CN1478865A - Method for increasing propylene production and reducing olefin content in gasoline by using C4 fraction - Google Patents
Method for increasing propylene production and reducing olefin content in gasoline by using C4 fraction Download PDFInfo
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- CN1478865A CN1478865A CNA021290369A CN02129036A CN1478865A CN 1478865 A CN1478865 A CN 1478865A CN A021290369 A CNA021290369 A CN A021290369A CN 02129036 A CN02129036 A CN 02129036A CN 1478865 A CN1478865 A CN 1478865A
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- 239000003502 gasoline Substances 0.000 title claims abstract description 108
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 50
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 53
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000004064 recycling Methods 0.000 claims abstract 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 40
- 238000004523 catalytic cracking Methods 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 4
- 238000001311 chemical methods and process Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 41
- 239000003921 oil Substances 0.000 description 41
- 239000000047 product Substances 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000010457 zeolite Substances 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 description 14
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000005336 cracking Methods 0.000 description 11
- 230000008929 regeneration Effects 0.000 description 10
- 238000011069 regeneration method Methods 0.000 description 10
- 239000002808 molecular sieve Substances 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000002283 diesel fuel Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000295 fuel oil Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000571 coke Substances 0.000 description 5
- -1 for example Substances 0.000 description 5
- 239000003209 petroleum derivative Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 238000001833 catalytic reforming Methods 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000005899 aromatization reaction Methods 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012958 reprocessing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000269350 Anura Species 0.000 description 1
- FYCKPACHMBIGMO-UHFFFAOYSA-N CCCC.CCC=C.CC(C)=C Chemical compound CCCC.CCC=C.CC(C)=C FYCKPACHMBIGMO-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 241000772415 Neovison vison Species 0.000 description 1
- 241001372564 Piona Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MEKDPHXPVMKCON-UHFFFAOYSA-N ethane;methane Chemical compound C.CC MEKDPHXPVMKCON-UHFFFAOYSA-N 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
一种利用C4馏分增产丙烯、降低汽油中烯烃含量的方法，是将富含C4馏分的气态烃、汽油原料注入流化床反应器中，与含有五元环高硅沸石的催化剂接触、反应，反应温度为500～650℃、催化剂与汽油原料和富含C4馏分气态烃的混合物的重量比为1～180∶1、床层重时空速为0.1～30小时－1；分离反应产物和待生催化剂；待生催化剂经汽提、全部或部分再生后返回反应器循环使用。该方法可用于生产丙烯和高品质汽油。A method for increasing the production of propylene and reducing the content of olefins in gasoline by using C4 cuts is to inject gaseous hydrocarbons rich in C4 cuts and gasoline raw materials into a fluidized bed reactor, contact and react with a catalyst containing five-membered ring silicalite, The reaction temperature is 500-650°C, the weight ratio of the catalyst to the mixture of gasoline raw material and gaseous hydrocarbons rich in C4 fraction is 1-180:1, and the bed weight hourly space velocity is 0.1-30 hours -1 ; Catalyst: The raw catalyst is stripped, fully or partially regenerated, and then returned to the reactor for recycling. This method can be used to produce propylene and high-quality gasoline.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of catalysis shifting method that utilizes the C 4 fraction propylene enhancing and reduce olefin(e) centent in the gasoline.
Background technology
Small-numerator olefins such as ethene, propylene and butylene are the most basic organic synthesis raw materials.Steam cracking method is mainly adopted in the production of small-numerator olefin in the world at present, but because the easy coking of high-temperature cracking furnace, therefore steam cracking device only is applicable to processing lightweight material oil, as Sweet natural gas, petroleum naphtha and solar oil etc., and a certain amount of aromatic hydrocarbons of by-product.Because the crude oil of China is heavier, light oil yields such as petroleum naphtha are lower, and the raw material imbalance between supply and demand of steam cracking and catalytic reforming is serious day by day.From the eighties since mid-term, Research Institute of Petro-Chemical Engineering of China Petrochemical Corp. just takes to the catalytic cracking family Study on Technology that heavy oil is produced low-carbon alkene, and has successfully developed catalytic pyrolysis (DCC) technology of maximum production of propylene and catalytic pyrolysis (CPP) technology that maximum is produced ethene.At present, catalytic cracking is the main second complete processing of China's heavy oil lighting, and a year amount of finish reaches 94.2 ten thousand tons, accounts for 35.87% of crude runs.But the small-numerator olefin productive rate of conventional catalytic cracking process is lower, general propylene mass yield only 3～5%, and ethylene yield is then lower.Therefore, will have huge economic benefit in existing catalytic cracking and cat-cracker increased low carbon olefine output.
CN1031834A discloses a kind of hydrocarbon conversion processes of low-carbon olefines high-output, with the petroleum hydrocarbon cut of the different boiling ranges of gasoline, kerosene, diesel oil, vacuum gas oil or its mixed fraction and residual oil, crude oil is raw material, use solid catalyst to carry out catalytic conversion reaction in fluidized-bed or moving-burden bed reactor, can obtain butylene and productivity of propylene is 40wt%.
Disclose the method for a kind of voluminous liquefied gas and gasoline among the CN1085885A, the raw material of employing is selected from the time processing distillate: gasoline, diesel oil, decompressed wax oil, residual oil; Be mixed with time processing distillate or its mixture of part wax tailings, deasphalted oil or other secondary processing distillate; Crude oil.In riser tube or fluidized-bed, contact with the solid acid catalyst that contains rare-earth five-membered ring supersiliceous zeolite, three kinds of zeolites of REY and high silicon Y, reaction conditions is as follows: 480～550 ℃ of temperature of reaction, 130～350 kPas of pressure, weight hourly space velocity 1～150 hour-1, agent-oil ratio are 4～15, the mass ratio of water vapor and raw material hydrocarbon is 0.05～0.21: 1, and yield of liquefied gas is 30～40wt% in the reaction product.
USP4826586 disclose a kind of be charging to be rich in alkane C3～C 4 fraction and heavy oil, adopt Y zeolite or macroporous catalyst such as unformed and beta-molecular sieve or mesopore to select two kinds of catalyst systems of type molecular sieve catalyst to react the production high-octane number component at upper and lower two reaction zones of single riser tube.To be rich in alkane C3～C 4 fraction is that to adopt temperature of reaction in the lower reaction zone of riser tube be that 593～815 ℃, agent-oil ratio are 50～200 to raw material: 1, the reaction times is to carry out heat cracking reaction under the condition in 10～50 seconds to generate small-numerator olefin.In the reaction zone of riser tube top, then carry out catalytic cracking reaction with heavy oil.Two kinds of catalyzer physical difference that adopted in the reaction are bigger, make second kind of catalyzer long than first kind of catalyzer in the residence time on riser tube top, and can isolate this two kinds of catalyzer in stripper.
USP4966681 disclose a kind of be charging to be rich in alkane C3～C 4 fraction and heavy oil, adopt Y zeolite or macroporous catalyst such as unformed and beta-molecular sieve or mesopore to select the method for two kinds of catalyst systems of type molecular sieve catalyst catalytic production high-octane number component in duo-lift tube reactor.First riser tube is raw material with heavy oil in temperature of reaction: 496～565 ℃, agent-oil ratio are 4～10: 1, the reaction times is to contact with above-mentioned two kinds of mixture of catalysts under 1～15 second condition to carry out catalyzed reaction and generate gas oil and C3～C 4 fraction.The bottom of second riser reaction zone is that 599～816 ℃, agent-oil ratio are 50～200 so that to contain C3～C 4 fraction be raw material in temperature of reaction: 1, the reaction times is to react the generation small-numerator olefin under the condition in 15～35 seconds.Select the type molecular sieve catalyst to make temperature of reaction be that 204～537 ℃, agent-oil ratio are 5～40 and introduce new beta-molecular sieve or mesopore at the top of riser tube reaction zone: 1, the reaction times is to generate the high-octane rating product under the condition in 5～45 seconds.
It is that (coke content is that the method that dehydrogenation reaction is produced alkene takes place in 0.2～10wt%) contact to raw material at the catalyzer of pre-carbon deposit with C2～C10 alkane that USP5414181 discloses a kind of.Catalyzer recommends to use the oxide compound that contains the tetrahedron crystalline structure.
USP5447622 discloses a kind of employing tandem back-mixing regeneration system rapidly formation part and has hung the charcoal catalytic cracking catalyst as dehydrogenation catalyst, is that raw material is produced alkene with C2～C10 alkane.
It is the method for raw material production alkene with the long residuum that USP5879535 discloses a kind of two-stage reactor structure that adopts.First step reactor is for to move horizontally the heat cracking reaction that fluidized-bed carries out short residence time(SRT) (less than 2 seconds), and temperature of reaction is 500～600 ℃.Second stage reactor (riser reactor) is that raw material is the heat cracking reaction that carries out short contacting time (less than 1 second) under 700～1100 ℃ of conditions in temperature of reaction with first step reaction product, and adopts chilling technique can obtain the olefins yield of 20～50wt% at second stage reaction zone.
USP6207115 discloses a kind of utilization and has been rich in the C 4 fraction of alkene and ethene and carries out metathesis reaction and produce the propylene technology.The catalyzer that adopts is a loading type rubidium oxide catalyzer, and temperature of reaction is 0～100 ℃.
It is that 460～700 ℃, working pressure are that 140～700 kPas, weight hourly space velocity are 0.05～10hr in temperature of reaction that USP6049017 discloses a kind of C4 that utilizes the cracking ethylene device or the above cut of C4
-1Under the condition with nonzeolite small pore molecular sieve catalyst ((EL
XAl
YP
Z) O
2) contact reacts production ethene and propylene.Wherein, EL can be respectively Si, Mg, Zn, Fe, Co, Ni, Mn, Cr or and composition thereof, its aperture is less than 0.5 nanometer.
It is that raw material carries out catalytic cracking reaction selectivity production C2～C4 alkene at two-stage reactor that USP6106697 discloses with wax oil or residual oil.In first step reaction zone, be that raw material carries out popular response and generates the gas oil fraction product on macroporous catalyst (mean pore size is greater than 0.7nm) with wax oil or residual oil.Second reaction zone is a raw material in temperature of reaction with the first reaction zone gas oil fraction product: 500～650 ℃, agent-oil ratio are 4～10: 1, hydrocarbon partial pressure is that intermediate pore molecular sieve catalyst (mean pore size is less than 0.7nm) contact is carried out catalysis and reacted the generation small-numerator olefin under 70～280 kPas of conditions.
In addition, along with the increasingly stringent of environment to the specification of quality of gasoline products, can produce low alkene, sulphur and nitrogen content cleaning high-quality gasoline and other oil fuel product have become the key point that the interior oil refining enterprise of worldwide is able to survival and development.The reformulated gasoline standard that formulate in countries in the world and area is not quite similar, but total principle be in the gasoline fraction olefin(e) centent 20% heavy below, sulphur content is below 100ppm.
The content of the alkene in the commercial gasoline weighs % 35～65 in China at present, and is rich in the gasoline poor heat stability of alkene.Alkene can be oxidized to alluvial deposit attached to the main oil mass mouth of carburettor, the inwall of idling jet and the surface of butterfly under the temperature condition of fuel of internal combustion engine system in the automobile driving process, cause the vehicle in use unstable idle speed very soon, the speed-raising fuel feeding is smooth, gasoline combustion is insufficient, make hydrocarbon polymer, CO (carbon monoxide converter) emission increase contaminate environment.
CN1244568A discloses a kind of catalysis conversion method of gasoline upgrading, be that the bottom of the low octane value gasoline after the preheating from riser tube entered, highly olefinic gasoline enters from the middle part of riser tube or the bottom of fluidized-bed, contacts with catalyzer, and reaction back effluent enters settling vessel; Reaction product isolated, spent agent returns riser tube and recycles after stripping, regeneration.The method that adopts this invention to provide, the alkene during gasoline is formed can be reduced to 20wt%, and the isoparaffin during gasoline is formed can be increased to more than the 30wt%, and the RON of gasoline is about 90.
CN1244569A discloses a kind of catalysis conversion method that reduces gasoline olefin, sulphur and nitrogen content, being the gasoline stocks after the preheating to be entered in riser tube or the fluidized-bed reactor contact with catalyzer, is that 100～600 ℃, weight hourly space velocity are 1～120hr in temperature of reaction
-1, catalyzer and gasoline stocks weight ratio be 2～15: 1, the weight ratio of water vapor and stock oil is to carry out catalytic conversion reaction under 0～0.1: 1 condition; Reaction product isolated, spent agent returns riser tube and recycles after stripping, regeneration.The method that adopts this invention to provide, the alkene during gasoline is formed can be reduced to 20wt%, and the isoparaffin during gasoline is formed can be increased to more than the 66wt%.
CN1245202A discloses the catalysis conversion method that reduces olefin(e) centent in liquefied gas and the gasoline, be to enter with catalyzer at riser tube or by the bottom that in riser tube and the compound reactor that fluidized-bed constitutes the conventional cracking stock oil after the preheating is entered riser tube to contact, the oil gas that reaction back generates goes upward to the middle part of riser tube or riser tube top and contact with catalyzer after the cooling and proceed reaction, and effluent enters settling vessel after reacting; Reaction product isolated, spent agent is divided into two portions after stripping, regeneration, and wherein a part enters the riser tube bottom, and another part enters the middle part of riser tube after cooling or the bottom cycle of riser tube is used.The method that adopts this invention to provide, the butylene in the liquefied gas is reduced to 17.5wt%, and Trimethylmethane rises to 37.04wt%, and the alkene during gasoline is formed can be reduced to 12.32wt%, and the isoparaffin during gasoline is formed can be increased to more than the 41.83wt%.
CN1279970A discloses the catalysis conversion method of a kind of high-yield diesel oil and liquefied gas, be to have in four sections riser tube or the fluidized-bed reactor at one to carry out, gasoline stocks injects the gasoline cracking zone and contacts with high-temperature regenerated catalyst, the heavy % part in 20 heavy % of conventional cracking stock～100 separately or be mixed with slurry oil and/or heavy cycle oil injects the mink cell focus cracking zone together, the heavy % part in 0 heavy % of conventional cracking stock～80 separately or be mixed with slurry oil and/or heavy cycle oil injects the light-oil cracking section together, the reaction terminating medium injects the reaction terminating section stops reaction, reaction product isolated, reclaimable catalyst enters revivifier through stripping, recycles after burning.This method can improve the yield of liquefied gas and diesel oil simultaneously, reduces sulphur content, olefin(e) centent in the catalytic gasoline, and gasoline octane rating increases.
CN1065900C discloses a kind of method of catalytic aromatization of gasoline fraction, be to make stock oil after the preheating and water vapour in fluidized-bed reactor, contact with the microspherical catalyst that contains the five-ring supersiliceous zeolite of heat, be that the weight ratio of 500～650 ℃, catalyzer and gasoline fraction is 5～15 in temperature of reaction: 1, the bed weight hourly space velocity is 1～6 hour
-1, water-oil ratio is 0.05～0.50: 1, pressure is 1.5～4.0 * 10
5React under the condition of handkerchief; Reaction product, water vapour and reclaimable catalyst carry out gas solid separation; The product liquid that reaction product isolated obtains being rich in the gaseous product of propylene and butylene and is rich in aromatic hydrocarbons; Spent agent Returning reactor behind water vapor stripping and coke burning regeneration recycles.The characteristics of this method make the successive reaction-reprocessing cycle operating method that adopts fluidized-bed reactor and catalyst fluidization attitude to carry carry out aromatization.
In sum, do not relate to as yet in the prior art with gasoline and the hydrocarbon gas that is rich in C 4 fraction and be raw material, utilize catalytic conversion process to produce the technological process of propylene and high-quality gasoline.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of C 4 fraction propylene enhancing that utilizes, reduce the petroleum hydrocarbon catalytic conversion method of content of olefin in gasoline simultaneously.
Method provided by the invention is as follows: hydrocarbon gas, the gasoline stocks that will be rich in C 4 fraction inject fluidized-bed reactor, contact, react with the catalyzer that contains the five-ring supersiliceous zeolite, temperature of reaction is that 500～650 ℃, catalyzer and gasoline stocks and the weight ratio that is rich in the mixture of C 4 fraction hydrocarbon gas are 1～180: 1, the bed weight hourly space velocity is 0.1～30 hour
-1Reaction product isolated and reclaimable catalyst; Reclaimable catalyst Returning reactor after stripping, all or part of regeneration recycles.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
1, the present invention adopt fluidized-bed reactor carry out successive reaction-reprocessing cycle operating method carry out catalyzed conversion take into account voluminous small-numerator olefin, particularly propylene and the cleaning high-quality gasoline.
2, the present invention can handle the gasoline that olefin(e) centent is the gasoline, particularly high olefin content of 20～90 heavy %, is suitable for the dissimilar five-ring high-silica zeolite catalyzer that contain.
3, the present invention can handle the C4 hydrocarbon-fraction that is rich in alkene of different process technology processing output.
4, the present invention does not have particular requirement to foreign matter content in the raw material, does not therefore need stock oil is carried out pre-treatment.
5, the main products of method provided by the present invention is gasoline and the dry gas that is rich in small-numerator olefin, liquefied gas, also has a spot of diesel oil, heavy oil etc. in addition.Alkene in the gasoline products, sulphur and nitrogen content are lower, can satisfy new standard of fuel, are rich in small-numerator olefins such as ethene and propylene in dry gas and the liquefied gas.
Embodiment
The hydrocarbon gas that is rich in C 4 fraction of the present invention is meant with the C 4 fraction to be the low-molecular-weight hydrocarbon that exists with gas form under the normal temperature, normal pressure of main component, comprises C4 and following alkane, alkene and alkynes thereof.It can be the gaseous hydrocarbon products that is rich in C 4 fraction from catalytic cracking unit or cat-cracker, also can be the hydrocarbon gas that is rich in C 4 fraction that other oil refining or chemical process are produced.In the described hydrocarbon gas that is rich in C 4 fraction, the content of C4 alkene is preferably greater than 50 heavy % greater than 40 heavy %, preferably more than 60 heavy %.
Gasoline stocks of the present invention is selected from: the mixture of one or more in the gasoline fraction that catalytic cracking raw gasline, stable gasoline, coker gasoline, viscosity breaking gasoline and other oil refining or chemical process are produced, preferably: the mixture of one or more in catalytic cracking raw gasline, stable gasoline, the coker gasoline, most preferably: catalytic cracking raw gasline and/or stable gasoline.The olefin(e) centent of described gasoline stocks is 20～95 heavy %, and preferred 25～90 heavy % are preferably in more than the 50 heavy %.Described gasoline stocks can be the gasoline fraction of full range, and for example, 40～204 ℃ also can be part narrow fraction wherein, for example, and 90～204 ℃.
In method provided by the invention, being rich in the hydrocarbon gas of C 4 fraction and the weight ratio of gasoline stocks is 0.1～2: 1, preferred 0.2～1.5: 1, most preferably 0.4～1.0: 1.
In method provided by the invention, the hydrocarbon gas, the gasoline stocks that are rich in C 4 fraction are injected fluidized-bed reactor, contact, react with the catalyzer that contains the five-ring supersiliceous zeolite, temperature of reaction is 500～650 ℃, preferred 550～600 ℃, catalyzer and gasoline stocks are 1～180: 1 with the weight ratio that is rich in the mixture of C 4 fraction hydrocarbon gas, preferred 10～100: 1, and the bed weight hourly space velocity is 0.1～30 hour
-1, preferred 0.5～5 hour
-1
The reaction pressure that the invention provides method is normal pressure～450 kPa, preferred normal pressure～300 kPas, and water vapor and gasoline stocks are 0～0.50: 1 with the weight ratio that is rich in the mixture of C 4 fraction hydrocarbon gas, preferred 0.01～0.25: 1.
Catalyzer of the present invention is the catalyzer that contains the five-ring supersiliceous zeolite, and this activity of such catalysts component is made up of one or more the mixture among ZSM-5 series zeolite or supersiliceous zeolite with five-membered ring structure and the Y that contains or do not contain rare earth or HY type zeolite, the ultrastable Y that contains or do not contain rare earth, β zeolite, ferrierite, the SAPO.The carrier of this catalyzer is selected from the carrier of conventional FCC catalyzer, and for example, aluminum oxide, pure aluminium silicate, natural clay add aluminum oxide etc.
Hydrocarbon gas, gasoline stocks that the present invention will be rich in C 4 fraction inject fluidized-bed reactor, contact with the catalyzer that contains the five-ring supersiliceous zeolite and also carry out catalytic conversion reaction under these conditions.Described gasoline stocks can be through preheating, also can be without preheating.The catalyzer of reaction product isolated and reaction back band charcoal, reaction product further are separated into product liquids such as the gaseous product that is rich in propylene and C 4 fraction and gasoline, diesel oil through fractionating system.The hydrocarbon gas that is rich in C 4 fraction in the described gaseous product can be back to further reaction in the fluidized-bed reactor, and its freshening amount accounts for 0～60 heavy % of total petroleum hydrocarbon raw material, preferred 10～50 heavy %.Product liquid, for example, gasoline or diesel oil also can be according to the particular case and the oil property part freshenings of device.The catalyzer of reaction back band charcoal is after water vapor stripping and part or all of regeneration, and Returning reactor recycles.
In method provided by the present invention, can be selected from the catalyzer that contains the five-ring supersiliceous zeolite that the hydrocarbon gas that is rich in C 4 fraction contacts with gasoline stocks: the mixture of one or more in regenerated catalyst, half regenerated catalyst, the reclaimable catalyst, preferred regenerated catalyst.
The following examples will be further specified the present invention, but not thereby limiting the invention.Employed catalyzer and raw material properties are listed in table 1 and table 2 respectively among the embodiment.Catalyzer in the table 1 is by Qilu Petrochemical company of Sinopec Group catalyst plant industrial production, and trade names are CIP.
Embodiment 1
Present embodiment explanation: with the hydrocarbon gas and the full distillation gasoline that are rich in C 4 fraction is raw material, uses the CIP catalyzer to carry out the test of one way catalyzed conversion in the small-sized fluidized bed reactor.
Gasoline A enters in the fluidized-bed reactor shown in hydrocarbon gas that is rich in C 4 fraction as shown in table 3 and the table 2, is 550 ℃ in temperature of reaction, and reactor head pressure is 200 kPas, and water hydrocarbon mass ratio is to contact with catalyzer under 0.08: 1 the condition to carry out catalyzed reaction.Reaction product, steam and spent agent separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and the spent agent catalyzer is gone out the hydrocarbon product that adsorbs on the spent agent by the water vapor stripping.Spent agent behind the stripping contacts with the warm air that heated regenerates, and the catalyzer after the regeneration carries out new catalytic conversion reaction again.Test conditions and main result see Table 3.
From the test-results of table 3 as can be seen, the mixture of gasoline and hydrocarbon gas 550 ℃ with the catalyzer contact reacts after can reduce olefin content in gasoline significantly, with olefin(e) centent in the raw material is that 57.85 heavy % compare and reduced by 21.84 percentage points, alkane, naphthenic hydrocarbon and aromaticity content all have increase by a relatively large margin, wherein isoparaffin content increases to 27.46 heavy % from 12.31 heavy %, alkane content increases to 40.91 heavy % by 22.79 heavy %, cause the RON and the MON of gasoline to increase by 3.6 and 5.6 units respectively, the productive rate of propylene is 12.25 heavy % simultaneously, is higher than conventional catalytic cracking process far away.
Comparative Examples
The explanation of this Comparative Examples: when not with the petroleum hydrocarbon that is rich in C 4 fraction as raw material, only adopt gasoline stocks, catalyzer, the operational condition identical to carry out catalyzed conversion and test resulting result with embodiment 2.
Gasoline B as shown in table 2 injects in the fluidized-bed reactor, is 550 ℃ in temperature of reaction, and reactor head pressure is 200 kPas, and water hydrocarbon mass ratio is to contact with the CIP catalyzer under 0.10: 1 the condition to carry out catalyzed reaction.Reaction product, steam and spent agent separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and the spent agent catalyzer is gone out the hydrocarbon product that adsorbs on the spent agent by the water vapor stripping.Spent agent behind the stripping contacts with the warm air that heated regenerates, and the catalyzer after the regeneration carries out new catalytic conversion reaction again.Test conditions and main result see Table 3.
From the test-results of table 3 as can be seen, gasoline B is under 550 ℃ temperature of reaction condition, alkene is reduced to 35.56 heavy % by 73.91 heavy % in the raw material, about 38.35 percentage points have been reduced, alkane, naphthenic hydrocarbon and aromaticity content all have increase by a relatively large margin, wherein isoparaffin content increases to 25.84 heavy % from 12.26 heavy %, alkane content increases to 39.80 heavy % by 20.95 heavy %, the RON of gasoline and MON have increased by 0.5 and 1.0 unit respectively, the productive rate of propylene is 18.16 heavy % simultaneously, but the dry gas yied in the product is up to 7.12 heavy %, and product distributes undesirable.
Embodiment 2
Present embodiment explanation: with the hydrocarbon gas and the narrow fraction gasoline that are rich in C 4 fraction is raw material, uses the CIP catalyzer to carry out the situation of catalyzed conversion test in the small-sized fluidized bed reactor.
Gasoline B enters in the fluidized-bed reactor shown in hydrocarbon gas that is rich in C 4 fraction as shown in table 3 and the table 2, in temperature of reaction is 550 ℃, reactor head pressure is 200 kPas, and water hydrocarbon mass ratio is to contact with the CIP catalyzer under 0.05～0.15: 1 the condition to carry out catalyzed reaction.Reaction product, steam and spent agent separate in settling vessel, and reaction product isolated obtains gaseous product and product liquid, and the spent agent catalyzer is gone out the hydrocarbon product that adsorbs on the spent agent by the water vapor stripping.Spent agent behind the stripping contacts with the warm air that heated regenerates, and the catalyzer after the regeneration carries out new catalytic conversion reaction again.Test conditions and main result see Table 3.
When being rich in C 4 fraction hydrocarbon gas and gasoline B combined feed, with the basic identical operational condition of Comparative Examples under, C 4 fraction and gasoline B are under 550 ℃ temperature of reaction condition, alkene is reduced to 33.42 heavy % by 73.91 heavy % in the raw material, about 40.49 percentage points have been reduced, alkane, naphthenic hydrocarbon and aromaticity content all have increase by a relatively large margin, wherein isoparaffin content increases to 28.35 heavy % from 12.26 heavy %, alkane content increases to 41.89 heavy % by 20.95 heavy %, gasoline RON and MON slightly increase, the productive rate of propylene is 16.17 heavy %, and the purer gasoline B catalytic reforming of product distribution simultaneously has improvement, and dry gas and coke yield all decrease.
Change operation, as agent-oil ratio is 10 o'clock, with C 4 fraction and gasoline B combined feed under 550 ℃ temperature of reaction condition, alkene is reduced to 26.36 heavy % by 73.91 heavy % in the raw material, about 47.55 percentage points have been reduced, purer gasoline upgrading alkene has reduced by 8.7 percentage points, alkane, naphthenic hydrocarbon and aromaticity content all have increase by a relatively large margin, wherein isoparaffin content increases to 20.16 heavy % from 12.26 heavy %, alkane content increases to 33.29 heavy % by 20.95 heavy %, the productive rate of propylene is 13.55 heavy %, and the purer gasoline B catalytic reforming of product distribution simultaneously has improvement, and dry gas and coke yield have reduction greatly.
Table 1
| The catalyzer brand | ????CIP |
| Active component | ????ZRP+USY |
| Chemical constitution, % Fe 2O 3????Al 2O 3????Na 2O | ????0.63 ????56.3 ????0.14 |
| The physical properties specific surface, m 2/ g pore volume, ml/g apparent bulk density, g/cm 3 | ????82 ????0.137 ????0.86 |
| Screening, V% 0～40 μ m 40～80 μ m＞80 μ m | ????27.2 ????55.7 ????17.1 |
| Micro-activity after the burin-in process | ????62 |
Table 2
* chromatography
| Project | Full distillation gasoline (A) | Petroleum naphtha (B) |
| Density (200 ℃), g/cm 3 | ????0.7246 | ????0.6696 |
| Mercaptan sulfur, μ g/g | ????51 | ????29 |
| Maleic value, gI 2/100g | ????1.7 | ????1.0 |
| Elementary composition, % C H S, mg/L N, mg/L | ????86.29 ????13.54 ????550 ????67 | ????85.18 ????14.44 ????152 ????11 |
| PIONA*, m% normal paraffin isoparaffin alkene naphthenic hydrocarbon aromatic hydrocarbons | ????10.48 ????12.31 ????57.85 ????6.60 ????12.80 | ????8.69 ????12.26 ????73.91 ????3.39 ????1.76 |
| Octane value MON RON | ????79.7 ????90.6 | ????85.1 ????94.2 |
| Boiling range, 0 ℃ of initial boiling point, 10% 50% 90% final boiling point | ????38 ????51 ????80 ????155 ????192 | ????32 ????40 ????48 ????65 ????77 |
Table 3
| Stock oil | ????C 4 | Embodiment 1 | Comparative Examples | Embodiment 2 | |
| Temperature of reaction, ℃ | ???????????????????????????????550 | ||||
| Air speed, h -1 | ????--- | ????0.9 | ????0.9 | ????0.9 | ????1.0 |
| Agent-oil ratio, m/m | ????--- | ????20 | ????20 | ????20 | ????10 |
| Product distributes, heavy % H 2～C 2??C 3～C 4??C 5+ gasoline, diesel coke adds up to | ????--- ????--- ????--- ????--- ????--- | ????4.00 ????51.14 ????41.04 ????0.98 ????2.84 ????100.00 | ????7.12 ????37.14 ????52.10 ????0.68 ????2.96 ????100.00 | ????4.44 ????52.26 ????39.87 ????0.57 ????2.85 ????100.00 | ????3.79 ????46.42 ????46.66 ????0.94 ????2.20 ????100.00 |
| The heavy % ethylene, propylene of gas olefins yield butylene ethene+propylene+butylene | ????--- ????--- ????--- ????--- | ????2.79 ????12.25 ????19.32 ????34.36 | ????5.46 ????18.16 ????10.73 ????34.35 | ????3.45 ????16.17 ????16.98 ????36.60 | ????2.89 ????13.55 ????15.04 ????31.49 |
| Gas composition, heavy % hydrogen methane ethane and ethylene propane propylene iso-butane normal butane butene-1 isobutene cis-butene-2 trans-butene-2 amounts to | ????0.00 ????0.00 ????0.00 ????0.00 ????13.11 ????1.40 ????14.35 ????7.64 ????11.91 ????26.87 ????14.82 ????9.90 ????100.00 | ????0.27 ????1.24 ????0.69 ????5.07 ????10.71 ????22.22 ????17.98 ????6.79 ????5.42 ????14.22 ????8.91 ????6.48 ????100.00 | ????0.42 ????2.08 ????1.26 ????12.33 ????5.54 ????41.04 ????10.58 ????2.52 ????3.82 ????10.35 ????5.82 ????4.26 ????100.00 | ????0.19 ????0.94 ????0.61 ????6.08 ????10.47 ????28.52 ????17.38 ????5.85 ????4.59 ????12.75 ????7.36 ????5.25 ????100.00 | ????0.23 ????0.97 ????0.58 ????5.76 ????11.05 ????27.00 ????18.06 ????6.39 ????4.57 ????12.66 ????7.43 ????5.31 ????100.00 |
| Gasoline hydrocarbon is formed: NP IP O N A | ????--- ????--- ????--- ????--- | ????13.45 ????27.46 ????36.01 ????8.49 ????14.57 | ????13.96 ????25.84 ????35.56 ????8.53 ????16.1 | ????13.54 ????28.35 ????33.42 ????8.70 ????16.01 | ????12.68 ????20.61 ????26.36 ????8.98 ????31.37 |
| Chromatography MON RON | ????--- ????--- | ????85.3 ????94.2 | ????86.1 ????94.8 | ????85.3 ????94.3 | ????81.2 ????91.6 |
Claims (13)
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| CN1333046C (en) * | 2004-04-29 | 2007-08-22 | 中国石油化工股份有限公司 | Catalytic conversion process for petroleum hydrocarbons |
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