CN102199441A - Catalytic conversion method capable of improving product selectivity - Google Patents
Catalytic conversion method capable of improving product selectivity Download PDFInfo
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- CN102199441A CN102199441A CN201010132016XA CN201010132016A CN102199441A CN 102199441 A CN102199441 A CN 102199441A CN 201010132016X A CN201010132016X A CN 201010132016XA CN 201010132016 A CN201010132016 A CN 201010132016A CN 102199441 A CN102199441 A CN 102199441A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 44
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 29
- 239000000571 coke Substances 0.000 claims abstract description 22
- 239000003502 gasoline Substances 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims description 79
- 239000007789 gas Substances 0.000 claims description 43
- 239000000047 product Substances 0.000 claims description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims description 22
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 22
- 239000010457 zeolite Substances 0.000 claims description 22
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- 238000011069 regeneration method Methods 0.000 claims description 18
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- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 10
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 7
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 6
- 240000006909 Tilia x europaea Species 0.000 claims description 6
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- 239000003209 petroleum derivative Substances 0.000 claims description 6
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- 238000012546 transfer Methods 0.000 claims description 6
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- 239000003245 coal Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
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- 239000002994 raw material Substances 0.000 abstract description 9
- 239000003208 petroleum Substances 0.000 abstract description 6
- 238000004523 catalytic cracking Methods 0.000 description 15
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- 229910052760 oxygen Inorganic materials 0.000 description 8
- 238000005336 cracking Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
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- 238000009826 distribution Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000003610 charcoal Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
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- 229930195733 hydrocarbon Natural products 0.000 description 5
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 229910052621 halloysite Inorganic materials 0.000 description 4
- -1 polynite Chemical compound 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000002010 green coke Substances 0.000 description 3
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- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000004113 Sepiolite Substances 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
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- 235000019355 sepiolite Nutrition 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
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- 241000196324 Embryophyta Species 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 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
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
提高产品选择性的催化转化方法，其中原料油在反应器内与含炭催化剂接触进行反应，其特征是催化剂含炭量为0.15～0.8重％。本发明涉及提高产品选择性的催化转化方法，特别是在将重质原料转化为高价值产品如汽油等，同时使干气和焦炭产率大幅度降低，从而实现石油资源的高效利用的方法。
A catalytic conversion method for improving product selectivity, wherein the raw oil is reacted in contact with a carbon-containing catalyst in a reactor, and the characteristic is that the carbon content of the catalyst is 0.15-0.8% by weight. The invention relates to a catalytic conversion method for improving product selectivity, especially a method for converting heavy raw materials into high-value products such as gasoline, while greatly reducing dry gas and coke yields, thereby realizing efficient utilization of petroleum resources.
Description
Technical field
The present invention relates to improve the catalysis conversion method of product selectivity, particularly heavy feed stock is converted into high-value product for example gasoline etc. simultaneously, thereby make dry gas and coke yield reduce the method for the efficient utilization that realizes petroleum resources significantly.
Background technology
Catalytic cracking has been topmost light materialization of heavy oil process since being born the forties in 20th century always.Reason one is that its raw material sources are extensive, can adopt wax oil, can also adopt the deasphalted oil of long residuum, vacuum residuum or part to mix vacuum residuum; The 2nd, its products scheme is flexible, can be fuel type, also can be the fuel chemical industry type, as voluminous gasoline, high-yield diesel oil, producing more propylene etc.; The 3rd, its product property can be adjusted accordingly by the adjustment of catalyst formulation and the variation of processing parameter, as improving gasoline octane rating, reducing content of olefin in gasoline etc.
The process of in fact also a kind of continuous pursuit product selectivity of the evolution of catalytic cracking.For example catalytic cracking catalyst develops into the synthetic silica-alumina catalyst from the natural clay catalyzer, and the molecular sieve catalyst that uses has up till now again realized improving the purpose of product selectivity by updating of catalyzer, and dry gas and coke yield reduce gradually.And catalytic cracking process also develops into moving-bed, dense phase fluidized bed gradually and uses the riser catalytic cracking technology at present from fixed bed, by these technological changes, dry gas and coke yield further reduce, and have realized effective utilization of petroleum resources to a certain extent.
Oil is a kind of Nonrenewable resources, and along with the development of society, energy dilemma highlights gradually.How to effectively utilize the direction that limited petroleum resources become new technology development more.Catalytic cracking is that heavy raw oil is converted into one of lighting end most effectual way, therefore around how also to have launched a lot of research work by the productive rate that reduces catalytic cracking process dry gas and coke.
CN101275081A discloses a kind of method that reduces catalytic cracked dry gas, hot regenerated catalyst is transported to reactor bottom by pre-lift gas, contact with active ingredient with the conventional cracking stock oil of preheating and react, the add-on of active ingredient is 10 * 10 of a conventional cracking stock oil quality
-6～500 * 10
-6, catalyzer and stock oil weight ratio are 1～40: 1,0.2～7 second reaction times, 460 ℃～600 ℃ of temperature of reaction.Reaction product, pre-lift gas, reclaimable catalyst carry out gas solid separation by cyclonic separator, reaction product enters the separation column separation and obtains product, and reclaimable catalyst is introduced into stripper, the water steam stripped goes out the hydrocarbon product that adsorbs on the catalyzer, return revivifier through the reclaimable catalyst inclined tube again, in the presence of oxygen-containing gas, carry out coke burning regeneration and recycle.This method has reduced the generation of dry gas, has improved the product distribution.
Catalytic cracking has that the material choice scope is wide, quality product is high, product restructuring is flexible and the relative characteristic of simple of equipment, so catalytic cracking technology is one of important heavy oil lighting means.Oil is a kind of Nonrenewable resources, and along with the development of society, crude oil price is growing, and the heavy oil demand descends day by day, the countries in the world catalytic cracking technology heavy oil fluid catalytic cracking of progressively marching toward.But carbon residue and metal content are higher in heavy oil and/or the residual oil, and in reaction process, catalyzer will deposit a large amount of cokes, cause catalyst activity seriously to descend, in order to recover catalyst activity, and must be with the burning-off in regenerative process of the carbon distribution on the catalyzer.The common claimed range of regenerated catalyst carbon content is 0.05～0.10 heavy % (referring to CN1221022A) at present.
USP3,563,911 disclose a kind of two-stage regeneration, and reclaimable catalyst is in proper order by first dense phase fluidized bed and second dense phase fluidized bed, contact with oxygen containing gas and to make that coke carries out combustion reactions on the catalyst surface, the flue gas that is produced mixes and entrained catalyst enters the dilute phase settling section.The first dense phase fluidized bed regeneration temperature is greater than 1050 °F (promptly 565.5 ℃); The gas superficial linear velocity of second dense phase fluidized bed is 1.25 feet per seconds～6 feet per seconds (i.e. 0.381 meter per second～1.83 meter per seconds), and regeneration temperature is 1125～1350 °F (promptly 607.2～732.2 ℃).This method is compared with catalyzer single hop renovation process, and under the not high condition of regenerative process carbon-burning load, it is nearly 40% that the reserve of revivifier inner catalyst can reduce, and the carbon content of regenerated catalyst can be lower than 0.1% weight.
CN1052688A discloses a kind of two-stage oxidizing regenerative method of fluid catalyst, reclaimable catalyst contacts the combustion reactions of concurrent green coke charcoal with oxygen containing gas in first dense phase fluidized bed, the gas superficial linear velocity of first dense phase fluidized bed is 0.8～2.5 meter per second, the catalyzer mean residence time is 0.6～1.0 minute, and regeneration temperature is 650～750 ℃; Catalyzer is removed most of coke in the first fluidized bed after, the catalyzer of partial regeneration and gas pass sparger together and on flowing to, enter second fluidized-bed, contact the combustion reactions of concurrent green coke charcoal again with oxygen containing gas, the gas superficial linear velocity of second dense phase fluidized bed is 1.2～3.0 meter per seconds, the catalyzer mean residence time is 1.0～2.2 minutes, regeneration temperature is 700～800 ℃, after catalyzer is fully regenerated, regenerated catalyst separates with flue gas, part regenerated catalyst enters reactor, and another part regenerated catalyst turns back to the first fluidized bed.This method has been simplified the structure and the reclaiming process flow process of revivifier.
CN1221022A discloses a kind of lapping type two-stage regeneration technology of heavy oil fluidized catalystic cracking, this method comprises two revivifiers of arranged superposed, one section regeneration is last, the temperature of first section revivifier is 650～720 ℃, two sections regeneration are following, the temperature of second section revivifier is 650～780 ℃, be connected as a single entity with the low pressure drop grid distributor between two revivifiers, make full use of contain certain excess oxygen content two sections regenerated flue gas as one section regenerative combustion gas, to save the oxygen-containing gas consumption is save energy and productive expense, and two revivifiers only need be with a flue and double slide valve or butterfly valve, simple in structure, be convenient to control, because minimizing equipment, thereby the compact construction investment that reduced arranged.
Reclaimable catalyst is subjected to air film diffusion, grieshoch diffusion and chemical reaction control in regenerative process.In order to obtain fast coke velocity and lower regenerated catalyst carbon content, the measure of taking normally improves regeneration temperature, raising bed layer flow speed, increases the mode of recovery time and increase oxygen level.For heavy-oil catalytic, need usually to adopt two-stage regeneration could satisfy the requirement of lower carbon on regenerated catalyst.When pursuing the selectivity of purpose product, cross the selectivity raising that low regenerated catalyst carbon content is unfavorable for the purpose product.
CN101362959A discloses a kind of catalysis conversion method of producing propylene and stop bracket gasoline, and difficult cracked raw material contacts with hot regenerated catalyst earlier, at 600～750 ℃ of temperature, weight hourly space velocity 100～800h
-1, pressure 0.10～1.0MPa, catalyzer and raw material weight ratio 30～150, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05～1.0 the condition, reactant flow is mixed with easy cracked stock oil, at 450～620 ℃ of temperature, weight hourly space velocity 0.1～100h
-1, pressure 0.10～1.0MPa, catalyzer and raw material weight ratio 1.0～30, the weight ratio of water vapor and raw material is to carry out cracking reaction under 0.05～1.0 the condition; Reclaimable catalyst is with after reaction oil gas separates, reclaimable catalyst enters stripper, Returning reactor behind stripping, coke burning regeneration, reaction oil gas obtains purpose product propylene and stop bracket gasoline and cracked raw material again through separation, and it is that 180～260 ℃ cut, heavy aromatics raffinated oil that the described raw material of cracked again comprises boiling range.The productive rate and the selectivity of this method propylene significantly increase, and the productive rate and the octane value of gasoline improve significantly, and dry gas yied reduces amplitude up to more than the 80 heavy %.This method is based on reaction space-time restriction effect theory, adopt Reaction Separation technology separating with alkane building stone in the stock oil and aromatic hydrocarbons building stone, saturated branch in the alkane building stone and light aromatic hydrocarbons are converted into liquid product through relaxing catalytic cracking process, part bituminous matter in the aromatic hydrocarbons building stone is adsorbed by the catalyzer outside surface, polycyclic aromatic hydrocarbons and colloid are retained in the distillate behind the upgrading as far as possible, thereby realize alkane and this notion of alkane building stone selective cracking.Containing more polycyclic aromatic hydrocarbons and gelationus distillate, carry out hydrogenation in the hydrotreatment unit saturated or carry out extracting in heavy aromatics extracting unit, the saturated distillate of hydrogenation or to raffinate oil be the fine catalytically cracked stock, improve the selectivity of catalytic cracking unit production purpose product, thereby realize that petroleum resources rationally and efficiently utilize.The employed catalyzer of this method preferably activity of such catalysts is more even with other property distribution, thereby helps the control of reaction parameter.
The contriver is by discovering, in the catalytic cracking reaction process, the conversion of hydro carbons is subjected to the influence of catalyst surface acidity to a great extent, and in general strong more its adsorptive power of acidity is big more, and the big more easy more generation dehydrogenative condensation reaction of sour density.Various hydrocarbon in the adsorptive power size of catalyst surface are: condensed-nuclei aromatics＞condensed ring naphthenic hydrocarbon＞alkene＞mononuclear aromatics＞single-ring naphthene＞alkane, be adsorbed on the strong acid acid position so condensed-nuclei aromatics is the easiest, and be difficult to desorption, finally show that at catalyzer dehydrogenative condensation generates coke, cause dry gas and coke yield to increase.Therefore in order to avoid the reaction of condensed-nuclei aromatics dehydrogenative condensation as far as possible, often by adopting new catalytic material and different catalyst treatment modes to obtain the catalyzer of the strong and sour density of appropriate acid.Can realize suitable control catalyst activity by burying the sour position of strong acid and part by suitable control regenerated catalyst carbon content.
Summary of the invention
The present invention relates to improve the catalysis conversion method of product selectivity, particularly heavy feed stock is converted into high-value product for example gasoline etc. simultaneously, thereby make dry gas and coke yield reduce the method for the efficient utilization that realizes petroleum resources significantly.
First kind of embodiment of the present invention is as follows:
Stock oil contacts and reacts with containing Pd/carbon catalyst in reactor, it is characterized in that the catalyzer carbon content is that 0.15～0.8 heavy %, temperature of reaction are 400～650 ℃, weight hourly space velocity 2～100h
-1, catalyzer and stock oil weight ratio be 1～30.
Described catalyzer carbon content is preferably 0.16～0.6 heavy %, more preferably 0.17～0.5 heavy %.
Described temperature of reaction is preferably 450～600 ℃, more preferably 480～540 ℃.
Described weight hourly space velocity is preferred 5～80h
-1, more preferably 8～60h
-1
Described catalyzer and stock oil weight ratio are preferably 2～25, and more preferably 3～14.
Described reaction pressure is 0.10MPa～1.0MPa.
Described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, the hydrogenation wax oil, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
Described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is large pore zeolite and/or mesopore zeolite, the preferred Y series zeolite of large pore zeolite wherein, preferred ZSM series zeolite of mesopore zeolite and/or ZRP zeolite.
Described inorganic oxide is selected from silicon-dioxide (SiO as matrix
2) and/or aluminium sesquioxide (Al
2O
3).In butt, the heavy % in silica comprises 50 heavy～90 in the inorganic oxide, aluminium sesquioxide accounts for the heavy % in 10 heavy～50.
Described clay is as caking agent, is selected from kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.
The catalyzer that preferred coarse grain directly distributes, its size-grade distribution is: account for all particulate volume ratios less than 40 microns particles and be lower than 10%, be preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
Described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
A position described stock oil is introduced in the reactor, or described stock oil is introduced in the reactor in the position of identical or different height more than.
Second kind of embodiment of the present invention is as follows:
Stock oil in reactor with contain Pd/carbon catalyst and contact and react, it is characterized in that catalyzer carbon content, temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil, wherein said catalyzer carbon content is that 0.15～0.8 heavy %, described weight hourly space velocity are 2～100h
-1, described temperature of reaction is 400～650 ℃, described catalyzer and stock oil weight ratio are 1～30.
Described catalyzer carbon content is preferably 0.16～0.6 heavy %, more preferably 0.17～0.5 heavy %.
Described temperature of reaction is preferably 450～600 ℃, more preferably 480～540 ℃.
Described weight hourly space velocity is preferred 5～80h
-1, more preferably 8～60h
-1
Described catalyzer and stock oil weight ratio are preferably 2～25, and more preferably 3～14.
Described reaction pressure is 0.10MPa～1.0MPa.
Described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, the hydrogenation wax oil, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
In some embodiments of second aspect, described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is large pore zeolite and/or mesopore zeolite, the preferred Y series zeolite of large pore zeolite wherein, preferred ZSM series zeolite of mesopore zeolite and/or ZRP zeolite.
Described inorganic oxide is selected from silicon-dioxide (SiO as matrix
2) and/or aluminium sesquioxide (Al
2O
3).In butt, the heavy % in silica comprises 50 heavy～90 in the inorganic oxide, aluminium sesquioxide accounts for the heavy % in 10 heavy～50.
Described clay is as caking agent, is selected from kaolin, halloysite, polynite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, the wilkinite one or more.
The catalyzer that preferred coarse grain directly distributes, its size-grade distribution is: account for all particulate volume ratios less than 40 microns particles and be lower than 10%, be preferably lower than 5%; Account for all particulate volume ratios greater than 80 microns particles and be lower than 15%, be preferably lower than 10%, all the other are 40～80 microns particle.
Described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
A position described stock oil is introduced in the reactor, or described stock oil is introduced in the reactor in the position of identical or different height more than.
Described method also comprises separates reaction product with catalyzer, catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises products such as propylene, gasoline and catalytic wax oil.
Described catalytic wax oil is that initial boiling point is not less than 260 ℃ cut, is preferably the cut that initial boiling point is not less than 330 ℃, and hydrogen richness is not less than 10.5 heavy % and preferably is not less than 10.8 heavy %.
The present invention compared with prior art has following technique effect:
1, dry gas yied reduces, and the dry gas selectivity improves;
2, coke yield reduces, and coke selectivity improves;
3, the intensity reduction is burnt in regeneration, and energy consumption reduces.
Description of drawings
Accompanying drawing is the synoptic diagram of the catalysis conversion method of one embodiment of the present invention.
Embodiment
Further specify method provided by the present invention below in conjunction with accompanying drawing, but therefore the present invention is not subjected to any restriction.
Accompanying drawing is the basic procedure synoptic diagram that improves the catalysis conversion method of product selectivity provided by the invention.
As shown in drawings, reclaimable catalyst enters revivifier 2 through inclined tube 1 to be generated, oxygen-containing gas is entered the bottom of revivifier 2 by main air grid distributor 4 through pipeline 3, contact the combustion reactions of concurrent green coke charcoal with reclaimable catalyst, flue gas is through revivifier dilute phase section 5, cyclonic separator 6 and flue gas pipeline 7 enter smoke energy recovering system 8, regenerated catalyst after the regeneration enters riser reactor 12 bottoms through regenerator sloped tube 9, it is up that pre-lifting medium enters riser reactor bottom lifting regenerated catalyst through pipeline 10, stock oil enters riser reactor through pipeline 11 and contacts with regenerated catalyst and carry out catalytic cracking reaction, and reaction oil gas is successively through settling vessel 14, cyclonic separator 15 and gas pipeline 16 enter separation system 17 and obtain the purpose product.Reclaimable catalyst enters inclined tube 1 to be generated through settling vessel 14 and stripper 13 and turns back to revivifier 2 and carry out next round regeneration.
The following examples will be further specified the present invention, but not thereby limiting the invention.Employed stock oil is the hydrogenation wax oil in embodiment and the Comparative Examples, and its character is listed in table 1.Catalyzer is produced by catalyzer branch office of Sinopec Group Shandong catalyst plant, and goods number is MLC-500, and its character is listed in table 2.The catalyzer carbon content is measured (RIPP 107-90) standard method test according to the carbon content of catalytic cracking catalyst in " petrochemical complex analytical procedure: RIPP test method " (Yang Cuiding etc. write, Science Press, nineteen ninety publication).
Embodiment 1
This embodiment tests on the middle-scale device of riser reactor according to the flow process of accompanying drawing, and stock oil enters riser reactor at 500 ℃ of temperature of reaction, weight hourly space velocity 12h
-1The weight ratio of catalyzer and stock oil is 5.2, the catalyzer carbon content is 0.21 heavy %, the weight ratio of water vapor and stock oil is to carry out cracking reaction under 0.05 condition, reaction product oil gas separates at settling vessel with band charcoal catalyzer to be generated, product cuts by boiling range in separation system, thereby obtains products such as propylene, gasoline and catalytic wax oil.Operational condition and product distribute and list in table 3.
Embodiment 2
Embodiment 2 adopts flow process and the operational condition identical with embodiment 1, and just the catalyzer carbon content is 0.28 weight %.Concrete operations condition and product distribute and list in table 3.
Comparative Examples
Comparative Examples adopts flow process and the operational condition identical with embodiment 1, and just the catalyzer carbon content is 0.05 weight %.Concrete operations condition and product distribute and list in table 3.
As can be seen from Table 3, compare with Comparative Examples, dry gas and the coke yield of embodiment 1 and embodiment 2 reduce significantly, and the selectivity of dry gas and coke is improved significantly.
Table 1
| The stock oil type | The hydrogenation wax oil |
| Stock oil character | |
| Density (20 ℃), g/cm 3 | 0.8911 |
| Sulphur content, ppm | 1800 |
| Nitrogen content, ppm | 400 |
| C, heavy % | 87.08 |
| H, heavy % | 12.92 |
| Boiling range (ASTM D-1160), ℃ | |
| IBP | 286 |
| 10％ | 353 |
| 30％ | 389 |
| 50％ | 415 |
| 70％ | 452 |
| 90％ | 504 |
| 95％ | 526 |
| Group composition, heavy % | |
| Stable hydrocarbon | 87.7 |
| Aromatic hydrocarbons | 11.2 |
Table 2
| The catalyzer goods number | MLC-500 |
| Chemical constitution, heavy % | |
| Aluminum oxide | 50.2 |
| Sodium oxide | 0.321 |
| Ferric oxide | / |
| Rare earth | |
| Apparent density, kilogram/rice 3 | 700 |
| Pore volume, milliliter/gram | 0.38 |
| Specific surface area, rice 2/ gram | 229 |
| Abrasion index is when weighing % -1 | 1.9 |
| Size-grade distribution, heavy % | |
| 0～40 micron | 17.3 |
| 40～80 microns | 49.3 |
| ＞80 microns | 33.4 |
Table 3
| Embodiment 1 | Embodiment 2 | Comparative Examples | |
| Operational condition | |||
| Temperature of reaction, ℃ | 500 | 500 | 500 |
| Weight hourly space velocity, h -1 | 12 | 12 | 12 |
| The weight ratio of water vapor/stock oil | 0.05 | 0.05 | 0.05 |
| Agent-oil ratio, m/m | 5.2 | 5.2 | 5.2 |
| Catalyzer contains charcoal, heavy % | 0.21 | 0.28 | 0.05 |
| Product distributes, heavy % | |||
| Dry gas | 1.23 | 1.16 | 1.78 |
| Liquefied gas | 13.54 | 12.07 | 14.12 |
| Gasoline | 50.82 | 46.39 | 59.26 |
| Diesel oil | 17.91 | 18.93 | 16.09 |
| Catalytic wax oil | 16.00 | 21.19 | 7.61 |
| Coke | 0.50 | 0.26 | 1.15 |
| Add up to | 100.00 | 100.00 | 100.00 |
| Transformation efficiency, heavy % | 66.00 | 59.78 | 76.30 |
| Product selectivity | |||
| The dry gas selectivity | 0.0187 | 0.0195 | 0.0233 |
| Coke selectivity | 0.0076 | 0.0043 | 0.0151 |
Annotate: product selectivity=product yield/transformation efficiency
Claims (17)
1. improve the catalysis conversion method of product selectivity, wherein stock oil contacts and reacts with containing Pd/carbon catalyst in reactor, it is characterized in that the catalyzer carbon content is that 0.15～0.8 heavy %, temperature of reaction are 400～650 ℃, weight hourly space velocity 2～100h
-1, catalyzer and stock oil weight ratio be 1～30.
2. improve the catalysis conversion method of product selectivity, wherein stock oil in reactor with contain Pd/carbon catalyst and contact and react, it is characterized in that catalyzer carbon content, temperature of reaction, weight hourly space velocity, catalyzer and stock oil weight ratio are enough to make reaction to obtain comprising the reaction product that accounts for stock oil 12～60 heavy % catalytic wax oil, wherein said catalyzer carbon content is that 0.15～0.8 heavy %, described weight hourly space velocity are 2～100h
-1, described temperature of reaction is 400～650 ℃, described catalyzer and stock oil weight ratio are 1～30.
3. according to the method for claim 1 or 2, it is characterized in that described catalyzer carbon content is 0.16～0.6 heavy %.
4. according to the method for claim 3, it is characterized in that described catalyzer carbon content is 0.17～0.5 heavy %.
5. according to the method for claim 1 or 2, it is characterized in that described temperature of reaction is 450～600 ℃, weight hourly space velocity is 5～80h
-1
6. according to the method for claim 5, it is characterized in that described temperature of reaction is 480～540 ℃, weight hourly space velocity is 8～60h
-1
7. according to the method for claim or 1 or 2, it is characterized in that described catalyzer and stock oil weight ratio are 2～25.
8. according to the method for claim 1 or 2, it is characterized in that described reaction pressure is 0.10MPa～1.0MPa.
9. according to the method for claim 1 or 2, it is characterized in that described stock oil is selected from or comprises petroleum hydrocarbon and/or other mineral oil, wherein petroleum hydrocarbon is selected from one or more the mixture in vacuum gas oil, atmospheric gas oil, coker gas oil, deasphalted oil, vacuum residuum, long residuum, the hydrogenation wax oil, and other mineral oil is one or more the mixture in liquefied coal coil, tar sand oil, the shale oil.
10. according to the method for claim 1 or 2, it is characterized in that described catalyzer comprises zeolite, inorganic oxide and optional clay, each component accounts for total catalyst weight respectively: zeolite 1～50 heavy %, inorganic oxide 5～99 heavy %, clay 0～70 heavy %, its mesolite is large pore zeolite and/or mesopore zeolite.
11. method according to claim 1 or 2, it is characterized in that described catalyst grain size is distributed as: account for all particulate volume ratios less than 40 microns particles and be lower than 10%, account for all particulate volume ratios greater than 80 microns particles and be lower than 15%, all the other are 40～80 microns particle.
12., it is characterized in that described catalyst grain size is distributed as: account for all particulate volume ratios less than 40 microns particles and be lower than 5% according to the method for claim 11; Account for all particulate volume ratios greater than 80 microns particles and be lower than 10%, all the other are 40～80 microns particle.
13. method according to claim 1 or 2, it is characterized in that described reactor be selected from riser tube, etc. one or more the combination in the fluidized-bed, isodiametric fluidized-bed, upstriker transfer limes, downstriker transfer limes of linear speed, or with the two or more combinations of a kind of reactor, described combination comprises series connection or/and in parallel, and wherein riser tube is the isodiametric riser tube of routine or the riser tube of various forms reducing.
14. according to the method for claim 1 or 2, it is characterized in that described stock oil being introduced in the reactor, or described stock oil introduced in the reactor in the position of identical or different height more than a position.
15. according to the method for claim 2, it is characterized in that described catalytic wax oil is that initial boiling point is not less than 260 ℃ cut, hydrogen richness is not less than 10.5 heavy %.
16. according to the method for claim 2, it is characterized in that described catalytic wax oil is that initial boiling point is not less than 330 ℃ cut, hydrogen richness is not less than 10.8 heavy %.
17. according to the method for claim 2, it is characterized in that described method also comprises separates reaction product with catalyzer, catalyzer is Returning reactor behind stripping, coke burning regeneration, and the product after the separation comprises products such as propylene, gasoline and catalytic wax oil.
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