CN1159416C - Catalytic conversion process of preparing ethylene and propylene - Google Patents
Catalytic conversion process of preparing ethylene and propylene Download PDFInfo
- Publication number
- CN1159416C CN1159416C CNB011309849A CN01130984A CN1159416C CN 1159416 C CN1159416 C CN 1159416C CN B011309849 A CNB011309849 A CN B011309849A CN 01130984 A CN01130984 A CN 01130984A CN 1159416 C CN1159416 C CN 1159416C
- Authority
- CN
- China
- Prior art keywords
- oil
- reaction
- catalyzer
- crude material
- hydrocarbon oil
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a catalytic conversion method for preparing ethylene and propylene. After being preheated, hydrocarbon oil A used as raw material is injected into a dilute phase reaction area; the hydrocarbon oil contacts a catalyst which contains fivemembered ring high-silicon zeolite, and the hydrocarbon oil reacts with the catalyst; the reaction temperature is from 630 to 750 DEG C, the reaction pressure is from 0.15 to 0.40MPa, the reaction time is from 0.2 to 3 seconds, the weight ratio of the catalyst to raw material oil is equal to 15 to 40: 1, and the weight ratio of water vapor to the raw material oil is equal to 0.3 to 1.2: 1; reacting substances flow into a dense phase reaction area; the reacting substances contact hydrocarbon oil B which is used as raw material and is injected into the dense phase reaction area, and the reacting substances react with the hydrocarbon oil B; the reaction temperature is from 500 to 600 DEG C, the reaction pressure is from 0.15 to 0.40MPa, the reaction time is from 3 to 30 seconds, the weight ratio of the catalyst to raw material oil is equal to 7 to 20: 1, and the weight ratio of water vapor to the raw material oil is equal to 0.15 to 0.6: 1; reaction oil gas and a catalyst of carbon deposition after the reaction are separated; the oil gas is inputted into a subsequent separation system, and the catalyst of carbon deposition returns to a reactor to be circularly used through stripping operation and regenerating operation; the quality flow quantity ratio of the hydrocarbon oil A as the raw material to the hydrocarbon oil B as the raw material is equal to 0.5 to 2: 1. The method has the high yield rate of ethylene, propylene and butylene.
Description
Technical field
The invention belongs to the catalysis conversion method of petroleum hydrocarbon under the situation that does not have hydrogen, more particularly, is a kind of catalysis conversion method of producing ethene and propylene.
Background technology
The traditional method that petroleum hydrocarbon is produced ethene is the steam heat cracking process, and suitable raw material is light petroleum hydrocarbons such as ethane, propane, butane, Sweet natural gas, petroleum naphtha or solar oil.Along with crude oil becomes heavy day by day, the output of light petroleum hydrocarbon is restricted.In recent years, some patent documentations disclose and have used heavy petroleum hydrocarbon to produce the method for low-carbon alkene.
CN1004878B discloses a kind of catalytic cracking method of producing propylene and butylene, adopts fluidized-bed or moving-burden bed reactor and solid acid catalyst, is 500～600 ℃ in temperature of reaction, and the feed weight air speed is 0.2～20 o'clock
-1, agent-oil ratio is to react under 2～12 the condition, as uses ZSM-5 to be active ingredient, the kaolin catalyzer as carrier, with decompression fraction oil is raw material, and when temperature of reaction was 580 ℃, ethylene yield was 5.9 heavy %, productivity of propylene is 21.9 heavy %, and the butylene productive rate is 15.6 heavy %.
CN1069016A discloses and a kind of heavy hydrocarbon has been transformed in fluidized-bed or plug flow reactor, produce double propylene and the butylene of producing of ethene, its principal reaction condition is that temperature of reaction is 650～900 ℃, pressure is 0.13～0.28MPa, reaction times is 0.1～3 second, agent-oil ratio is 5～35, and the main products yield is that ethylene yield is 17～27 heavy %, and the productive rate sum of ethene+propylene+butylene is 30～40 heavy %.
CN1218786A disclose a kind of with heavy hydrocarbon in riser tube or downstriker transfer limes reactor, with contain clay molecular sieve with layer structure and/or contact through the catalyzer of phosphorus with the five-ring supersiliceous zeolite of aluminium or magnesium or calcium modification, in temperature of reaction is 650～750 ℃, pressure is 0.15～0.40MPa, reaction times is 0.2～5 second, the weight ratio of catalyzer and stock oil is 15～40: 1, and the weight ratio of water vapor and stock oil is to carry out the catalytic pyrolysis reaction under 0.3～1: 1 the condition.The ethene of this method, productivity of propylene are all above 18 heavy %.
Summary of the invention
The object of the present invention is to provide a kind of is that catalytic material transforms the method for producing ethene and propylene with the heavy petroleum hydrocarbon.
Method provided by the invention is: the hydrocarbon oil crude material A after the preheating injects the dilute phase reaction zone, contact, react with the catalyzer that contains the five-ring supersiliceous zeolite, temperature of reaction is 630～750 ℃, reaction pressure is 0.15～0.40MPa, reaction times is 0.2～3 second, the weight ratio of catalyzer and stock oil is 15～40: 1, and the weight ratio of water vapor and stock oil is 0.3～1.2: 1; Reactant flow enters Mi Xiangfanyingqu, and contact, react with the hydrocarbon oil crude material B that injects wherein, temperature of reaction is 500～600 ℃, reaction pressure is 0.15～0.40MPa, reaction times is 3～30 seconds, the weight ratio of catalyzer and stock oil is 7～20: 1, and the weight ratio of water vapor and stock oil is 0.15～0.6: 1; The catalyzer of separating reaction oil gas and reaction back carbon deposit, oil gas is sent into subsequent separation system, and the catalyzer of carbon deposit Returning reactor after stripping, regeneration recycles; Wherein, hydrocarbon oil crude material A is 0.5～2: 1 with the ratio of the mass rate of hydrocarbon oil crude material B.
The invention has the advantages that:
1, combines existing catalytic pyrolysis and catalytic thermocracking process advantage, under lower temperature of reaction, generate higher ethene and productivity of propylene, and in certain scope, can regulate the productive rate of ethene, propylene and butylene.
2, compare with the method for existing catalytic cracking to prepare lower carbon olefin, the ethylene yield that the present invention generated increases substantially.And utilize the catalyzer of band charcoal to produce low-carbon alkene, help selectivity of light olefin and improve.
3, compare with the method that existing catalytic pyrolysis is produced ethene and propylene, the present invention has adopted than low reaction temperatures, and riser tube outlet logistics is not needed to inject heat-eliminating medium or only injects a spot of heat-eliminating medium, reduces excessive heat cracking reaction, simultaneously, cut down the consumption of energy and to the equipment material requirement.
Description of drawings
Fig. 1 is the schematic flow sheet of method provided by the present invention.
Fig. 2 is the schematic flow sheet of method provided by the present invention.
Embodiment
Hydrocarbon oil crude material A after the preheating is injected the dilute phase reaction zone, and contact with the catalyzer that contains the five-ring supersiliceous zeolite after the regeneration, and react under following condition: temperature of reaction is 630～750 ℃, is preferably 650～720 ℃; Reaction times is 0.2～3 second, is preferably 0.3～1 second; The weight ratio of catalyzer and stock oil is 15～40: 1, is preferably 20～30: 1; Reaction pressure is 0.15～0.40MPa, is preferably 0.15～0.30MPa; The weight ratio of water vapor and stock oil is 0.3～1.2: 1, is preferably 0.5～1: 1.Temperature before catalyzer contacts with hydrocarbon ils should be preferably greater than 730 ℃, more preferably greater than 750 ℃ greater than 700 ℃.Reactant flow enters Mi Xiangfanyingqu, and contacts, reacts with the hydrocarbon oil crude material B that injects wherein, and temperature of reaction is 500～600 ℃, preferred 530～580 ℃; Reaction pressure is 0.15～0.40MPa, preferred 0.15～0.30MPa; Reaction times is 3～30 seconds, preferred 5～15 seconds; The weight ratio of catalyzer and stock oil is 7～20: 1, preferred 8～15: 1; The weight ratio of water vapor and stock oil is 0.15～0.6: 1, preferred 0.25～0.40: 1.The catalyzer of separating reaction oil gas and reaction back carbon deposit, oil gas is sent into subsequent separation system, and the catalyzer of carbon deposit is sent into revivifier behind the water vapor stripping, coke burning regeneration under the effect of oxygen-containing gas, the catalyzer Returning reactor after the regeneration recycles.
In method provided by the present invention, hydrocarbon oil crude material A is 0.5～2: 1 with the ratio of the mass rate of hydrocarbon oil crude material B, preferred 0.8～1.5: 1.Described hydrocarbon oil crude material A is selected from: the mixture of one or more in decompressed wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil, hydrotreatment tail oil or the shale oil.Described hydrocarbon oil crude material B is selected from: the mixture of one or more in gasoline fraction, diesel oil distillate, decompressed wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil, hydrotreatment tail oil or the shale oil; Wherein, the olefin(e) centent of described gasoline fraction should be greater than 15v%, more preferably greater than 25v%.
In method provided by the present invention, catalyst system therefor is the solid acid catalyst that contains the five-ring supersiliceous zeolite, described five-ring supersiliceous zeolite be selected from have ZSM-5, the supersiliceous zeolite of ZSM-8 or ZSM-11 structure, this supersiliceous zeolite can be a Hydrogen, also can be through rare earth and/or phosphorus modification, or the five-ring supersiliceous zeolite of process phosphorus and aluminium or magnesium or calcium modification.The preparation method of described five-ring supersiliceous zeolite can be referring to CN1027632C, CN1059133C or CN1211469A.
In addition, the modified product that the used catalyzer of the present invention can also contain catalytic cracking field y-type zeolite commonly used and obtain after ion-exchange or the processing of various physical chemistry method, for example HY, REY, REHY, USY, RE-USY etc.
The carrier of catalyst system therefor of the present invention is various carriers commonly used in the catalytic cracking catalyst, for example SiO
2Al
2O
3, Al
2O
3-clay, SiO
2-clay etc.
In method provided by the present invention, the catalyzer that contacts with hydrocarbon oil crude material B can be the long-pending catalyzer that a certain amount of coke is arranged from the dilute phase reaction zone, also can be the mixture of the regenerated catalyst of 550～630 ℃ of the above-mentioned long-pending catalyzer that a certain amount of coke arranged and another strands.Here of particular note, the above-mentioned catalyzer that a certain amount of coke arranged from dilute phase reaction zone long-pending can be identical catalyzer with 550～630 ℃ regenerated catalyst, also can be to form and the different catalyzer of filling a prescription.When both catalyst activity components not simultaneously, in device, be convenient to separate in order to make two kinds of catalyzer, should be prepared as catalyzer with different physical properties, such as, different particle diameters, different apparent bulk density etc.Above-mentioned two kinds of catalyzer enter different reaction zones respectively, contact with stock oil and react.For example, contain phosphorus and aluminium or calcium or magnesium-modified five-ring supersiliceous zeolite and the bigger catalyzer of particle diameter and contact with hydrocarbon oil crude material A and react, to improve selectivity of ethylene; And after containing the less catalyzer of the five-ring supersiliceous zeolite of y-type zeolite and modification and particle diameter and from dilute phase reaction zone long-pending the catalyst mix of a certain amount of coke being arranged, contact with hydrocarbon oil crude material B and react, with the increase heavy oil conversion performance; Above-mentioned two kinds of catalyzer are after finish separates, and common stripping and regeneration after being separated according to the difference of its physical properties in revivifier, are delivered to different reaction zones and recycle.The different catalyzer of granular size can 30～40 microns be divided for standard, and the catalyzer that apparent bulk density is different can 0.6～0.7g/cm
3For standard is divided.
Reactor of the present invention both can be the riser reactor of reducing, also can be common riser tube+bed reactor.The structure of the riser reactor of described reducing is referring to CN1237477A.
In method provided by the present invention, the pre-lifting medium of riser reactor bottom can be selected from: the mixture of one or more in steam, dry gas, ethane, propane, butane, Sweet natural gas, straight-run spirit or the solar oil, and preferred: the mixture of one or more in ethane, propane, butane, Sweet natural gas or the straight-run spirit.
Further specify method provided by the invention below in conjunction with accompanying drawing.
As shown in Figure 1, the regenerated catalyst of heat enters the bottom of reducing riser reactor through regenerator sloped tube 16, and quickens upwards to flow under the effect of the pre-lifting medium that is injected by pipeline 1.Hydrocarbon oil crude material A after the preheating with after atomizing steam from pipeline 3 mixes by a certain percentage, injects the dilute phase reaction zone 5 of reducing riser reactor through pipeline 4, contacts, reacts with thermocatalyst.Above-mentioned reactant flow upwards flows into close phase reaction district 7, and contacts, reacts with hydrocarbon oil crude material B from pipeline 6.Hydrocarbon oil crude material B injects before the close phase reaction district 7 with atomizing steam from pipeline 2 and mixes by a certain percentage.Reaction oil gas and catalyzer continue upwards to flow in close phase reaction district, after the outlet of reducing riser reactor enters settling vessel 8, under the effect of gas-solid sharp separation equipment, reaction oil gas and catalyst separating, oil gas is sent into later separation and absorption-stable system through pipeline 9, and the catalyzer of reaction back carbon deposit enters stripper 12, and stripped vapor injects through pipeline 13, with the catalyzer counter current contact, stripping is clean as much as possible for the reaction oil gas that catalyzer is entrained.Catalyzer behind the stripping is sent into revivifier 15 coke burning regenerations through pipeline 10 to be generated.Oxygen-containing gas, for example air injects through pipeline 17, and regenerated flue gas is drawn through pipeline 18.Catalyzer after the regeneration recycles through regeneration pipeline 16 Returning reactors.
Except above-mentioned reaction process, in close phase reaction district, can mix with one regenerator (shown among Fig. 1 11) of 550～630 ℃ from revivifier in addition from the reactant flow of dilute phase reaction zone, the temperature that makes oil gas and catalyzer suitably after the reduction, contacts, reacts with hydrocarbon oil crude material B again.For the temperature that makes regenerator is reduced to 550～630 ℃, the cooling measure that this area is commonly used, for example, the interchanger etc. that catalyst cooler, catalyzer and other logistics are set all can adopt.
As shown in Figure 2, the regenerated catalyst of heat enters riser reactor 14 through regenerator sloped tube 16, the bottom of dilute phase reaction zone promptly of the present invention, and under the effect of the pre-lifting medium that injects by pipeline 1, quicken upwards to flow.Hydrocarbon oil crude material A after the preheating contacts, reacts with thermocatalyst in pipeline 4 and injecting lift pipe reactor after atomizing steam from pipeline 3 mixes by a certain percentage.Above-mentioned reactant flow upwards flows into fluidized-bed reactor 19, in the close phase reaction promptly of the present invention district, and contacts, reacts with hydrocarbon oil crude material B from pipeline 6.Hydrocarbon oil crude material B injects before the Mi Xiangfanyingqu with atomizing steam from pipeline 2 and mixes by a certain percentage.Reaction oil gas and catalyzer in close phase reaction district thorough mixing, the reaction after, under the effect of gas-solid sharp separation equipment, reaction oil gas and catalyst separating.Oil gas is sent into later separation and absorption-stable system through settling vessel 8 and pipeline 9, and the catalyzer of reaction back carbon deposit enters stripper 12, and stripped vapor injects through pipeline 13, with the catalyzer counter current contact, and the entrained reaction oil gas of stripping catalyst as much as possible.Catalyzer behind the stripping is sent into revivifier 15 coke burning regenerations through pipeline 10 to be generated.Oxygen-containing gas, for example air injects through pipeline 17, and regenerated flue gas is drawn through pipeline 18.Catalyzer after the regeneration recycles through regeneration pipeline 16 Returning reactors.
Except above-mentioned reaction process, in fluidized-bed reactor, reactant flow from the dilute phase reaction zone can be mixed with other one regenerator (shown among Fig. 2 11) of 550～630 ℃ from revivifier, after making suitable reduction of temperature of oil gas and catalyzer, contact, react with hydrocarbon oil crude material B again.For the temperature that makes regenerator is reduced to 550～630 ℃, the cooling measure that this area is commonly used, for example, the interchanger etc. that catalyst cooler or catalyzer and other logistics are set all can adopt.
The following examples will be further specified the present invention, but not thereby limiting the invention.The character of employed stock oil and catalyzer is listed in table 1 and table 2 respectively in embodiment, the Comparative Examples.Catalyzer in the table 2 is by Qilu Petrochemical company of Sinopec Group catalyst plant industrial production.
Present embodiment explanation: utilize medium-sized reducing riser reactor to implement the resulting test-results of method provided by the invention.
The total height of testing used medium-sized reducing riser reactor is 15 meters, and the diameter of its dilute phase reaction zone is 0.025 meter, and it highly is 4.5 meters; The diameter of its Mi Xiangfanyingqu is 0.1 meter, highly is 9.0 meters.The structure of this reactor is referring to CN1237477A.
Stock oil in the employing table 1 1. with table 2 in four kinds of catalyzer test respectively.Main testing sequence is as follows: as shown in Figure 1, the regenerated catalyst of heat enters the bottom of reducing riser reactor through regenerator sloped tube 16, and quickens upwards to flow under the effect of the pre-lifting medium that is injected by pipeline 1.The stock oil of 50 heavy % after the preheating 1. through pipeline 4 with after atomizing steam from pipeline 3 mixes, inject the dilute phase reaction zone 5 of reducing riser reactor, contact, react with thermocatalyst.Above-mentioned reactant flow upwards flows into close phase reaction district 7, and 1. contacts, reacts with stock oils from all the other 50 heavy % of pipeline 6.1. stock oil inject before the close phase reaction district 7 with atomizing steam from pipeline 2 and mix.Reaction oil gas and catalyzer continue upwards to flow in close phase reaction district, after the outlet of reducing riser reactor enters settling vessel 8, under the effect of gas-solid sharp separation equipment, reaction oil gas and catalyst separating, oil gas is sent into later separation and absorption-stable system through pipeline 9, further be separated into and be rich in ethene, the gas of propylene and butylene and the gasoline and the other products that are rich in aromatic hydrocarbons; And the catalyzer of reaction back carbon deposit enters stripper 12, and stripped vapor injects through pipeline 13, and with the catalyzer counter current contact, stripping is clean as much as possible for the reaction oil gas that catalyzer is entrained.Catalyzer behind the stripping is sent into revivifier 15 coke burning regenerations through pipeline 10 to be generated.Oxygen-containing gas, for example air injects through pipeline 17, and regenerated flue gas is drawn through pipeline 18.Catalyzer after the regeneration recycles through regeneration pipeline 16 Returning reactors.
Main operational condition and product distribute and list in table 3.As can be seen from Table 3, the difference of catalyst type has bigger influence to the productive rate of low-carbon alkene, helps low-carbon alkene with the pentacyclic catalyzer of phosphorus modification and generates, and the productive rate of its ethene+propylene+butylene is 48.02 heavy %.
The present embodiment explanation: with hydrocarbon ils of different nature is raw material, adopts the resulting test-results of method provided by the invention.
It is identical with embodiment 1 to test used medium-sized reducing riser reactor.Adopting listed catalyst A in the table 2, is that raw material is tested with four kinds of hydrocarbon ils in the table 1 respectively, and main testing sequence is identical with embodiment 1.
The operational condition of test and product distribute and list in table 4.As can be seen from Table 4, the nature difference of hydrocarbon oil crude material has bigger influence to productivity of low carbon olefin hydrocarbon, and ethylene yield changes greatly, is 10.46～16.05 heavy %; The productivity of propylene variation is taken second place, and is 15.36～20.76 heavy %; The butylene productive rate changes less, is 9.26～11.21 heavy %.
Present embodiment explanation: different operational conditions is to the influence of the implementation result that the invention provides method.
It is identical with embodiment 1 to test used medium-sized reducing riser reactor.1. listed catalyst A and the stock oil in the table 1 are tested in the employing table 2, and main testing sequence is identical with embodiment 1.
The operational condition of test and product distribute and list in table 5.As can be seen from Table 5, different operational conditions is different to the influence degree of productivity of low carbon olefin hydrocarbon, and ethylene yield is 12.05～18.21 heavy %; Productivity of propylene is 21.10～23.40 heavy %; The butylene productive rate is 9.36～13.21 heavy %.
Present embodiment explanation: the reactor of different types is to the influence of the implementation result that the invention provides method.
Adopt medium-sized reducing riser reactor and riser tube+fluidized-bed reactor to test respectively.1. with listed stock oil in the table 1 is raw material, and listed catalyst A is tested in the employing table 2.Testing sequence is basic identical with embodiment 1.
The operational condition of test and product distribute and list in table 6.As can be seen from Table 6, adopt the resulting product distribution situation of medium-sized reducing riser reactor to be better than riser tube+fluidized-bed reactor.
Comparative Examples 1
This Comparative Examples explanation: adopt the resulting test-results of existing increased low carbon olefine output catalysis conversion method, to further specify implementation result of the present invention.
1. with listed stock oil in the table 1 is raw material, and listed catalyst A is tested in the employing table 2.Testing apparatus is conventional riser catalytic cracking middle-scale device.Main testing sequence is as follows: the stock oil after the preheating is the bottom of injecting lift pipe reactor 1., in the presence of water vapor, contacts with the regenerated catalyst A of heat and reacts.Reaction product isolated obtains the gasoline and the other products that are rich in the gas of ethene, propylene and butylene and are rich in aromatic hydrocarbons.Reclaimable catalyst enters the revivifier coke burning regeneration through stripping, and the catalyzer Returning reactor after the regeneration recycles.
1. with listed stock oil in the table 1 is raw material, and listed catalyst B is tested in the employing table 2.Testing apparatus is conventional fluid catalystic cracking middle-scale device.Main testing sequence is as follows: 1. the stock oil after the preheating inject fluidized-bed reactor, in the presence of water vapor, contacts with the regenerated catalyst A of heat and react.Reaction product isolated obtains the gasoline and the other products that are rich in the gas of ethene, propylene and butylene and are rich in aromatic hydrocarbons.Reclaimable catalyst enters the revivifier coke burning regeneration through stripping, and the catalyzer Returning reactor after the regeneration recycles.
The operational condition of test and product distribute and list in table 6.The test-results of embodiment in the table 6 and Comparative Examples is compared as can be seen, with respect to catalytic pyrolysis process (riser reactor in the Comparative Examples), method provided by the invention institute production ethylene yield is lower than catalytic pyrolysis, and propylene+butylene productive rate is higher than catalytic pyrolysis, selectivity of light olefin is higher than catalytic pyrolysis, is that 73.0 heavy % are to 69.4 heavy %; With respect to catalytic pyrolysis process (fluidized-bed reactor in the Comparative Examples), method provided by the invention institute production ethylene yield is higher than catalytic pyrolysis, and propylene+butylene productive rate is lower than catalytic pyrolysis, but ethene, propylene, butylene three productive rate sum are higher than catalytic pyrolysis, are that 48.02 heavy % are to 41.78 heavy %.
Table 1
| The | ① | ② | ③ | ④ |
| Stock oil title density (20 ℃), kilogram/rice
3Kinematic viscosity, millimeter
2/ second 80 ℃ of 100 ℃ of carbon residues, heavy % condensation point, ℃ basic nitrogen, the ppm total nitrogen, heavy % sulphur, heavy % carbon, heavy % hydrogen, heavy % heavy metal content, ppm nickel vanadium iron copper sodium boiling range, ℃ | Wax oil 873.0 13.01 8.04 0.15 50 340 0.10 0.073 86.5 13.24＜0.1＜0.1 54＜0.1-346 411 437 462 489 523 546 | Wax oil 890.5 7.93 5.08 0.7 40 0.16 0.53 85.00 12.62 0.16 0.15--0.45 242 322 380 410 437 480 516 | Reduced crude 897.4 54.20 30.02 4.5 47 0.27 0.14 86.26 12.91 5.2＜0.1 4.2＜0.1 5.5 324 408 486---- | Decompression residuum 920.9/114.4 8.2 25 0.33 0.21 86.91 12.55 8.8 0.1 1.8＜0.1 3.0 415 545----- |
Table 2
| Catalyzer numbering trade names zeolite type pentasil zeolites accounts for active ingredient, heavy % chemical constitution, heavy % aluminum oxide sodium oxide ferric oxide apparent density, kilogram/rice 3Pore volume, milliliter/gram specific surface area, rice 2/ gram abrasion index is when weighing % -1Size composition, 0～40 micron 40～80 microns＞80 microns aging condition micro-activity of heavy % | A CEP-1 P-Ca/Mg/Al- ZRP-5 100 52.1 / / 890 / / 2.1 16.6 42.0 41.4 790℃，27hr 100％H 2O 62(520℃) | B CRP-1 REY+ZRP-5 50～90 54.2 0.03 / 860 0.26 160 1.2 26.0 60.8 13.2 790℃，17hr， 100％H 2O 58(520℃) | C CIP-2 USY+P- ZRP-5 25～75 49.0 0.1 0.35 800 0.30 202 1.3 20.7 40.7 38.6 790℃，17hr 100％H 2O 66(460℃) | D RAG-1 REY+USY+Z RP-5 10～50 44.6 0.13 620 0.36 232 2.5 13.1 54.9 32.0 790℃，15hr 100％H 2O 68(460℃) |
Table 3
| The catalyzer title | A | B | C | D |
| Hydrocarbon oil crude material A/ hydrocarbon oil crude material B (weight) | 1∶1 | 1∶1 | 1∶1 | 1∶1 |
| Operating condition: regenerated catalyst temperature; ℃ reaction temperature; ℃ dilute phase reaction zone outlet Mi Xiangfanyingqu outlet reaction time, second close phase reaction of dilute phase reaction zone close phase reaction district's oil ratio dilute phase reaction zone district water-oil factor dilute phase reaction zone Mi Xiangfanyingqu | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 |
| Product distributes; Heavy % cracked gas ethylene, propylene butylene gasoline light oil heavy oil coke ethene+propylene+butylene, heavy % | 65.79 16.05 20.76 11.21 18.22 6.45 3.68 5.86 48.02 | 64.02 15.06 20.35 12.00 19.26 7.02 3.69 6.01 47.41 | 57.76 12.21 16.34 12.25 22.65 9.31 4.02 6.26 45.80 | 55.16 11.36 14.35 11.01 23.38 9.98 4.62 6.86 36.72 |
Table 4
| The stock oil title | A | B | C | D |
| Hydrocarbon oil crude material A/ hydrocarbon oil crude material B (weight) | 1∶1 | 1∶1 | 1∶1 | 1∶1 |
| Operating condition: regenerated catalyst temperature; ℃ reaction temperature; ℃ dilute phase reaction zone outlet Mi Xiangfanyingqu outlet reaction time, second close phase reaction of dilute phase reaction zone close phase reaction district's oil ratio dilute phase reaction zone district water-oil factor dilute phase reaction zone Mi Xiangfanyingqu | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 |
| Product distributes; Heavy % cracked gas ethylene, propylene butylene gasoline light oil heavy oil coke ethene+propylene+butylene, heavy % | 65.79 16.05 20.76 11.21 18.22 6.45 3.68 5.86 48.02 | 60.19 13.56 18.96 11.11 22.01 7.45 4.01 6.34 43.63 | 58.24 12.32 18.03 10.24 22.14 7.10 4.65 7.87 40.59 | 54.34 10.46 15.36 9.26 23.15 7.56 4.78 10.17 35.08 |
Table 5
| Hydrocarbon oil crude material A/ hydrocarbon oil crude material B (weight) | 1∶1 | 1∶1 | 2∶1 | 1∶2 |
| Operating condition: regenerated catalyst temperature; ℃ reaction temperature; ℃ dilute phase reaction zone outlet Mi Xiangfanyingqu outlet reaction time, second close phase reaction of dilute phase reaction zone close phase reaction district's oil ratio dilute phase reaction zone district water-oil factor dilute phase reaction zone Mi Xiangfanyingqu | 750 680 600 0.8 6.0 26 13 0.8 0.4 | 700 630 550 0.8 6.0 16 8 0.8 0.4 | 765 640 580 0.5 6.0 20 13 0.6 0.40 | 720 700 580 1.0 6.0 30 10 1.2 0.4 |
| Product distributes; Heavy % cracked gas ethylene, propylene butylene gasoline light oil heavy oil coke ethene+propylene+butylene, heavy % | 69.02 18.21 21.45 9.36 16.37 5.01 3.54 6.06 49.02 | 60.72 13.15 21.86 11.96 22.45 7.08 4.18 5.57 46.97 | 67.03 17.15 21.10 11.01 17.14 6.14 3.68 6.01 49.26 | 63.70 12.05 23.40 13.21 20.24 6.60 3.87 5.59 48.66 |
Table 6
| Project | Embodiment | Comparative Examples | ||
| Type of reactor | The reducing riser tube | Riser tube+fluidized-bed | Riser tube | Stream skill bed |
| The catalyzer title | A | A | A | B |
| Hydrocarbon oil crude material A/ hydrocarbon oil crude material B (weight) | 1∶1 | 1∶1 | / | / |
| Operating condition: regenerated catalyst temperature; ℃ reaction temperature; ℃ dilute phase reaction zone outlet Mi Xiangfanyingqu outlet reaction time, second close phase reaction of dilute phase reaction zone close phase reaction district's oil ratio dilute phase reaction zone district water-oil factor dilute phase reaction zone Mi Xiangfanyingqu | 750 650 580 0.8 6.0 20.0 10.0 0.80 0.40 | 750 650 580 0.8 10.0 20 10 0.80 0.40 | 760 620 2.1 22.5 0.57 | 720 580 10.0 9.6 0.22 |
| Product distributes; Heavy % cracked gas ethylene, propylene butylene gasoline light oil heavy oil coke ethene+propylene+butylene, heavy % | 65.79 16.05 20.76 11.21 18.22 6.45 3.68 5.86 48.02 | 67.12 16.12 20.63 11.01 17.28 5.98 3.56 6.06 47.76 | 69.31 24.89 15.45 7.76 11.88 7.96 3.84 7.01 48.10 | 57.36 6.40 22.33 13.05 24.16 9.28 3.78 5.42 41.78 |
| Selectivity of light olefin *, % | 73.0 | 71.2 | 69.4 | 72.8 |
* selectivity of light olefin=(ethene+propylene+butylene) productive rate/reacted gas productive rate
Claims (12)
1, a kind of catalysis conversion method of producing ethene and propylene, it is characterized in that: the hydrocarbon oil crude material A after the preheating injects the dilute phase reaction zone, contact, react with the catalyzer that contains the five-ring supersiliceous zeolite, temperature of reaction is 630～750 ℃, reaction pressure is 0.15～0.40MPa, reaction times is 0.2～3 second, and the weight ratio of catalyzer and stock oil is 15～40: 1, and the weight ratio of water vapor and stock oil is 0.3～1.2: 1; Reactant flow enters Mi Xiangfanyingqu, and contact, react with the hydrocarbon oil crude material B that injects wherein, temperature of reaction is 500～600 ℃, reaction pressure is 0.15～0.40MPa, reaction times is 3～30 seconds, the weight ratio of catalyzer and stock oil is 7～20: 1, and the weight ratio of water vapor and stock oil is 0.15～0.6: 1; The catalyzer of separating reaction oil gas and reaction back carbon deposit, oil gas is sent into subsequent separation system, and the catalyzer of carbon deposit Returning reactor after stripping, regeneration recycles; Wherein, hydrocarbon oil crude material A is 0.5～2: 1 with the ratio of the mass rate of hydrocarbon oil crude material B; Described hydrocarbon oil crude material A is selected from: the mixture of one or more in decompressed wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil, hydrotreatment tail oil or the shale oil; Described hydrocarbon oil crude material B is selected from: the mixture of one or more in gasoline fraction, diesel oil distillate, decompressed wax oil, long residuum, vacuum residuum, wax tailings, deasphalted oil, hydrotreatment tail oil or the shale oil.
2,, it is characterized in that the described hydrocarbon oil crude material A and the ratio of the mass rate of hydrocarbon oil crude material B are 0.8～1.5: 1 according to the method for claim 1.
3,, it is characterized in that when hydrocarbon oil crude material B was gasoline fraction, olefin content in gasoline should be greater than 15v% according to the method for claim 2.
4,, it is characterized in that when hydrocarbon oil crude material B was gasoline fraction, olefin content in gasoline should be greater than 25v% according to the method for claim 3.
5, according to the method for claim 1, it is characterized in that described five-ring supersiliceous zeolite be selected from have ZSM-5, the supersiliceous zeolite of ZSM-8 or ZSM-11 structure, and this zeolite can be a Hydrogen, also can be through rare earth and/or phosphorus modification, or process phosphorus and aluminium or magnesium or calcium modification.
6, according to the method for claim 1, it is characterized in that the reaction conditions of described hydrocarbon oil crude material A is: the weight ratio of 650～720 ℃ of temperature of reaction, reaction pressure 0.15～0.30MPa, 0.3～1 second reaction times, catalyzer and stock oil is 20～30: 1, the weight ratio of water vapor and stock oil is 0.5～1: 1; The reaction conditions of hydrocarbon oil crude material B is: the weight ratio of 530～580 ℃ of temperature of reaction, reaction pressure 0.15～0.30MPa, 5～15 seconds reaction times, catalyzer and stock oil is 8～15: 1, the weight ratio of water vapor and stock oil is 0.25～0.40: 1.
7, according to the method for claim 1, it is characterized in that the described catalyzer that contacts with hydrocarbon oil crude material B can be the catalyzer from the carbon deposit of dilute phase reaction zone, also can be the mixture of the regenerator of 550～630 ℃ of the catalyzer of above-mentioned carbon deposit and another strands.
8, according to the method for claim 7, the catalyzer that it is characterized in that described carbon deposit from the dilute phase reaction zone can be identical catalyzer with the regenerator of 550～630 ℃ of another strands, also can be to form and the different catalyzer of filling a prescription.
9,, it is characterized in that described reactor is the riser reactor or the riser tube+bed reactor of reducing according to the method for claim 1.
10,, it is characterized in that the described catalyzer that contacts with hydrocarbon oil crude material A is greater than 700 ℃ according to the method for claim 1.
11,, it is characterized in that the pre-lifting medium that this method adopts is selected from: the mixture of one or more in steam, dry gas, ethane, propane, butane, Sweet natural gas, straight-run spirit or the solar oil according to the method for claim 1.
12,, it is characterized in that described pre-lifting medium is selected from: the mixture of one or more in ethane, propane, butane, Sweet natural gas or the straight-run spirit according to the method for claim 11.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011309849A CN1159416C (en) | 2001-08-29 | 2001-08-29 | Catalytic conversion process of preparing ethylene and propylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011309849A CN1159416C (en) | 2001-08-29 | 2001-08-29 | Catalytic conversion process of preparing ethylene and propylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403540A CN1403540A (en) | 2003-03-19 |
| CN1159416C true CN1159416C (en) | 2004-07-28 |
Family
ID=4670294
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011309849A Expired - Lifetime CN1159416C (en) | 2001-08-29 | 2001-08-29 | Catalytic conversion process of preparing ethylene and propylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1159416C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8246914B2 (en) | 2008-12-22 | 2012-08-21 | Uop Llc | Fluid catalytic cracking system |
| CN102585883A (en) * | 2012-03-05 | 2012-07-18 | 东北石油大学 | Pre-lifting process of FCC (Fluid Catalytic Cracking) device |
| CN110724550B (en) | 2018-07-16 | 2021-04-06 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting fast fluidized bed |
| CN110724553B (en) | 2018-07-16 | 2021-04-06 | 中国石油化工股份有限公司 | Method and system for catalytic cracking by adopting dilute phase conveying bed and rapid fluidized bed |
-
2001
- 2001-08-29 CN CNB011309849A patent/CN1159416C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1403540A (en) | 2003-03-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102051213B (en) | Catalytic cracking method | |
| CN100537721C (en) | A kind of catalysis conversion method of propylene enhancing | |
| CN103131464B (en) | A kind of hydrocarbons catalytic conversion method producing low-carbon alkene and light aromatic hydrocarbons | |
| CN102286294B (en) | Method for producing propylene and light arenes by catalytic conversion of hydrocarbons | |
| CN103131463B (en) | Hydrocarbon catalytic conversion method for increasing propylene yield | |
| CN102690679B (en) | Catalytic cracking method for producing propylene | |
| CN101029248B (en) | Method for increasing light olefin yield | |
| CN1076751C (en) | Method for catalytic conversion to prepare isobutane and isoalkane-enriched gasoline | |
| CN1137959C (en) | Catalytic converting process for producing low-alkene gasoline and high-yield diesel oil | |
| CN102690683B (en) | Catalytic cracking method and catalytic cracking device for producing propylene | |
| CN101045667A (en) | Combined catforming of high-production low carbon alkene | |
| CN1159416C (en) | Catalytic conversion process of preparing ethylene and propylene | |
| CN111423905B (en) | Catalytic cracking process and system | |
| CN1179018C (en) | Catalytic conversion process of heavy petroleum hydrocarbon for increasing output of ethylene and propylene | |
| CN1232070A (en) | Catalytic conversion method for preparing propylene, isobutane and isoalkane-enriched gasoline | |
| CN1212372C (en) | Catalytic conversion method using C4 fraction to increase small molecule olefine hydrocarbon yield | |
| CN101058744A (en) | Lift leg catalytic conversion process and apparatus | |
| CN1164718C (en) | Catalytic conversion process of preparing gaseous olefine and gasoline with low olefine content | |
| CN1152119C (en) | Catalytic conversion process of preparing propylene, butene and gasoline with low olefine content | |
| CN1184282C (en) | Method for catalyzing and cracking petroleum hydrocarbon in relaying mode | |
| CN1142249C (en) | Contact method for catalytic cracking of oil | |
| CN1184281C (en) | Method of catalyzing and cracking by using canular reactor with agent entering through two way | |
| CN1208435C (en) | Catalytic conversion method for extracting isobutane and gasoline richly containing isoparaffin | |
| CN1670133A (en) | Catalytic conversion method for preparing light olefins by using C4-C6 distillates | |
| CN111423904B (en) | Catalytic cracking process and system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20040728 |