CN1690174A - Catalytic conversion process for petroleum hydrocarbons - Google Patents
Catalytic conversion process for petroleum hydrocarbons Download PDFInfo
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- CN1690174A CN1690174A CN 200410037671 CN200410037671A CN1690174A CN 1690174 A CN1690174 A CN 1690174A CN 200410037671 CN200410037671 CN 200410037671 CN 200410037671 A CN200410037671 A CN 200410037671A CN 1690174 A CN1690174 A CN 1690174A
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 267
- 238000000034 method Methods 0.000 title claims abstract description 95
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- 229930195733 hydrocarbon Natural products 0.000 title claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 19
- 239000003208 petroleum Substances 0.000 title description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 24
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003921 oil Substances 0.000 claims description 121
- 239000002994 raw material Substances 0.000 claims description 54
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 36
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 230000035484 reaction time Effects 0.000 claims description 20
- 230000008929 regeneration Effects 0.000 claims description 20
- 238000011069 regeneration method Methods 0.000 claims description 20
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- 239000013058 crude material Substances 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 238000004523 catalytic cracking Methods 0.000 claims description 11
- 238000007670 refining Methods 0.000 claims description 6
- 238000001311 chemical methods and process Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
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- 238000004517 catalytic hydrocracking Methods 0.000 claims description 2
- 239000010779 crude oil Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 230000001172 regenerating effect Effects 0.000 abstract 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract 1
- 238000000151 deposition Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 65
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
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- 238000011049 filling Methods 0.000 description 15
- ISNYUQWBWALXEY-OMIQOYQYSA-N tsg6xhx09r Chemical compound O([C@@H](C)C=1[C@@]23CN(C)CCO[C@]3(C3=CC[C@H]4[C@]5(C)CC[C@@](C4)(O)O[C@@]53[C@H](O)C2)CC=1)C(=O)C=1C(C)=CNC=1C ISNYUQWBWALXEY-OMIQOYQYSA-N 0.000 description 14
- 150000001336 alkenes Chemical class 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 10
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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 7
- 230000009466 transformation Effects 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- 238000007233 catalytic pyrolysis Methods 0.000 description 2
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A method for catalytic conversion of petroleum hydrocarbon, which contains the following steps: (1) material of petroleum hydrocarbon into reaction area A of lift leg, contacting the regenerative agent inside and reaction, the mixture of the generated reaction oil gas and catalyst up-flowing along the lift leg, and entering into the reaction C of close phase bed; (2) the separated fraction of C4 and / or C5 from the separation part of the product being injected into reaction area B of lift leg, contacting the regenerative agent inside and reaction, the mixture of the generated reaction oil gas and catalyst up-flowing along the lift leg, and entering into the reaction C of close phase bed; (3) the mixture of the reaction oil gas and catalyst from reaction area A and B of the lift leg converging in reaction C of close phase bed, and reacting sequentially; (4) separating reaction oil gas from the catalyst depositing carbon after reaction, the reaction oil gas into the separation part of the product, and the carbon-deposited catalyst returning reaction part to serve circularly after striped, regenerated. With the method it can increase the yield of ethane, propone and BTX.
Description
Technical field
The present invention relates to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is the method for catalytic conversion of petroleum hydrocarbon of a kind of propylene enhancing and BTX.
Background technology
Light olefin is the important synthon of petroleum chemicals and fuel always, and now, light olefin is widely used in synthetic gasoline, polymkeric substance, frostproofer, petroleum chemicals, explosive, solvent, medicine, fumigant, resin, synthetic rubber and many other products.Propylene is the synthon that is only second to the second important petroleum chemicals of ethene.
At present worldwide, the synthetic main source of needed propylene of petrochemical industry is the byproduct of ethylene plant's pyrolysis in tubular furnace, the output of propylene is about 15 heavy %, account for 70% of market demand, refining of petroleum (almost all deriving from FCC) is second largest propylene source, account for market demand all the other 30%, and, almost 50% of the propylene market demand all derive from FCCU in the U.S..
Producing the low-carbon alkene main method from petroleum hydrocarbon has: with Sweet natural gas, petroleum naphtha or solar oil is the pyrolysis in tubular furnace of raw material, and its main purpose product is the alkene of low-carbon (LC); Heat carrier cracking with heavy hydrocarbon feedstocks; And be the catalysis conversion method of raw material with the low-carbon alcohol.Fluid catalytic cracking develops into the history that had more than 60 year today, is the main means of countries in the world oil refining always.It is the effective means that gas oil and residual oil is converted into lightweight oil.Catalytic cracking unit is the main technique of China petroleum refining industry secondary processing, is used to produce liquefied gas, catalytic gasoline and diesel oil.Since the eighties, Research Institute of Petro-Chemical Engineering has developed a series of catalytic cracking family technology in succession, makes catalytic cracking that very big variation arranged on the purpose product, mainly be to produce low-carbon alkene, or oil gas is taken into account.Propylene is an important chemical material, and the diversity in its source is also very important, needs to develop a kind of catalysis conversion method of propylene enhancing significantly for this reason.
Disclose a kind of catalytic pyrolysis among the CN1218786A and produced the method for ethene and propylene.It makes the heavy petroleum hydrocarbon of preheating in riser tube or downstriker transfer limes reactor, contact with catalyzer in the presence of water vapor, temperature of reaction 650-750 ℃, pressure 150-400 kPa, reaction times 0.2-5 second, agent-oil ratio are 15-40: 1, the weight ratio of water vapor and stock oil is 0.3-1: carry out the catalytic pyrolysis reaction under 1 the condition.The ethene of this method and productivity of propylene are all above 18 heavy %.Thermally splitting is occupied an leading position in this reaction.
Disclose a kind of a kind of catalysis conversion method of producing low-carbon alkene among the CN1102431A, temperature of reaction 480-680 ℃, pressure 120-400 kPa, reaction times 0.1-6 second, agent-oil ratio are that the weight ratio of 4-20, water vapor and stock oil is 0.01-0.5: 1.The highest productivity of propylene is near 20 heavy %.Will inject a large amount of water vapors in the reaction process, catalyzed reaction is occupied an leading position in this method.
USP5,846,403 disclose a kind of catalysis raw gasline method of cracking production maximum yield light olefin again.This method is to carry out in a riser reactor that contains two reaction zones, and reactor lower part is a upstream reaction zone, and top is the downstream reaction district.The raw material of upstream reaction zone is light catalytic naphtha (boiling point is below 140 ℃), and reaction conditions is: 620 ℃-775 ℃ of finish contact temperature, and the oil gas residence time is lower than 1.5 seconds, and agent-oil ratio 75-150, water vapor account for the heavy % of 2-50 of petroleum naphtha; The raw material in downstream reaction district is conventional catalytically cracked material (boiling point is 220 ℃-575 ℃), and reaction conditions is: 600 ℃-750 ℃ of temperature, the oil gas residence time is lower than 20 seconds.This method is compared with conventional catalytic cracking, and its upstream reaction zone oil gas residence time is too short, and yield of liquefied gas only improves 0.97-1.21 percentage point.
WO00/40672 has disclosed a kind of fluidized catalytic cracking method with high olefin output.This method adopts the pattern of double lifting leg FCC apparatus, make a conventional FCC raw material injection riser tube wherein, contact, react with the regenerated catalyst that contains USY and ZSM-5, and from the crackate that is generated, 15-149 ℃ light gasoline fraction is separated, inject second riser reactor, contact, react with regenerated catalyst.The productivity of propylene of this method is 3 times (being about 12 heavy %) of conventional riser tube FCC process.
USP6222087B1 has disclosed a kind of catalyst cracking method that generates light olefin.This method is a raw material with C4-C7 alkene and/or alkane, adopts the catalyzer as active ingredient with ZSM-5 or ZSM-11, at temperature of reaction 510-704 ℃, agent-oil ratio 0.1-10, weight hourly space velocity 1-20h
-1Reaction conditions under increasing output of ethylene and propylene, wherein, the productive rate sum of ethene and propylene is greater than 20 heavy %, the ratio of propylene and the weight of ethene is greater than 3.0, and the productive rate of the BTX that is generated is lower.
In sum, although prior art provides the method for multiple increased low carbon olefine output, the increasing degree of the productive rate of its low-carbon alkene, particularly productivity of propylene is more limited, does not all reach more than the 30 heavy %.
Summary of the invention
The objective of the invention is to: a kind of propylene enhancing significantly is provided on the basis of above-mentioned prior art, increase production the petroleum hydrocarbon catalytic conversion method of BTX simultaneously, so that make oil refining process that more high value industrial chemicals can be provided, thereby make the combination of oil refining and chemical process tightr.
Method provided by the invention comprises reaction, stripping, product separation and catalyst regeneration four parts, it is characterized in that this method may further comprise the steps:
(1) petroleum hydrocarbon raw material injecting lift tube reaction district A contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C;
(2) from the C4 and/or the C 5 fraction injecting lift tube reaction district B after separating of product separation part, contact, react with regenerator in it, reaction oil gas that is generated and mixture of catalysts make progress mobile along this riser tube, enter dense-phase bed reaction zone C;
(3) converge at dense-phase bed reaction zone C from the reaction oil gas of riser reaction zone A and mixture of catalysts and from reaction oil gas and the mixture of catalysts of riser reaction zone B, and continue in dense-phase bed reaction C, to react;
(4) catalyzer of separating reaction oil gas and reaction back carbon deposit, reaction oil gas is sent into the product separation part, and the catalyzer of reaction back carbon deposit returns reactive moieties and recycles after stripping, regeneration.
Compared with prior art, beneficial effect of the present invention is mainly reflected in following aspect:
1, method provided by the invention is raw material with the heavy petroleum hydrocarbon, is support with sophisticated FCC Technology, for chemical process provides a large amount of ethene, propylene and BTX.Wherein, productivity of propylene can reach the heavy % or higher of 25-35, and ethylene yield can reach the heavy % or higher of 10-14, and the productive rate of BTX is about 10 heavy %.
2, the content of aromatic hydrocarbon increases considerably in the gasoline products that the present invention generated, and can remedy the loss that alkene in the gasoline reduces the octane value that is brought, thereby makes gasoline octane rating can maintain higher level or increase.In addition, the increase of aromatic hydrocarbon content in the gasoline can also provide more aromatic hydrocarbon potential content for catforming process.Aromatic hydrocarbons is mainly the C6-C8 cut in the gasoline, so be mainly BTX.
3, the present invention can be used for all FCCU, comprises conventional FCC, RFCC, DCC, MGG, ARGG, MGD etc., utilizes existing catalytic cracking unit, can implement the present invention to its reactive moieties transformation.Therefore, less investment, the transformation cycle is short, and gain quick return, favourable promoting the use of.The present invention also can be used for newly-built catalytic convention design.
Description of drawings
Fig. 1 is the schematic flow sheet of method provided by the present invention.
Embodiment
Equipment
Method provided by the invention comprises reaction, stripping, product separation and catalyst regeneration four parts, and the function of each several part and conventional FCC similar process.Wherein said reactive moieties mainly comprises riser reaction zone A, riser reaction zone B and dense-phase bed reaction zone C, in addition, also comprises the settling section and the finish sharp separation equipment that are positioned at dense-phase bed reaction zone C top, for example, and cyclonic separator.The present invention does not have particular requirement for the setting of riser reaction zone A, riser reaction zone B and dense-phase bed reaction zone C, designs according to the device design requirements of conventional FCC process to get final product.The design requirements of stripping of the present invention, product separation and catalyst regeneration part is also identical with the device design requirements of conventional FCC process, as long as C4 and C 5 fraction can be separated from product oil gas, and they are delivered to reactive moieties react and gets final product.
In method provided by the invention, riser reaction zone A and riser reaction zone B are connected with dense-phase bed reaction zone C.For the set-up mode of riser reaction zone A, riser reaction zone B and dense-phase bed reaction zone C, the present invention does not have particular requirement.For example, riser reaction zone A and dense-phase bed reaction zone C can be for coaxial settings, and fixedly connected, and riser reaction zone B and the non-coaxial setting of dense-phase bed reaction zone C are fixedly connected still; Vice versa, that is, the position of reaction zone A and reaction zone B can be intercoursed.Can also make riser reaction zone A and riser reaction zone B and dense-phase bed reaction zone C be non-coaxial setting, but connection fixed to one another.
In method provided by the invention, be preferably in that revivifier is other sets up a cooling storage jar, make catalyzer after the regeneration this jar of flowing through earlier, and then deliver to riser reaction zone.The purpose of cooling storage jar is that the temperature of the catalyzer of delivering to riser reaction zone is controlled effectively.Described cooling storage jar can be provided with one, two or more.
In method provided by the invention, the density of dense-phase bed reaction zone C inner catalyst is 100-500 kilogram/rice
3, preferred 150-400 kilogram/rice
3The medial temperature of cooling storage jar inner catalyst is 500-700 ℃, preferred 560-650 ℃.
Catalyzer
The present invention is suitable for conventional catalytic cracking catalyst, i.e. solid acid catalyst.Can be 100% amorphous silicon aluminium, but preferably comprise molecular sieve active ingredient and the resistant to elevated temperatures matrix of porous, for example, silicon-dioxide (SiO
2), aluminium sesquioxide (Al
2O
3), clay and composition thereof etc.The total content of molecular sieve is generally the heavy % of 10-50 in the catalyzer, and remaining is matrix and caking agent.The molecular sieve active ingredient is generally y-type zeolite, comprises the super steady Y of REY, REHY, Different Silicon aluminum ratio, high silicon Y etc.Also can contain rare earth in the molecular sieve, the content of rare earth can be the heavy % of 0.1-10.Active ingredient preferably contains ZRP, ZSM-5 series zeolite or has the mixture of one or more and y-type zeolite in the supersiliceous zeolite of five-membered ring structure, β zeolite, the phosphorus aluminium zeolite.
In addition, various assistant for calalytic cracking also are applicable to the present invention.Auxiliary agent can add to separately in the device, also can add this adjuvant component in the Preparation of catalysts process.Auxiliary agent can be the composition that improves selectivity of light olefin, for example, shape-selective molecular sieve ZRP, ZSM-5, ZSM-11, ZSM-12, ZSM-21, TEA mordenite etc., and the above-mentioned molecular sieve of process ion-exchanged, ion-exchanged can adopt H, Cr, ZR, MN, CE, LA etc.Molecular sieve component is carried on and contains Al
2O
3, Al
2O
3-SiO
2, on the kaolinic carrier,, or sneak in the Primary Catalysts when the general catalytic cracking catalyst of preparation with the form of moiety as independent auxiliary agent, make the catalyzer that contains auxiliary component.The more detailed description of relevant ZRP zeolite is referring to CN1058382A; The more detailed description of ZSM-5 is referring to USP3702886; The more detailed description of ZSM-11 is referring to USP3709979; The more detailed description of ZSM-12 is referring to USP3832449; The more detailed description of ZSM-23 is referring to USP4076842, and U.S. Patent application 130442 is seen in the more detailed description of TEA.
Petroleum hydrocarbon raw material
In method provided by the invention, the petroleum hydrocarbon raw material of described injecting lift tube reaction district A is selected from: straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum, the mixture of one or more in long residuum or the crude oil, preferred straight-run gas oil or the physico-chemical property hydrocarbon ils cut suitable with straight-run gas oil, for example, the VGO that alkane content is high, the AGO that alkane content is high, the raffinate oil that hydrogen richness height and saturated hydrocarbon content are high, petroleum naphtha, the mixture of one or more in the wax oil after hydrotreatment, further preferred petroleum hydrocarbon raw material is the wax oil of UOPK 〉=12.5.
In method provided by the invention, the C4 of described injecting lift tube reaction district B and/or C 5 fraction both can comprise C4 and/or C5 alkene, also can comprise C4 and/or C5 alkane; Wherein, preferred C 4 fraction.Described C4 and/or C 5 fraction both can be to originate from the catalytic cracking unit of using the method for the invention, also can be from other oil refining, the C4 of chemical process, C 5 fraction, can also be the mixtures of above-mentioned two kinds of raw material sources.
Reaction conditions
In method provided by the invention, the reaction conditions of riser reaction zone A is basic identical with conventional catalytic cracking reaction condition.Wherein, the temperature that described regenerator enters riser reaction zone A is 580 ℃-700 ℃, and the reaction times is 2-10 second, and agent-oil ratio is 3-30, and the weight ratio of water vapor and hydrocarbon oil crude material is 0.02-0.40, and reaction pressure is 130-450kPa.Preferred reaction conditions is as follows: the temperature that regenerator enters riser reaction zone A is 620 ℃-650 ℃, and the reaction times is 2.5-8.0 second, and agent-oil ratio is 4-15, and the weight ratio of water vapor and hydrocarbon oil crude material is 0.15-0.30, and reaction pressure is 200-400kPa.
In method provided by the invention, the reaction conditions of riser reaction zone B is as follows: the temperature that regenerator enters riser reaction zone B is 550 ℃-750 ℃, reaction times is 1-8 second, agent-oil ratio is 10-40, the weight ratio of water vapor and hydrocarbon oil crude material is 0.02-0.40, and reaction pressure is 100-500kPa.Preferred reaction conditions is as follows: the temperature that regenerator enters riser reaction zone B is 590 ℃-690 ℃, and the reaction times is 2.5-7.0 second, and agent-oil ratio is 13-25, and the weight ratio of water vapor and hydrocarbon oil crude material is 0.15-0.40, and reaction pressure is 150-300kPa.
In method provided by the invention, the reaction conditions of dense-phase bed reaction zone C is as follows: temperature of reaction is 500 ℃-700 ℃, is preferably 560 ℃-660 ℃; Reaction pressure is a normal pressure-300 kPa, is preferably 100-230 kPa; Weight hourly space velocity is 0.5-6.0 hour
-1, be preferably 1-4 hour
-1The weight ratio of catalyzer and hydrocarbon oil crude material is 10-150, is preferably 20-80; The weight ratio of water vapor and hydrocarbon oil crude material is 0.05-0.80: 1; Be preferably 0.1-0.3: 1.Entering the follow-up continued access of dense-phase bed reaction zone C from the reaction oil gas of riser reaction zone A and B and mixture of catalysts respectively touches, reacts, make reaction depth obtain further raising, inject a large amount of water vapors at the dense-phase bed reaction zone simultaneously, to reduce the hydrocarbon ils dividing potential drop.
In method provided by the invention, the pre-lifting medium that adopt the bottom of described riser reaction zone A and riser reaction zone B is dry gas and/or steam.
In method provided by the invention, partly there is not any particular requirement for catalyst stripping, gas stripping process and equipment after conventional gas stripping process and equipment and the improvement all are applicable to the present invention.Also do not have what particular requirement for the catalyst regeneration part, renovation process and equipment after conventional renovation process and equipment and the improvement all are applicable to the present invention.
In method provided by the invention, catalyzer behind the stripping is sent into the revivifier coke burning regeneration, and the catalyzer after the regeneration preferably at first enters in the cooling storage jar that is arranged on the revivifier side, method by direct or indirect heat exchange is reduced the temperature of regenerator, for example, reduce to 580-700 ℃, return reactive moieties then and recycle.Catalyzer after the method for the invention is preferably regenerated is introduced into cooling storage jar, and then returns reactive moieties and recycle.Catalyzer after the further preferred regeneration of the method for the invention is introduced into cooling storage jar, and then return reactive moieties and recycle, and it is different with the temperature of the regenerated catalyst of riser reaction zone B to return riser reaction zone A, for example, return the temperature of regenerated catalyst of riser reaction zone A than the high 10-50 of temperature ℃ of the regenerated catalyst that returns riser reaction zone B.When the temperature of the regenerated catalyst that returns riser reaction zone A and riser reaction zone B not simultaneously, two cooling storage jars preferably are set.
Product
Method provided by the present invention is low-carbon alkenes such as increasing output of ethylene, propylene effectively, and wherein the effect of propylene enhancing is especially obvious, and it is above or higher that the content of propylene can reach 35 heavy %, and this method can also be increased production BTX simultaneously.
Below in conjunction with accompanying drawing method provided by the invention is given further instruction, but therefore the present invention is not subjected to any restriction.
As shown in Figure 1, promote steam 4 in advance and enter, drive regenerated catalyst along the riser tube accelerated motion that makes progress by the pre lift zone of riser reaction zone A bottom; Petroleum hydrocarbon raw material 1 is injected by nozzle 3 through atomizing steam 2 atomizing back and enters riser reaction zone A and also move upward with the catalyzer contact and react.C4～the C 5 fraction 27 that from liquefied gas 20 and gasoline 21, cuts out, C4～C 5 fraction enters riser reaction zone B bottom and contacts with catalyzer and move upward and react through pre-the lifting after steam 39 promotes, the final bottom of the dense-phase bed reaction zone C that enters the settling vessel bottom with oil gas and catalyzer from riser reaction zone A, oil gas continues to contact, react with catalyzer.Steam 7 enters the annular steam distribution pipe 9 of the dense-phase bed reaction zone C bottom of settling vessel 10 bottoms, guarantees the fluidization of dense-phase bed reaction zone C, reduces the oil gas dividing potential drop in this reaction zone simultaneously.Carbon deposit and catalyzer that carry a certain amount of oil gas secretly flows downward through the chev(e)ron baffle 6 of stripper 8 in the settling vessel, stripped vapor 5 carries out stripping at the chev(e)ron baffle place to spent agent, strip the entrained reaction oil gas of spent agent, oil gas and catalyzer are successively realized the initial gross separation of catalyzer and oil gas behind the stripping through thick cyclonic separator 12,15.Oil gas continues to enter secondary cyclone 13 and 14, the oil gas that goes out secondary cyclone 13 and 14 continues to enter collection chamber 16, the fine powder catalyst of being carried secretly in the thick cyclonic separator oil gas is through behind the secondary cyclone 13 and 14, and fine powder catalyst returns settling vessel by dipleg.Spent agent behind the stripping enters revivifier 29 through inclined tube 11, and main air 30 enters revivifier, and the coke on the burning-off reclaimable catalyst makes the catalyst regeneration of inactivation.Regenerated catalyst after the holomorphosis flows into cooling storage jar 33 through pipeline 32, and fluidized wind 36 is introduced through the fluidized wind grid distributor 35 of cooling storage pot bottom, and regenerated catalyst is carried out fluidisation, and vapour generator 34 makes the regenerator cooling in the cooling storage jar.A part is circulated back to riser reaction zone A bottom through the regenerated catalyst after the of short duration cooling by inclined tube 37, and the regenerated catalyst that another part was lowered the temperature through the relative long period flows into riser reaction zone B bottom cycle through inclined tube 38 and uses.Flue gas 31 enters the cigarette machine.Oil gas in the collection chamber 16 enters follow-up separation system 18, with production sharing dry gas 19, liquefied gas 20, gasoline 21, diesel oil 22, heavy cycle oil 23, clarified oil 24 and externally extracting oil 25 through main oil gas piping 17.Part in liquefied gas 20 gasoline 21 cuts out C4～C 5 fraction 27 and C6+ gasoline 28 through tripping device 26, and C4～C 5 fraction 26 returns riser reaction zone B and reacts.
The following examples will give further instruction to method provided by the invention, but therefore the present invention is not subjected to any restriction.
Embodiment 1
The present embodiment explanation: adopt method provided by the invention that productivity of propylene is obviously improved, the content of BTX increases in the gasoline products simultaneously.
Test is being carried out on the improved medium-sized catalytic convention design according to the method for the invention, and the structural representation of reaction, regeneration section is referring to Fig. 1.The physico-chemical property of used petroleum hydrocarbon raw material sees Table the raw material a in 1 in the test.Catalyst system therefor is by Qilu Petrochemical branch office of China petroleum chemical engineering Stock Co., Ltd catalyst plant industrial production, and trade names are RMP, and its physico-chemical property sees Table 2.The weight composition of used C 4 fraction sees Table 3 raw material A.Main operational condition and product situation see Table 4.
Testing sequence is as follows: the raw material a in the table 1 is injecting lift tube reaction district A after preheating, contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C.The raw material A of table 3, i.e. C 4 fraction injecting lift tube reaction district B contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C.Converge at dense-phase bed reaction zone C from the reaction oil gas of riser reaction zone A and mixture of catalysts and from reaction oil gas and the mixture of catalysts of riser reaction zone B, and continue under dense-phase bed reaction atmosphere, to react.The catalyzer of separating reaction oil gas and reaction back carbon deposit, reaction oil gas is sent into the product separation part, and the catalyzer of reaction back carbon deposit returns reactive moieties and recycles after stripping, regeneration.
By the product distributed data in the table 4 as can be seen, ethylene yield is about 10 heavy %; Productivity of propylene is about 35 heavy %; About BTX productive rate 10 heavy %;
Embodiment 2
The present embodiment explanation: adopt method provided by the invention that productivity of propylene is obviously improved, the content of BTX increases in the gasoline products simultaneously.
Test is being carried out on the improved medium-sized catalytic convention design according to the method for the invention, and the structural representation of reaction, regeneration section is referring to Fig. 1.The physico-chemical property of used petroleum hydrocarbon raw material sees Table the raw material b in 1 in the test.Catalyst system therefor is identical with embodiment 1.The weight composition of used C 5 fraction sees Table 3 raw material B.Main operational condition and product situation see Table 5.
Testing sequence is as follows: the raw material b in the table 1 is injecting lift tube reaction district A after preheating, contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C.The raw material B of table 3, i.e. C 5 fraction injecting lift tube reaction district B contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C.Converge at dense-phase bed reaction zone C from the reaction oil gas of riser reaction zone A and mixture of catalysts and from reaction oil gas and the mixture of catalysts of riser reaction zone B, and continue under dense-phase bed reaction atmosphere, to react.The catalyzer of separating reaction oil gas and reaction back carbon deposit, reaction oil gas is sent into the product separation part, and the catalyzer of reaction back carbon deposit returns reactive moieties and recycles after stripping, regeneration.
By the product distributed data in the table 5 as can be seen, ethylene yield is between the heavy % of 7.68-12.52; Productivity of propylene is about 30 heavy %; The productive rate of ethene, productivity of propylene all has tangible reduction than embodiment 2.Because the amount of C5 is very little.
Embodiment 3
The present embodiment explanation: adopt method provided by the invention that productivity of propylene is obviously improved, the content of BTX increases in the gasoline products simultaneously.
Test is being carried out on the improved medium-sized catalytic convention design according to the method for the invention, and the structural representation of reaction, regeneration section is referring to Fig. 1.The physico-chemical property of used petroleum hydrocarbon raw material sees Table the raw material b in 1 in the test.Catalyst system therefor is identical with embodiment 1.The weight composition of used C4-C5 cut sees Table 3 raw material C.Main operational condition and product situation see Table 6.
Testing sequence is as follows: the raw material b in the table 1 is injecting lift tube reaction district A after preheating, contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C.The raw material C of table 3, i.e. C4-C5 cut injecting lift tube reaction district B contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C.Converge at dense-phase bed reaction zone C from the reaction oil gas of riser reaction zone A and mixture of catalysts and from reaction oil gas and the mixture of catalysts of riser reaction zone B, and continue under dense-phase bed reaction atmosphere, to react.The catalyzer of separating reaction oil gas and reaction back carbon deposit, reaction oil gas is sent into the product separation part, and the catalyzer of reaction back carbon deposit returns reactive moieties and recycles after stripping, regeneration.
By the product distributed data in the table 6 as can be seen, the productive rate of ethene, propylene, BTX is than the increase that has of embodiment 1.
Comparative Examples 1
This Comparative Examples adopts USP5,846,403 described methods, and utilize petroleum hydrocarbon raw material described in the embodiment 1 and catalyzer to test resulting result.
Main operational condition and product distribution situation are referring to table 7.As can be seen from Table 7, adopt method of the present invention, the productive rate of ethene, propylene, BTX is than Comparative Examples USP5, and 846,403 described methods have raising significantly, and the variation of matter has taken place.
Comparative Examples 2
This Comparative Examples adopts the described method of WO00/40672, and utilizes petroleum hydrocarbon raw material described in the embodiment 1 and catalyzer to test resulting result.
Main operational condition and product distribution situation are referring to table 8.As can be seen from Table 8, adopt method of the present invention, the productive rate of ethene, propylene, BTX has raising significantly than the described method of Comparative Examples WO00/40672, and the variation of matter has taken place.
Table 1
| The stock oil title | Grand celebration VGO | VGO behind the hydrogenation |
| The stock oil label | Raw material a | Raw material b |
| Density, g/cm 3 | ??0.8764 | ??0.8836 |
| Kinematic viscosity, mm 2/s?80℃ | ??20.39 | ??24.2 |
| ??100℃ | ??12.06 | ??- |
| Condensation point, ℃ | ??＞50 | ??31 |
| Aniline point, ℃ | ??117.7 | ??- |
| Carbon residue, m% | ??0.93 | ??0.61 |
| Basic nitrogen, ppm | ??412 | ??100 |
| Elementary composition, heavy % | ||
| ??C | ??86.70 | ??86.85 |
| ??H | ??13.48 | ??13.23 |
| ??S | ??0.13 | ??0.041 |
| ??N | ??0.13 | ??0.01 |
| Group composition, heavy % | ||
| Stable hydrocarbon | ??75.0 | ??77.4 |
| Aromatic hydrocarbons | ??19.8 | ??20.2 |
| Colloid | ??5.2 | ??2.4 |
| Bituminous matter | ??＜0.1 | ??＜0.05 |
| Boiling range, ℃ | ||
| Initial boiling point | ??246 | ??267 |
| ??5％ | ??402 | ??373 |
| ??10％ | ??430 | ??399 |
| ??30％ | ??482 | ??429 |
| ??50％ | ??519 | ??449 |
| ??70％ | ??573(75.2％) | ??464 |
| Distillation yield (350 ℃), % | ??1.5 | ??1.3 |
| Distillation yield (500 ℃), % | ??39.4 | ??45.9 |
| Liquid temperature＞400 ℃, % | ??61.6(538℃) | ??- |
Table 2
| Analysis project | ??RMP |
| ??Al 2O 3Content | ??50.1 |
| ??Fe 2O 3Content | ??0.44 |
| ??Na 2O content | ??0.054 |
| Burning decrement, % | ??11.8 |
| Pore volume | ??0.28 |
| Specific surface area | ??204 |
| Heap is than (ABD) | ??0.79 |
| Abrasion index | ??1.4 |
| Micro-activity | ??76 |
| Size-grade distribution | ??15.8 ??90.5 ??76.9 |
Table 3
| The composition of C4-C5 cut | Raw material A | Raw material B | Raw material C |
| Trimethylmethane | ??14.29 | ??0.00 | ??14.87 |
| Normal butane | ??6.32 | ??0.00 | ??6.89 |
| Butene-1 | ??13.82 | ??0.00 | ??13.00 |
| Iso-butylene | ??33.03 | ??0.00 | ??31.51 |
| Instead-butene-2 | ??18.60 | ??0.00 | ??17.2 |
| Suitable-butene-2 | ??13.69 | ??0.00 | ??13.23 |
| Divinyl-1,3 | ??0.25 | ??0.00 | ??0.29 |
| Normal paraffin C5 | ??0.00 | ??6.3 | ??0.19 |
| Isoparaffin C5 | ??0.00 | ??7.9 | ??0.24 |
| Alkene C5 | ??0.00 | ??85.8 | ??2.58 |
| Amount to | ??100.00 | ??100.00 | ??100.00 |
Table 4
| Riser reaction zone A: | |||
| Regenerator enters, ℃ | ??580 | ??620 | ??650 |
| Reaction times, second | ??3 | ??4 | ??6 |
| Agent-oil ratio | ??5 | ??10 | ??15 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 | ??10 |
| Riser reaction zone B: | |||
| Regenerator enters, ℃ | ??590 | ??640 | ??690 |
| Reaction times, second | ??2.5 | ??4 | ??6 |
| Agent-oil ratio | ??15 | ??20 | ??25 |
| Water filling (accounting for raw material), heavy % | ??5 | ??5 | ??5 |
| Dense-phase bed reaction zone C: | |||
| Temperature of reaction, ℃ | ??580 | ??580 | ??580 |
| Reaction pressure, kPa | ??260 | ??260 | ??260 |
| Agent-oil ratio | ??25 | ??50 | ??65 |
| Weight hourly space velocity, l/h | ??2 | ??3 | ??4 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 | ??10 |
| Material balance, heavy % | |||
| Dry gas | ??17.90 | ??20.86 | ??24.10 |
| Liquefied gas | ??47.82 | ??48.63 | ??46.69 |
| ??C 5 +Gasoline | ??18.5 | ??16.17 | ??15.39 |
| Diesel oil | ??5.86 | ??4.42 | ??3.35 |
| Heavy oil | ??2.47 | ??2.0 | ??1.48 |
| Coke | ??7.45 | ??7.92 | ??8.99 |
| Amount to | ??100.00 | ??100.00 | ??100.00 |
| Transformation efficiency, heavy % | |||
| Ethylene yield, heavy % | ??11.42 | ??12.4 | ??13.7 |
| Productivity of propylene, heavy % | ??35.64 | ??36.01 | ??34.89 |
| Benzene, heavy % | ??1.45 | ??1.67 | ??1.89 |
| Toluene, heavy % | ??2.44 | ??2.83 | ??3.50 |
| Dimethylbenzene, heavy % | ??7.38 | ??8.01 | ??9.20 |
Table 5
| Riser reaction zone A: | |||
| Regenerator enters, ℃ | ??580 | ??620 | ??650 |
| Reaction times, second | ??3 | ??4 | ??6 |
| Agent-oil ratio | ??5 | ??10 | ??15 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 | ??10 |
| Riser reaction zone B: | |||
| Regenerator enters, ℃ | ??590 | ??640 | ??690 |
| Reaction times, second | ??2.5 | ??4 | ??6 |
| Agent-oil ratio | ??15 | ??20 | ??25 |
| Water filling (accounting for raw material), heavy % | ??5 | ??5 | ??5 |
| Dense-phase bed reaction zone C: | |||
| Temperature of reaction, ℃ | ??580 | ??580 | ??580 |
| Reaction pressure, kPa | ??260 | ??260 | ??260 |
| Agent-oil ratio | ??25 | ??50 | ??65 |
| Weight hourly space velocity, l/h | ??2 | ??3 | ??4 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 | ??10 |
| Material balance, heavy % | |||
| Dry gas | ??12.38 | ??16.37 | ??23.05 |
| Liquefied gas | ??54.96 | ??53.62 | ??49.23 |
| ??C 5 +Gasoline | ??18.69 | ??16.72 | ??13.65 |
| Diesel oil | ??4.76 | ??4.12 | ??3.44 |
| Heavy oil | ??3.20 | ??2.80 | ??2.28 |
| Coke | ??6.02 | ??6.36 | ??8.36 |
| Amount to | ??100.00 | ??100.00 | ??100.00 |
| Transformation efficiency, heavy % | |||
| Ethylene yield, heavy % | ??7.68 | ??10.27 | ??12.52 |
| Productivity of propylene, heavy % | ??29.48 | ??31.15 | ??30.65 |
| Benzene, heavy % | ??1.05 | ??1.23 | ??1.50 |
| Toluene, heavy % | ??2.21 | ??2.39 | ??3.18 |
| Dimethylbenzene, heavy % | ??6.89 | ??7.01 | ??8.20 |
Table 6
| Riser reaction zone A: | |||
| Regenerator enters, ℃ | ??580 | ??620 | ??650 |
| Reaction times, second | ??3 | ??4 | ??6 |
| Agent-oil ratio | ??5 | ??10 | ??15 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 | ??10 |
| Riser reaction zone B: | |||
| Regenerator enters, ℃ | ??590 | ??640 | ??690 |
| Reaction times, second | ??2.5 | ??4 | ??6 |
| Agent-oil ratio | ??15 | ??20 | ??25 |
| Water filling (accounting for raw material), heavy % | ??5 | ??5 | ??5 |
| Dense-phase bed reaction zone C: | |||
| Temperature of reaction, ℃ | ??580 | ??580 | ??580 |
| Reaction pressure, kPa | ??260 | ??260 | ??260 |
| Agent-oil ratio | ??25 | ??50 | ??65 |
| Weight hourly space velocity, l/h | ??2 | ??3 | ??4 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 | ??10 |
| Material balance, heavy % | |||
| Dry gas | ??18.02 | ??21.25 | ??24.3 |
| Liquefied gas | ??48.67 | ??49.31 | ??47.14 |
| ??C 5 +Gasoline | ??17.47 | ??15.01 | ??14.9 |
| Diesel oil | ??5.86 | ??4.42 | ??3.32 |
| Heavy oil | ??2.47 | ??2.0 | ??1.42 |
| Coke | ??7.51 | ??8.01 | ??8.92 |
| Amount to | ??100.00 | ??100.00 | ??100.00 |
| Transformation efficiency, heavy % | |||
| Ethylene yield, heavy % | ??11.81 | ??13.01 | ??14.18 |
| Productivity of propylene, heavy % | ??35.98 | ??36.81 | ??34.95 |
| Benzene, heavy % | ??1.46 | ??1.67 | ??1.90 |
| Toluene, heavy % | ??2.51 | ??2.84 | ??3.50 |
| Dimethylbenzene, heavy % | ??7.58 | ??8.21 | ??9.40 |
Table 7
| Riser reaction zone A: | Comparative Examples | The present invention |
| Regenerator enters, ℃ | ??580 | ??620 |
| Reaction times, second | ??3 | ??3 |
| Agent-oil ratio | ??10 | ??15 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 |
| Riser reaction zone B: | ||
| Regenerator enters, ℃ | ??/ | ??640 |
| Reaction times, second | ??/ | ??4 |
| Agent-oil ratio | ??/ | ??20 |
| Water filling (accounting for raw material), heavy % | ??/ | ??5 |
| Dense-phase bed reaction zone C: | ||
| Temperature of reaction, ℃ | ??/ | ??580 |
| Reaction pressure, kPa | ??/ | ??260 |
| Agent-oil ratio | ??/ | ??50 |
| Weight hourly space velocity, l/h | ??/ | ??4 |
| Water filling (accounting for raw material), heavy % | ??/ | ??10 |
| Material balance, heavy % | ||
| Dry gas | ??8.90 | ??21.25 |
| Liquefied gas | ??15.82 | ??49.31 |
| ??C 5 +Gasoline | ??36.11 | ??15.01 |
| Diesel oil | ??7.60 | ??4.42 |
| Heavy oil | ??25.40 | ??2.0 |
| Coke | ??6.17 | ??8.01 |
| Amount to | ??100.00 | ??100.00 |
| Transformation efficiency, heavy % | ||
| Ethylene yield, heavy % | ??1.7 | ??13.01 |
| Productivity of propylene, heavy % | ??5.45 | ??36.81 |
| Benzene, heavy % | ??0.89 | ??1.67 |
| Toluene, heavy % | ??2.1 | ??2.84 |
| Dimethylbenzene, heavy % | ??4.2 | ??8.21 |
Table 8
| Riser reaction zone A: | Comparative Examples | Present method |
| Regenerator enters, ℃ | ??620 | ??620 |
| Reaction times, second | ??3 | ??3 |
| Agent-oil ratio | ??10 | ??15 |
| Water filling (accounting for raw material), heavy % | ??10 | ??10 |
| Riser reaction zone B: | ||
| Regenerator enters, ℃ | ??640 | ??640 |
| Reaction times, second | ??4 | ??4 |
| Agent-oil ratio | ??20 | ??20 |
| Water filling (accounting for raw material), heavy % | ??5 | ??5 |
| Dense-phase bed reaction zone C: | ||
| Temperature of reaction, ℃ | ??- | ??580 |
| Reaction pressure, kPa | ??- | ??260 |
| Agent-oil ratio | ??- | ??50 |
| Weight hourly space velocity, l/h | ??- | ??4 |
| Water filling (accounting for raw material), heavy % | ??10 | |
| Material balance, heavy % | ||
| Dry gas | ??5.4 | ??21.25 |
| Liquefied gas | ??29.6 | ??49.31 |
| ??C 5 +Gasoline | ??27.9 | ??15.01 |
| Diesel oil | ??17.7 | ??4.42 |
| Heavy oil | ??13.5 | ??2.0 |
| Coke | ??5.9 | ??8.01 |
| Amount to | ??100.00 | ??100.00 |
| Transformation efficiency, heavy % | ||
| Ethylene yield, heavy % | ??3.6 | ??13.01 |
| Productivity of propylene, heavy % | ??14.1 | ??36.81 |
| Benzene, heavy % | ??1.01 | ??1.67 |
| Toluene, heavy % | ??1.98 | ??2.84 |
| Dimethylbenzene, heavy % | ??4.01 | ??8.21 |
Claims (19)
1, a kind of method for catalytic conversion of petroleum hydrocarbon comprises reaction, stripping, product separation and catalyst regeneration four parts, it is characterized in that this method may further comprise the steps:
(1) petroleum hydrocarbon raw material injecting lift tube reaction district A contacts, reacts with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C;
(2) C4 and/or C 5 fraction injecting lift tube reaction district B contact, react with regenerator in it, and reaction oil gas that is generated and mixture of catalysts upwards flow along this riser tube, enter dense-phase bed reaction zone C;
(3) converge at dense-phase bed reaction zone C from the reaction oil gas of riser reaction zone A and mixture of catalysts and from reaction oil gas and the mixture of catalysts of riser reaction zone B, and continue in dense-phase bed reaction C, to react;
(4) catalyzer of separating reaction oil gas and reaction back carbon deposit, reaction oil gas is sent into the product separation part, and the catalyzer of reaction back carbon deposit returns reactive moieties and recycles after stripping, regeneration.
2, according to the method for claim 1, it is characterized in that described riser reaction zone A and the coaxial setting of dense-phase bed reaction zone C, and fixedly connected, and riser reaction zone B and the non-coaxial setting of dense-phase bed reaction zone C, and fixedly connected; Perhaps described riser reaction zone B and dense-phase bed reaction zone C can be for coaxial settings, and fixedly connected, and riser reaction zone A and the non-coaxial setting of dense-phase bed reaction zone C are fixedly connected still; Perhaps described riser reaction zone A and riser reaction zone B and dense-phase bed reaction zone C are non-coaxial setting, but connection fixed to one another.
3, according to the method for claim 1, it is characterized in that the other cooling storage jar of setting up of described revivifier, make catalyzer after the regeneration this jar of flowing through earlier, and then deliver to riser reaction zone.
4,, it is characterized in that described cooling storage jar is one, two or more, and the medial temperature of cooling storage jar inner catalyst is 500-700 ℃ according to the method for claim 3.
5,, it is characterized in that the medial temperature of described cooling storage jar inner catalyst is 560-650 ℃ according to the method for claim 1.
6,, it is characterized in that described activity of such catalysts component is selected from ZRP, ZSM-5 series zeolite or has the mixture of one or more and y-type zeolite in the supersiliceous zeolite, β zeolite, phosphorus aluminium zeolite of five-membered ring structure according to the method for claim 1.
7,, it is characterized in that the petroleum hydrocarbon raw material of described injecting lift tube reaction district A is selected from: the mixture of one or more in straight-run gas oil, wax tailings, deasphalted oil, hydrofined oil, hydrocracking tail oil, vacuum residuum, long residuum or the crude oil according to the method for claim 1.
8,, it is characterized in that the petroleum hydrocarbon raw material of described injecting lift tube reaction district A is selected from: the wax oil of straight-run gas oil, the wax oil after hydrotreatment or UOPK 〉=12.5 according to the method for claim 7.
9, according to the method for claim 1, the petroleum hydrocarbon that it is characterized in that described injecting lift tube reaction district B is a C 4 fraction.
10, according to the method for claim 1, it is characterized in that the reaction conditions of described riser reaction zone A is as follows: the temperature that regenerator enters riser reaction zone A is that 580 ℃-700 ℃, reaction times are that 2-10 second, agent-oil ratio are that the weight ratio of 3-30, water vapor and hydrocarbon oil crude material is that 0.02-0.40, reaction pressure are 130-450kPa.
11, according to the method for claim 10, it is characterized in that the reaction conditions of described riser reaction zone A is as follows: the temperature that regenerator enters riser reaction zone A is that 620 ℃-650 ℃, reaction times are that 2.5-8.0 second, agent-oil ratio are that the weight ratio of 4-15, water vapor and hydrocarbon oil crude material is that 0.15-0.30, reaction pressure are 200-400kPa.
12, according to the method for claim 1, it is characterized in that the reaction conditions of described riser reaction zone B is as follows: the temperature that regenerator enters riser reaction zone B is that 550 ℃-750 ℃, reaction times are that 1-8 second, agent-oil ratio are that the weight ratio of 10-40, water vapor and hydrocarbon oil crude material is that 0.02-0.40, reaction pressure are 100-500kPa.
13, according to the method for claim 12, it is characterized in that the reaction conditions of described riser reaction zone B is as follows: the temperature that regenerator enters riser reaction zone B is that 590 ℃-690 ℃, reaction times are that 2.5-7.0 second, agent-oil ratio are that the weight ratio of 13-25, water vapor and hydrocarbon oil crude material is that 0.15-0.40, reaction pressure are 150-300kPa.
14, according to the method for claim 1, it is characterized in that the reaction conditions of described dense-phase bed reaction zone C is as follows: temperature of reaction is that 500 ℃-700 ℃, reaction pressure are that normal pressure-300 kPa, weight hourly space velocity are that the weight ratio of 0.5-6.0 hour-1, catalyzer and hydrocarbon oil crude material is that the weight ratio of 10-150, water vapor and hydrocarbon oil crude material is 0.05-0.80: 1.
15, according to the method for claim 14, it is characterized in that the reaction conditions of described dense-phase bed reaction zone C is as follows: temperature of reaction is that 560 ℃-660 ℃, reaction pressure are that 100-230 kPa, weight hourly space velocity are 1-4 hour
-1, catalyzer and hydrocarbon oil crude material weight ratio be that the weight ratio of 20-80, water vapor and hydrocarbon oil crude material is 0.1-0.3: 1.
16,, it is characterized in that the catalyzer after the described regeneration is introduced into cooling storage jar, and then return reactive moieties and recycle, and it is different with the temperature of the regenerated catalyst of riser reaction zone B to return riser reaction zone A according to the method for claim 1.
17, according to the method for claim 16, the temperature that it is characterized in that the described regenerated catalyst that returns riser reaction zone A is than the high 10-50 of temperature ℃ of the regenerated catalyst that returns riser reaction zone B.
18, according to the method for claim 1, the propylene that it is characterized in that this method is more than the 35 heavy %.
19, according to the method for claim 1, it is characterized in that the C4 of described injecting lift tube reaction district B and/or C 5 fraction are from the catalytic cracking unit of using the method for the invention, perhaps from other oil refining, chemical process, or the mixture of the raw material in above-mentioned two kinds of sources.
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Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1029407C (en) * | 1992-07-16 | 1995-08-02 | 中国石油化工总公司 | Catalytic cracking method for adaptable multieffect hydrocarbons |
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- 2004-04-29 CN CNB2004100376711A patent/CN1333046C/en not_active Expired - Lifetime
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