CN101293806B - Catalytic conversion method for improving productivity of low carbon olefin hydrocarbon - Google Patents
Catalytic conversion method for improving productivity of low carbon olefin hydrocarbon Download PDFInfo
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Abstract
A catalytic conversion method for improving the yield of low-carbon olefin comprises the following steps: hydrocarbon oil raw material is injected into a riser or/and a fluidized bed reactor via a feed nozzle, comes into contact with catalyst containing shape-selective zeolite with an average pore size being smaller than 0.7 nm and reacts; gas rich in hydrogen is injected into the reactor; reaction oil gas and carbon deposited catalyst after reaction are separated, wherein the reaction oil gas is separated to obtain a target product containing ethylene and propylene; and the carbon deposited catalyst is returned to the reaction for reutilization after being stripped and regenerated. By injecting gas rich in hydrogen, the method can remarkably inhibit reconversion reaction of the generated low-carbon olefin to improve the yield of low-carbon olefin, particularly of propylene. When vacuum gas oil is adopted as raw material and double risers combined with a fluidized bed reactor are adopted, ethylene yield reaches 8.97 wt%, and propylene yield reaches 31.38 wt%, which are respectively improved by 2.93% and 6.81% in comparison with a process without injection of gas rich in hydrogen.
Description
Technical field
The invention belongs to the catalysis conversion method of hydrocarbon ils, more particularly, is the method that a kind of hydrocarbon ils catalyzed conversion under the effect of catalyzer is produced low-carbon alkenes such as ethene, propylene.
Background technology
The traditional method of producing low-carbon alkene at present is the tube furnace steam splitting process, and the raw material that this method is suitable for is light petroleum hydrocarbons such as ethane, propane, butane, petroleum naphtha or solar oil.Along with crude oil becomes heavy day by day, the supply of light petroleum hydrocarbon is restricted, and forces the investigator to have to diversion is produced low-carbon alkene to the raw material that uses the more wide region that comprises heavy petroleum hydrocarbon.
In recent years, some patent documentations disclose the method for using heavy petroleum hydrocarbon, petroleum naphtha and C4～raw materials such as C6 lighter hydrocarbons on acid zeolite, to produce low-carbon alkene through catalytic cracking reaction.Compare with steam cracking; Because the introducing of catalyzer; These class methods greatly reduce the activation energy of reaction; Make reaction be able to comparatively carrying out under the demulcent condition, thereby simplified the tube furnace reactor drum because the structure of reactor problem that needs high-intensity tube wall heat transfer to be brought reaches the demand to high temperature alloy.Simultaneously; Utilize sophisticated FCC engineering; These class methods can be utilized the granules of catalyst of fluidized will react the coke that generates and take out of, have solved the coking problem that heavy feed stock brings, therefore; These class methods both can be handled the low-density oil hydrocarbon feed, also can handle the heavy crude hydrocarbon feed.
A kind of catalytic cracking method of producing propylene and butylene is disclosed among the CN1004878B.This method adopts fluidized-bed or moving-burden bed reactor and solid acid catalyst, is 500～650 ℃ in temperature of reaction, and the feed weight air speed is 0.2～20 o'clock
-1, the weight ratio of catalyzer and raw oil is to react under 2～12 the condition.When using ZSM-5 as active ingredient, kaolin catalyzer as carrier, be raw material with the vacuum gas oil, and when under 580 ℃, reacting, its ethylene yield is 5.9 heavy %, productivity of propylene is 21.9 heavy %, the butylene productive rate is 15.6 heavy %.
CN1083092A discloses the method that a kind of catalytic pyrolysis is produced ethene and propylene.This method is delivered to the petroleum hydrocarbon of preheating in the transfer limes reactor drum; In the presence of high-temperature steam, contacting with the acid molecular sieve catalyst that contains clay molecular sieve with layer structure and/or contain the five-ring supersiliceous zeolite of rare earth, is that 680～780 ℃, reaction pressure are 1.5～4.0 * 10 in temperature of reaction
5Handkerchief, reaction times are that the weight ratio of 0.1～3 second, catalyzer and raw oil is that the weight ratio of 5～40:1, water vapor and raw oil is to carry out the catalytic pyrolysis reaction under the condition of 0.2～2.0:1.The ethene of this method and productivity of propylene are all above 18 heavy %.
CN1566272A discloses a kind of method of utilizing low-density oil cut catalyzed conversion to produce ethene and propylene.This method contacts the low-density oil cut that C4, C5 and gasoline fraction etc. are rich in alkene and reaction under catalyticing conversioning condition with the five-ring high silica zeolite catalyst of heat in main reaction region; Reaction product isolated and reclaimable catalyst; After being drawn by main reaction region, reaction product further is separated into following cut of the C4 that is rich in ethene, propylene and C4 and the above cut of C4; Reclaimable catalyst gets into revivifier behind stripping, coke burning regeneration in the presence of oxygen-containing gas; The regenerated catalyst of heat is introduced into pre-reaction zone above-mentioned C4 and the above cut of C4 interior and from main reaction region and contacts, reacts, and the finish mixture that is generated returns main reaction region and recycles.The reaction conditions of main reaction region is following: 500～700 ℃ of temperature of reaction, reaction pressure 5～4 * 10
5Pa, charging weight hourly space velocity 0.5～50h
-1, catalyzer and raw oil the weight ratio 0.05～0.5:1 of weight ratio 10～100:1, water vapor and raw oil; The reaction conditions of said pre-reaction zone is following: 650～800 ℃ of temperature of reaction, 0.1～2 second reaction times.When using steam cracking C4 as raw material, its ethylene yield is 16.6 heavy %, and productivity of propylene is 36.2 heavy %; When using the catalytically cracked gasoline cut as raw material, its ethylene yield is 10.4 heavy %, and productivity of propylene is 32.8 heavy %.
US6,106,697 disclose and a kind ofly are raw material, adopt two-stage reactor to carry out the method that the catalytic cracking reaction selectivity is produced C2～C4 alkene with wax oil or residual oil.Wax oil or residual oil raw material contact with macro-porous zeolite catalyst under conventional catalytic cracking condition and carry out catalytic cracking reaction and generate the different boiling ranges product that comprises gasoline fraction in first step reactor drum; The gasoline fraction that first step reactor drum generates gets in the reactor drum of the second stage, is that 4～10:1, hydrocarbon partial pressure are contact with central hole zeolite catalyst under 70～280 kPas of conditions further to react generation C2～C4 alkene at 500～650 ℃ of temperature of reaction, agent-oil ratio.
In sum; The means of increased low carbon olefine output are mainly the employing temperature of reaction higher than conventional catalytic cracking, agent-oil ratio and steam IR in the catalytic conversion technique of existing low-carbon olefines high-output, and employing contains the catalyzer of selecting shape zeolite of mean pore size less than 0.7 nanometer.Above-mentioned means all can be strengthened progressively cracking generation low-carbon alkene reaction of petroleum hydrocarbon, and promptly prior art all will be strengthened the reaction that generates low-carbon alkene reaches increasing output of ethylene, propylene as technological line purpose.Yet; The contriver finds through laboratory study: in the presence of the reaction conditions and acid zeolite of hydrocarbon ils preparing low carbon alkene by catalytic conversion; Propylene can transform into other hydro carbons, hydrogen and coke in a large number, apace after generating, and then causes propene yield obviously to descend.Therefore, in the formation reaction of reinforced low-carbon alkene, suppressing the again conversion reaction of low-carbon alkene after generating, will be a kind of novel method that prior art further improves ethene, productivity of propylene.
Summary of the invention
The object of the invention proposes a kind of catalysis conversion method that improves productivity of low carbon olefin hydrocarbon just on the basis that the contriver finds.
Method provided by the invention comprises: hydrocarbon oil crude material through raw material nozzles injecting lift pipe or/and in the fluidized-bed reactor; With contain the shape-selective zeolite catalysts of mean pore size and contact and react less than 0.7 nanometer; With the gas injecting reactor that is rich in hydrogen; With the catalyst separating of reaction oil gas with reaction back carbon deposit, wherein reaction oil gas obtains containing the purpose product of ethene, propylene through separation, and the catalyzer of carbon deposit Returning reactor after stripping, regeneration recycles.
Hydrocarbon oil crude material of the present invention is selected from one or more the mixture in oil hydrocarbon ils, MO and the synthetic oil, wherein one or more the mixture of petroleum hydrocarbon grease separation in C4～C6 cut, petroleum naphtha, atmospheric gas oil, vacuum gas oil, coker gas oil, deasphalted oil, hydrogenation tail oil, long residuum, vacuum residuum and crude oil; MO is selected from one or more the mixture in liquefied coal coil, tar sand oil and the shale oil; Synthetic oil is that coal, Sweet natural gas or pitch are through the synthetic distillate that obtains of F-T.
Mean pore size of the present invention is selected from ZSM series zeolite, ZRP zeolite, ferrierite, chabazite, dachiardite, erionite, A type zeolite, epistilbite, lomontite less than the shape zeolite of selecting of 0.7 nanometer, and one or more the mixture among the above-mentioned zeolite that after physics and/or chemical process are handled, obtains; The ZSM series zeolite is selected from one or more the mixture among the zeolite of ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures; The more detailed description of relevant ZSM-5 is referring to US3; 702,886; The more detailed description of relevant ZRP is referring to US5, and 232,675.
Method provided by the invention be applicable to riser reactor, fluidized-bed reactor, riser tube+fluidized-bed compound reactor and on their basis improved reactor drum pattern, wherein riser tube and fluidized-bed can be that isodiametric riser tube and fluidized-bed also can be the riser tube and the fluidized-bed of various change diameters.
The gas that is rich in hydrogen of the present invention is or comprises hydrogen, this device and separate one or more the mixture in the logistics that the dry gas that obtains, dry gas that other catalytic cracking is produced, coking dry gas and other contain hydrogen.
Hydrogen content in the gas that is rich in hydrogen of the present invention is preferably greater than 20 body % greater than 10 body %.
The downstream injecting reactor that is rich in the gas of hydrogen by raw material nozzles of the present invention.
When adopting riser reactor or fluidized-bed reactor; Raw material nozzles with reactor drum is a starting point; And the useful length of reactor drum is defined as 100% along the flow direction of raw material; The gas that preferably is rich in hydrogen injects at 20%～90% place of reactor drum, but because the different in kind of raw material and catalyzer, does not get rid of the gas that is rich in hydrogen other position injecting reactor from the raw material nozzles downstream.
When adopting riser tube+fluidized-bed compound reactor, the gas that preferably is rich in hydrogen injects from fluidized-bed reactor, but because the different in kind of raw material and catalyzer, does not get rid of the gas that is rich in hydrogen other position injecting reactor from the raw material nozzles downstream.
Two of at least one preferred employings of said riser reactor.When adopting two riser tubes or two riser tubes+fluidized-bed; Wherein advance in heavier raw material such as vacuum gas oil, coker gas oil, deasphalted oil, hydrogenation tail oil, long residuum, the vacuum residuum one or more in riser tube, advance in lighter raw material such as C4～C6 cut, petroleum naphtha, the atmospheric gas oil one or more in another root riser tube.
With the weight of hydrocarbon oil crude material serves as to calculate benchmark, and the described weight ratio that is rich in hydrogen and hydrocarbon oil crude material in the hydrogen gas is 0.05～3 heavy %, preferred 0.1～1 heavy %.
In the method for the invention, be rich in hydrogen gas and can one way use, also can from reaction product, separate, purification rear section or recycle fully.
Reaction product of the present invention is accomplished in the product separating device that this area is used always with the sepn process of being rich in hydrogen gas.
In the method for the invention, the temperature of reaction of hydrocarbon oil crude material, the temperature out of refering in particular to reactor drum is 500～700 ℃, preferred 550～650 ℃; Being used to make the pressure of reaction oil gas and the isolating settling vessel of carbon deposited catalyst is 1.5～4 * 10
5Handkerchief, preferred 1.5～3.5 * 10
5Handkerchief; Reaction times is 0.5～10 second, preferred 1～5 second; The weight ratio of catalyzer and hydrocarbon oil crude material is 6～40, preferred 10～30; The weight ratio of water vapor and hydrocarbon oil crude material is 0.1～1:1, preferred 0.2～0.6:1.
Compared with prior art, the present invention has the following advantages:
1, the present invention can significantly suppress the again conversion reaction of low-carbon alkene after generating through in reactor drum, injecting the means that are rich in hydrogen gas, thereby improves the particularly productive rate of propylene of low-carbon alkene; When be raw material with the vacuum gas oil, when adopting double lifting leg+fluidized-bed reactor, ethylene yield is up to 8.97 heavy %, productivity of propylene is up to 31.38 heavy %, improved 2.93 percentage points and 6.81 percentage points during respectively than injecting inhibitor not.
2, method raw material sources of the present invention are extensive, comprise C4～C6 cut, naphtha fraction and various heavy hydrocarbon, wider application range.
3, the gas that is rich in hydrogen of the present invention is the gas common in the common refinery, that added value is lower; And conventional device is done to change slightly can the described method of embodiment of the present invention, so the present invention can significantly improve the yield of high added value hydro carbons through the mode of cheapness.
Description of drawings
Fig. 1 is the catalysis conversion method schematic flow sheet of raising productivity of low carbon olefin hydrocarbon provided by the invention, and reactor drum is a riser tube in the figure, and the gas that is rich in hydrogen injects and the one way use from the riser tube middle part.
Fig. 2 is the catalysis conversion method schematic flow sheet of raising productivity of low carbon olefin hydrocarbon provided by the invention, and reactor drum is riser tube+fluidized-bed in the figure, and the gas that is rich in hydrogen injects from the fluidized-bed bottom and recycles.
Fig. 3 is the catalysis conversion method schematic flow sheet of raising productivity of low carbon olefin hydrocarbon provided by the invention, and reactor drum is double lifting leg+fluidized-bed in the figure, and the gas that is rich in hydrogen injects from the fluidized-bed bottom and recycles.
Embodiment
Because the gas that is rich in hydrogen of the present invention can be injected by different positions; Thereby the present invention can have multiple embodiment according to the different in kind of raw material and catalyzer; Specify method provided by the invention below in conjunction with Fig. 1 and Fig. 2, but therefore the present invention does not receive any restriction.
Fig. 1 is when adopting riser reactor, and the gas that is rich in hydrogen injects the schematic flow sheet when also one way is used from the riser tube middle part.In the method shown in this figure, the regenerated catalyst of heat gets into the bottom of riser tube 4 through regenerator line of pipes 11, and under the effect of the preparatory lifting medium that is injected by pipeline 1, quickens upwards to flow.Hydrocarbon oil crude material after the preheating through pipeline 2 with mix by the part by weight of 0.1～1:1 from the atomizing steam of pipeline 3 after, injecting lift pipe 4.The gas that is rich in hydrogen injects from the riser reactor middle part through pipeline 17, and the hydrogen and the weight ratio of hydrocarbon oil crude material that are rich in the hydrogen gas are 0.05～3%.The temperature out of riser tube 4 is 500～700 ℃, and the pressure of settling vessel 8 is 1.5～4 * 10
5Handkerchief, the reaction times is 0.5～10 second, the weight ratio of catalyzer and hydrocarbon oil crude material is 6～40.The reaction oil gas and the mixture of catalysts that contain hydrogen get into settling vessel 8 after riser tube goes upward to the riser tube exit, contain the catalyst separating of the reaction oil gas and the carbon deposit of hydrogen at settling vessel 8.The reaction oil gas that contains hydrogen is sent into subsequent separation system through pipeline 9 and is separated and obtain the purpose product.The catalyzer of reaction back carbon deposit gets into stripper 6, and stripped vapor injects through pipeline 5, and with the catalyzer counter current contact of carbon deposit, stripping is clean as much as possible for the reaction oil gas that the catalyzer of carbon deposit is entrained.Catalyzer behind the stripping is sent into revivifier 13 coke burning regenerations through spent agent line of pipes 10.Oxygen-containing gas such as air inject revivifier 13 through pipeline 12, and regenerated flue gas is drawn through pipeline 14.Catalyzer after the regeneration returns riser tube 4 through regenerator line of pipes 11 and recycles.
Fig. 2 is when adopting riser tube+fluidized-bed reactor, the schematic flow sheet of the gas that is rich in hydrogen when the fluidized-bed bottom is injected and recycle.In the method shown in this figure, the regenerated catalyst of heat gets into the bottom of riser tube 4 through regenerator line of pipes 11, and under the effect of the preparatory lifting medium that is injected by pipeline 1, quickens upwards to flow.Hydrocarbon oil crude material after the preheating through pipeline 2 with mix by the part by weight of 0.1～1:1 from the atomizing steam of pipeline 3 after, injecting lift pipe 4.Reaction oil gas and mixture of catalysts get into fluidized-beds 7 through riser tube 4 outlet, and the gas that is rich in hydrogen injects from the fluidized-bed bottom through pipeline 17, and the hydrogen and the weight ratio of hydrocarbon oil crude material that are rich in the hydrogen gas are 0.05～3%.The temperature out of fluidized-bed 7 is 500～700 ℃, and the pressure of settling vessel 8 is 1.5～4 * 10
5Handkerchief, total reaction time are 0.5～10 second, and the weight ratio of catalyzer and hydrocarbon oil crude material is 6～40.The reaction oil gas and the mixture of catalysts that contain hydrogen get into settling vessel 8 through fluidized-bed, contain the catalyst separating of the reaction oil gas and the carbon deposit of hydrogen at settling vessel 8.The reaction oil gas that contains hydrogen is sent into subsequent separation system 15 continuation separation through pipeline 9; Obtain products (not marking among the figure) such as hydrocarbon gas, gasoline, diesel oil, heavy oil after the separation and be rich in the gas of hydrogen; The gas that a part is rich in hydrogen is drawn through pipeline 16, and the gas that another part is rich in hydrogen then gets into the fluidized-bed bottom cycle through pipeline 17 and uses.The catalyzer of reaction back carbon deposit gets into stripper 6, and stripped vapor injects through pipeline 5, and with the catalyzer counter current contact of carbon deposit, stripping is clean as much as possible for the reaction oil gas that carbon deposited catalyst is entrained.Catalyzer behind the stripping is sent into revivifier 13 coke burning regenerations through spent agent line of pipes 10.Oxygen-containing gas such as air inject revivifier 13 through pipeline 12, and regenerated flue gas is drawn through pipeline 14.Catalyzer after the regeneration returns riser tube 4 through regenerator line of pipes 11 and recycles.
Fig. 3 is when adopting double lifting leg+fluidized-bed reactor, the schematic flow sheet of the gas that is rich in hydrogen when the fluidized-bed bottom is injected and recycle.In the method shown in this figure, the regenerated catalyst of heat gets into the bottom of riser tube 4 and 22 respectively through regenerator line of pipes 11 and 23, and under the effect of the preparatory lifting medium that is injected by pipeline 1 and 19, quickens upwards to flow respectively.Heavier hydrocarbon oil crude material after the preheating through pipeline 2 with after atomizing steam from pipeline 3 mixes by a certain percentage, injecting lift pipe 4.Reaction oil gas and mixture of catalysts get into fluidized-bed 7 through riser tube 4 outlets.Lighter hydrocarbon oil crude material after the preheating through pipeline 20 with after atomizing steam from pipeline 21 mixes by a certain percentage, injecting lift pipe 22.Reaction oil gas and mixture of catalysts get into fluidized-bed 7 through riser tube 22 outlets.The gas that is rich in hydrogen injects from the fluidized-bed bottom through pipeline 17, and the hydrogen and the weight ratio of hydrocarbon oil crude material that are rich in the hydrogen gas are 0.05～3%.The temperature out of fluidized-bed 7 is 500～700 ℃, and the pressure of settling vessel 8 is 1.5～4 * 10
5Handkerchief, total reaction time are 0.5～10 second, and the weight ratio of catalyzer and hydrocarbon oil crude material is 6～40.The reaction oil gas and the mixture of catalysts that contain hydrogen get into settling vessel 8 through fluidized-bed, contain the catalyst separating of the reaction oil gas and the carbon deposit of hydrogen at settling vessel 8.The reaction oil gas that contains hydrogen is sent into subsequent separation system 15 continuation separation through pipeline 9; Obtain products (not marking among the figure) such as hydrocarbon gas, gasoline, diesel oil, heavy oil after the separation and be rich in the gas of hydrogen; The gas that a part is rich in hydrogen is drawn through pipeline 16, and the gas that another part is rich in hydrogen then gets into the fluidized-bed bottom cycle through pipeline 17 and uses.The catalyzer of reaction back carbon deposit gets into stripper 6, and stripped vapor injects through pipeline 5, and with the catalyzer counter current contact of carbon deposit, stripping is clean as much as possible for the reaction oil gas that carbon deposited catalyst is entrained.Catalyzer behind the stripping is sent into revivifier 13 coke burning regenerations through spent agent line of pipes 10.Oxygen-containing gas such as air inject revivifier 13 through pipeline 12, and regenerated flue gas is drawn through pipeline 14.Catalyzer after the regeneration returns riser tube 4 through regenerator line of pipes 11 and recycles.
Further specify method provided by the invention through embodiment below, but therefore the present invention does not receive any restriction.
Employed catalyzer is by catalyzer Shandong branch office of Sinopec Group industrial production among the embodiment, and trade names are MMC-2.Used raw material A is the pure propylene gas of density of propylene greater than 99.9 body % among the embodiment, and raw material B is a kind of vacuum gas oil, and its main character is seen table 1.
Present embodiment explanation: adopt method provided by the invention, the catalytic reaction activity situation of low-carbon alkene on the small fixed flowing bed experimental installation when hydrogen (purity is 99.99 body %) injecting reactor.
Experiment is raw material with the raw material A, adopts andnon-continuous operation manner, and raw material, hydrogen and atomizing steam get into the fluidized-bed reactor bottom through feed nozzle after preheating oven is heated to about 350 ℃, contacts with the catalyzer of heat and carries out catalytic conversion reaction.Get into product separation system after reaction product and hydrogen and the catalyst separating, reaction product further separates into gaseous product and product liquid.Reaction finishes the back and gets into the stripping stage, is gone out the hydrocarbon product that adsorbs on the reclaimable catalyst by the water vapor stripping.In reactor drum, feed oxygen-containing gas behind the stripping and carry out the regeneration of reclaimable catalyst, can react behind the catalyst regeneration next time.The main operational condition and the result of experiment list in table 2.
Comparative Examples 1
This Comparative Examples explanation: in reactor drum, do not inject the catalytic reaction activity of low-carbon alkene under the situation that is rich in hydrogen gas in the reaction process, to further specify implementation result of the present invention.
Experiment is raw material with the raw material A, and used reactor drum and main experimental procedure, other operational condition are identical with embodiment 1, and main operational condition and result list in table 2.
Can find out that propylene has quite high reactive behavior under the reaction conditions of conventional catalytic cracking alkene after the experimental result of embodiment in the table 21 and Comparative Examples 1 compared, propylene conversion reaction transformation efficiency reaches 64.01 heavy %.And the method that the present invention proposes can significantly suppress the chemical conversion reaction of propylene, and propylene conversion has descended 29.97 percentage points among the embodiment 1.
The present embodiment explanation: adopt method provided by the invention, the heavy hydrocarbon catalyzed conversion is produced the situation of ethene and propylene when the catalytic cracked dry gas that is rich in hydrogen (hydrogen content is 30.58 body %) injecting reactor.
Experiment is a raw material with raw material B, on the medium-sized riser arrangement of successive reaction-regenerative operation, carries out the catalyzed conversion experiment.The internal diameter of this riser tube is 16 millimeters, highly is 6 meters.Raw material nozzles with riser tube is a starting point, and along the flow direction of raw material the useful length of riser tube is defined as 100%, and the injection phase of being rich in the gas of hydrogen is 40% place of riser tube.
The operating method that experiment adopts one way to pass through.Temperature is that the regenerated catalyst about 700 ℃ gets into the bottom of riser tube conversion zone through regenerator sloped tube, and under the effect that promotes steam in advance, upwards flows.Raw oil after preheating oven is heated to about 350 ℃ with the atomized water steam after, enter in the riser tube contact through feed nozzle and carry out catalytic conversion reaction with the catalyzer of heat, hydrogen is in the injection of 40% place of riser tube simultaneously.The reaction oil gas and the reclaimable catalyst that contain hydrogen enter into settling vessel from the riser tube outlet; Contain the reaction oil gas and the catalyzer sharp separation of hydrogen at settling vessel; The reaction oil gas that contains hydrogen further separates into gaseous product and product liquid; And reclaimable catalyst enters into stripper by action of gravity, and the water stripping steam stripped gets into the gas solid separation system after going out the hydrocarbon product that adsorbs on the reclaimable catalyst.Reclaimable catalyst behind the stripping enters into revivifier, contacts with the air that heated and regenerates.Catalyzer after the regeneration is the water steam stripped in line of pipes, with the non-hydrocarbon gas impurity of removing regenerated catalyst absorption and carrying.Regenerated catalyst behind the stripping turns back in the riser tube and recycles.
The main operational condition and the result of experiment list in table 3.Can find out that from table 3 ethene, productivity of propylene are respectively up to 4.61 heavy % and 18.25 heavy %.
The present embodiment explanation: adopt method provided by the invention, the heavy hydrocarbon catalyzed conversion is produced the situation of ethene and propylene when the catalytic cracked dry gas that is rich in hydrogen (hydrogen content is 30.58 body %) injecting reactor.
Experiment is a raw material with raw material B, and it is identical with embodiment 2 to test used reaction unit and main experimental procedure.The injection phase of being rich in the gas of hydrogen is 70% place of riser tube.
The main operational condition and the result of experiment list in table 3.Can find out that from table 3 ethene, productivity of propylene are respectively up to 4.62 heavy % and 18.86 heavy %.
Comparative Examples 2
The explanation of this Comparative Examples: in reactor drum, not injecting in the reaction process and be rich under the situation of hydrogen gas, is that catalytic material transforms the situation of producing ethene and propylene with the heavy hydrocarbon, to further specify implementation result of the present invention.
Experiment is a raw material with raw material B, and used reaction unit and main experimental procedure, other operational condition are identical with embodiment 2, and main operational condition and result list in table 3.Dividing potential drop equates raw material B in the riser tube ingress in embodiment 2, embodiment 3 and the Comparative Examples 2, does not receive dividing potential drop to change the influence that is brought with the conversion that guarantees raw material.
Can find out after the experimental result of embodiment in the table 32, embodiment 3 and Comparative Examples 2 compared; On the basis of existing hydrocarbon ils preparing low carbon alkene by catalytic conversion technology; Method provided by the invention can obtain higher ethene, productivity of propylene; Compare with the Comparative Examples of not injecting hydrogen-rich gas under the equivalent responses condition, productivity of low carbon olefin hydrocarbon, especially productivity of propylene significantly improves.
Present embodiment explanation: adopt method provided by the invention; The gas circulation that is the gas (content of hydrogen is 38.97 body %) that is rich in hydrogen to install self-produced catalytic cracked dry gas, is rich in hydrogen is used and when injecting in the fluidized-bed bottom, the heavy hydrocarbon catalyzed conversion is produced the situation of ethene and propylene.
Experiment is a raw material with raw material B, on the medium-sized riser tube+fluidizer of successive reaction-regenerative operation, carries out the catalyzed conversion experiment.Wherein the internal diameter of riser tube is 16 millimeters, highly is 6 meters, is fluidized-bed more than the riser tube outlet, and the internal diameter of this fluidized-bed is 64 millimeters, highly is 0.3 meter.
The operating method that experiment adopts one way to pass through.Temperature is that the regenerated catalyst about 700 ℃ gets into the bottom of riser tube conversion zone through regenerator sloped tube, and under the effect that promotes steam in advance, upwards flows.Raw oil enters in riser tube and the fluidized-bed through feed nozzle after preheating oven is heated to about 350 ℃ and after the atomized water steam successively, contacts with the catalyzer of heat and carries out catalytic conversion reaction.The reaction oil gas and the reclaimable catalyst that contain hydrogen enter into settling vessel from the fluidized-bed outlet; Contain the reaction oil gas and the catalyzer sharp separation of hydrogen at settling vessel; Contain the reaction oil gas of hydrogen and further separate into gaseous product and product liquid; The catalytic cracked dry gas that wherein is rich in hydrogen returns the fluidized-bed bottom, and reclaimable catalyst enters into stripper by action of gravity, and the water stripping steam stripped gets into the gas solid separation system through fluidized-bed after going out the hydrocarbon product that adsorbs on the reclaimable catalyst.Reclaimable catalyst behind the stripping enters into revivifier, contacts with the air that heated and regenerates.Catalyzer after the regeneration is the water steam stripped in line of pipes, with the non-hydrocarbon gas impurity of removing regenerated catalyst absorption and carrying.Regenerated catalyst behind the stripping turns back in the riser tube and recycles.
The main operational condition and the result of experiment list in table 3.Can find out that from table 3 ethene, productivity of propylene are respectively up to 8.85 heavy % and 29.31 heavy %.
Comparative Examples 3
The explanation of this Comparative Examples: in reactor drum, not injecting in the reaction process and be rich under the situation of hydrogen gas, is that catalytic material transforms the situation of producing ethene and propylene with the heavy hydrocarbon, to further specify implementation result of the present invention.
Experiment is a raw material with raw material B, and used reaction unit and main experimental procedure, other operational condition are identical with embodiment 4, and main operational condition and result list in table 3.Dividing potential drop equates raw material B in riser tube conversion zone ingress in embodiment 4 and the Comparative Examples 3, does not receive dividing potential drop to change the influence that is brought with the conversion that guarantees raw material.
Can find out after the experimental result of embodiment in the table 34 and Comparative Examples 3 compared; On the basis of existing hydrocarbon ils preparing low carbon alkene by catalytic conversion technology; Method provided by the invention can obtain higher ethene, productivity of propylene; Compare with the Comparative Examples of not injecting hydrogen-rich gas under the equivalent responses condition, productivity of low carbon olefin hydrocarbon, especially productivity of propylene significantly improves; Therein ethylene, productivity of propylene have improved 2.74 percentage points and 6.04 percentage points respectively.
Present embodiment explanation: adopt method provided by the invention; The gas circulation that is the gas (content of hydrogen is 50.19 body %) that is rich in hydrogen to install self-produced catalytic cracked dry gas, is rich in hydrogen is used and when injecting in the fluidized-bed bottom, the heavy hydrocarbon catalyzed conversion is produced the situation of ethene and propylene.
Experiment is raw material with the raw material A, on the medium-sized double lifting leg+fluidizer of successive reaction-regenerative operation, carries out the catalyzed conversion experiment.Wherein the internal diameter of two riser tubes is 16 millimeters, highly is 6 meters, is fluidized-bed more than the riser tube outlet, and the internal diameter of this fluidized-bed is 64 millimeters, highly is 0.3 meter.
The operating method that experiment adopts one way to pass through.Temperature is that the regenerated catalyst about 700 ℃ divides two portions to get into the bottom of two riser tube conversion zones through regenerator sloped tube, and under the effect that promotes steam in advance, upwards flows.Enter into successively after C4～C6 cut and the atomized water steam wherein in a riser tube and the fluidized-bed; After being preheated to the raw oil and atomized water steam about 350 ℃; Enter into successively in another root riser tube and the said fluidized-bed through feed nozzle, contact with the catalyzer of heat and carry out catalytic conversion reaction.The reaction oil gas and the reclaimable catalyst that contain hydrogen enter into settling vessel from the fluidized-bed outlet; Contain the reaction oil gas and the catalyzer sharp separation of hydrogen at settling vessel; Contain the reaction oil gas of hydrogen and further separate into gaseous product and product liquid; The catalytic cracked dry gas that wherein is rich in hydrogen returns the fluidized-bed bottom, and reclaimable catalyst enters into stripper by action of gravity, and the water stripping steam stripped gets into the gas solid separation system through fluidized-bed after going out the hydrocarbon product that adsorbs on the reclaimable catalyst.Reclaimable catalyst behind the stripping enters into revivifier, contacts with the air that heated and regenerates.Catalyzer after the regeneration is the water steam stripped in line of pipes, with the non-hydrocarbon gas impurity of removing regenerated catalyst absorption and carrying.Regenerated catalyst behind the stripping turns back in the riser tube and recycles.
The main operational condition and the result of experiment list in table 4.Can find out that from table 4 ethene, productivity of propylene are respectively up to 8.97 heavy % and 31.38 heavy %.
Comparative Examples 4
The explanation of this Comparative Examples: in reactor drum, not injecting in the reaction process and be rich under the situation of hydrogen gas, is that catalytic material transforms the situation of producing ethene and propylene with the heavy hydrocarbon, to further specify implementation result of the present invention.Compare with embodiment 5, be rich in the hydrogen gas except in reactor drum, not injecting, other is all identical.
Can find out after the experimental result of embodiment in the table 45 and Comparative Examples 4 compared; On the basis of existing hydrocarbon ils preparing low carbon alkene by catalytic conversion technology; Method provided by the invention can obtain higher ethene, productivity of propylene; Compare with the Comparative Examples of not injecting hydrogen-rich gas under the equivalent responses condition, productivity of low carbon olefin hydrocarbon, especially productivity of propylene significantly improves; Therein ethylene, productivity of propylene have improved 2.93 percentage points and 6.81 percentage points respectively.
Table 1
| The raw oil title | B |
| Density (20 ℃), gram per centimeter 3 | 0.8617 |
| Kinematic viscosity (80 ℃), millimeter 2/ second | 7.33 |
| Kinematic viscosity (100 ℃), millimeter 2/ second | 4.864 |
| Condensation point, ℃ | 42 |
| Aniline point, ℃ | 105.3 |
| Molecular weight (calculating) | 391 |
| Carbon residue, heavy % | 0.02 |
| The H/C mol ratio | 1.895 |
| Basic nitrogen, ppm | 206 |
| Elementary composition | |
| C, heavy % | 86.3 |
| H, heavy % | 13.63 |
| N，ppm | 560 |
| S，ppm | 810 |
| Group composition, heavy % | |
| Stable hydrocarbon | 85.0 |
| Aromatic hydrocarbons | 12.0 |
| Colloid | 3.0 |
| Bituminous matter | <0.1 |
| Metal content, ppm | |
| Ca | - |
| Cu | <0.1 |
| |
2 |
| Na | 1.8 |
| Ni | <0.1 |
| V | <0.1 |
| Boiling range, ℃ | |
| Over point | 286 |
| 5％ | 343 |
| 10％ | 368 |
| 30％ | 410 |
| 50％ | 437 |
| 70％ | 465 |
| 90％ | 498 |
| 95％ | 512 |
Table 2
| | Embodiment | 1 | Comparative Examples 1 |
| Operational condition | |||
| Temperature of reaction, ℃ | 580 | 580 | |
| The apparent reaction times, second | 0.74 | 0.75 | |
| Settling vessel pressure, 10 5Handkerchief | 1.8 | 1.8 | |
| Catalyzer and raw |
10 | 10 | |
| Hydrogen and raw material weight ratio, % | 0.45 | 0 | |
| Product distributes, heavy % | |||
| Dry gas | 6.65 | 6.31 | |
| C4+ propane | 17.61 | 24.73 | |
| Gasoline | 9.09 | 29.68 | |
| Diesel oil | 0.34 | 1.77 | |
| Heavy oil | - | 0.31 | |
| Coke | 0.35 | 1.46 | |
| Propylene conversion, heavy % | 34.04 | 64.01 |
The weight percent transformation efficiency of definition propylene is following:
Table 3
| | Embodiment | 2 | |
Comparative Examples 2 | |
Comparative Examples 3 |
| Operational condition | ||||||
| Temperature of reaction, ℃ | 560 | 560 | 560 | 610 | 610 | |
| Total apparent reaction times, second | 2.9 | 2.9 | 3.1 | 4.2 | 4.5 | |
| Settling vessel pressure, 10 5Handkerchief | 1.8 | 1.7 | 1.7 | 2.5 | 2.3 | |
| Catalyzer and raw |
15 | 15 | 15 | 22 | 22 | |
| Hydrogen and raw material weight ratio, % | 0.34 | 0.34 | 0 | 0.56 | 0 | |
| Product distributes, heavy % | ||||||
| Reacted gas | 56.77 | 58.02 | 52.36 | 64.21 | 61.73 | |
| Therein ethylene | 4.61 | 4.62 | 3.78 | 8.85 | 6.11 | |
| Propylene | 18.25 | 18.86 | 16.10 | 29.31 | 23.27 | |
| Gasoline | 23.38 | 22.56 | 27.29 | 21.27 | 23.52 | |
| Diesel oil | 6.72 | 6.31 | 6.83 | 3.96 | 3.49 | |
| Heavy oil | 6.55 | 6.34 | 6.39 | 2.14 | 2.29 | |
| Coke | 6.58 | 6.77 | 7.13 | 8.42 | 8.97 |
Table 4
| | Embodiment | 5 | Comparative Examples 4 |
| Operational condition | |||
| Temperature of reaction, ℃ | 620 | 620 | |
| The apparent reaction times, second | 4.1 | 4.1 | |
| Settling vessel pressure, 10 5Handkerchief | 2.2 | 2.2 | |
| Catalyzer and raw |
20 | 20 | |
| Hydrogen and raw material weight ratio, % | 0.87 | 0 | |
| Product distributes, heavy % | |||
| Reacted gas | 63.74 | 61.09 | |
| Therein ethylene | 8.97 | 6.04 | |
| Propylene | 31.38 | 24.57 | |
| Gasoline | 18.21 | 20.18 | |
| Diesel oil | 7.72 | 8.12 | |
| Heavy oil | 3.06 | 2.97 | |
| Coke | 7.27 | 7.64 |
Claims (17)
1. catalysis conversion method that improves productivity of low carbon olefin hydrocarbon; It is characterized in that this method comprise hydrocarbon oil crude material through raw material nozzles injecting lift pipe or/and in the fluidized-bed reactor; With contain the shape-selective zeolite catalysts of mean pore size and contact and react less than 0.7 nanometer; With the gas injecting reactor that is rich in hydrogen; With the catalyst separating of reaction oil gas with reaction back carbon deposit, wherein reaction oil gas obtains containing the purpose product of ethene, propylene through separation, and the catalyzer of carbon deposit Returning reactor after stripping, regeneration recycles.
2. according to the method for claim 1; It is characterized in that described hydrocarbon oil crude material is selected from one or more the mixture in oil hydrocarbon ils, MO and the synthetic oil, wherein one or more the mixture of petroleum hydrocarbon grease separation in C4～C6 cut, petroleum naphtha, atmospheric gas oil, vacuum gas oil, coker gas oil, deasphalted oil, hydrogenation tail oil, long residuum, vacuum residuum and crude oil; MO is selected from one or more the mixture in liquefied coal coil, tar sand oil and the shale oil; Synthetic oil is that coal, Sweet natural gas or pitch are through the synthetic distillate that obtains of F-T.
3. according to the method for claim 1; It is characterized in that described mean pore size is selected from ZSM series zeolite, ZRP zeolite, ferrierite, chabazite, dachiardite, erionite, A type zeolite, epistilbite, lomontite less than the shape zeolite of selecting of 0.7 nanometer, and one or more the mixture among the above-mentioned zeolite that after physics and/or chemical process are handled, obtains.
4. according to the method for claim 3, it is characterized in that described ZSM series zeolite is the ZSM-5 zeolite.
5. according to the method for claim 1, it is characterized in that the described gas that is rich in hydrogen is to comprise hydrogen, this device to separate one or more the mixture in the logistics that the dry gas that obtains, dry gas that other catalytic cracking is produced, coking dry gas and other contain hydrogen.
6. according to the method for claim 1, it is characterized in that hydrogen content in the described gas that is rich in hydrogen is greater than 10 body %.
7. according to the method for claim 1, it is characterized in that hydrogen content in the described gas that is rich in hydrogen is greater than 20 body %.
8. according to the method for claim 1, it is characterized in that the described downstream injecting reactor that is rich in the gas of hydrogen by raw material nozzles.
9. according to the method for claim 1; It is characterized in that when adopting riser reactor or fluidized-bed reactor; Raw material nozzles with reactor drum is a starting point, and along the flow direction of raw material the useful length of reactor drum is defined as 100%, and the gas that is rich in hydrogen injects at 20%～90% place of reactor drum.
10. according to the method for claim 1, it is characterized in that the gas that is rich in hydrogen injects from fluidized-bed reactor when adopting riser tube+fluidized-bed compound reactor.
11. according to the method for claim 1, it is characterized in that the weight with hydrocarbon oil crude material serves as to calculate benchmark, the described weight ratio that is rich in hydrogen and hydrocarbon oil crude material in the hydrogen gas is 0.05～3 weight %.
12. according to the method for claim 1, it is characterized in that the weight with hydrocarbon oil crude material serves as to calculate benchmark, the described weight ratio that is rich in hydrogen and hydrocarbon oil crude material in the hydrogen gas is 0.1～1 weight %.
13., it is characterized in that being rich in the hydrogen gas one way and use, perhaps from reaction product, separate, purification rear section or recycle fully according to the method for claim 1.
14. according to the method for claim 1, the temperature of reaction that it is characterized in that hydrocarbon oil crude material is 500～700 ℃, the pressure of settling vessel is 1.5～4.0 * 10
5Handkerchief, the reaction times is 0.5～10 second, and the weight ratio of catalyzer and hydrocarbon oil crude material is 6～40, and the weight ratio of water vapor and hydrocarbon oil crude material is 0.1～1: 1.
15. according to the method for claim 1, the temperature of reaction that it is characterized in that hydrocarbon oil crude material is 550～650 ℃, the pressure of settling vessel is 1.5～3.5 * 10
5Handkerchief, the reaction times is 1～5 second, and the weight ratio of catalyzer and hydrocarbon oil crude material is 10～30, and the weight ratio of water vapor and hydrocarbon oil crude material is 0.2～0.6: 1.
16. according to claim 1,9 or 10 method, it is characterized in that said riser reactor at least one.
17., it is characterized in that said riser reactor is two according to the method for claim 16.
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| CN109722287B (en) * | 2017-10-30 | 2021-08-06 | 中国石油化工股份有限公司 | Catalytic conversion method for increasing propylene yield and improving light oil quality and system for method |
| CN112745903B (en) * | 2019-10-31 | 2022-06-28 | 中国石油化工股份有限公司 | Process and apparatus for catalytic conversion of heavy petroleum hydrocarbon feedstocks |
| CN114195612A (en) * | 2020-09-02 | 2022-03-18 | 青岛京润石化设计研究院有限公司 | Method and device for preparing propylene and ethylene by catalytic conversion of petroleum hydrocarbon |
| CN115725330B (en) * | 2021-08-30 | 2024-04-02 | 中国石油化工股份有限公司 | Catalytic conversion method for producing low-carbon olefin |
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