CN103540359B - Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefin and gasoline - Google Patents
Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefin and gasoline Download PDFInfo
- Publication number
- CN103540359B CN103540359B CN201210241292.9A CN201210241292A CN103540359B CN 103540359 B CN103540359 B CN 103540359B CN 201210241292 A CN201210241292 A CN 201210241292A CN 103540359 B CN103540359 B CN 103540359B
- Authority
- CN
- China
- Prior art keywords
- oil
- enters
- reaction
- catalytic
- gasoline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 60
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 27
- 239000003502 gasoline Substances 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 25
- 239000000295 fuel oil Substances 0.000 title claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000003921 oil Substances 0.000 claims abstract description 92
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 239000002002 slurry Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- 239000002283 diesel fuel Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000005336 cracking Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000004939 coking Methods 0.000 claims abstract description 7
- 230000003111 delayed effect Effects 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims description 35
- 239000004215 Carbon black (E152) Substances 0.000 claims description 18
- 229930195733 hydrocarbon Natural products 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000008929 regeneration Effects 0.000 claims description 6
- 238000011069 regeneration method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000571 coke Substances 0.000 abstract description 6
- -1 carbon olefin Chemical class 0.000 abstract description 3
- 238000004821 distillation Methods 0.000 abstract description 3
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 238000005194 fractionation Methods 0.000 description 10
- 239000002994 raw material Substances 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000006276 transfer reaction Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000007809 chemical reaction catalyst Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002010 green coke Substances 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000009719 regenerative response Effects 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000010504 bond cleavage reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010763 heavy fuel oil Substances 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical class O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000007017 scission Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 206010027439 Metal poisoning Diseases 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 208000010501 heavy metal poisoning Diseases 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
An inferior heavy oil catalytic conversion process for improving the yield of low-carbon olefin and gasoline comprises the following steps: (1) the inferior heavy oil raw oil enters a first reaction zone (zone I) of a two-section lifting pipe to carry out catalytic cracking reaction, and the generated oil gas enters a fractionating tower; (2) the outlet at the top of the fractionating tower is a mixture of dry gas, liquefied gas and gasoline, the outlet at the middle part is diesel oil, the outlet at the lower part is catalytic wax oil, and the outlet at the bottom is oil slurry. The catalytic wax oil and diesel oil enter a second reaction zone (II zone) of the two-section lifting pipe together, and the oil slurry enters a reduced pressure distillation tower; (3) the light fraction material with lower carbon residue at the upper outlet of the vacuum distillation tower and the heavy fraction material with higher carbon residue at the middle outlet enter a hydrogenation device together; the bottom ultrahigh carbon residue slurry oil enters a delayed coking device; (4) the low carbon residue easy cracking material from the hydrogenation device enters the lifting pipe I area for reaction again. The present invention has the features of long catalyst life, low dry gas and coke yield and high low carbon olefin and gasoline yield.
Description
Technical field
The present invention relates to a kind of catalytic conversion process of mink cell focus, in particular, relate to a kind of inferior heavy oil catalytic conversion process improving low-carbon alkene and yield of gasoline.
Background technology
Petroleum resources are heaviness and in poor quality increasingly, the density being mainly manifested in crude oil becomes large, viscosity uprises, and heavy metal content, sulphur content, resin and asphalt content are more and more higher, and the residual oil thus after air distillation and underpressure distillation also presents the trend of heaviness day by day.From inferior heavy oil, how to obtain more, better product, as gasoline, diesel oil, low-carbon alkene, improving its economic use value is to greatest extent the key issue that scientific research personnel studies for a long time.
Catalytic cracking unit is the important means of oil secondary processing, in each refinery, occupy very important status.In catalytic cracking production process, heavy oil and catalyzer are in riser tube internal high temperature contact reacts, after reaction, decaying catalyst enters high temperature regeneration in revivifier after stripping, and the oil gas generated enters separation column and carries out cut cutting, a large amount of slurry oils can be produced in the bottom of separation column, this part slurry oil is generally greater than the high carbon residue cut of 500-550 DEG C and boiling point by boiling point and is less than 500-550 DEG C low carbon residue cut and forms, and often kind of a cut accounts for about 50%.Usually, slurry oil can use as heavy fuel oil (HFO) or be back in riser tube and carry out freshening.As heavy fuel oil (HFO), it is cheap does not have economic worth; As recycle stock, the cut that its mid-boiling point is greater than 500-550 DEG C, because carbon residue is higher, very easily cause freshening device green coke, catalyzer heavy metal poisoning rapid deactivation, not only add energy consumption and the maintenance cost of device, and reduce the working ability of device, add refining losses, greatly have impact on economic benefit.Thus, how effectively to utilize a large amount of slurry oils of fractionation column base, make it be converted into more valuable clear gusoline and low-carbon alkene has attracted the sight of scientific research personnel.
US4713221 discloses on the residual hydrogenation and catalytic cracking combined basis of routine, and the heavy cycle oil that catalytic cracking produces is circulated to residual hydrogenation equipment, after residual oil mixed hydrogenation, then enters catalytic cracking unit processing.
CN1382776 discloses a kind of residual hydrocracking and catalytically cracking heavy oil method, this patented method proposes the clarified oil in the heavy cycle oil of catalytic cracking unit production and slurry oil to be mixed as a part for residual oil device charging, return catalytic cracking unit after this logistics hydro-upgrading again to process together with other charging, catalytic cracking unit gasoline and diesel yield can be improved.
After CN1422327A discloses and the HCO that catalytic cracking unit is produced is carried out hydrotreatment or mix laggard external independently catalytic cracking unit with petroleum naphtha and process the method increasing production small-numerator olefin and gasoline, the method to propose in the second external riser catalytic cracking reactor cracked cycle oil again and can suppress to be blended in when single riser reactor react with other charging undesirable hydrogen transfer reactions occurs, thus to further raising light olefins yields is favourable.
CN101899323A discloses the catalysis conversion method that a kind of inferior heavy oil is converted into lightweight and clean fuel oil, that inferior feedstock oil is introduced riser tube, reacted catalytic wax oil of carrying granules of catalyst introduces vacuum fractionation tower, the lighting end of vacuum fractionation top of tower obtains hydrogenation catalyst wax oil after hydrotreatment, hydrogenation catalyst wax oil is introduced riser tube again and is carried out catalytic cracking reaction, and the last running of vacuum fractionation tower bottom is as product or loop back catalytic cracking unit freshening.
Above-mentioned patent utilization hydrogenation and catalytic cracking combined technique or 2 stage catalytic cracking techniques process the slurry oil bottom catalytic cracking fractionating tower, the yield of gasoline or diesel oil can be improved to a certain extent, or improve the yield of light olefin, but not there is the effect simultaneously improving gasoline and yield of light olefins.
Summary of the invention
Technical problem to be solved by this invention is on the basis of existing technology, a kind of inferior heavy oil catalytic conversion process improving low-carbon alkene and yield of gasoline is provided, this catalytic conversion process also can reduce the productive rate of dry gas and coke while improving low-carbon alkene and yield of gasoline, thus realizes effective utilization of petroleum resources.
Improve an inferior heavy oil catalytic conversion process for low-carbon alkene and yield of gasoline, comprise the following steps:
(1) the first reaction zone (be called for short riser tube I district) that the inferior heavy oil stock oil of preheating enters two-stage riser reactor contacts with hot catalytic cracking catalyst high temperature short contact time high agent-oil ratio carries out catalytic cracking reaction, and the oil gas of generation enters separation column;
(2) separation column top exit product is the mixture of dry gas, liquefied gas and gasoline, and centre exit product is diesel oil, and lower part outlet is the catalytic wax oil of relatively difficult cracking, and bottom is slurry oil.Catalytic wax oil enters the second reaction zone (being called for short riser tube II district) of two-stage riser reactor together with diesel oil, and slurry oil enters vacuum still;
(3) the lower carbon residue light-fraction material of vacuum still upper outlet and the higher carbon residue last running material of centre exit jointly enter hydrogenation unit and carry out hydrotreatment; Bottom superelevation carbon residue slurry oil enters delayed coking unit after slurry oil filter process;
(4) the easy cracking material of hydrogenation unit low carbon residue out enters riser tube I district and again reacts;
Catalytic cracking reaction condition in riser tube I district of the present invention is: the weight ratio of water and heavier hydrocarbon feeds is 0.1 ~ 2.5%, preferably 0.3 ~ 1.5%; Heavier hydrocarbon feeds and catalyst reaction temperatures are 550 ~ 750 DEG C, preferably 580 ~ 680 DEG C.Reaction times is 0.1 ~ 20 second, preferably 0.2 ~ 10 second; Weight ratio 2 ~ the 30:1 of catalyzer and heavier hydrocarbon feeds, is preferably 6 ~ 22:1;
Catalytic cracking reaction condition in riser tube II district of the present invention is: the weight ratio of water and heavier hydrocarbon feeds is 0.1 ~ 2.5%, preferably 0.3 ~ 1.5%; Heavier hydrocarbon feeds and catalyst reaction temperatures are 550 ~ 720 DEG C, preferably 580 ~ 650 DEG C.Reaction times is 0.1 ~ 20 second, preferably 0.2 ~ 6 second; Weight ratio 2 ~ the 20:1 of catalyzer and heavier hydrocarbon feeds, is preferably 6 ~ 15:1;
The regeneration temperature of catalytic cracking catalyst of the present invention is 600 ~ 800 DEG C, and preferred regeneration temperature is 680 ~ 700 DEG C;
Inferior heavy oil in the present invention to be boiling range the be distillate of 220 ~ 550 DEG C, as decompressed wax oil, long residuum, vacuum residuum, wax tailings, solvent-deasphalted oils and composition thereof etc.
The material of vacuum still top of the present invention and centre exit is incorporated in hydrogenator, and hydrogenation reaction can be carried out in one or more stage.Under the atmosphere of hydrogen, with the catalyst exposure of hydrotreatment, be 1.0 ~ 20.0MPa in hydrogen dividing potential drop, temperature of reaction is 200 ~ 500 DEG C, and hydrogen to oil volume ratio is 200 ~ 2000v/v, and volume space velocity is 0.1 ~ 3.0h
-1reaction conditions under carry out hydrotreatment reaction, the hydrotreatment high quality raw material obtained, be introduced into riser tube first reaction zone and again react.
The slurry oil density that fractionation column base outlet of the present invention and vacuum still outlet at bottom produce is 0.95 ~ 1.05g/cm
3, boiling range is 300 ~ 750 DEG C, and temperature is 250 ~ 500 DEG C, and level of catalyst fines is 0.1 ~ 5g/L.
The present invention the hydrogenation catalyst that is suitable for be the catalyzer of periodic table of elements VIB, VIIB and one or more metals of group VIII, catalyzer can be water-soluble, oil soluble, solid powder th-1 catalyst etc., catalyzer is 50 ~ 2000 μ g/g in the total add-on of metal, preferably 60 ~ 600 μ g/g.
The present invention the catalytic cracking catalyst that is suitable for contain following component: in catalyzer total mass for 100%:
The zeolite molecular sieve of (1) 20 ~ 55 quality %, preferably 25 ~ 45 quality %;
The acid slurries of mixing containing modified kaolin of (2) 2 ~ 50 quality %, preferably 10 ~ 30 quality %(are in solid content);
The clay of (3) 0 ~ 50 quality %, preferably 10 ~ 45 quality %;
The inorganic oxide of (4) 0 ~ 40 quality %, preferably 10 ~ 30 quality %;
The binding agent of (5) 0 ~ 35 quality %, preferably 5 ~ 15 quality %(are with oxide basis).
Fig. 1 is a kind of inferior heavy oil catalytic conversion process schematic diagram improving low-carbon alkene and yield of gasoline.Wherein, 1-riser tube, 2-revivifier, 3-inclined tube to be generated, 4-regenerator sloped tube, 5-separation column, 6-vacuum still, 7-hydrogenator, 8-slurry oil strainer, 9-delayed coking, 10-settling vessel, 11-bottom feed mouth, opening for feed in the middle part of 12-riser tube, 13-gas pipeline, 51-separation column top exit, 52-separation column centre exit, 53-separation column lower part outlet, 54-fractionation column base exports, 61-top pumped vacuum systems, 62-vacuum still upper outlet, 63-vacuum still centre exit, 64-vacuum still outlet at bottom.
Below in conjunction with Fig. 1, the present invention is further elaborated.
(1) inferior heavy oil of preheating enters the bottom feed mouth 11 of riser tube 1, in riser tube I district, carry out high temperature short contact time high agent-oil ratio contact carry out catalytic cracking reaction with the catalytic cracking catalyst from regenerator sloped tube 4, the oil gas generated carries out the relative catalytic cracking reaction relaxed with the catalytic wax oil raw material of separation column centre exit 52 and separation column lower part outlet 53 in riser tube II district, hydrogen transfer reactions and isomerization reaction, catalyzer with part carbon deposit after reaction terminates carries out gas-oil separation at settling vessel 10, catalyzer after separation enters in revivifier 2 through inclined tube 3 to be generated and carries out regenerative response, and enter in separation column 5 through gas pipeline 13 after reaction product and catalyst separating and carry out cut cutting.
(2) separation column top exit 51 fractionates out the mixture of dry gas, liquefied gas and gasoline, and the catalytic wax oil component of the diesel oil fractionated out by centre exit 52 difficult cracking relative to lower part outlet 53 merges to be introduced opening for feed 12 in the middle part of riser tube and enter riser tube II district and react.Be the slurry oil containing a large amount of catalyst fines bottom separation column 5, introduced in vacuum still 6 through fractionation column base outlet 54 by this part slurry oil, vacuum still system pressure is provided by top pumped vacuum systems 61.
(3) after the last running that the lighting end that fractionates out of vacuum still upper outlet 62 and vacuum still centre exit 63 fractionate out merges and introduces hydrogenator 7 hydrogenation, then introduce riser tube bottom feed mouth 11 and react with catalyst exposure.Vacuum still outlet at bottom 64 is containing high concentration catalyst fine powder and the heavy slurry oil containing high carbon residue height heavy metal content, this part heavy slurry oil is entered delayed coking 9 after slurry oil strainer 8 filters and reprocesses.
Compared with prior art, the invention has the advantages that:
(1) I district in riser tube, the raw material of comparative good-quality generates the low-carbon alkenes such as ethylene, propylene under high temperature short contact time greatly oil ratio reaction conditions, enters riser tube II district and react under the reaction conditions relatively relaxed with relative raw material inferior after the reaction of riser tube I district terminates.
(2) in riser tube II district, catalytic cracking catalyst with react from the diesel oil of separation column centre exit 52 and the catalytic wax oil contact raw of separation column lower part outlet 53, compare riser tube I district, riser tube II district catalyst member green coke and active reduction, there is less second pyrolysis reaction in riser tube II district in the low-carbon alkene product such as ethylene, propylene from riser tube I district, reduces dry gas and coke yield.And under the relative catalytic cracking reaction condition relaxed, generate more gasoline with part green coke catalyzer with the raw material of vacuum still from separation column, avoid relatively high carbon residue raw material and generate too much dry gas and coke.
(3) high carbon residue slurry oil is not introduced in riser reactor by the present invention, the material such as many cyclophanes lopps of cracking and the heavy metal of high-content is difficult to containing higher in high carbon residue slurry oil, this kind of material enters riser tube will cause catalytic cracking catalyst rapid deactivation, thus yield of light olefins will reduce.The beneficial effect produced extends catalyst life, reduces dry gas and coke yield, is conducive to low-carbon olefines high-output and gasoline.
Embodiment 1
(1) inferior heavy oil of preheating enters the bottom feed mouth 11 of riser tube 1, in riser tube I district, carry out high temperature short contact time high agent-oil ratio contact carry out catalytic cracking reaction with the catalytic cracking catalyst from regenerator sloped tube 4, it is 655 DEG C in temperature of reaction, reaction times is 1.45 seconds, the weight ratio 11:1 of catalyzer and heavier hydrocarbon feeds, the weight ratio of water and heavier hydrocarbon feeds is, under the reaction conditions of 0.3%, high-temperature catalytic scission reaction occurs.
(2) raw material of the oil gas generated and separation column centre exit 52 and separation column lower part outlet 53 carry out in riser tube II district relative relax catalytic cracking reaction, hydrogen transfer reactions and isomerization reaction, catalyzer with carbon deposit after reaction terminates carries out gas-oil separation at settling vessel 10, catalyzer after separation enters in revivifier 2 through inclined tube 3 to be generated and carries out regenerative response, and the regeneration temperature of catalyzer is 755 DEG C; Enter in separation column 5 through gas pipeline 13 after reaction product and catalyst separating and carry out cut cutting.
(3) separation column top exit 51 fractionates out the mixture of dry gas, liquefied gas and gasoline, and the catalytic wax oil component of the diesel oil fractionated out by centre exit 52 difficult cracking relative to lower part outlet 53 merges to be introduced opening for feed 12 in the middle part of riser tube and introduce riser tube II district and react.Be the slurry oil containing a large amount of catalyst fines bottom separation column 5, introduced in vacuum still 6 through fractionation column base outlet 54 by this part slurry oil, vacuum still system pressure is provided by top pumped vacuum systems 61.
(4) after the last running that the lighting end that fractionates out of vacuum still upper outlet 62 and vacuum still centre exit 63 fractionate out merges and introduces hydrogenator 7 hydrogenation, then introduce riser tube bottom feed mouth 11 and react with catalyst exposure.Hydroprocessing technique condition is: hydrogen dividing potential drop 16MPa, and temperature of reaction is 375 DEG C, and hydrogen to oil volume ratio is 1250v/v, and volume space velocity is 1.28h
-1.
(5) vacuum still outlet at bottom 64 is containing high concentration catalyst fine powder and the heavy slurry oil containing high carbon residue height heavy metal content, this part heavy slurry oil is entered delayed coking 9 after slurry oil strainer 8 filters and reprocesses.Slurry oil density is 1.001g/cm
3, boiling range is 300 ~ 750 DEG C, and temperature is 320 DEG C, and level of catalyst fines is 1.19g/L.
Embodiment 2
(1) inferior heavy oil of preheating enters the bottom feed mouth 11 of riser tube 1, and in riser tube I district, carrying out high temperature short contact time high agent-oil ratio with the catalytic cracking catalyst from regenerator sloped tube 4 contact and carry out catalytic cracking reaction, is 615 DEG C in temperature of reaction.Reaction times is 1.9 seconds; The weight ratio 10:1 of catalyzer and heavier hydrocarbon feeds; The weight ratio of water and heavier hydrocarbon feeds is, under the reaction conditions of 0.3%, high-temperature catalytic scission reaction occurs.
(2) raw material of the oil gas generated and separation column centre exit 52 and separation column lower part outlet 53 carry out in riser tube II district relative relax catalytic cracking reaction, hydrogen transfer reactions and isomerization reaction, catalyzer with carbon deposit after reaction terminates carries out gas-oil separation at settling vessel 10, catalyzer after separation enters in revivifier 2 through inclined tube 3 to be generated and carries out regenerative response, and the regeneration temperature of catalyzer is 755 DEG C; Enter in separation column 5 through gas pipeline 13 after reaction product and catalyst separating and carry out cut cutting.
(3) separation column top exit 51 fractionates out the mixture of dry gas, liquefied gas and gasoline, and the catalytic wax oil component of the diesel oil fractionated out by centre exit 52 difficult cracking relative to lower part outlet 53 merges to be introduced opening for feed 12 in the middle part of riser tube and introduce riser tube II district and react.Be the slurry oil containing a large amount of catalyst fines bottom separation column 5, introduced in vacuum still 6 through fractionation column base outlet 54 by this part slurry oil, vacuum still system pressure is provided by top pumped vacuum systems 61.
(4) vacuum still centre exit 64 fractionate out for containing the relatively high last running of carbon residue, after hydrogenator 7 hydrogenation is introduced in this part last running, then introduce riser tube bottom feed mouth 11 and react with catalyst exposure.Hydroprocessing technique condition is: hydrogen dividing potential drop 19.5MPa, and temperature of reaction is 365 DEG C, and hydrogen to oil volume ratio is 1320v/v, and volume space velocity is 1.27h
-1.
(5) vacuum still outlet at bottom 65 is containing high concentration catalyst fine powder and the heavy slurry oil containing high carbon residue height heavy metal content, this part heavy slurry oil is entered delayed coking 9 after slurry oil strainer 8 filters and reprocesses.Slurry oil density is 1.003g/cm
3, boiling range is 315 ~ 750 DEG C, and temperature is 335 DEG C, and level of catalyst fines is 1.3gL.
Comparative example
Adopt embodiment 1 catalytic cracking reaction condition, reacted oil gas product enters separation column and carries out cut cutting, and catalytic wax oil and bottom slurry oil do not enter vacuum fractionation tower but directly enter riser tube and carry out freshening.
Embodiment 1 and embodiment 2 riser tube fcc raw material oil nature as shown in table 1, FCC catalyzer is the LBO-16 catalyzer that Lanzhou Petrochemical catalyst plant is produced, physical and chemical performance is as shown in table 2, and hydrogenation catalyst characteristic is as shown in table 3, embodiment and comparative example reaction result as shown in table 4.
Table 1 riser tube fcc raw material oil nature
Table 2 Lanzhou Petrochemical catalyst plant LBO-16 catalyzer physical and chemical performance
| Project | Embodiment 1 | Embodiment 2 |
| Micro-activity (17h), m% | 63 | 63 |
| Specific surface area, m 2/g | 289 | 301 |
| Pore volume, ml/g | 0.36 | 0.38 |
| Abrasion index, m% | 1.6 | 1.6 |
| Zeolite molecular sieve, m% | 38.2 | 39.1 |
| Modified kaolin, m% | 24.2 | 23.1 |
| Clay, m% | 21 | 20 |
| Inorganic oxide, m% | 17 | 17 |
| Binding agent, m% | 9.5 | 9.5 |
Table 3 hydrogenation catalyst physicochemical characteristic
| Project | Embodiment 1 | Embodiment 2 |
| Active | >95％ | >95％ |
| Granularity, order | 100-200 | 100-200 |
| Metallic impurity | <0.3％ | <0.3％ |
| Selectivity | >90％ | >90％ |
| Tungstic oxide, m% | 26.9 | 27.8 |
| Nickel oxide, m% | 5.8 | 5.2 |
| Aluminum oxide, m% | 67.5 | 66.4 |
Table 4 catalytic cracking product distributes
| Product slates | Embodiment 1 | Embodiment 2 | Comparative example |
| Dry gas | 8.25 | 8.59 | 9.51 |
| Gasoline | 19.25 | 20.57 | 13.42 |
| Diesel oil | 13.56 | 14.25 | 22.33 |
| Heavy oil | 6.59 | 6.45 | 10.05 |
| Coke | 9.59 | 9.28 | 11.45 |
| Low-carbon alkene (ethene+propylene) | 19.14 | 19.19 | 13.57 |
Claims (2)
1. improve an inferior heavy oil catalytic conversion process for low-carbon alkene and yield of gasoline, comprise the following steps:
(1) the first reaction zone (be called for short riser tube I district) that the inferior heavy oil stock oil of preheating enters two-stage riser reactor contacts with hot catalytic cracking catalyst high temperature short contact time high agent-oil ratio carries out catalytic cracking reaction, and the oil gas of generation enters separation column;
(2) separation column top exit product is the mixture of dry gas, liquefied gas and gasoline, centre exit product is diesel oil, lower part outlet is the catalytic wax oil of relatively difficult cracking, bottom is slurry oil, catalytic wax oil enters the second reaction zone (being called for short riser tube II district) of two-stage riser reactor together with diesel oil, and slurry oil enters vacuum still;
(3) the lower carbon residue light-fraction material of vacuum still upper outlet and the higher carbon residue last running material of centre exit jointly enter hydrogenation unit and carry out hydrotreatment; Bottom superelevation carbon residue slurry oil enters delayed coking unit after slurry oil filter process;
(4) the easy cracking material of hydrogenation unit low carbon residue out enters riser tube I district and again reacts;
Wherein, catalytic cracking reaction condition in described riser tube I district is: the weight ratio of water and heavier hydrocarbon feeds is 0.1 ~ 2.5%, heavier hydrocarbon feeds and catalyst reaction temperatures are 550 ~ 750 DEG C, reaction times is 0.1 ~ 20 second, weight ratio 2 ~ the 30:1 of catalyzer and heavier hydrocarbon feeds, wherein said heavier hydrocarbon feeds is the inferior heavy oil in step (1) and the easy cracking material of low carbon residue in step (4); Catalytic cracking reaction condition in riser tube II district is: the weight ratio of water and heavier hydrocarbon feeds is 0.1 ~ 2.5%, heavier hydrocarbon feeds and catalyst reaction temperatures are 550 ~ 720 DEG C, reaction times is 0.1 ~ 20 second, weight ratio 2 ~ the 20:1 of catalyzer and heavier hydrocarbon feeds, wherein said heavier hydrocarbon feeds is catalytic wax oil and the diesel oil of step (2); The regeneration temperature of described catalytic cracking catalyst is 600 ~ 800 DEG C.
2. improve the inferior heavy oil catalytic conversion process of low-carbon alkene and yield of gasoline according to claim 1, it is characterized in that described inferior heavy oil to be boiling range be the distillate of 220 ~ 550 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210241292.9A CN103540359B (en) | 2012-07-12 | 2012-07-12 | Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefin and gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210241292.9A CN103540359B (en) | 2012-07-12 | 2012-07-12 | Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefin and gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103540359A CN103540359A (en) | 2014-01-29 |
| CN103540359B true CN103540359B (en) | 2015-11-18 |
Family
ID=49964234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210241292.9A Active CN103540359B (en) | 2012-07-12 | 2012-07-12 | Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefin and gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103540359B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105586075B (en) * | 2014-10-20 | 2017-12-22 | 中国石油化工股份有限公司 | A kind of Grading And Zoning catalytic cracking conversion method of wax tailings |
| WO2017004356A1 (en) * | 2015-06-30 | 2017-01-05 | Exxonmobil Research And Engineering Company | Fuel production from fcc products |
| CN110055099B (en) * | 2019-05-21 | 2021-03-12 | 山东京博石油化工有限公司 | Treatment method of catalytic cracking recycle oil |
| CN115841050B (en) * | 2023-02-20 | 2023-06-06 | 新疆独山子石油化工有限公司 | Catalytic cracking regenerated catalyst and molecular composition raw oil premixing temperature calculation method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302843A (en) * | 2000-12-13 | 2001-07-11 | 中国石油天然气股份有限公司 | Catalytic cracking technology with two-stage lift pipe |
| CN102453542A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for processing residuum |
-
2012
- 2012-07-12 CN CN201210241292.9A patent/CN103540359B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302843A (en) * | 2000-12-13 | 2001-07-11 | 中国石油天然气股份有限公司 | Catalytic cracking technology with two-stage lift pipe |
| CN102453542A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for processing residuum |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103540359A (en) | 2014-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101531558A (en) | Catalytic conversion method for preparing propylene and aromatic hydrocarbons | |
| CN110938464A (en) | Integrated process method for producing low-carbon aromatic hydrocarbon and olefin from gas oil | |
| CN102453543B (en) | Combined process of hydrotreatment and catalytic cracking for residuum | |
| CN102344828B (en) | Processing method of inferior residual oil | |
| CN103540359B (en) | Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefin and gasoline | |
| CN107557064B (en) | Coal tar combined bed hydrogenation method and system for coal tar combined bed hydrogenation | |
| CN103540356B (en) | Inferior heavy oil catalytic conversion process for improving yield of low-carbon olefins and diesel oil | |
| CN105713662A (en) | Hydrotreating and catalytic cracking combined process | |
| CN102041093B (en) | Catalytic conversion method for improving cetane number and yield of diesel | |
| CN113817503B (en) | Combined process for preparing chemical products from crude oil | |
| CN101942339A (en) | Boiling-bed residual-oil hydrocracking and catalytic-cracking combined process method | |
| CN101875856A (en) | Wax oil hydrogenated treatment and catalytic cracking combined method | |
| CN102373085B (en) | Catalytic conversion method for maximum production of high-cetane diesel oil | |
| CN101139529B (en) | Method for producing lower-carbon olefin by fraction of coked diesel oil | |
| CN1200083C (en) | Catalytic cracking combined process | |
| CN109694743B (en) | Method for producing clean gasoline by taking Fischer-Tropsch synthetic wax as raw material | |
| CN100549143C (en) | A kind of working method of petroleum hydrocarbon | |
| CN1176185C (en) | Catalytic cracking method and equipment | |
| CN115678607B (en) | Heavy crude oil processing method and system for multi-product chemicals | |
| CN109777492B (en) | Refinery gas hydrogenation combined processing method | |
| CN107557069B (en) | Method and system for hydro-conversion of coal tar raw material | |
| CN101899320B (en) | Catalytic conversion method for producing high cetane number light diesel oil | |
| CN109777507B (en) | Refinery gas hydrogenation combined processing method | |
| CN107557068B (en) | Coal tar hydrogenation method and system for coal tar hydrogenation | |
| CN109777518B (en) | Refinery gas hydrogenation combination method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |