CN101045884A - Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil - Google Patents
Process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil Download PDFInfo
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Abstract
The process of producing clean diesel oil and low carbon olefin with residual oil and heavy fraction oil includes: deasphalting residual oil through mixing residual oil and optional catalytic cracking oil slurry in a solvent deasphalting unit; hydrocracking of the deasphalted oil and optional heavy fraction oil with hydrogen in a hydrogenating unit and separating the products to obtain light and heavy naphtha fraction, diesel oil fraction and hydrogenated tail oil; catalytically cracking the hydrogenated tail oil in a catalytically cracking unit and separating products to obtain low carbon olefin, gasoline fraction, diesel oil fraction and oil slurry; returning all the catalytically cracked diesel oil fraction to the catalytically cracking reactor and returning all or partial catalytically cracked oil slurry to the solvent deasphalting unit. The process has high yield of clean diesel oil and low carbon olefin and high quality of the diesel oil product.
Description
Technical field
The invention belongs to a hydroprocessing technique process, one does not exist catalytic cracking step under the situation of hydrogen and one treating process under the situation that does not have hydrogen to handle the multistage processes of hydrocarbon ils, more particularly, be a kind of method that residual oil solvent deasphalting, heavy distillate hydrocracking and three kinds of technological processs of hydrogenation tail oil catalytic pyrolysis is organically combined production clean diesel and low-carbon alkene.
Background technology
Chinese national economy is expected to keep the quick growth more than 20 years, and statistic data shows, if GDP growth 1%, then the oil product demand growth 0.5%, petroleum chemicals demand growth 1%.As seen, following oil product and petroleum chemicals demand all will maintain sustained and rapid growth, and wherein the speed of petroleum chemicals demand growth is far above oil product.Limited crude resources and how maximum ground obtain to produce between the basic material (as ethene and aromatic hydrocarbons etc.) of petroleum chemicals, will become the conspicuous contradiction that following for some time petrochemical industry must be faced.
The development of following Chinese petroleum refining industry will be combined closely with ethene, fibrous material industrial development, put forth effort to realize that oil-refining chemical is integrated, improve the whole competitiveness of petrochemical industry.Chemical industry light oil is one of oiling bonded key, and in the chemical industry light oil of home consumption, about 78% is used to produce ethene at present, and about 17% is used to produce p-Xylol.According to the economic target of constructing well-off society, the occupancy volume per person of Chemicals will have very big growth, and this is directly connected to the demand of industrial chemicals.Estimate that Chinese ethene ability in 2007 will reach about 1,100 ten thousand tons, leap to the 2nd in the world; 2010 and the year two thousand twenty whole nation ethene ability will reach ten thousand tons of 1,400 ten thousand tons and 2200-2400 respectively.In addition, estimate that 2010 terephthalic acids (PTA) ability will reach 7,660,000 tons.Estimate that 2010 domestic chemical industry light oil demands are about about 5,300 ten thousand tons, ten thousand tons of the about 8400-9000 of the year two thousand twenty.After bigger growth appearred in the chemical industry light oil demand, the mode that relies on domestic refinery to increase crude runs was difficult to satisfy its demand.
Meanwhile, the Middle East is that the ethylene cracker of raw material puts into operation on a large scale with ethane, and its ethylene yield height, production cost are very low, for China's ethylene production very big impact are arranged; But such device does not produce propylene substantially, causes ethene and propylene supply unbalanced situation to occur.Therefore, producing industrial chemicals such as low-carbon alkene, aromatic hydrocarbons by oil refining apparatus from heavy feed stock, is to solve the insufficient only way of chemical industry light oil.
WO0031215 discloses a kind of catalyst cracking method of producing alkene, this method is raw material with the vacuum gas oil, the catalyzer that adopts is made up of matrix and ZSM series molecular sieve, its mesostroma partly comprises inert base and a small amount of active matrix, molecular sieve then adopts large pore molecular sieve, the yield of light olefins of this method can surpass 13 heavy %, than conventional catalyst cracking method height.
WO0040677 discloses the combined technical method of a kind of hydrotreatment and catalytic cracking.This method comprises at least two hydrotreaters and two catalytic cracking unit.Stock oil obtains first hydrogenation tail oil through first hydrotreater earlier; First hydrogenation tail oil enters first catalytic cracking unit, obtain petroleum naphtha, diesel oil and heavy oil, wherein heavy oil enters second hydrotreater and carries out hydrogenation, obtains second hydrogenation tail oil, second hydrogenation tail oil to the second catalytic cracking unit carried out cracking, obtains corresponding product again.This method flow complexity, investment and running cost height, productivity of propylene is lower.
CN1171978C has announced a kind of process for transforming high-sulfur high-metal residual oil.This method is that whole organic assembling has been carried out in solvent deasphalting, hydrotreatment and catalytic cracking by adopting partial material round-robin method, can reduce investment and process cost by a relatively large margin, has improved the yield and the quality of lightweight oil.But this method is the main purpose product with light Fuels such as gasoline, diesel oil, and productivity of low carbon olefin hydrocarbon is very low.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of producing clean diesel and low-carbon alkene by residual oil and heavy distillate.
Method provided by the invention comprises the following steps:
(1) residual oil enters the solvent deasphalting unit with optional from the unitary slurry oil of catalytic pyrolysis, obtains de-oiled asphalt and deasphalted oil after low molecular solvent is carried out solvent extraction;
(2) deasphalted oil enters hydrogenation unit with the heavy distillate of choosing wantonly, contact with hydrocracking catalyst with Hydrobon catalyst successively in the presence of hydrogen and carry out hydrofining reaction and hydrocracking reaction, reaction product isolated obtains light naphtha fraction, heavy naphtha fraction, diesel oil distillate and hydrogenation tail oil;
(3) hydrogenation tail oil enters the catalytic pyrolysis unit, under the effect of catalytic cracking catalyst, carry out scission reaction, reaction product isolated obtains low-carbon alkene, gasoline fraction, diesel oil distillate and slurry oils such as ethene, propylene, wherein whole catalytic pyrolysis diesel oil distillates loop back the catalytic cracking reaction device, and all or part of catalytic cracking slurry oil returns the solvent deasphalting unit.
Adopt method provided by the invention can be produced the clean diesel of low-carbon alkene such as propylene, ethene and low-sulfurs, low aromatic hydrocarbons, high hexadecane value by residual oil and heavy distillate maximum ground, wherein propene yield is greater than 27 heavy %, and diesel oil can reach Europe IV emission standard.In addition, distillate that can also other high value of by-product, as be rich in the pyrolysis gasoline cut fraction of aromatic hydrocarbons, it can produce aromatic hydrocarbons such as obtaining benzene,toluene,xylene.
Accompanying drawing is a methodological principle schematic flow sheet of being produced clean diesel and low-carbon alkene by residual oil and heavy distillate provided by the present invention.
Embodiment
Method provided by the invention is so concrete enforcement:
(1) solvent deasphalting unit
Residual oil enters the solvent deasphalting unit with optional from the unitary slurry oil of catalytic pyrolysis, obtains de-oiled asphalt and deasphalted oil after low molecular solvent is carried out solvent extraction.Described residual oil is long residuum and/or vacuum residuum, preferred vacuum residuum.Described low molecular solvent is a kind of or its mixture that is selected from C3～C8 alkane or alkene, condensate oil, light naphthar, the petroleum naphtha.The principle of solvent deasphalting is to utilize low molecular solvent that naphthenic hydrocarbon, alkane and low molecule aromatic hydrocarbon are had sizable solubleness, to colloid, bituminous matter then indissoluble or insoluble,practically characteristic, colloid, bituminous matter is removed in vacuum residuum and circulation slurry oil.Because the contained heavy metal overwhelming majority is present in its colloid, the bituminous matter in the vacuum residuum, so also just sloughed metals such as most of nickel, vanadium in the deasphalting process simultaneously.The composition of the resulting de-oiled asphalt of solvent deasphalting is based on bituminous matter and colloid, and contains polycyclic aromatic hydrocarbons, can be used for producing road bitumen, gas making or generating.
The solvent deasphalting unit mainly comprises extracting part and solvent recuperation part: vacuum residuum and catalytic pyrolysis circulation slurry oil carry out extracting under the undercritical conditions of solvent, promptly service temperature and pressure are lower than the critical temperature and the emergent pressure of solvent respectively; Solvent in the deasphalted oil solution reclaims by critical recovery, flash distillation and steam stripped method successively; Solvent in the de-oiled asphalt solution reclaims by flash distillation and steam stripped method successively.The main operational condition of extracting part is: 50～280 ℃ of extraction temperatures, and extraction tower pressure 1.0～6.0MPa, solvent ratio is 1～15v/v.
The unitary slurry oil of catalytic pyrolysis contains a certain amount of alkane and low condensation aromatic hydrocarbons and a large amount of high condensed aromatics, though high condensed aromatics is the green coke precursor, it is again the blend component of high-quality asphalt simultaneously.Therefore, with catalytic cracking slurry oil with after vacuum residuum mixes jointly as the unitary charging of solvent deasphalting, not only can make full use of valuable component in the slurry oil, and the catalytic cracking catalyst powder in the energy effective elimination slurry oil, avoid it to be deposited on and cause reactor pressure decrease to rise in the unitary reactor of follow-up hydrogenation.The relative molecular weight of catalytic pyrolysis circulation slurry oil is littler than the relative molecular weight of vacuum residuum, but its aromaticity is very strong, especially the content of condensed-nuclei aromatics is very high, relative molecular weight makes solubleness increase for a short time, aromaticity forces solubleness to reduce, and its net effect is that the solubleness of vacuum residuum in solvent of mixing behind the slurry oil reduces.Therefore, catalytic pyrolysis circulation slurry oil advances the viscosity that deasphalting unit both can reduce vacuum residuum, can improve the deasphalted oil yield again, can also improve deasphalted oil character and asphalt quality.
(2) hydrogenation unit
Enter hydrogenation unit from unitary deasphalted oil of solvent deasphalting and the heavy distillate of choosing wantonly, in the presence of hydrogen, contact with Hydrobon catalyst earlier, 280～450 ℃ of temperature of reaction, hydrogen dividing potential drop 3.0～15.0MPa, volume space velocity 0.2～10.0h
-1, hydrogen to oil volume ratio 200～3000Nm
3/ m
3Reaction conditions under, carry out hydrogenating desulfurization, hydrodenitrification, aromatic hydrocarbons is saturated and a spot of olefin saturation.Its resultant of reaction contacts with hydrocracking catalyst without separating, 300～450 ℃ of temperature of reaction, and hydrogen dividing potential drop 3.0～15.0MPa, volume space velocity 0.1～10.0h
-1, hydrogen to oil volume ratio 300～3000Nm
3/ m
3Reaction conditions under, carry out the reaction that cracking, open loop and isomery equimolecular structure change, its reaction effluent obtains hydrogen-rich gas and liquid product after refrigerated separation.Hydrogen-rich gas recycles as recycle hydrogen, and liquid product obtains light naphtha fraction, heavy naphtha fraction, diesel oil distillate and hydrogenation tail oil after fractionating system is separated.
Described heavy distillate is vacuum gas oil or coker gas oil or their mixture.Preferred vacuum gas oil, its boiling range is generally 350 ℃～600 ℃.
Hydrobon catalyst can be seated in the different beds of reactor with hydrocracking catalyst, also can be seated in respectively in two reactors, and the reaction effluent between each reactor does not separate.A plurality of beds are arranged in the reactor, use the mode of annotating cold hydrogen between each bed to control bed temperature.In the hydrogenation protecting agent of Hydrobon catalyst bed top loading some amount, to remove metal and the carbon residue in the charging, delay the speed that the beds pressure drop is risen, and prevent that the downstream Hydrobon catalyst is because of deposition heavy metal inactivation.The hydrogenation protecting agent is 1: 20～1: 4 with the admission space ratio of Hydrobon catalyst, and the two definite filling ratio is decided on carbon residue, metal and asphalt content in the hydrogenation unit feed oil.
Described Hydrobon catalyst is a loaded catalyst, its carrier is unformed aluminum oxide and/or sial, the metal component of load is group vib metal and/or VIII family base metal, preferred molybdenum of the metal of group vib and/or tungsten, preferred cobalt of the base metal of VIII family and/or nickel.
Described hydrocracking catalyst is a kind of by zeolite and the carrier loaded at least a group VIII of aluminum oxide composite molding and the metal component of at least a group vib and the catalyzer of organic additive.Consisting of of preferred hydrocracking catalyst: with the catalyzer benchmark, zeolite 3～60 heavy %, aluminum oxide 10～80 heavy %, nickel oxide 1～15 heavy %, Tungsten oxide 99.999 5～40 heavy %, organic additive content are 0.1～40 heavy %.Described zeolite is selected from, and described organic additive is selected from and contains in oxygen or the nitrogenous organism one or more.Described oxygenatedchemicals is selected from one or more in organic alcohol, the organic acid, and nitrogenous compound is an organic amine.Used hydrocracking catalyst is by coordinating the function of metal component and carrier, strengthened its selective opening ability, can make the hydrocarbon system of heavy feed stock form the generation considerable change, wherein the content of stable hydrocarbon such as paraffinic hydrocarbons, naphthenic hydrocarbon increases greatly, the aromatic hydrocarbons especially content of polycyclic aromatic hydrocarbons reduces, and makes the hydrogen richness of hydrogenation tail oil be improved significantly.
Deasphalted oil is compared with vacuum gas oil, and not only cut is heavier, and carbon residue, metal and bituminous matter equal size all are higher than the latter.High carbon residue content easily causes the quick coking of hydrogenation catalyst, causes the quick rise of the inactivation and the hydrogenator bed pressure drop of hydrogenation catalyst; Metal deposition also is to cause bed pressure drop another reason that goes up, and metal blocking catalyst duct can cause the permanent inactivation of catalyzer; Bituminous matter causes very easily that as the coking precursor micropore in the hydrogenation catalyst stops up, and causes rapid inactivation.Therefore present method has adopted rational catalyst grating mode, and has adopted the strong hydrocracking catalyst of anti-poisoning capability in order to alleviate the processing bed pressure drop fast rise that deasphalted oil brought and the problems such as inactivation of hydrogenation catalyst.In addition, owing to selected aromatic hydrogenation activity height and the high hydrocracking catalyst of open loop cracking selectivity for use, deasphalted oil and optional bad heavy distillate can be converted into the hydrogenation tail oil that foreign matter content is low, hydrogen richness is high to greatest extent, distillate that can also other high value of by-product, for example the light naphtha fraction sulphur content of gained is low, be fine hydrogen feedstock or preparing ethylene by steam cracking raw material also be the blending component of low-sulphur oil; It is high that heavy naphtha fraction sulphur and nitrogen content are low, virtue is dived, and is the high quality raw material of catalytic reforming; Diesel oil distillate sulphur and aromaticity content are low, cetane value is high, are the fine clean diesels, can reach Europe IV emission standard.
(3) catalytic pyrolysis unit
Hydrogenation tail oil from hydrogenation unit enters the catalytic pyrolysis unit, under the effect of catalytic cracking catalyst, carry out scission reaction, reaction product isolated obtains low-carbon alkene, gasoline fraction, diesel oil distillate and slurry oils such as ethene, propylene, wherein whole catalytic pyrolysis diesel oil distillates loop back the catalytic cracking reaction device, and all or part of catalytic cracking slurry oil returns the solvent deasphalting unit.Pyrolysis gasoline cut fraction is rich in aromatic hydrocarbons, can be used for producing aromatic hydrocarbons such as benzene,toluene,xylene, and diesel oil distillate can be kept catalytic pyrolysis unit thermal equilibrium and increase production alkene simultaneously as recycle stock.
The catalytic cracking reaction device that adopts is the compound reactor of any reactor or any two combination of reactors in riser reactor, fluidized-bed reactor or the moving-burden bed reactor, wherein the compound reactor of any two combination of reactors comprise the compound reactor that constitutes by riser tube and fluidized-bed, the compound reactor that constitutes by two or more riser tubes, the compound reactor that constitutes by two or more fluidized-beds, the compound reactor that constitutes by two or more moving-beds.Above-mentioned reactor can use existing catalyst cracker, also can carry out necessary transformation to existing catalyst cracker, can also use and the similar reactor of existing catalyst cracker 26S Proteasome Structure and Function.Catalytic cracking catalyst in each reactor in the compound reactor can be identical, also can be different.
The reaction conditions of riser reactor is: the weight ratio 0.1～0.6 of weight ratio 5～40, water vapor and the catalytic pyrolysis stock oil of 500～650 ℃ of temperature of reaction, reaction pressure (absolute pressure) 0.10～0.50MPa, 1～10 second residence time, catalytic cracking catalyst and catalytic pyrolysis stock oil.The fluidized-bed in fluidized-bed reactor, moving-burden bed reactor, the compound reactor and/or the reaction conditions of moving-bed are: 500～650 ℃ of temperature of reaction, reaction pressure (absolute pressure) 0.10～0.50MPa, air speed 1.0～20.0h
-1, catalytic cracking catalyst and catalytic pyrolysis stock oil the weight ratio 0.1～0.6 of weight ratio 5～40, water vapor and catalytic pyrolysis stock oil.
Described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each components contents is respectively: zeolite 15～60 heavy %, inorganic oxide 5～85 heavy %, clay 0～70 heavy %, its mesolite is the mixture of mesopore zeolite and the y-type zeolite of choosing wantonly, mesopore zeolite is selected from the ZSM series zeolite, i.e. the mixture of 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.Y-type zeolite is selected from one or more the mixture among Rare Earth Y (REY), rare earth hydrogen Y (REHY), super steady Y and the high silicon Y.Inorganic oxide is selected from silicon-dioxide and/or aluminium sesquioxide as binding agent.Clay is selected from kaolin and/or halloysite as carrier.
Below in conjunction with accompanying drawing method provided by the invention is further detailed, but does not therefore limit the present invention.
Accompanying drawing is a methodological principle schematic flow sheet of being produced clean diesel and low-carbon alkene by residual oil and heavy distillate provided by the invention.
The method flow of producing clean diesel and low-carbon alkene by residual oil and heavy distillate provided by the present invention is: enter solvent deasphalting unit 2 after mixing from the vacuum residuum of pipeline 1 and the optional catalytic cracking slurry oil from pipeline 18, after low molecular solvent extracting, obtain de-oiled asphalt and deasphalted oil from pipeline 19, wherein de-oiled asphalt is through pipeline 3 withdrawing devices, deasphalted oil is extracted out and is entered hydrogenation unit 7 after heavy distillate from pipeline 5 mixes through pipeline 4, in the presence of hydrogen from pipeline 6, contact Hydrobon catalyst successively and hydrocracking catalyst reacts, the light naphtha fraction of its reaction effluent gained after separating, heavy naphtha fraction, diesel oil distillate and hydrogenation tail oil are respectively through pipeline 8,9,10,11 extract out.Hydrogenation tail oil enters the catalytic pyrolysis unit through pipeline 11, under the effect of catalytic cracking catalyst, carry out catalytic cracking reaction, reaction product isolated obtains low-carbon alkene, gasoline fraction, turning oil and slurry oil, low-carbon alkene and gasoline fraction are extracted out through pipeline 13 and 14 respectively, turning oil loops back the catalytic pyrolysis unit through pipeline 15, slurry oil is divided into two-way after pipeline 16 is extracted out, the one tunnel is circulated back to the solvent deasphalting unit, another route pipeline 17 withdrawing devices through pipeline 18.
The present invention organically combines solvent deasphalting unit, hydrogenation unit and catalytic pyrolysis unit, by the rational proportion of catalyzer, the choose reasonable of reaction conditions and the optimum combination of flow process, heavy feed stock is converted into industrial chemicals to greatest extent, for the refinery provides a kind of by the effective ways of single oil refining to production industrial chemicals and development of high added value derived product and extension.
Adopt method provided by the invention, can be produced the clean diesel of low-carbon alkene such as propylene, ethene and low-sulfurs, low aromatic hydrocarbons, high hexadecane value by residual oil and heavy distillate maximum ground, wherein propene yield is greater than 27 heavy %, and diesel oil can reach Europe IV emission standard.In addition, distillate that can also other high value of by-product, as be rich in the pyrolysis gasoline cut fraction of aromatic hydrocarbons, it can produce aromatic hydrocarbons such as obtaining benzene,toluene,xylene; The light naphtha fraction sulphur content is low, be fine hydrogen feedstock or preparing ethylene by steam cracking raw material also be the blending component of low-sulphur oil; It is high that heavy naphtha fraction sulphur and nitrogen content are low, virtue is dived, and is the high quality raw material of catalytic reforming.
The used Hydrobon catalyst and the trade names of hydrocracking catalyst are respectively RN-2 and RHC-1 among the embodiment, produce by Sinopec catalyzer branch office Chang Ling catalyst plant.The trade names of used catalytic cracking catalyst are MMC-2 among the embodiment, are produced by Sinopec catalyzer branch office Shandong catalyst plant.
The used raw material of present embodiment is a vacuum residuum and mixture from catalytic pyrolysis unit slurry oil, and mixing raw material character is as shown in table 1.Mixing raw material and iso-pentane solvent enter from the upper and lower of extraction tower respectively, carry out counter current contact in extraction tower, 180 ℃ of extracting tower top temperatures, and extraction tower pressure 4.0MPa, solvent ratio 6.0v/v carries out one section extracting under the condition of 30 minutes residence time.The liquid stream that comes out from the extraction tower top obtains deasphalted oil successively behind critical solvent recovery, flash distillation, stripping, the extraction tower bottoms obtains de-oiled asphalt through flash distillation, stripping after reclaiming solvent successively.The main character of gained deasphalted oil is as shown in table 1, and as can be seen from Table 1, the sulphur content of deasphalted oil is 2.0 heavy %, and metal content is 15.3 μ g/g, and asphalt content is 0.005 heavy %, and the yield of deasphalted oil is 67.2 heavy %.
The deasphalted oil that the used raw material of present embodiment obtains for embodiment 1 and a kind of vacuum gas oil are with 1: 1 mixed mixture of weight ratio, and vacuum gas oil character is as shown in table 2.This mixing raw material enters first hydrogenator and contacts with Hydrobon catalyst and react in the presence of hydrogen, reaction product is not separated and is entered second hydrogenator and contact with hydrocracking catalyst and react, its reaction effluent obtains light naphtha fraction, heavy naphtha fraction, diesel oil distillate and hydrogenation tail oil after cooling, separation and fractionation, reaction conditions and product main character are as shown in table 3.
As can be seen from Table 3, the light naphtha fraction sulphur content of gained＜1 μ g/g, be fine hydrogen feedstock or preparing ethylene by steam cracking raw material also be the blending component of low-sulphur oil; The heavy naphtha fraction sulphur of gained and nitrogen content less than 0.5 μ g/g and fragrant potential content height, are the high quality raw material of catalytic reforming all; The sulphur content of diesel fraction of gained is less than 10 μ g/g, and cetane value is 55, and polycyclic aromatic hydrocarbon content is fine clean diesels less than 5 heavy %, can reach Europe IV emission standard.The hydrogen richness of tail oil cut is the unitary high quality raw material of catalytic pyrolysis up to 13.9 heavy %.
Present embodiment with the hydrogenation tail oil of embodiment 2 gained as raw material, in fluidized-bed reactor, react, then product is separated, reaction product isolated obtains low-carbon alkene, gasoline fraction, diesel oil distillate and slurry oils such as ethene, propylene, wherein whole diesel oil distillates loops back the catalytic cracking reaction device, and all or part of slurry oil returns the solvent deasphalting unit.The operational condition of catalytic pyrolysis and product distribute as shown in table 4.As can be seen from Table 4, propylene and yield of ethene are respectively up to 27.3 heavy % and 10.6 heavy %.
Table 1
| Vacuum residuum+cracking slurry oil | Deasphalted oil | |
| Density (20 ℃), g/cm 3 | 1.0108 | 0.9398 |
| Sulphur content, heavy % | 4.3 | 2.0 |
| Nitrogen content, heavy % | 0.36 | 0.27 |
| Metal content, μ g/g | 120 | 15.3 |
| Bituminous matter, heavy % | 6.1 | 0.005 |
| Carbon residue, heavy % | 19.2 | 3.7 |
| Yield, heavy % | 67.2 | |
| Boiling range (ASTM D-1160), | ||
| 5％ | - | 455 |
| 30％ | - | 550 |
| 50％ | - | 584 |
| 70％ | - | 612 |
| 90％ | - | 655 |
| 95％ | - | 659 |
| Final boiling point | - | 682 |
Table 2
| Vacuum gas oil | Vacuum gas oil | ||
| Density (20 ℃), g/cm 3 | 0.9163 | Boiling range (D-1160), ℃ | |
| Sulphur content, heavy % | 1.8 | 5％ | 349 |
| Nitrogen content, heavy % | 0.11 | 30％ | 419 |
| Metal content, μ g/g | 1.1 | 50％ | 446 |
| Bituminous matter, heavy % | 23 | 95％ | 511 |
| Carbon residue, heavy % | 0.19 | Final boiling point | 562 |
Table 3
| Reaction conditions | Hydrofining | Hydrocracking |
| The hydrogen dividing potential drop, MPa | 14.0 | 14.0 |
| Temperature of reaction, ℃ | 375 | 375 |
| Volume space velocity, h -1 | 0.9 | 1.4 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 900 | 900 |
| Liquid product yield | ||
| Light naphtha fraction, heavy % | 0.5 | |
| Heavy naphtha fraction, heavy % | 8.1 | |
| Diesel oil distillate, heavy % | 27.1 | |
| Hydrogenation tail oil, heavy % | 64.3 | |
| The product main character | ||
| Light naphtha fraction | Heavy naphtha fraction | |
| Density, (20 ℃), g/cm 3 | 0.669 | 0.750 |
| Sulphur content, μ g/g | ＜1 | ＜0.5 |
| Nitrogen content, μ g/g | - | ＜0.5 |
| Virtue is dived, heavy % | 59 | |
| Diesel oil distillate | Hydrogenation tail oil | |
| Density, (20 ℃), g/cm 3 | 0.8331 | 0.8681 |
| Sulphur content, μ g/g | ＜30 | - |
| Cetane value | 55 | - |
| Polycyclic aromatic hydrocarbon content, heavy % | ＜5 | |
| Hydrogen richness, heavy % | - | 13.9 |
Table 4
| The catalytic cracking reaction condition | |
| Temperature of reaction, ℃ | 600 |
| Reaction pressure (absolute pressure), MPa | 0.195 |
| Air speed, h -1 | 6.0 |
| Agent- | 15 |
| Water vapor and stock oil weight ratio | 0.47 |
| The catalytic pyrolysis product distributes, heavy % | |
| H 2-C 2(disregarding ethene) | 5.30 |
| Ethene | 10.60 |
| C 3-C 4(disregarding propylene) | 9.90 |
| Propylene | 27.30 |
| C 5 +Gasoline | 27.00 |
| Diesel oil | 8.55 |
| Slurry oil | 5.15 |
| Coke | 6.20 |
Claims (11)
1, a kind of method of producing clean diesel and low-carbon alkene by residual oil and heavy distillate comprises the following steps:
(1) residual oil enters the solvent deasphalting unit with optional from the unitary slurry oil of catalytic pyrolysis, obtains de-oiled asphalt and deasphalted oil after low molecular solvent is carried out solvent extraction;
(2) deasphalted oil enters hydrogenation unit with the heavy distillate of choosing wantonly, contact with hydrocracking catalyst with Hydrobon catalyst successively in the presence of hydrogen and carry out hydrofining reaction and hydrocracking reaction, reaction product isolated obtains light naphtha fraction, heavy naphtha fraction, diesel oil distillate and hydrogenation tail oil;
(3) hydrogenation tail oil enters the catalytic pyrolysis unit, under the effect of catalytic cracking catalyst, carry out scission reaction, reaction product isolated obtains low-carbon alkene, gasoline fraction, diesel oil distillate and slurry oils such as ethene, propylene, wherein whole catalytic pyrolysis diesel oil distillates loop back the catalytic cracking reaction device, and all or part of catalytic cracking slurry oil returns the solvent deasphalting unit.
2,, it is characterized in that the unitary operational condition of described solvent deasphalting is: 50～280 ℃ of extraction temperatures, extraction tower pressure 1.0～6.0MPa, solvent ratio 1～15v/v according to the method for claim 1.
3,, it is characterized in that described low molecular solvent is a kind of or its mixture that is selected from C3～C8 alkane or alkene, condensate oil, light naphthar, the petroleum naphtha according to the method for claim 1.
4, according to the method for claim 1, it is characterized in that described residual oil is long residuum and/or vacuum residuum, described heavy distillate is vacuum gas oil and/or coker gas oil.
5,, it is characterized in that described hydrofining reaction condition is: 280～450 ℃ of temperature of reaction, hydrogen dividing potential drop 3.0～15.0MPa, volume space velocity 0.2～10.0h according to the method for claim 1
-1, hydrogen to oil volume ratio 200～3000Nm
3/ m
3The hydrocracking reaction condition is: 300～450 ℃ of temperature of reaction, hydrogen dividing potential drop 3.0～15.0MPa, volume space velocity 0.1～10.0h
-1, hydrogen to oil volume ratio 300～3000Nm
3/ m
3
6, according to the method for claim 1, it is characterized in that described hydrocracking catalyst is a kind of by zeolite and the carrier loaded at least a group VIII of aluminum oxide composite molding and the metal component of at least a group vib and the catalyzer of organic additive, described organic additive is selected from and contains in oxygen or the nitrogenous organism one or more.
7, according to the method for claim 1 or 6, it is characterized in that described hydrocracking catalyst, with the catalyzer benchmark, it consists of: zeolite molecular sieve 3～60 heavy %, aluminum oxide 10～80 heavy %, nickel oxide 1～15 heavy %, Tungsten oxide 99.999 5～40 heavy %, organic additive content are 0.1～40 heavy %.
8,, it is characterized in that the unitary catalytic cracking reaction device of described catalytic pyrolysis is the compound reactor of any reactor or any two combination of reactors in riser reactor, fluidized-bed reactor or the moving-burden bed reactor according to the method for claim 1.
9, according to the method for claim 8, it is characterized in that the reaction conditions of described riser reactor is: the weight ratio 0.1～0.6 of weight ratio 5～40, water vapor and the catalytic pyrolysis stock oil of 500～650 ℃ of temperature of reaction, reaction pressure 0.10～0.50MPa, 1～10 second residence time, catalytic cracking catalyst and catalytic pyrolysis stock oil.
10,, it is characterized in that the fluidized-bed in described fluidized-bed reactor, moving-burden bed reactor, the compound reactor and/or the reaction conditions of moving-bed are: 500～650 ℃ of temperature of reaction, reaction pressure 0.10～0.50MPa, air speed 1.0～20.0h according to the method for claim 8
-1, catalytic cracking catalyst and catalytic pyrolysis stock oil the weight ratio 0.1～0.6 of weight ratio 5～40, water vapor and catalytic pyrolysis stock oil.
11, according to the method for claim 1, it is characterized in that described catalytic cracking catalyst comprises zeolite, inorganic oxide and optional clay, each components contents is respectively: zeolite 15～60 heavy %, inorganic oxide 5～85 heavy %, clay 0～70 heavy %, its mesolite is the mixture of mesopore zeolite and the y-type zeolite of choosing wantonly.
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