comprised of reactor and stripping tower, by contacting in reactor with hydrotreating catalyst greater than being preferably greater than 330 ℃ of heavy oil greater than 260 ℃ that the catalytic pyrolysis unit generates, under different reaction conditionss, react, reacted oil gas enters the stripping tower stripping, light constituent returns fractionation unit, and hydrogenation heavy oil turns back to the catalytic pyrolysis unit or return another set of conventional catalytic cracking unit.
Fractionation unit:
Fractionation unit is comprised of separation column, vapor-liquid separation tank and stripping tower, is divided into rich gas, light aromatic hydrocarbons material (being C7-160 ℃ of cut), freshening material (being 160-260 ℃ of cut) and heavy oil material (namely greater than 260 ℃ of cuts) at the fractionation unit reaction oil gas.
The catalytic cracking reaction oil gas that comes from the cracking unit is sent into separation column and is separated.
Extracting the boiling range scope out from the separation column middle and lower part through fractionation is heavy oil greater than 260 ℃, mainly contains double ring arene and polycyclic aromatic hydrocarbons in this heavy oil fraction.Therefore, after filtering out a small amount of catalyst fines that wherein carries, will deliver to hydrotreating unit greater than 260 ℃ cut and process, and process back end hydrogenation heavy oil and turn back to the catalytic pyrolysis unit or return another set of conventional catalytic cracking unit.
Extracting boiling range out from the separation column middle and upper part is 160～260 ℃ of preferred cuts of 170～250 ℃, mainly contain paraffinic hydrocarbons, naphthenic hydrocarbon and part mononuclear aromatics in this cut, the low-carbon olefines high-output of high-quality and the raw material of aromatic hydrocarbons, returning the cracking unit further reacts, make the side chain fracture on paraffinic hydrocarbons and the mononuclear aromatics, produce to greatest extent low-carbon alkene and aromatic hydrocarbons.
The oil gas of discharging from the fractionation cat head enters vapor-liquid separation tank after condensation, cooling separates, the rich gas of the telling body separating unit of supplying gas, and the thick light aromatic hydrocarbons material of telling gives the processing of the stripping tower this unit in, recycles after the water treatment of telling.
Stripping tower is actually a depentanizer, and thick light aromatic hydrocarbons material is divided into C in stripping tower
6 +Cut and C
5 -Cut.C
6 +Mainly containing mononuclear aromatics in the cut, is the light aromatics extraction raw material of high-quality, through the selective hydrogenation unit, delivers to light Aromatics Extractive Project cell processing, and aromatic hydrocarbons and stable hydrocarbon are separated, and stable hydrocarbon is as the raw material of catalytic pyrolysis unit, and aromatic hydrocarbons is as industrial chemicals.C
5 -Cut is delivered to gas separation unit and is processed.
Gas separation unit:
Gas separation unit is comprised of rich gas compressor, depropanizing tower, demethanizing tower, deethanizing column, ethylene rectification tower and propylene rectification tower.
Rich gas is sent into depropanizing tower, the C of fractionation unit after rich gas compressor improves pressure
5 -Cut is also sent into depropanizing tower.Through separating, discharge C4 and C 5 fraction at the bottom of the depropanizing tower, after cooling, enter debutanizing tower.The logistics of debutylize cat head enters the butylene rectifying tower, and the debutanizing tower bottoms stream is discharged C 5 fraction, and the reactor that this cut returns the cracking unit further reacts.The butylene of butylene rectifying tower top returns the catalytic pyrolysis unit or enters transposable element or go out device, and the butane at the bottom of the butylene rectifying tower returns the catalytic pyrolysis unit or goes out device.The depropanizing cat head is discharged C
3 -Cut is sent into demethanizing tower after cooling.The demethanizing cat head is discharged the fuel gas that mainly contains methane and hydrogen, and the demethanizing tower bottoms stream is sent into deethanizing column.Ethylene rectification tower is sent in the logistics of deethanizing cat head, and the deethanizing column bottoms stream is sent into propylene rectification tower.Ethylene distillation cat head polymer grade ethylene goes out device or advances transposable element, and ethane goes out device or returns the catalytic pyrolysis unit as product at the bottom of the ethylene rectification tower.Propylene rectification tower top polymerization-grade propylene goes out device, and propane goes out device or returns the catalytic pyrolysis unit as product at the bottom of the propylene rectification tower.
Transposable element
In this unit, the ethene of catalytic pyrolysis and butylene be at temperature 10-450 ℃, pressure 0.1-3.0MPa, butylene weight space velocity 0.01-3h
-1, ethylene/butylene is than obtaining purpose product propylene for contacting the generation metathesis reaction with metathesis catalyst under the 0.2-10 condition.
The selective hydrogenation unit
In this unit, light aromatic hydrocarbons material (being C6-160 ℃ of cut) contacts with hydrogen, selective hydrogenation catalyst, at hydrogen dividing potential drop 1.2～8.0MPa (absolute pressure), 150～300 ℃ of temperature of reaction, hydrogen to oil volume ratio 150～600Nm
3/ m
3, volume space velocity 1～20h
-1React under the condition, obtain the selective hydrogenation petroleum naphtha; Deliver to light Aromatics Extractive Project 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 that high to take off diene active and desulphurizing activated.
Light Aromatics Extractive Project unit
Light Aromatics Extractive Project comprises solvent tower, extractive distillation solvent recovery tower, liquid liquid extraction tower, stripping tower, liquid liquid extracting and reclaiming tower etc.
In this unit, the selective hydrogenation petroleum naphtha obtains aromatic hydrocarbons and light aromatic hydrocarbons is raffinated oil through solvent extraction, and wherein aromatic hydrocarbons is one of purpose product, and light aromatic hydrocarbons is raffinated oil and returned the catalytic pyrolysis unit as one of raw material of catalytic pyrolysis.
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 process flow diagram of embodiments of the present invention one.
Its technical process is as follows:
The pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 18 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, the raw material of type three through pipeline 3 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of type three, and upwards accelerated motion.The raw material of type two through pipeline 5 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone II of pipeline 6, mix with the existing logistics of riser reactor, cracking reaction occurs at the hotter catalyzer that contains a small amount of charcoal in type two raw materials, and upwards accelerated motion; The raw material of type one through pipeline 7 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone III of pipeline 8, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of the lesser temps that contains certain charcoal in type one raw material, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 10 through pipeline 9, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 11, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 12 in the settling vessel, contacts with steam from pipeline 13.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 11 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 15 through inclined tube 14, main air enters revivifier through pipeline 16, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, flue gas enters cigarette machine 17 through pipeline, and the catalyzer after the regeneration enters riser tube through inclined tube 18.
Oil gas in the collection chamber 11 enters follow-up separation system 20 through main oil gas piping 19, separates the propylene that obtains and draws through pipeline 21; And C 4 olefin is drawn through pipeline 22, and the part C 4 olefin returns riser tube 2 through pipeline 41; The catalytic pyrolysis dry gas is drawn through pipeline 23; Catalytic pyrolysis ethene is drawn through pipeline 34; Catalytic pyrolysis ethane is drawn through pipeline 35; Catalytic pyrolysis propane is drawn through pipeline 36; The catalytic pyrolysis butane is drawn through pipeline 37; Catalytic pyrolysis C5 draws through pipeline 38; Light aroamtic hydrocarbon raw material is drawn through pipeline 24, enters selective hydrogenation device 25; And then enter light aromatic extraction unit 26, and to tell aromatic hydrocarbons and draw through pipeline 27, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) enters the bottom that pipeline 3 returns riser tube 2 reaction zone I through pipeline 28; 160～260 ℃ cut is drawn the bottom of returning riser tube 2 reaction zone II through pipeline 29; Heavy oil material greater than 260 ℃ is drawn out to hydrotreating unit 31 through pipeline 30, and isolated light constituent is drawn through pipeline 32, and hydrogenation heavy oil returns the bottom of riser tube 2 reaction zone III through pipeline 33.
Fig. 2 is the process flow diagram of embodiments of the present invention two.
Its technical process is as follows:
The pre-lift medium is entered by riser reactor 2 bottoms through pipeline 1, from the regenerated catalyst of pipeline 18 under the castering action of pre-lift medium along the riser tube accelerated motion that makes progress, the raw material of type three through pipeline 3 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone I of pipeline 4, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of heat in the raw material of type three, and upwards accelerated motion.The raw material of type two through pipeline 5 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone II of pipeline 6, mix with the existing logistics of riser reactor, cracking reaction occurs at the hotter catalyzer that contains a small amount of charcoal in type two raw materials, and upwards accelerated motion; The raw material of type one through pipeline 7 with the bottom from the atomizing steam injecting lift pipe 2 reaction zone III of pipeline 8, mix with the existing logistics of riser reactor, cracking reaction occurs at the catalyzer of the lesser temps that contains certain charcoal in type one raw material, and upwards accelerated motion.The oil gas that generates and the reclaimable catalyst of inactivation enter cyclonic separator in the settling vessel 10 through pipeline 9, realize separating of reclaimable catalyst and oil gas, and oil gas enters collection chamber 11, and catalyst fines returns settling vessel by dipleg.Reclaimable catalyst flows to stripping stage 12 in the settling vessel, contacts with steam from pipeline 13.The oil gas that stripping goes out from reclaimable catalyst enters collection chamber 11 behind cyclonic separator.Reclaimable catalyst behind the stripping enters revivifier 15 through inclined tube 14, and main air enters revivifier through pipeline 16, and the coke on the burning-off reclaimable catalyst makes the reclaimable catalyst regeneration of inactivation, and flue gas enters cigarette machine 17 through pipeline.Catalyzer after the regeneration enters riser tube through inclined tube 18.
Oil gas in the collection chamber 11 enters follow-up separation system 20 through main oil gas piping 19, separates the propylene that obtains and draws through pipeline 21; And butylene is drawn through pipeline 22 and is entered transposable element 35; Catalytic pyrolysis ethene enters transposable element 35 through pipeline 34; Catalytic pyrolysis hydrogen and methane are drawn through pipeline 23; Catalytic pyrolysis ethane is drawn through pipeline 37; Propane is drawn through pipeline 38; Butane is drawn through pipeline 39; C5 draws through pipeline 40; Light aroamtic hydrocarbon raw material is drawn through pipeline 24, enters selective hydrogenation device 25; And then enter light aromatic extraction unit 26, and to tell aromatic hydrocarbons and draw through pipeline 27, non-aromatics (being that light aromatic hydrocarbons is raffinated oil) is returned riser tube 2 through pipeline 28; 160～260 ℃ cut is drawn through pipeline 29 and is returned riser tube 2; Heavy oil material greater than 260 ℃ is drawn out to hydrotreating unit 31 through pipeline 30, and isolated light constituent is drawn through pipeline 32, and hydrogenation heavy oil returns riser tube 2 through pipeline 33; Transposable element purpose product propylene is drawn through pipeline 36.
The method is produced the low-carbon alkenes such as propylene to greatest extent from heavy feed stock, wherein the productive rate of propylene is more than the 40 heavy %, simultaneously the aromatic hydrocarbons such as coproduction toluene and dimethylbenzene.This technical scheme organically combines the techniques such as catalytic pyrolysis and solvent extraction, hydrotreatment, produces to greatest extent low-carbon alkene especially propylene and aromatic hydrocarbons from the lower heavy feed stock of hydrogen richness.The present invention compared with prior art has following unforeseeable technique effect:
1, productivity of propylene and the propylene selectivity in liquefied gas increases considerably, and for the VGO raw material, productivity of propylene can reach more than the 40 heavy %.
2, the aromatics yield such as toluene and dimethylbenzene increases significantly.
3, in the situation that productivity of propylene increases considerably, dry gas yied reduces significantly, can reduce to reach more than the 80 heavy %.
4, yield of light oil increases significantly, and the slurry oil productive rate reduces significantly, thereby the petroleum resources utilising efficiency improves.
5, the hydrotreater operational cycle is improved significantly, and hydrogenation heavy oil character is significantly improved.
Adopt several method provided by the invention, can realize the technological breakthrough of refinery's concept, change to chemical refinery from traditional fuel type and fuel-Lube Type refinery production model, make the refinery from single oil refining to industrial chemicals and the production development of high added value derived product and extension, both solved the problem of petrochemical material shortage, improved again the economic benefit of refinery, realized that petroleum resources efficiently utilize.
The following examples will be further described present method, but therefore not limit present method.
Used raw material is the decompressed wax oil (VGO) of paraffinic base and intermediate base among the embodiment, 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, adds 100g (butt) crystallization product ZRP-1 zeolite (production of Qilu Petrochemical Company catalyst plant, SiO in this solution
2/ Al
2O
3=30, content of rare earth RE
2O
3=2.0 heavy %), behind 90 ℃ of exchange 0.5h, filter to get 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 process 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
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 with 75.4kg halloysite (Suzhou china clay company Industrial products, solid content 71.6m%) making beating, add again 54.8kg pseudo-boehmite (Shandong Aluminum Plant's Industrial products, solid content 63m%), with hydrochloric acid its PH is transferred to 2-4, 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), with step 1) MFI structure mesopore zeolite (butt is 22.5kg) and DASY zeolite (the Qilu Petrochemical Company catalyst plant Industrial products of the phosphorous and iron of preparation, 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 1m%) washing, the flush away Na that dissociates
+, being drying to obtain the catalytic cracking catalyst sample, consist of 15 heavy % MFI structure mesopore zeolite, 3 heavy %DASY zeolites, the 32 heavy % pseudo-boehmites, 6 phosphorous and iron of this catalyzer weigh % aluminium colloidal sol and surplus kaolin.
Hydrotreating 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)
218H
2O, chemical pure), water is made into 200mL solution.Solution is joined in alumina supporter 50 gram, at room temperature flooded 3 hours, used the ultrasonication steeping fluid 30 minutes in steeping process, cooling is filtered, and is put in the microwave oven dry about 15 minutes.Consisting of of this catalyzer: 30.0 heavy %WO
3, 3.1 heavy %NiO and surplus aluminum oxide.
Selective hydrogenation 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)
218H
2O, chemical pure), water is made into 200mL solution.Solution is joined in the 100 gram alumina supporters, at room temperature flooded 4 hours, after the separation, wet catalyzer is placed on 120 ℃ of baking oven inner dryings 4 hours, 500 ℃ of roastings of tube furnace blowing air 4 hours.Consisting of of this catalyzer: 25.3 heavy %WO
3, 2.3 heavy %NiO and surplus aluminum oxide.
Embodiment 1
This embodiment tests according to the flow process of Fig. 1.The total height of the pre lift zone of the reducing riser reactor of this flow process, the first reaction zone, second reaction zone and the 3rd reaction zone is 21 meters, and the pre lift zone diameter is 0.25 meter, and it highly is 1.5 meters; The first reaction zone diameter is 0.25 meter, and it highly is 3.5 meters; The second reaction zone diameter is 0.5 meter, and it highly is 7 meters; The 3rd reaction zone diameter is 1 meter, and it highly is 9 meters; It is 45 degree that trapezoidal drift angle is wanted in the longitudinal sections of first and second reaction zone joint portion and second and third reaction zone joint portion etc.
Stock oil A directly as the raw material of catalytic pyrolysis, is being tested by the middle-scale device of riser reactor.Light aromatic hydrocarbons is raffinated oil and C
3-C
5Hydro carbons enters reaction zone I bottom, and at reaction zone I, light aromatic hydrocarbons is raffinated oil and C
3-C
5Hydro carbons is at 680 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, the weight ratio 60 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.25 condition; 160～260 ℃ cut injects the bottom of reaction zone II, and at reaction zone II, 160～260 ℃ cut is at 640 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 30 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction 0.20 time; Hydrogenation heavy oil and stock oil A enter reaction zone III bottom, and at reaction zone III, oil gas is at 550 ℃ of temperature of reaction, weight hourly space velocity 30h
-1, the weight ratio of water vapor and raw material is to carry out cracking reaction 0.15 time, and oil gas separates at settling vessel with the catalyzer for the treatment of charcoal, and product separates in separation system, thereby obtains propylene and C
3-C
5Hydro carbons, C
3-C
5Hydro carbons carries out freshening, and light aroamtic hydrocarbon raw material is through selective hydrogenation, hydrogen dividing potential drop 3.0MPa (absolute pressure), 200 ℃ of temperature of reaction, hydrogen to oil volume ratio 300Nm
3/ m
3, volume space velocity 5h
-1, obtain the selective hydrogenation petroleum naphtha; Deliver to light Aromatics Extractive Project unit, extraction temperature is 80 ℃, volume ratio between solvent and the raw material is 3.0, tell stable hydrocarbon and aromatic hydrocarbons, the stable hydrocarbon conduct is cracking stock again, heavy oil feedstock is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1000v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, hydrogenation heavy oil and raw material behind the hydrogenation are mixed into riser reactor.Operational condition and product distribute and list in table 2.
As can be seen from Table 2, propene yield is up to 44.34 heavy %, and ethylene yield only is 2.46 heavy %, and toluene and dimethylbenzene yield are respectively 6.87 heavy % and 11.58 heavy %, and slurry oil and coke yield sum only have 7.55 heavy %, thereby realize that petroleum resources efficiently utilize.
This embodiment is identical with embodiment 1 device flow process, and stock oil B directly as the raw material of catalytic pyrolysis, is being tested by the middle-scale device of riser reactor.Light aromatic hydrocarbons is raffinated oil and C
3-C
5Hydro carbons enters reaction zone I bottom, and at reaction zone I, light aromatic hydrocarbons is raffinated oil and C
3-C
5Hydro carbons is at 680 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, the weight ratio 60 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction 0.25 time; 160～260 ℃ cut injects the bottom of reaction zone II, and at reaction zone II, 160～260 ℃ cut is at 640 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 30 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.20 condition; Hydrogenation heavy oil and stock oil B enter reaction zone III bottom, take out the steam stripped reclaimable catalyst of part from stripping stage simultaneously and add to reaction zone III bottom, with temperature and the reaction weight hourly space velocity that reduces reaction zone III.At reaction zone III, oil gas is at 550 ℃ of temperature of reaction, weight hourly space velocity 20h
-1, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.15 condition, and oil gas separates at settling vessel with the catalyzer for the treatment of charcoal, and product separates in separation system, thereby obtains propylene and C
3-C
5Hydro carbons, C
3-C
5Hydro carbons carries out freshening, and light aroamtic hydrocarbon raw material is through selective hydrogenation, hydrogen dividing potential drop 3.0MPa (absolute pressure), 200 ℃ of temperature of reaction, hydrogen to oil volume ratio 300Nm
3/ m
3, volume space velocity 5h
-1, obtain the selective hydrogenation petroleum naphtha; Deliver to light Aromatics Extractive Project unit, extraction temperature is 80 ℃, volume ratio between solvent and the raw material is 3.0, tell stable hydrocarbon and aromatic hydrocarbons, the stable hydrocarbon conduct is cracking stock again, heavy oil feedstock is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1000v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, hydrogenation heavy oil and raw material behind the hydrogenation are mixed into riser reactor.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, propene yield is up to 43.32 heavy %, and toluene and dimethylbenzene yield are respectively 7.56 heavy % and 12.13 heavy %, and slurry oil and coke yield sum only have 9.05 heavy %, thereby realizes that petroleum resources efficiently utilize.
This embodiment is identical with embodiment 1 device flow process, and stock oil B directly as the raw material of catalytic pyrolysis, is being tested by the middle-scale device of riser reactor.Light aromatic hydrocarbons is raffinated oil and C
3-C
5Hydro carbons enters reaction zone I bottom, and at reaction zone I, light aromatic hydrocarbons is raffinated oil and C
3-C
5Hydro carbons is at 680 ℃ of temperature of reaction, weight hourly space velocity 180h
-1, the weight ratio 60 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.25 condition; 160～260 ℃ cut injects the bottom of reaction zone II, and at reaction zone II, 160～260 ℃ cut is at 640 ℃ of temperature of reaction, weight hourly space velocity 100h
-1, the weight ratio 30 of catalytic cracking catalyst and raw material, the weight ratio of water vapor and raw material are to carry out cracking reaction under 0.20 condition; Hydrogenation heavy oil and stock oil B enter reaction zone III bottom, take out the part hot regenerated catalyst from revivifier simultaneously and add to reaction zone III bottom, with temperature and the reaction weight hourly space velocity that increases reaction zone III.At reaction zone III, oil gas is at 550 ℃ of temperature of reaction, weight hourly space velocity 20h
-1, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.15 condition, and oil gas separates at settling vessel with the catalyzer for the treatment of charcoal, and product separates in separation system, thereby obtains propylene and C
3-C
5Hydro carbons, C
3-C
5Hydro carbons carries out freshening, light aroamtic hydrocarbon raw material is through Sulfolane Extraction, extraction temperature is 80 ℃, volume ratio between solvent and the raw material is 3.0, tell stable hydrocarbon and aromatic hydrocarbons, the stable hydrocarbon conduct is cracking stock again, and heavy oil feedstock is through hydrotreatment, at hydrogen dividing potential drop 18.0MPa, 350 ℃ of temperature of reaction, hydrogen to oil volume ratio 1000v/v, volume space velocity 1.5h
-1Reaction conditions under carry out hydrotreatment, hydrogenation heavy oil and raw material behind the hydrogenation are mixed into riser reactor.Operational condition and product distribute and list in table 3.
As can be seen from Table 3, propene yield is 43.65 heavy %, and toluene and dimethylbenzene yield are respectively 7.79 heavy % and 12.40 heavy %, and slurry oil and coke yield sum only have 8.99 heavy %, thereby realizes that petroleum resources efficiently utilize.
Embodiment 4
This embodiment and embodiment 2 device flow processs are basic identical, the stock oil that adopts also is identical, just the ethene that produces of cat-cracker and butylene enter transposable element and carry out metathesis reaction and generate propylene, under 250 ℃ of temperature of reaction ethene and butylene are converted into propylene.Operational condition and product distribute and list in table 4.
As can be seen from Table 4, propene yield is up to 48.80 heavy %, and slurry oil and coke yield sum only have 9.09 heavy %, thereby realizes that petroleum resources efficiently utilize.
Table 1
| The stock oil numbering | A | B |
| Stock oil character | ||
| Density (20 ℃), g/cm 3 | 0.8886 | 0.9134 |
| Sulphur content, ppm | 4700 | 5800 |
| Nitrogen content, ppm | 1600 | 2900 |
| Aromatic hydrocarbons, heavy % | 26.3 | 32.6 |
| C, heavy % | 86.46 | 86.23 |
| H, heavy % | 12.86 | 12.69 |
| Boiling range (ASTM D-1160), ℃ | ||
| IBP | 312 | 327 |
| 10％ | 361 | 363 |
| 30％ | 412 | 409 |
| 50％ | 452 | 450 |
| 70％ | 478 | 482 |
| 90％ | 506 | 504 |
| 95％ | 532 | 526 |
| EP | 546 | 542 |
Table 2
| Embodiment 1 | |
| The stock oil numbering | A |
| The catalytic pyrolysis unit | |
| Operational condition | |
| Riser tube | |
| Outlet temperature of riser, ℃ | 550 |
| Reaction zone I | |
| Temperature of reaction, ℃ | 680 |
| Agent-oil ratio, m/m | 60 |
| Water vapor/raw material weight ratio | 0.25 |
| Reaction zone II | |
| Temperature of reaction, ℃ | 640 |
| Agent-oil ratio, m/ |
30 |
| Water vapor/raw material weight ratio | 0.20 |
| Reaction zone III/ fluidized-bed | |
| Temperature of reaction, ℃ | 550 |
| Weight hourly space velocity, |
30 |
| Water vapor/raw material weight ratio | 0.15 |
| Product distributes, heavy % | |
| H 2+CH 4 | 2.20 |
| Ethene | 2.46 |
| Propylene | 44.34 |
| Ethane+propane | 4.78 |
| C 4 | 17.72 |
| Benzene | 2.5 |
| Toluene | 6.87 |
| Dimethylbenzene | 11.58 |
| Slurry oil | 1.50 |
| Coke | 6.05 |
Table 3
| |
|
|
| The stock oil numbering | B | B |
| The catalytic pyrolysis unit | ||
| Operational condition | ||
| Riser tube | ||
| Outlet temperature of riser, ℃ | 530 | 550 |
| Reaction zone I | ||
| Temperature of reaction | 680 | 680 |
| Agent-oil ratio, m/m | 60 | 60 |
| Water vapor/raw material weight ratio | 0.25 | 0.25 |
| Reaction zone II | ||
| Temperature of reaction, ℃ | 640 | 640 |
| Agent-oil ratio, m/ |
30 | 30 |
| Water vapor/raw material weight ratio | 0.20 | 0.20 |
| Reaction zone III/ fluidized-bed | ||
| Temperature of reaction, ℃ | 550 | 550 |
| Weight hourly space velocity, |
20 | 20 |
| Water vapor/raw material weight ratio | 0.15 | 0.15 |
| Product distributes, heavy % | ||
| H 2+CH 4 | 2.00 | 2.25 |
| Ethene | 2.30 | 2.41 |
| Propylene | 43.32 | 43.65 |
| Ethane+propane | 4.27 | 3.79 |
| C 4 | 16.62 | 15.62 |
| Benzene | 2.7 | 3.1 |
| Toluene | 7.56 | 7.79 |
| Dimethylbenzene | 12.13 | 12.40 |
| Slurry oil | 2.55 | 2.18 |
| Coke | 6.55 | 6.81 |
Table 4
| Embodiment 4 | |
| The stock oil numbering | B |
| The catalytic pyrolysis unit | |
| Operational condition | |
| Riser tube | |
| Outlet temperature of riser, ℃ | 550 |
| Reaction zone I | |
| Temperature of reaction, ℃ | 680 |
| Agent-oil ratio, m/m | 60 |
| Water vapor/raw material weight ratio | 0.25 |
| Reaction zone II | |
| Temperature of reaction | 640 |
| Agent-oil ratio, m/ |
30 |
| Water vapor/raw material weight ratio | 0.20 |
| Reaction zone III/ fluidized-bed | |
| Temperature of reaction, ℃ | 550 |
| Weight hourly space velocity, |
20 |
| Water vapor/raw material weight ratio | 0.15 |
| The metathesis reaction unit | |
| Temperature of reaction, ℃ | 250 |
| Product distributes, heavy % | |
| H 2+CH 4 | 2.10 |
| Ethane+propane | 4.1 |
| Propylene | 48.80 |
| C 4 | 12.52 |
| Benzene | 3.2 |
| Toluene | 7.89 |
| Dimethylbenzene | 12.30 |
| Slurry oil | 2.5 |
| Coke | 6.59 |
Claims (13)
1. the catalysis conversion method of a preparing propone and aromatic hydrocarbons is characterized in that the method comprises the following steps:
(1), the raw material of type three contacts with hot regeneration catalyzing catalyst for cracking first, at 650 ℃-800 ℃ of temperature of reaction, weight hourly space velocity 100h
-1-800h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 30-150, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0, the raw material of described type three is embarrassed cracking stock, during being selected from carbonatoms is 4～8 alkane, gently aromatic hydrocarbons is raffinated oil more than one, wherein said carbonatoms is that 4～8 alkane install from this, perhaps conventional catalytic cracking, coking, thermally splitting, hydrogenation unit;
(2), the reaction effluent of step (1) separates without finish, mixes with the raw material of type two, the raw material of type two is at 550 ℃-720 ℃ of temperature of reaction, weight hourly space velocity 10h
-1-300h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 10-100, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0, the raw material of described type two is more difficult cracking stock, is selected from slurry oil, diesel oil, gasoline, carbonatoms and is the alkene of 4-8, in the cut that boiling range is 160～260 ℃ more than one;
(3), the reaction effluent of step (2) mixes with the raw material of type one again, the stock oil of type one is at 450 ℃-620 ℃ of temperature of reaction, weight hourly space velocity 0.1h
-1-100h
-1, reaction pressure 0.10MPa-1.0MPa (absolute pressure), catalytic cracking catalyst and raw material weight ratio 1.0-30, the weight ratio of water vapor and raw material is to carry out cracking reaction under the condition of 0.05-1.0, the raw material of described type one is easy cracking stock, be selected from petroleum hydrocarbon and/or other mineral oil, its Petroleum Hydrocarbon is selected from raffinating oil more than one of vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, heavy aromatics; Other mineral oil is liquefied coal coil, tar sand oil, shale oil;
(4), reclaimable catalyst and the reaction oil gas of separating step (3), reclaimable catalyst is Returning reactor after regeneration, separating reaction oil gas is isolated to purpose product propylene, aromatic hydrocarbons, again cracking stock and heavy oil feedstock.
(5), step (4) heavy oil feedstock under there is situation in hydrogen, contact with hydrotreating catalyst, 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
-1Reaction conditions under carry out hydrotreatment, resulting hydrogenation heavy oil can be used as the stock oil of step (3) or the stock oil of conventional catalytic cracking unit.
2. according to the method for claim 1, it is characterized in that the described gasoline of step (2) is selected from more than one in the method gained catalytic cracking gasoline of claim 1, catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, the hydrogenated gasoline, wherein catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline, hydrogenated gasoline are from the outer gasoline of this device.
3. according to the method for claim 1, it is characterized in that the described diesel oil of step (2) is more than one in the method gained catalytic pyrolysis diesel oil that is selected from claim 1, catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, the hydrogenated diesel oil, wherein catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, thermally splitting diesel oil, hydrogenated diesel oil are from the outer diesel oil of this device.
4. according to the method for claim 1, it is characterized in that the described carbonatoms of step (2) is that 4～8 alkene installs from this, perhaps conventional catalytic cracking, coking, thermally splitting, hydrogenation unit.
5. according to the method for claim 1, the raw material that it is characterized in that the described type two of described step (2) is that boiling range is 160～260 ℃ cut.
6. according to the method for claim 5, the raw material that it is characterized in that the described type two of step (2) is that boiling range is 170～250 ℃ cut.
7. according to the method for claim 1 or 5, it is characterized in that the described boiling range of step (2) is that 160～260 ℃ cut, 170～250 ℃ cut install from this, perhaps conventional catalytic cracking, coking, thermally splitting, hydrogenation unit.
8. according to the method for claim 1, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each component accounts for respectively total catalyst weight: the heavy % of zeolite 1 heavy %-50, the heavy % of inorganic oxide 5 heavy %-99, the heavy % of clay 0 heavy %-70, its mesolite is mesopore zeolite and optional large pore zeolite, mesopore zeolite accounts for the heavy % of 50 heavy %-100 of zeolite gross weight, large pore zeolite accounts for the heavy % of 0 heavy %-50 of zeolite gross weight, mesopore zeolite is selected from ZSM series zeolite and/or ZRP zeolite, and large pore zeolite is selected from the Y-series zeolite.
9. according to the method for claim 1, it is characterized in that used reactor be selected from riser tube, etc. one or both series combinations in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, wherein riser tube is conventional isodiametric riser tube or the riser tube of various forms reducing.
10. according to the method for claim 1, the raw material that it is characterized in that the described again cracking of step (4) be selected from that boiling range is 160～260 ℃ cut, light aromatic hydrocarbons is raffinated oil and hydrogenation heavy oil in more than one.
11. the method according to claim 1 or 10; it is characterized in that described light aromatic hydrocarbons raffinate oil be boiling range be C6～160 ℃ cut first after selective hydrogenation again through the solvent extraction gained; the solvent of light Aromatics Extractive Project is selected from by in tetramethylene sulfone, N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, TEG, dimethyl sulfoxide (DMSO) and the N-formyl morpholine ether more than one; the temperature of solvent extraction is 40-120 ℃, and the volume ratio between solvent and the solvent extraction raw material is 2-6.
12. according to the method for claim 1, it is characterized in that described hydrotreating catalyst is group vib metal and/or the VIII family metal catalyst that loads on aluminum oxide and/or the amorphous silicon aluminium carrier.
13. according to the method for claim 1, it is characterized in that ethene that step (4) is separated and butylene at temperature 10-450 ℃, pressure 0.1-3.0MPa, butylene weight space velocity 0.01-3h
-1, ethylene/butylene is than obtaining purpose product propylene for contacting the generation metathesis reaction with metathesis catalyst under the 0.2-10 condition.
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