CN109705894A - The hydrocarbon oil processing method and system of processing of high output of ethylene and propylene - Google Patents
The hydrocarbon oil processing method and system of processing of high output of ethylene and propylene Download PDFInfo
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- CN109705894A CN109705894A CN201711013839.9A CN201711013839A CN109705894A CN 109705894 A CN109705894 A CN 109705894A CN 201711013839 A CN201711013839 A CN 201711013839A CN 109705894 A CN109705894 A CN 109705894A
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Abstract
The invention discloses the hydrocarbon oil processing methods and system of processing of a kind of high output of ethylene and propylene.This method includes catalytic pyrolysis step and Oil-gas Separation post-processing step, catalytic pyrolysis step include: by feedstock oil, the light diesel fuel of freshening and catalytic cracking catalyst in the first reaction zone haptoreaction, generate the first gas mixture；Then by the first gas mixture and C4 alkene, haptoreaction generates the second gas mixture in second reaction zone；By the haptoreaction in third reaction zone of raffinating oil with catalytic cracking catalyst after the light naphthar of freshening, heavy naphtha Aromatics Extractive Project, third gas mixture is generated；Second gas mixture and the third gas mixture are sent into settler progress reclaimable catalyst and Oil-gas Separation obtains product oil gas.Using the present invention by practice with specific route low value-added product produced during Oil-gas Separation, ethylene, propylene and aromatics yield can be effectively improved, and then improve the economic benefit and crude oil utilization rate of original catalytic pyrolysis.
Description
Technical field
The present invention relates to the fields of hydrocarbon ils processing ethylene and propylene, and more particularly to a kind of high output of ethylene and propylene
Hydrocarbon oil processing method and system of processing.
Background technique
Ethylene is important organic chemical industry's base stock, mainly for the production of polyethylene, EP rubbers, polyvinyl chloride
Deng.Ethylene is also one of maximum chemical products in the world simultaneously, accounts for 75% or more of global entire petroleum chemicals yield；Propylene
Also it is important Organic Chemicals, is mainly used for acrylonitrile production, propylene oxide, acetone etc..Ethylene and propylene are to produce
A variety of important Organic Chemicals, generation synthetic resin, synthetic rubber and a variety of fine chemicals etc., as in important chemical industry
Between object demand it is growing.
It is larger to the chemical industry lighter hydrocarbons demand such as lighter hydrocarbons, naphtha using traditional preparing ethylene by steam cracking, propylene route,
It is expected that the year two thousand twenty needs 700,000 tons/year of chemical industry light oil, and domestic crude oil is generally laid particular stress on, and chemical industry light oil is difficult to meet ethylene, propylene original
The demand of material, in the insufficient situation of petroleum resources, the diversification of steam crack material has become ethylene, propylene industrial development becomes
Gesture.Steam crack material mainly has lighter hydrocarbons (such as ethane, propane and butane), naphtha, diesel oil, condensate and hydrogenation tail oil,
In, the mass fraction of naphtha accounts for about 50% or more, the yield of ethene of typical naphtha steam cracking about 29%-34%, propylene
Yield is 13%-16%, and than about 0.5, lower propylene/ethylene output ratio is difficult to meet current propylene demand propylene/ethylene
Status.
It can effectively improve low using petroleum hydrocarbon catalytic pyrolysis technology by the optimization of technological parameter and catalyst property
Carbene hydrocarbon-selective, while voluminous light aromatic hydrocarbons, which is the research of current or even following low-carbon alkene and Aromatics Production Technology
Hot spot.In order to improve the yield of low-carbon alkene especially ethylene, the yield of propylene and light aromatic hydrocarbons, prior art master has:
CN1234426A is by heavy petroleum hydrocarbon and vapor in the compound reactor of riser and dense-phase fluidized bed composition
Lower part is contacted with catalyst；The i.e. dense-phase fluidized bed bottom in top that light petroleum hydrocarbon enters compound reactor is contacted with catalyst.
Feedstock oil or partial hydrogenation recycle oil are being catalyzed by CN1667089A with regenerated catalytic cracking catalyst, vapor
Haptoreaction in cracking reactor.
CN101362669A is to contact in the hydro carbons of different cracking performances with raw material with catalytic cracking catalyst, in fluidized bed
Cracking reaction is carried out in reactor obtains the raw material of purpose product low-carbon alkene, aromatic hydrocarbons and recracking, then light aromatic hydrocarbons are hydrogenated,
After extracting, can cracked stock return riser, wherein C2-C4 alkane enters steam cracking and further reacts, ethylene and propylene
Yield is more than 20 weight %, while the aromatic hydrocarbons such as coproduction toluene and dimethylbenzene.
CN101362961A proposes that the raw material for being 160-260 DEG C by boiling range is contacted with catalytic cracking catalyst, in fluidized bed
Cracking reaction is carried out in reactor and obtains purpose product low-carbon alkene and aromatic hydrocarbons, so that ethylene and productivity of propylene and selectivity increase
Add.
CN101469275B discloses a kind of method of producing light olefin from inferior crude, it is characterised in that after pretreatment
Total acid number be greater than 0.5mgKOH/g, characterization factor K value greater than 12.1 crude oil it is preheated after be introduced directly into catalytic cracking reaction
It contacts in device with catalyst, and is reacted under the conditions of catalytic cracking reaction, the oil gas and reclaimable catalyst after separation reaction,
Reaction oil pneumatic transmission obtains the product of different boiling ranges to subsequent separation system, reclaimable catalyst stripped, regenerate after be recycled,
The technology, which overcomes to process this quasi-oil in the prior art and generate the more lower gasoline of octane number, causes economic benefit is lower to lack
It falls into, is conducive to low-carbon olefines high-output, improve octane number, improve the economic benefit of such crude oil with poor quality processing.
CN102337154A is proposed under catalytic cracking condition, by hydrocarbon raw material and catalytic cracking catalyst in recombination reaction
It is contacted in device, obtains low-carbon alkene, rich in the products such as light aromatic hydrocarbons gasoline, further isolated light aromatic hydrocarbons.
CN102344832A discloses a kind of petroleum hydrocarbon catalytic conversion method, it is characterised in that feedstock oil in reactor with
Catalyst contact rich in mesopore zeolite is reacted, and separates reclaimable catalyst and reaction oil gas, reclaimable catalyst is after regeneration
Returning reactor, separation reaction oil gas obtain include ethylene, propylene, propane, butane and the catalytic gasoline rich in aromatic hydrocarbons product,
After wherein the chosen property of catalytic gasoline adds hydrogen, into the isolated purpose product light aromatic hydrocarbons of aromatic extraction unit, and raffinate oil with
Propane, butane further produce ethylene, propylene through steam cracking.
From the point of view of the above prior art, the exploitation of the technology of hydrocarbons catalytic conversion production low-carbon alkene focuses primarily upon heavy
In terms of oily deep catalytic cracking technology, due to boiling range wider range of heavy oil, hydrocarbon molecules are larger, product structure numerous and complicated, non-mesh
It is higher to mark products collection efficiency, in order to improve yield of light olefins, generallys use higher reaction temperature, causes increasing low-carbon alkene
In the case of yield, dry gas yied especially methane production is increased considerably.
And it is in development phase using lightweight material oil such as naphtha as the deep catalytic cracking technology of raw material, with regard to world wide
Speech, ethylene production is always with lighter hydrocarbons and naphtha for main cracking stock, and paraffinic base, intermediate based raw material institute in cracking stock
Accounting example is very few, but China's light hydrocarbon feedstocks oil resource is limited, and most of crude oil category mink cell focus, and straight-run naphtha yield is seldom,
Force wax oil raw material proportion in ethylene production higher.
In order to meet the growing low-carbon alkene especially demand of propylene demand and light aromatic hydrocarbons, and improve heavy original
Expect such as normal pressure wax oil resource utilization, it is necessary to a kind of reduction catalytic cracking reaction temperature is developed, meanwhile, most by wax oil fraction
It is converted into limits the catalysis conversion method of ethylene and propylene, and then realizes the efficient utilization of petroleum resources.
Summary of the invention
It is one of of the existing technology the purpose of the invention is to overcome the problems, such as, a kind of high output of ethylene and propylene are provided
Hydrocarbon oil processing method and system of processing, with increasing output of ethylene propylene and aromatic hydrocarbons (BTX) simultaneously.
To achieve the goals above, the first aspect of the present invention provides the hydrocarbon ils processing side of a kind of high output of ethylene and propylene
Method, this method include catalytic pyrolysis step and Oil-gas Separation post-processing step, which includes: by feedstock oil, returns
The light diesel fuel and catalytic cracking catalyst of refining haptoreaction in the first reaction zone generate the first gas mixture；Then by
One gas mixture and C4 the alkene haptoreaction in second reaction zone generate the second gas mixture；By the pumice brain of freshening
Oil, the haptoreaction in third reaction zone of raffinating oil with catalytic cracking catalyst after heavy naphtha Aromatics Extractive Project, generate third
Gas mixture；By second gas mixture and the third gas mixture be sent into settler carry out reclaimable catalyst and
Oil-gas Separation obtains product oil gas；The product oil gas is further divided into hydrogen, first in the Oil-gas Separation post-processing step
Alkane, product ethylene and propylene, ethane, propane, C4 alkane, C4 alkene, light naphthar, heavy naphtha, light diesel fuel, heavy diesel fuel and with
Upper component, and the heavy naphtha is subjected to Aromatics Extractive Project to form raffinating oil after light aromatic hydrocarbons and heavy naphtha Aromatics Extractive Project；
Wherein the C4 alkene is back to together to raffinating oil after light naphthar, light diesel fuel and heavy naphtha Aromatics Extractive Project corresponding anti-
Answer area.
Meanwhile in the second aspect of the present invention, the hydrocarbon ils system of processing of a kind of high output of ethylene and propylene is additionally provided, it is described
System includes catalyst cracking unit, and the catalyst cracking unit includes: the first riser reactor, and described first promotes tube reaction
Device is equipped with raw material oil-in, light diesel fuel freshening mouth and the outlet of the first reaction mixture；Second riser reactor, described second
Riser reactor be equipped with first reaction mixture outlet be connected reaction mixture entrance, C4 alkene freshening mouth,
And second reaction mixture outlet；Third riser reactor, the third riser reactor are equipped with heavy naphtha virtue
Freshening mouth of raffinating oil, light naphthar freshening mouth and third mixture outlet after hydrocarbon extracting；Sedimentation device, on the sedimentation device
Equipped with respectively with second reaction mixture outlet and the reaction mixture entrance that is connected of third reaction mixture outlet,
And spent agent exports and product oil gas vent；Regenerating unit, the regenerating unit is equipped with to be connected with spent agent outlet
Spent agent entrance and regenerative agent outlet, regenerative agent outlet respectively with the first riser reactor and the second riser
The catalyst inlet of reactor is connected.
Using the hydrocarbon oil processing method and system of processing of high output of ethylene provided by the present invention and propylene, by the way that oil gas is divided
Practice with specific route from low value-added product produced in the process, ethylene, propylene and aromatic hydrocarbons can be effectively improved
Yield, and then improve the economic benefit and crude oil utilization rate of original catalytic pyrolysis.
Detailed description of the invention
Fig. 1 shows the structural schematic diagram of riser reaction unit in embodiment according to the present invention；
Fig. 2 shows the structural schematic diagrams of catalyst cracking unit in embodiment according to the present invention；
Fig. 3 shows the structural schematic diagram of hydrocarbon ils system of processing in embodiment according to the present invention.
Description of symbols
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The hydrocarbon oil processing method of a kind of high output of ethylene and propylene is provided in the present invention, and this method includes catalytic pyrolysis step
Rapid and Oil-gas Separation post-processing step, the catalytic pyrolysis step include: to urge feedstock oil, the light diesel fuel of freshening and catalytic pyrolysis
Agent haptoreaction in the first reaction zone generates the first gas mixture；Then the first gas mixture and C4 alkene are existed
Haptoreaction generates the second gas mixture in second reaction zone；After the light naphthar of freshening, heavy naphtha Aromatics Extractive Project
It raffinates oil with catalytic cracking catalyst the haptoreaction in third reaction zone, generates third gas mixture；By second oil
Gas mixture and the third gas mixture are sent into settler progress reclaimable catalyst and Oil-gas Separation obtains product oil gas；Institute
State in Oil-gas Separation post-processing step by the product oil gas be further divided into hydrogen, methane, product ethylene and propylene, ethane,
Propane, C4 alkane, C4 alkene, light naphthar, heavy naphtha, light diesel fuel, heavy diesel fuel and the above component, and by the heavy naphtha
Aromatics Extractive Project is carried out to form raffinating oil after light aromatic hydrocarbons and heavy naphtha Aromatics Extractive Project；Wherein by the C4 alkene and pumice brain
Raffinating oil after oil, light diesel fuel and heavy naphtha Aromatics Extractive Project is back to respective reaction zones together.
Method according to the invention it is possible to can be according to product needs by aforementioned mentioned freshening raw material, part or complete
Portion's freshening.
It according to the method for the present invention, include top nozzle and lower nozzle inside first reaction zone, in order to increase freshening
The conversion ratio of light diesel fuel, under preferable case, the feedstock oil is fed from top nozzle, and freshening light diesel fuel is from lower nozzle material-feeding；
Preferably, in the section in first reaction zone between upper and lower nozzle, the residence time of hydrocarbon ils is 0.2-5
Second, preferably 0.5-2 seconds, such as can be any two institute structure in 0.5,0.8,1,1.2,1.5,1.8,2 and these ratios
At range in any time value (second).Oil ratio is 10-100, preferably 30-75, for example, can for 30,32,35,38,
42,45,48,50,52,58,62,68,70,75 and these ratios in the range that is constituted of any two in any ratio
Value；In top nozzle into the section between outlet, residence time of hydrocarbon ils is 0.8-9.8 seconds, preferably 2-6 seconds, such as can be
2,2.5,2.8,3.2,3.5,4.2,4.8,5.2,5.8,6 and these ratios in the range that is constituted of any two in appoint
It anticipates time value (second)；Oil ratio is 4-50, preferably 5-12, such as can be 5,6,7,8,9,10,11,12 and these ratios
In the range that is constituted of any two in any ratio.
According to the method for the present invention, in the second reaction zone, the residence time of hydrocarbon ils is 2-30 seconds, preferably 6-15
Second.It is not individually added into catalyst in second reaction zone, wherein catalyst is carried along by hydrocarbon ils in the first reaction zone
Second reaction zone.Wherein C4 alkene is to return to practice with the 10-100wt% of C4 olefin product total amount, and hydrocarbon ils ratio therein is in 4-50 model
In enclosing, preferably 5-12, such as can be made of any two in 5,6,7,8,9,10,11,12 and these ratios
Any ratio in range.
According to the method for the present invention, internal in the third reaction zone includes top nozzle and lower nozzle, in order to increase weight
The conversion ratio raffinated oil after naphtha Aromatics Extractive Project, under preferable case, the light naphthar is fed from top nozzle, the scheelite
Raffinating oil from lower nozzle material-feeding after cerebrol Aromatics Extractive Project；
Preferably, in the section in the third reaction zone between upper and lower nozzle, the residence time of hydrocarbon ils is 0.2-5
Second, preferably 0.5-3 seconds, such as can be any two in 0.5,0.8,1.2,1.5,2.2,2.5,2.8,3 and these ratios
Any time value (second) in a constituted range；Oil ratio is 10-100, preferably 25-42, for example, can for 25,28,
32,35,38,42 and these ratios in the range that is constituted of any two in any ratio；In top nozzle to exporting it
Between section in, residence time of hydrocarbon ils is 0.8-9.8 second, preferably 1-8 seconds, such as can be 0.8,1.5,2.0,2.6,3.2,
4.2,5.6,6.2,7.3,8 and these ratios in the range that is constituted of any two in any time value (second), agent oil
It than for 5-60, preferably 10-20, such as can be any two institute structure in 10,12,14,16,18,20 and these ratios
At range in any ratio.
According to the method for the present invention, hydrocarbon ils is entered from the lower part of reaction zone, is flowed up, wherein being fed by " lower nozzle "
Material be introduced into reaction zone, and reaction zone is entered by the rear of " top nozzle " charging, and with the material hybrid reaction that first feeds.
According to the method for the present invention, aforementioned " oil ratio " referred to refers to the weight ratio of catalyst and hydrocarbon ils, wherein hydrocarbon ils
Refer to the summation of the raw material hydrocarbon ils into corresponding " section ", such as in hydrocarbon in " section between upper and lower nozzle " in the first reaction zone
Oil is the amount of freshening light diesel fuel, and hydrocarbon ils is the total amount of feedstock oil and freshening light diesel fuel in " top nozzle to the section between outlet ".
According to the method for the present invention, wherein haptoreaction for the first reaction zone, second reaction zone and third reaction zone
Condition can be selected in more wide in range range；Under preferable case, the haptoreaction condition of first reaction zone includes: reaction
Temperature is 500-700 DEG C, preferably 520-590 DEG C, such as can be 520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 560 DEG C, 570
DEG C, 580 DEG C, the arbitrary temp value (DEG C) in the range that is constituted of any two in 590 DEG C and these point values；Pressure is
0.1-1.0MPa, preferably 0.2-0.4MPa.
Under preferable case, the catalytic operating condition of the second reaction zone includes: that reaction temperature is 490-680
DEG C, preferably 510-580 DEG C, such as can be 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 560 DEG C, 570 DEG C, 580 DEG C
And the arbitrary temp value (DEG C) in the range that is constituted of any two in these point values；Pressure is 0.1-1.0MPa, preferably
For 0.2-0.4MPa.
Under preferable case, the haptoreaction condition of the third reaction zone includes: that reaction temperature is 510-750 DEG C, preferably
Be 620-690 DEG C, for example, can for 620 DEG C, 630 DEG C, 640 DEG C, 650 DEG C, 660 DEG C, 670 DEG C, 680 DEG C, 690 DEG C and these
Arbitrary temp value (DEG C) in the range that any two in point value are constituted；Pressure is 0.1-1.0MPa, preferably 0.2-
0.4MPa。
According to the method for the present invention, it is passed through pre-lift medium, in the first reaction zone and second reaction zone to drive catalysis
Catalyst for cracking rises, and then forms the catalytic cracking catalyst piston flow of even density in reactor bottom.Wherein pre-lift
Medium can be one of vapor, refinery dry gas, light paraffins, light olefin or a variety of.
According to the method for the present invention, wherein haptoreaction can carry out in arbitrary catalytic cracking reaction device three times, example
It such as can not only carry out, but also can be carried out in riser reactor in a fluidized bed reactor；It both can be in upstriker reactor
Middle progress, and can be carried out in down-flow reactor；Under preferable case, above-mentioned haptoreaction three times is in riser reactor
Middle progress, and when being carried out in riser reactor, itself dry gas of preferred catalytic cracker replaces pre-lift steam, portion
Point/all atomizing steam is replaced to introduce reactor later, by raising dry gas hydrogen partial pressure, dry gas yied is reduced, it is possible thereby into
The selectivity of one step raising propylene.
According to the method for the present invention, with emphasis on the improvement for process flow, wherein for being adopted in catalytic pyrolysis process
Catalytic cracking catalyst can not have particular/special requirement, as long as being suitable as catalytic cracking catalyst use, preferably
In the case of, the catalytic cracking catalyst is the catalytic cracking catalyst containing mesopore zeolite；The more preferable catalytic pyrolysis is urged
Agent is on the basis of its total weight, the zeolite containing 2-60 weight %, the inorganic oxide of 10-99 weight %, 0-70 weight %
Clay；It include wherein mesopore zeolite and optional large pore zeolite in the zeolite, preferably using the total weight of the zeolite as base
Standard, the large pore zeolite of the mesopore zeolite containing 50-95 weight % and 5-50 weight % in the zeolite, in the more preferable zeolite
The large pore zeolite of mesopore zeolite containing 70-95 weight % and 5-30 weight %.
In catalytic cracking catalyst used in the present invention, the mesopore zeolite and large pore zeolite continue to use this field routine
Definition, the i.e. average pore size of mesopore zeolite are 0.5-0.6nm, and the average pore size of large pore zeolite is 0.7-1.0nm.In the present invention
The mesopore zeolite that can be selected is preferably the zeolite with MFI structure, such as ZSM series zeolite and/or ZRP zeolite；It is preferred that feelings
Under condition, selected mesopore zeolite be can be through the transition gold such as the nonmetalloids such as phosphorus and/or iron, cobalt, nickel in the present invention
Belong to the mesopore zeolite that element is modified；Wherein it may refer to the note in US5,232,675 about the detailed description of ZRP zeolite
It carries, such as ZRP-1；Wherein about ZSM series zeolite be selected from ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38,
The zeolite of ZSM-48 and other similar structures one or more of mixture, wherein the detailed description about ZSM-5 can
Referring to US3,702,886.Large pore zeolite can be selected from super steady Y, the high silicon Y structure obtained by Rare Earth Y, rare earth hydrogen Y, distinct methods
At one of this group of zeolite or more mixture.
In catalytic cracking catalyst used in the present invention, the inorganic oxide primarily serves the effect of bonding agent, excellent
Choosing is selected from silica and/or aluminum oxide.Wherein silica precursor is that can be changed into two under conditions of roasting
The substance of silica preferably can be silica solution；Wherein alumina precursor is that can be changed into three oxygen under conditions of roasting
Change the substance of two aluminium, preferably hydrated alumina and/or Aluminum sol；The hydrated alumina is selected from boehmite, intends thin water
One or more of aluminium stone, hibbsite and amorphous hydroted alumina.
In catalytic cracking catalyst used in the present invention, the clay primarily serves the effect of matrix, preferably described viscous
Soil is selected from diatomite, expanded perlite, kaolin, halloysite, silicalite, hydrolysis oxidation silicon, macropore silicon oxide and silicon
It is one or more of in glue, it is preferably selected from kaolin and/or halloysite.
According to the method for the present invention, catalytic cracking catalyst forms reclaimable catalyst after undergoing catalytic cracking reaction, should
Reclaimable catalyst forms regenerative agent by regeneration, is formed by regenerative agent and is transported to the first reaction zone and second reaction zone again
Using wherein the process conditions of regeneration treatment are used with the conventional regeneration conditions of corresponding catalyst.
According to the method for the present invention, for further increasing output of ethylene and propylene product, under preferable case, the Oil-gas Separation
Post-processing step further includes by the ethane, propane and C4 alkane and vapor haptoreaction to generate product ethylene and propylene,
And by-product ethane, propane, C4 alkane, C4 alkene and steam cracking light naphthar, the preferably described Contact Temperature are 700-1000 DEG C；
It is preferred that the ethane of by-product, propane, C4 alkane backflow are continued and vapor haptoreaction；It is preferred that the C4 alkene of by-product is returned
It is back to third reaction zone.
According to the method for the present invention, the heavy naphtha is being subjected to Aromatics Extractive Project to form light aromatic hydrocarbons and heavy naphtha virtue
Hydrocarbon extracting after the step of raffinating oil in, extraction solvent can not limited, for example, the extraction solvent be selected from sulfolane,
In N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, tetraethylene glycol, dimethyl sulfoxide and N- formyl-morpholine ether
It is one or more of；Can there is no particular/special requirement, such as the operating condition packet of the Aromatics Extractive Project for the operating condition of Aromatics Extractive Project
Include: temperature is 40-120 DEG C, and the volume ratio of extraction solvent and heavy naphtha is 0.5-5:1.
In the case of with the method for the invention it is preferred to, the feedstock oil is mink cell focus；More preferable feedstock oil is hydrotreating
Heavy wax oil, preferably process are greater than 350 DEG C of hydrotreating heavy wax oil.
In the case of with the method for the invention it is preferred to, as raw material the mink cell focus be selected from or include petroleum hydrocarbon with/
Or other mineral oil.Wherein petroleum hydrocarbon is selected from vacuum gas oil (VGO), AGO (atmospheric gas oil), coker gas oil, deasphalted oil, normal pressure slag
Oil, hydrotreating residual oil, hydrotreating gas oil, catalytic diesel oil, one or more of light cycle oil, other mineral oil
Selected from liquefied coal coil, tar sand oil, one or more of shale oil.It is preferred that the mink cell focus is paraffinic base or intermediate based raw material,
It is preferred that the density of the mink cell focus is 0.87-0.93g/cm3.Preferably 0.88-0.91g/cm3.Carbon residue is 0-6wt%, preferably
For 0-2wt%.
In the case of with the method for the invention it is preferred to, the prevailing operating conditions of the hydrotreating include: that reaction temperature is
350-400 DEG C, preferably 360-390 DEG C, such as can be appointing in 360 DEG C, 370 DEG C, 380 DEG C, 390 DEG C and these point values
Any number in two ranges constituted of anticipating；Reaction pressure is 7-15MPa, preferably 9-13MPa, volume space velocity 0.5-
1.5h-1, preferably 0.6-1.2h-1, hydrogen-oil ratio 400-1500, preferably 600-1200.
In the case of with the method for the invention it is preferred to, hydrogenation catalyst employed in the hydrotreating includes: carrier
With load group VIB metal on the carrier and/or the VIIIth race's non-noble metal oxide and with the hydrogenation catalyst
On the basis of total weight, content of the group VIB metal in terms of oxidation state be 3-35 weight %, the VIIIth race's base metal with
The content of oxidation state meter is 0.3-8 weight %；It is preferred that the carrier is aluminium oxide and/or silica-alumina supports；It is preferred that group VIB metal
For Mo and/or W；It is preferred that group VIII metal is Co and/or Ni.Wherein silica-alumina supports refer to compound containing aluminium oxide and silica
Carrier.
According to the method for the present invention, in order to further decrease low value-added product, and on the basis of not increasing energy consumption, increase
Ethylene, propylene and aromatic hydrocarbon are produced, under preferable case, the step of by the heavy diesel fuel and the above component backflow to the hydrotreating
In, preferably in actual operation, lower slurry in heavy diesel fuel and the above component is discharged, and upper layer oil plant is back to described plus hydrogen
The step of processing.
Meanwhile the hydrocarbon oil processing method corresponding to above-mentioned high output of ethylene and propylene provided herein, in the present invention
Additionally provide the hydrocarbon ils system of processing of a kind of high output of ethylene and propylene, the system comprises catalyst cracking unit 30, the catalysis
Cracking unit 30 includes: that the first riser reactor A, the first riser reactor A is equipped with raw material oil-in, light diesel fuel
Freshening mouth and the outlet of the first reaction mixture；Second riser reactor B, the second riser reactor B are equipped with and institute
State the connected reaction mixture entrance in the first reaction mixture outlet, C4 alkene freshening mouth and the outlet of the second reaction mixture；
Third riser reactor C, the third riser reactor C are equipped with the freshening of raffinating oil after heavy naphtha Aromatics Extractive Project
Mouth, light naphthar freshening mouth and third mixture outlet；Sedimentation device 32, the sedimentation device 32 are equipped with respectively with described the
The two reaction mixtures outlet and third reaction mixture reaction mixture entrance that is connected of outlet and spent agent export with
Product oil gas vent；Regenerating unit 33, the regenerating unit 33, which is equipped with, exports the spent agent entrance being connected with the spent agent,
And regenerative agent outlet, the regenerative agent export the catalysis with the first riser reactor A and the second riser reactor B respectively
Agent entrance is connected.
Above system according to the present invention, wherein sedimentation device 32 and regenerating unit 33 are all made of conventional equipment, sink
It include cyclone separator 321 and stripper 322 in falling unit 32；It include cyclone separator 331 and main wind point in regenerating unit 33
Fabric swatch 332；Spent agent circulation slide valve 323 is formed on spent agent conveyance conduit between sedimentation device 32 and regenerating unit 33；
It is set respectively on regenerative agent conveyance conduit between regenerating unit 33 and the first riser reactor A and the second riser reactor B
It is equipped with regenerant recycle slide valve 333.
The system according to the present invention, under preferable case, the first riser reactor A be internally provided with top nozzle and under
Nozzle, the top nozzle and raw material oil-in, the lower nozzle are connected with light diesel fuel freshening mouth.
The system according to the present invention, under preferable case, the third riser reactor C be internally provided with top nozzle and under
Nozzle, the top nozzle are connected with light naphthar freshening mouth, raffinating oil back after the lower nozzle and heavy naphtha Aromatics Extractive Project
Mouth is refined to be connected.
The system according to the present invention, under preferable case, the system also includes feedstock oil supply unit, the feedstock oil is supplied
Raw material oil-in on unit and the first riser reactor A is answered to be cooperatively connected, for supplying into the first riser reactor A
Answer feedstock oil；
The system according to the present invention, as shown in figure 3, the system also includes catalytic pyrolysis fractionation units under preferable case
40, gas separation unit, weight gasoline separative unit 50 and weight diesel oil separative unit 60；The catalytic pyrolysis fractionation is single
Member 40 is cooperatively connected with the sedimentation device 32, for being fractionated the isolated product oil gas of sedimentation device for dry gas 42a, liquid
Change gas 42b, naphtha 41b, 42c, diesel oil and the above component 41c；The gas separation unit 50 is fractionated with the catalytic pyrolysis
Unit 40 is cooperatively connected, for by the dry gas 42a and the isolated hydrogen of liquefied gas 42b, methane, product ethylene and propylene,
Ethane, propane, C4 alkane and C4 alkene, wherein C4 alkene is back to the second riser reactor B as C4 alkene；It is described
Weight naphtha separative unit 50 and the catalytic pyrolysis fractionation unit 40 are cooperatively connected, for being by naphtha 41b and 42c points
Light naphthar 51a and heavy naphtha 51b, wherein the light naphthar 51a is back to the third riser reactor C；It is described
Weight diesel oil separative unit 60 and the catalytic pyrolysis fractionation unit 40 are cooperatively connected, and are used for the diesel oil and the above component
41c points are light diesel fuel 61a and heavy diesel fuel and the above component 61b, wherein the light diesel fuel 61a is back to first riser
Reactor A.
The system according to the present invention, wherein catalytic pyrolysis fractionation unit 40 is mainly used for carrying out catalytic pyrolysis product oil gas
Fractionation, including catalytic pyrolysis main fractionating tower 41 and light component knockout drum 42；Wherein passing through catalytic pyrolysis main fractionating tower 41 will
The isolated product oil gas fractionation of sedimentation device is tower top oil gas 41a, naphtha 41b and diesel oil and the above component 41c.
Light component knockout drum 42 includes absorption tower, Analytic Tower, reabsorber, stabilizer etc., can will be by catalytic pyrolysis main fractionating tower
The tower top oil gas 41a of 41 discharges is separated into dry gas 42a, liquefied gas 42b and naphtha 42c, wherein dry gas 42a, liquefied gas 42b quilt
It is delivered to subsequent gases separative unit, and naphtha 42c is transported to weight gasoline separative unit.
The system according to the present invention, wherein gas separation unit is mainly used for being fractionated catalytic pyrolysis fractionation unit 40 and obtain
Dry gas 42a and liquefied gas 42b in low-carbon alkene carry out separating treatment.It include rich gas compression in the gas separation unit
Machine, depropanizing tower, debutanizing tower, domethanizing column, dethanizer, ethylene rectifying column, propylene rectification tower and the dilute rectifying column of fourth etc..?
In practical operation, the dry gas and liquefied gas that the fractionation of catalytic pyrolysis fractionation unit 40 obtains are sent into after rich gas compressor improves pressure
Depropanizing tower.By separating, C4 and C 5 fraction at the row of depropanizing tower bottom enter debutanizing tower, debutanization overhead materials after cooling
Stream enters butylene rectifying column, and C 5 fraction is discharged in debutanizing tower bottoms stream, which can be used as gently with after light naphthar cocurrent
Naphtha is back to third riser reactor C；The C4 alkene of butylene rectifying tower top discharge returns the in catalyst cracking unit 30
Two riser reactor B, butylene rectifying column bottom C4 alkane, which optionally returns to catalyst cracking unit 30 or is delivered to subsequent distillation, to be split
Solve unit.Depropanizing tower top row goes out C3—Fraction, is sent into domethanizing column after cooling, domethanizing column top row go out mainly containing methane and
The fuel gas of hydrogen, domethanizing column bottoms stream are sent into dethanizer；Deethanization overhead stream is sent into ethylene rectifying column, dethanizer
Bottoms stream is sent into propylene rectification tower, and ethylene rectifying column top row goes out polymer grade ethylene, and the ethane of ethylene distillation tower bottom discharge is subsequent to be sent
Steam cracking unit.Propylene rectification tower top row goes out polymerization-grade propylene, and the propane of propylene rectification tower bottom discharge send cracking unit.
The system according to the present invention, for further increasing output of ethylene and propylene, under preferable case, the system also includes steamings
Cracking unit is evaporated, the distillation cracking unit and the gas separation unit are cooperatively connected, are used for ethane, propane and C4 alkane
With vapor haptoreaction with generate product ethylene and propylene and by-product ethane, propane, C4 alkene and C4 alkane, C5 component and
Steam cracking light naphthar, wherein the ethane of by-product, propane and C4 alkane backflow to the distillation crack unit；The C4 alkene of by-product
Hydrocarbon is back to the second riser reactor B, and the steam cracking light naphthar reproduced is back to the third riser reactor C.
The distillation cracks description of the reaction condition referring to preceding method part of unit.
The system according to the present invention, under preferable case, the system also includes Aromatics Extractive Project unit, the Aromatics Extractive Project list
It is first to be cooperatively connected with the weight naphtha separative unit 50, for carrying out aromatic hydrocarbons extraction to heavy naphtha and obtaining heavy naphtha
Raffinating oil after Aromatics Extractive Project, raffinating oil after the heavy naphtha Aromatics Extractive Project can be back to the third and promote tube reaction
Device C can also be delivered to steam cracking unit and be cracked.Wherein aromatic hydrocarbons extraction unit can be using conventional Aromatics Extractive Project list
Member, such as may include extraction distillation tower, extractive distillation solvent recovery tower, liquid liquid extraction tower, stripping in Aromatics Extractive Project unit
Tower and liquid liquid extracting and reclaiming tower etc..The reaction condition of the Aromatics Extractive Project unit and used extraction solvent are referring to preceding method portion
The description divided.
The system according to the present invention, under preferable case, the system also includes hydrofinishing units 10 and hydrogenation fractionating list
Member 20, the hydrofinishing unit 10 are cooperatively connected with the feedstock oil supply unit, obtain for feedstock oil described in hydrogenation treatment
To hydrogenated products；The hydrogenation fractionating unit 20 is cooperatively connected with the hydrofinishing unit 10, is used for the hydrogenated products
Fractionation obtains hydrotreating heavy wax oil；The hydrogenation fractionating unit 20 and the first riser in the catalyst cracking unit 30 are anti-
The raw material oil-in of device A is answered to be cooperatively connected, for supplying hydrotreating heavy wax oil into the first riser reactor A.
The system according to the present invention, wherein hydrotreating unit 10 can use conventional hydrotreating unit, such as its
In mainly include make-up hydrogen compressor 11, raw material preheating furnace 12, hydrofining reactor 13, heat exchanger 14, water cooler 15, high pressure
Separator 16 and low pressure separator 17.Wherein make-up hydrogen compressor 11 passes through raw material preheating furnace 12 and 13 phase of hydrofining reactor
Even, the outlet end of hydrofining reactor 13 passes through the high-pressure separator 16 being successively arranged and low pressure separator 17 and adds with subsequent
Hydrogen fractionation unit is connected, the Hydrogen Separation that high-pressure separator 16 will mix in hydrotreated product, this part circulating hydrogen
It is back in raw material preheating furnace 12, wherein low pressure separator 17 removes the tower overhead gas in hydrotreated product.In addition, for shape
At the thermal balance of whole system, and it is suitable for the temperature of high-pressure separator 16, under preferable case, in 13 He of hydrofining reactor
Heat exchanger 14 and water cooler 15 are also formed between high-pressure separator 16.The reaction condition of the hydrofining reactor 13 is referring to before
State the description of method part.
The system according to the present invention, wherein hydrogenation fractionating unit 20 is mainly used for being fractionated hydrotreated product,
In include hydrogenation refining fractionation tower 21, and hydrotreated product be fractionated do not coagulated for tower top by the hydrogenation refining fractionation tower 21
Gas 21a, naphtha cut 21b, boat coal fraction 21c, high-quality derv fuel fraction 21d and tower bottom heavy wax oil 21e (add at hydrogen
Heavy wax oil is managed, preferably boiling range is greater than 350 DEG C of heavy component), wherein tower bottom heavy wax oil is fed through subsequent catalysis
Cracking Unit.
The system according to the present invention reduces low value-added production to further increase the utilization rate of catalytic pyrolysis byproduct
Product, under preferable case, heavy diesel fuel that the separation of weight diesel oil separative unit 70 obtains and the above component backflow to described plus hydrogen
Refined unit.
Hydrocarbon oil processing method and processing below in conjunction with specific embodiment and comparative example to invention high output of ethylene and propylene
System is further described.
The heavy raw oil 1 used in following examples and comparative examples is from Sinopec Group
Zhenghai branch company adds hydrogen wax oil, and heavy raw oil 2 is the decompression from China National Petroleum company Daqing Petrochemical Company
Wax oil, main character are as shown in table 1.
Table 1.
| Project | Heavy raw oil 1 | Heavy raw oil 2 |
| Density (20 DEG C, g/cm3 | 0.903 | 0.8582 |
| Kinematic viscosity (100 DEG C), mm2/s | 8.325 | 4.174 |
| Condensation point, DEG C | -15 | -20 |
| Kinematic viscosity (80 DEG C), mm2/s | 12.582 | 6.143 |
| Aniline point, DEG C | - | 103.4 |
| Refraction index, (nD70) | - | 1.4585 |
| Carbon residue, wt% | 0.52 | 0.21 |
| Basic nitrogen, ppm | 236 | 155 |
| C, | 84.53 | 85.98 |
| N, ppm | 582 | 417 |
| H, | 12.56 | 13.66 |
| S, ppm | 1352 | 885 |
| Initial boiling point | 268 | 262 |
| 5% | 321 | 310 |
| 10% | 345 | 333 |
| 30% | 395 | 382 |
| 50% | 523 | 414 |
| 70% | 451 | 444 |
| 90% | 502 | 490 |
| 95% | 526 | 513 |
| Paraffinicity, wt% | 28 | 14 |
The catalytic cracking catalyst preparation method used in following examples and comparative examples is summarized as follows:
1) by 20gNH4Cl is dissolved in 1000g water, and 100g crystallization product ZRP-1 zeolite is added into this solution, and rare earth contains
Measure RE2O3=2.0 weight %), after 90 DEG C of exchange 0.5h, filter to obtain filter cake；4.0gH is added3PO4With 4.5gFe (NO3)3It is dissolved in
In 90g water, it is mixed with dipping and dries with filter cake；Then it is handled in 550 DEG C of roasting temperatures and obtains within 2 hours the phosphorous MFI knot with iron
Structure mesopore zeolite, through elementary analytical chemistry, which includes: the Na of 0.1wt%2O, the Al of 5.1wt%2O3, 2.4wt%
P2O5, 1.5wt% Fe2O3, 3.8wt% RE2O3And the SiO of 88.1wt%2。
2) 75.4kg halloysite is beaten with 250kg decationized Y sieve water, adds 54.8kg boehmite, uses salt
Its PH is adjusted to 2-4 by acid, is stirred evenly, and stands aging 1 hour at 60-70 DEG C, and holding PH is 2-4, cools the temperature to 60 DEG C
Hereinafter, 41.5kg Aluminum sol is added, stirs 40 minutes, obtain mixed serum.
3) the MFI structure mesopore zeolite of the phosphorous and iron of step 1) preparation and DASY zeolite are added to step 2) and obtained
Mixed serum in, stir evenly, spray drying forming is washed with ammonium dihydrogen phosphate, washes away free Na+, it is drying to obtain
Catalytic cracking catalyst sample, the group of the catalyst become phosphorous MFI structure mesopore zeolite, the 2 weight % with iron of 18 weight %
The kaolin of DASY zeolite, the aluminium oxide of 36 weight % and 44 weight %.
The main character of the catalytic cracking catalyst of above-mentioned preparation is as shown in table 2.
Table 2.
The hydrotreating catalyst preparation method used in following examples and comparative examples is summarized as follows:
Ammonium metatungstate and nickel nitrate are weighed, is made into 200mL solution with water.Solution is added in alumina support 50g,
It impregnates 3 hours, is used ultrasonication maceration extract 30 minutes in dipping process at room temperature, cooling, filtering is put into micro-wave oven
It is about 15 minutes dry.The composition of the catalyst are as follows: 30.0 weight %WO3, 3.1 weight %NiO and 66.9 weight % aluminium oxide.
The extraction solvent used in following examples and comparative examples is sulfolane, and chemistry is pure.
Embodiment 1
Used hydrocarbon ils system of processing: as shown in Figure 3；
Used hydrocarbon oil processing method:
Heavy oil feed 1 (property such as table 1) is delivered to raw material preheating furnace 12, it is mixed with the hydrogen from make-up hydrogen compressor 11
It closes, after heating, into hydrofining reactor 13, (reaction condition includes: that temperature is 370 DEG C, hydrogen partial pressure 10MPa, hydrogen oil (body
Product) than being 800, volume space velocity 1.0h-1, wherein hydrogenation catalyst is the aforementioned hydrogenation catalyst provided).The hydrofinishing is anti-
Device 13 is answered to divide three reaction zones, middle area is passed through cold hydrogen to adjust reaction temperature.Oil gas after reaction enters heat exchanger 14, heat exchange
After material enters the further cooling of water cooler 15 afterwards, isolating recycle hydrogen into high-pressure separator 16, (recycle hydrogen passes through recycle hydrogen
Enter raw material preheating furnace 12 after compressor compresses), the heavy constituent after high-pressure separator 16 separates enters low pressure separator 17, laggard
Enter hydro-refining unit fractionating column 21；Tower top isolates tower top fixed gas 21a and enters gas in hydro-refining unit fractionating column 21
Official website, fractionation midsection extract naphtha cut 21b, and the tune 21d and tower bottom stream of boat coal fraction 21c and high-quality derv fuel out
Journey is greater than 350 DEG C of heavy component (hydrotreating heavy wax oil).
Hydrotreating heavy wax oil is preheated to 260 DEG C as feedstock oil, catalyst cracking unit is entered by riser pipeline
In the first riser reactor A (the first reaction zone) in, with light diesel fuel (LCO) 31a of freshening (hydrotreating heavy wax oil into
Enter top nozzle, LCO enters lower nozzle), atomizing steam and catalytic cracking catalyst be (for the aforementioned catalytic cracking catalysis provided
Agent) carry out the first reaction mixture of haptoreaction (reaction condition is referring to table 3) production；Then the first reaction mixture is delivered to
In second riser reactor B (second reaction zone), carrying out haptoreaction with the C4 alkene 31d of freshening, (reaction condition is referring to table
3) the second reaction mixture, is generated；At the same time, by after the heavy naphtha Aromatics Extractive Project of freshening (RAA) 31b that raffinates oil, with
And light naphthar (LCN) 31c (LCN enters top nozzle, and RAA enters lower nozzle) of freshening enters catalysis by reflux pipeline respectively
It cracks in the third riser reactor C (third reaction zone) in unit, (is aforementioned with atomizing steam and catalytic cracking catalyst
The catalytic cracking catalyst of offer) haptoreaction (reaction condition is referring to table 3) is carried out, generate third reaction mixture；So that the
One reaction mixture and third reaction mixture enter the cyclone separator 321 of sedimentation device 32 (pressure 0.13MPa) together
In isolate spent agent and product oil gas, spent agent enters stripper 322 and is stripped, and the spent agent after stripping passes through spent agent
Circulation slide valve 323 enters the air entered in regenerator 33 with regenerator bottoms main air distributing plate 332 and contacts that (pressure is
0.15MPa, temperature be 700 DEG C, bed density 3kg/m3) burn；Flue gas and regenerative agent produced pass through cyclone separator
331 are separated, and flue gas enters regenerator bottoms by entering flue, regenerative agent, are entered by regenerant recycle slide valve 333 and are urged
Change in cracking unit in the first riser reactor A and the second riser reactor B.
Catalytic pyrolysis main fractionating tower 41 is entered by oil gas pipeline by the product oil gas that the separation of sedimentation device 32 generates,
It is divided into tower top oil gas 41a, naphtha 41b and diesel oil and the above 41c.Wherein tower top oil gas 41a enters light by oil transfer line
Tower top oil gas 41a is separated into dry gas (mainly by absorption tower, Analytic Tower, reabsorber, stabilizer etc. by component knockout drum 42
For H2、CH4、C2Component) 42a, liquefied gas (C3, C4) 42b and naphtha 42c；
Dry gas 42a and liquefied gas 42b that the separation of light component knockout drum 42 generates are entered into gas by oil gas pipeline
Separative unit (including rich gas compressor, depropanizing tower, debutanizing tower, domethanizing column, dethanizer, ethylene rectifying column, propylene essence
Evaporate tower and the dilute rectifying column of fourth etc.), it is separated into hydrogen, methane, product ethylene and propylene, ethane, propane, C4 alkane, C4 alkene
And C 5 fraction；Wherein C4 alkene is back in the second riser reactor B and carries out freshening；
Ethane, propane and butane that gas separation unit generates are delivered to steam cracking unit and vapor at 830 DEG C
Lower haptoreaction, to generate product ethylene and propylene, ethane, propane, C4 alkene and C4 alkane, C5 component and steam cracking pumice
Cerebrol, wherein ethane, propane and C4 alkane backflow to steam cracking cellular manufacture ethylene and propylene, C4 alkene are back to second and mention
Freshening is carried out in riser reactors B, steam cracking light naphthar is back in third riser reactor C and carries out freshening；
The isolated naphtha 42c of naphtha 41b and light component knockout drum 42 that catalytic pyrolysis main fractionating tower 41 generates is led to
It crosses oil-gas pipeline and is delivered to weight naphtha separative unit 50, be separated into light naphthar 51a and heavy naphtha 51b；Wherein pumice
Cerebrol 51a is back in third riser reactor C and carries out freshening；
The heavy naphtha 51b separated in weight naphtha separative unit 50 is delivered to Aromatics Extractive Project unit, through sulfolane
Extracting, extraction temperature are 100 DEG C, and the volume ratio of sulfolane solvent and gasoline is that 3.0:1 separates light aromatic hydrocarbons (BTX) and catalysis scheelite
Raffinating oil after cerebrol Aromatics Extractive Project, wherein raffinating oil after catalysis heavy naphtha Aromatics Extractive Project, which is back to third, promotes tube reaction
Freshening is carried out in device C；
The diesel oil that catalytic pyrolysis main fractionating tower 41 is generated and the above component 41C are delivered to weight bavin by oil-gas pipeline
Oil separation unit 60 is separated into light diesel fuel 61a and heavy diesel fuel and the above 61b, and wherein it is anti-to be back to the first riser by light diesel fuel 61a
It answers and carries out freshening in device A；Heavy diesel fuel and the above component 61b are back to hydrofining reactor 13 and carry out freshening.
Product distribution after the device stable operation is as shown in table 4.
Embodiment 2-3
Used hydrocarbon ils system of processing: the hydrocarbon ils system of processing referring to shown in Fig. 3, it does not include hydrofinishing that difference, which is,
Reactor 13, hydro-refining unit fractionating column 21 and device relevant to the two；
Used hydrocarbon oil processing method: referring to embodiment 1, difference is, using heavy oil feed 2 (property such as table 1)
Instead of heavy oil feed 1；And heavy oil feed 2 is not preheated to 260 DEG C directly as feedstock oil through hydrogenated processing and passes through riser
Pipeline enters in catalyst cracking unit.In the hydrocarbon oil processing method first, second and third riser reaction condition such as table 3
Shown, the product distribution after the device stable operation is as shown in table 4.
Comparative example 1
Used hydrocarbon ils system of processing: referring to system in Fig. 3, it does not include three riser reactors, only that difference, which is,
Including a riser reactor；
Used hydrocarbon oil processing method: using the process in embodiment 1, difference is in catalytic cracking unit
In, it only includes a riser that hydrotreating heavy wax oil, which is preheated to 260 DEG C to enter as feedstock oil by riser pipeline,
In the catalyst cracking unit of reactor, and the mixture of LCO and LCN is back in the riser reactor (hydrotreating weight
Matter wax oil enters top nozzle, and the mixture of LCO and LCN enter lower nozzle).The reaction condition of riser reactor is such as in the system
Shown in table 3；Product distribution after the device stable operation is as shown in table 4.
Comparative example 2-3
Used hydrocarbon ils system of processing: referring to system in Fig. 3, difference is, 1) do not include hydrofining reactor 13,
Hydro-refining unit fractionating column 21 and device relevant to the two；2) do not include three riser reactors, only include one
Riser reactor；
Used hydrocarbon oil processing method: using the process in embodiment 2-3, difference is in catalytic cracking unit
In, it only includes a riser reactor that heavy oil feed 2, which is preheated to 260 DEG C to enter as feedstock oil by riser pipeline,
Catalyst cracking unit in, and the mixture of LCO and LCN is back in the riser reactor (hydrotreating heavy wax oil
Into top nozzle, the mixture of LCO and LCN enter lower nozzle).The reaction condition of riser reactor such as 3 institute of table in the system
Show；Product distribution after the device stable operation is as shown in table 4.
Table 3.
Table 4.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (20)
1. the hydrocarbon oil processing method of a kind of high output of ethylene and propylene, the method includes after catalytic pyrolysis step and Oil-gas Separation
Manage step, which is characterized in that the catalytic pyrolysis step includes:
By feedstock oil, the light diesel fuel of freshening and catalytic cracking catalyst in the first reaction zone haptoreaction, generate the first oil gas
Mixture；Then by the first gas mixture and C4 alkene, haptoreaction generates the second gas mixture in second reaction zone；
By raffinating oil with catalytic cracking catalyst in third reaction zone after the light naphthar of freshening, heavy naphtha Aromatics Extractive Project
Haptoreaction generates third gas mixture；
Second gas mixture and the third gas mixture are sent into settler and carry out reclaimable catalyst and oil gas point
From obtaining product oil gas；
In the Oil-gas Separation post-processing step by the product oil gas be further divided into hydrogen, methane, product ethylene and propylene,
Ethane, propane, C4 alkane, C4 alkene, light naphthar, heavy naphtha, light diesel fuel, heavy diesel fuel and the above component, and will be described heavy
Naphtha carries out Aromatics Extractive Project to form raffinating oil after light aromatic hydrocarbons and heavy naphtha Aromatics Extractive Project；Wherein by the C4 alkene with
Raffinating oil after light naphthar, light diesel fuel and heavy naphtha Aromatics Extractive Project is back to respective reaction zones together.
2. according to the method described in claim 1, including top nozzle and lower nozzle, institute inside first reaction zone wherein
It states feedstock oil to feed from top nozzle, freshening light diesel fuel is from lower nozzle material-feeding；
Preferably, in the section in first reaction zone between upper and lower nozzle, the residence time of hydrocarbon ils is 0.2-5 seconds,
It is preferred that 0.5-2 seconds, oil ratio 10-100, preferably 30-75；In top nozzle into the section between outlet, the stop of hydrocarbon ils
Time is 0.8-9.8 seconds, preferably 2-6 seconds；Oil ratio is 4-50, preferably 5-12.
3. in the second reaction zone, the residence time of hydrocarbon ils is 2-30 seconds according to the method described in claim 1, wherein,
It is preferred that 6-15 seconds.
4. according to the method described in claim 1, wherein, internal in the third reaction zone includes top nozzle and lower nozzle,
The light naphthar is fed from top nozzle, raffinating oil from lower nozzle material-feeding after the heavy naphtha Aromatics Extractive Project；
Preferably, in the section in the third reaction zone between upper and lower nozzle, the residence time of hydrocarbon ils is 0.2-5 seconds,
It is preferred that 0.5-3 seconds；Oil ratio is 10-100, preferably 25-42；In top nozzle into the section between outlet, the stop of hydrocarbon ils
Time be 0.8-9.8 seconds, preferably 1-8 seconds, oil ratio 5-60, preferably 10-20.
5. method as claimed in any of claims 1 to 4, wherein
The haptoreaction condition of first reaction zone includes: that reaction temperature is 500-700 DEG C, preferably 520-590 DEG C, is reacted
Pressure is 0.1-1.0MPa, preferably 0.2-0.4MPa；
The haptoreaction condition of the second reaction zone includes: that reaction temperature is 490-680 DEG C, preferably 510-580 DEG C, is reacted
Pressure is 0.1-1.0MPa, preferably 0.2-0.4MPa；
The haptoreaction condition of the third reaction zone includes: that reaction temperature is 510-750 DEG C, preferably 620-690 DEG C reaction
Pressure is 0.1-1.0MPa, preferably 0.2-0.4MPa.
6. method as claimed in any of claims 1 to 4, wherein the catalytic cracking catalyst is to contain mesoporous
The catalyst of zeolite；It is preferred that the catalytic cracking catalyst is on the basis of its total weight, zeolite, 10- containing 2-60 weight %
The clay of the inorganic oxide of 99 weight %, 0-70 weight %；It wherein include mesopore zeolite and optional macropore in the zeolite
Zeolite；
It is preferred that mesopore zeolite and 5-50 weight on the basis of the total weight of the zeolite, containing 50-95 weight % in the zeolite
The large pore zeolite of % is measured, the macropore of the mesopore zeolite containing 70-95 weight % and 5-30 weight % boiling in the more preferable zeolite
Stone.
7. method as claimed in any of claims 1 to 4, wherein the Oil-gas Separation post-processing step further includes
By the ethane, propane and C4 alkane and vapor haptoreaction to generate product ethylene and propylene, and by-product ethane, propane,
C4 alkane, C4 alkene and steam cracking light naphthar；It is preferred that the Contact Temperature is 700-1000 DEG C；It is preferred that by the second of by-product
Alkane, propane, C4 alkane backflow continue and vapor haptoreaction；It is preferred that the steam cracking light naphthar of by-product is back to second
Reaction zone, and the C4 alkene of by-product is back to third reaction zone.
8. method as claimed in any of claims 1 to 4, wherein the heavy naphtha is being carried out Aromatics Extractive Project
With formed after light aromatic hydrocarbons and heavy naphtha Aromatics Extractive Project the step of raffinating oil in, used extraction solvent be selected from sulfolane,
In N-Methyl pyrrolidone, diethylene glycol ether, triethylene glycol ether, tetraethylene glycol, dimethyl sulfoxide and N- formyl-morpholine ether
It is one or more of；It is preferred that it is 40-120 DEG C that the operating condition of the Aromatics Extractive Project, which includes: temperature, extraction solvent and heavy naphtha
Volume ratio is 0.5-5:1.
9. method as claimed in any of claims 1 to 4, wherein the feedstock oil is mink cell focus, preferably plus hydrogen
Heavy wax oil is handled, more preferably process is greater than 350 DEG C of hydrotreating heavy wax oil.
10. according to the method described in claim 9, wherein, the prevailing operating conditions of the hydrotreating include: that reaction temperature is
350-400 DEG C, preferably 360-390 DEG C, reaction pressure 7-15MPa, preferably 9-13MPa, volume space velocity 0.5-1.5h-1, preferably 0.6-1.2h-1, hydrogen-oil ratio 400-1500, preferably 600-1200.
11. according to the method described in claim 9, wherein, hydrogenation catalyst employed in the hydrotreating includes: carrier
With the load non-noble metal oxide of group VIB metal and/or the VIIIth race on the carrier and with the hydrogenation catalyst
Total weight on the basis of, content of the group VIB metal in terms of oxidation state be 3-35 weight %, the VIIIth race's base metal
Content in terms of oxidation state is 0.3-8 weight %；It is preferred that the carrier is aluminium oxide and/or silica-alumina supports；It is preferred that group VIB is golden
Belonging to is W；It is preferred that group VIII metal is Ni.
12. according to the method described in claim 9, wherein, the heavy diesel fuel and the above component backflow to the hydrotreating
In step.
13. the hydrocarbon ils system of processing of a kind of high output of ethylene and propylene, the system comprises catalyst cracking unit (30), and feature exists
In the catalyst cracking unit (30) includes:
First riser reactor (A), first riser reactor (A) are equipped with raw material oil-in, light diesel fuel freshening mouth
It is exported with the first reaction mixture；
Second riser reactor (B), second riser reactor (B) is equipped with to be exported with first reaction mixture
Connected reaction mixture entrance, C4 alkene freshening mouth and the outlet of the second reaction mixture；
Third riser reactor (C), the third riser reactor (C) are equipped with the raffinate after heavy naphtha Aromatics Extractive Project
Oily freshening mouth, light naphthar freshening mouth and third mixture outlet；
Sedimentation device (32), the sedimentation device (32) be equipped with respectively with second reaction mixture outlet and the third
The connected reaction mixture entrance in reaction mixture outlet and spent agent outlet and product oil gas vent；
Regenerating unit (33), the regenerating unit (33), which is equipped with, exports the spent agent entrance being connected with the spent agent, and
Regenerative agent outlet, the regenerative agent export the catalysis with the first riser reactor (A) and the second riser reactor (B) respectively
Agent entrance is connected.
14. system according to claim 13, wherein first riser reactor (A) is internally provided with top nozzle
With lower nozzle, the top nozzle is connected with raw material oil-in, and the lower nozzle is connected with light diesel fuel freshening mouth.
15. system according to claim 13, wherein the third riser reactor (C) is internally provided with top nozzle
With lower nozzle, the top nozzle is connected with light naphthar freshening mouth, the raffinate after the lower nozzle and heavy naphtha Aromatics Extractive Project
Oily freshening mouth is connected.
16. system described in any one of 3 to 15 according to claim 1, wherein
It is former on the feedstock oil supply unit and the first riser reactor (A) the system also includes feedstock oil supply unit
Expect that oil-in is cooperatively connected, for the oil that supplies raw material into first riser reactor (A)；
The system also includes catalytic pyrolysis fractionation unit (40), gas separation unit, weight gasoline separative unit (50) and
Weight diesel oil separative unit (60)；
The catalytic pyrolysis fractionation unit (40) and the sedimentation device (32) are cooperatively connected, for sedimentation device is isolated
The fractionation of product oil gas be dry gas (42a), liquefied gas (42b), naphtha (41b, 42c), diesel oil and the above component (41c)；
The gas separation unit (50) and the catalytic pyrolysis fractionation unit (40) are cooperatively connected, and are used for the dry gas
(42a) and the isolated hydrogen of liquefied gas (42b), methane, product ethylene and propylene, ethane, propane, C4 alkane and C4 alkene,
Wherein C4 alkene is back to second riser reactor (B) as C4 alkene；
The weight naphtha separative unit (50) and the catalytic pyrolysis fractionation unit (40) are cooperatively connected, and are used for naphtha
(41b) is divided into light naphthar (51a) and heavy naphtha (51b), is promoted wherein the light naphthar (51a) is back to the third
Pipe reactor (C)；
The weight diesel oil separative unit (60) and the catalytic pyrolysis fractionation unit (40) are cooperatively connected, and are used for the diesel oil
And the above component (41c) is divided into light diesel fuel (61a) and heavy diesel fuel and the above component (61b), wherein the light diesel fuel (61a) is returned
It flow to first riser reactor (A).
17. system according to claim 16, wherein the system also includes distillations to crack unit, the distillation cracking
Unit and the gas separation unit are cooperatively connected, for by ethane, propane and C4 alkane and vapor haptoreaction to generate
Product ethylene and propylene and by-product ethane, propane, C4 alkane, C4 alkene and steam cracking light naphthar, the wherein second of by-product
Alkane, propane and C4 alkane backflow to the distillation crack unit；The C4 alkene of by-product is back to second riser reactor
(B), the steam cracking light naphthar of by-product is back to the third riser reactor (C).
18. system according to claim 16, wherein the system also includes Aromatics Extractive Project unit, the Aromatics Extractive Project
Unit and the weight naphtha separative unit (50) are cooperatively connected, for carrying out aromatic hydrocarbons extraction to heavy naphtha and obtaining scheelite
Raffinating oil after cerebrol Aromatics Extractive Project, raffinating oil after the heavy naphtha Aromatics Extractive Project are back to the third and promote tube reaction
Device (C).
19. system according to claim 16, wherein the system also includes hydrofinishing unit (10) and hydrogenation fractionatings
Unit (20), the hydrofinishing unit (10) and the feedstock oil supply unit are cooperatively connected, for original described in hydrogenation treatment
Material oil obtains hydrogenated products；The hydrogenation fractionating unit (20) and the hydrofinishing unit (10) are cooperatively connected, and are used for institute
It states hydrogenated products fractionation and obtains hydrotreating heavy wax oil；The hydrogenation fractionating unit (20) and the catalyst cracking unit (30)
In the raw material oil-in of the first riser reactor (A) be cooperatively connected, for supply in first riser reactor (A)
Hydrotreating heavy wax oil.
20. system according to claim 19, wherein the heavy diesel fuel that weight diesel oil separative unit (70) separation obtains
And the above component backflow is to the hydrofinishing unit.
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