CN109722283A - Reduce the catalysis conversion method of dry gas and coke yield - Google Patents
Reduce the catalysis conversion method of dry gas and coke yield Download PDFInfo
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Abstract
This disclosure relates to which a kind of catalysis conversion method for reducing dry gas and coke yield obtains the first carbon deposited catalyst and the first product this method comprises: heavy hydrocarbon oil raw material is made to carry out the first catalysis reaction in the first reactor；So that light hydrocarbons is carried out the second catalysis reaction in the second reactor, obtains the second carbon deposited catalyst and the second product；First carbon deposited catalyst and the second carbon deposited catalyst are introduced into stripper and are stripped, the oxygen-containing fluidization regions that catalyst of the first part after stripping introduces regenerator are subjected to aerobic regeneration；The anaerobic fluidization regions that catalyst of the second part after stripping introduces regenerator are subjected to anaerobic regeneration at 600~800 DEG C.Compared with prior art, the disclosure can in heavy hydrocarbon oil catalyzed conversion low-carbon olefines high-output, while dry gas and coke yield are lower.
Description
Technical field
This disclosure relates to a kind of catalysis conversion method for reducing dry gas and coke yield.
Background technique
Modern petroleum processing technology is while pursuing voluminous high value products (such as ethylene, propylene, C8 aromatic hydrocarbons) yield, more
Filling reduces unit Raw material processing energy consumption again and reduces carbon emission.Modernize hydrogen, the first for processing by-product in refinery by petroleum hydrocarbon
Alkane, coke, are disposed often through burning, are the main sources of refinery's carbon emission, this greatly reduces the economy of atom processing
Property.
Patent CN102071054A discloses a kind of catalyst cracking method, including heavy charge is promoted tube reaction first
Device contacts progress cracking reaction less than the 0.7nm catalyst for selecting type zeolite with containing average pore size, by lightweight material and cracking masout
In the second riser reactor and fluidized-bed reactor with containing average pore size be less than 0.7nm select type zeolite catalyst contact into
The step of row cracking reaction.This method is used for heavy oil catalytic cracking, and heavy oil conversion rate and productivity of propylene are higher, and dry gas and coke produce
Rate is low.
Patent CN102690681A discloses a kind of catalyst cracking method for producing propylene, including by heavy charge first
Riser reactor contacts with the catalyst for being less than 0.7nm shape-selective zeolite containing average pore size and carries out cracking reaction, and light hydrocarbon is existed
The average pore size that contains for being 550~690 DEG C with temperature in second riser reactor and fluidized-bed reactor is less than the shape-selective boiling of 0.7nm
The step of catalyst contact of stone carries out cracking reaction.This method is used for heavy oil catalytic cracking, heavy oil conversion rate and productivity of propylene
Height, dry gas and coke yield are low.
Patent US6106697 discloses one kind and carries out catalytic cracking as raw material, using two-stage reactor using wax oil or residual oil
The method of reaction selectivity production C2~C4 alkene.Wax oil or residual oil raw material are in the first stage reactor, Conventional catalytic cracking
Under the conditions of contacted with macro-porous zeolite catalyst and carry out catalytic cracking reaction and generate different boiling ranges product including gasoline fraction；
First stage reactor generate gasoline fraction enter the second stage reactor in, 500~650 DEG C of reaction temperature, oil ratio be 4~
10:1, hydrocarbon partial pressure contact progress with central hole zeolite catalyst under the conditions of being 70~280 kPas further reaction generates C2~C4 alkene
Hydrocarbon.
From the point of view of the catalytic cracking increased low carbon olefine output technology disclosed in oneself, catalyst is main during catalytic cracking reaction
There are two effect, one is that temperature increases catalyst after burning-off coke in a regenerator, and the energy that the catalyst of high temperature carries is
Hydrocarbon oil crude material reaction provides reaction heat, second is that the shape-selective zeolite or mesopore zeolite in catalyst provide properly for lightweight material reaction
Catalytic environment.But catalyst is also easy to the active component of green coke other than containing shape-selective zeolite or mesopore zeolite containing other,
When contacting with lightweight material, it can be made to generate a part of coke and dry gas.
Carbon deposited catalyst is fully incorporated in regenerator by the prior art dryout net coke after, the regenerated catalyst of high temperature returns
Reactor cycles use, but dryout the catalyst of net coke and when light hydrocarbon feedstock haptoreaction, and can be on a catalyst
Coke is generated, and generates dry gas.Therefore there are catalyst between regenerator and reactor during recycling for the prior art,
The problem of light hydrocarbons are iteratively produced a large amount of coke and dry gas when with catalyst haptoreaction.
Summary of the invention
Purpose of this disclosure is to provide a kind of catalysis conversion methods for reducing dry gas and coke yield.
To achieve the goals above, the disclosure provides a kind of catalysis conversion method for reducing dry gas and coke yield, the party
Method includes:
Heavy hydrocarbon oil raw material is set to contact progress the first catalysis reaction with the first catalytic cracking catalyst in the first reactor,
Reaction gained mixture is separated in settler into qi-promoting prescription, the first carbon deposited catalyst and the first product are obtained；
Light hydrocarbons are made to contact progress the second catalysis reaction with the second catalytic cracking catalyst in the second reactor, by institute
It states the reaction mixture introducing third reactor comprising catalyst that second reactor obtains and continues third catalysis reaction, it will
Reaction mixture obtained by third reactor produces in the settler into isolated second carbon deposited catalyst of qi-promoting prescription and second
Object, the boiling range of the light hydrocarbons are 8~253 DEG C；
First carbon deposited catalyst and the second carbon deposited catalyst are introduced into the stripper being for example arranged in below settler
In stripped, the oxygen-containing fluidization regions that catalyst of the first part after stripping introduces regenerator are subjected to aerobic regeneration, are obtained
First regenerated catalyst makes first regenerated catalyst be sent into first reactor as first catalytic cracking catalyst
In；
The anaerobic fluidization regions that catalyst of the second part after stripping introduces regenerator are subjected to nothing at 600~800 DEG C
Oxygen regeneration, obtains the second regenerated catalyst, is sent into second regenerated catalyst as second catalytic cracking catalyst
In second reactor；
First product and the second product are introduced into product separation system and carry out product separation, obtains including low-carbon alkene
Product, gasoline product, the separation product of diesel product and heavy oil product.
Optionally, this method further include: the fluidized gas by oxygen content less than 3 volume % is introduced into anaerobic fluidization regions, institute
It states fluidized gas and contains inert gas not less than 97 volume %, the inert gas is in nitrogen, helium, neon, argon, krypton and xenon
At least one.
Optionally, the anaerobic fluidization regions of the regenerator include: low temperature catalyst delivery pipe, gas-solid separator, catalyst
Distributor takes hot comb, deaeration pipe and high temperature catalyst delivery pipe；
One end of the low temperature catalyst delivery pipe is connected to the stripper, and the other end is connected with gas-solid separator, institute
The lower section for stating gas-solid separator has catalyst distributor and what is be connected to the catalyst distributor take hot comb, described to take heat
Comb is that multiple groups are arranged in vertical and the pipeline of bottom end connection, and the deaeration pipe, which is connected to, described takes the lower end of hot comb simultaneously
Fluidized gas entrance is offered in junction, the deaeration pipe is the standpipe that lower end is connected with the high temperature catalyst delivery pipe, institute
High temperature catalyst delivery pipe is stated to be connected to the second reactor.
Optionally, the temperature of first regenerated catalyst is 560~800 DEG C, with the dry basis of the first regenerated catalyst
On the basis of amount, the carbon deposit content of first regenerated catalyst is 0.01~0.1 weight %.
Optionally, the temperature of second regenerated catalyst is 560~800 DEG C, with the dry basis of the second regenerated catalyst
On the basis of amount, the carbon deposit content of second regenerated catalyst is 0.5~1.9 weight %, preferably 0.9~1.3 weight %, into
One step is preferably 0.91~0.99 weight %.
Optionally, on the basis of the weight of the carbon deposit in the second regenerated catalyst, the carbon deposit of second regenerated catalyst
In hydrogen content be 0.1~0.65 weight %, preferably 0.1~0.5 weight %.
Optionally, the heavy hydrocarbon oil raw material is selected from petroleum hydrocarbon oil, synthetic oil, liquefied coal coil, tar sand oil and shale oil
At least one of, preferably petroleum hydrocarbon oil, the petroleum hydrocarbon oil are selected from AGO (atmospheric gas oil), vacuum gas oil (VGO), coker gas
At least one of oil, deasphalted oil, hydrogenation tail oil, reduced crude, decompression residuum and crude oil.
Optionally, the average molecular mass of the heavy hydrocarbon oil raw material is not less than 200.
Optionally, the light hydrocarbons are 9~160 DEG C, further preferably 9~60 DEG C；
On the basis of the total weight of the light hydrocarbons, the olefin(e) centents of the light hydrocarbons is 30~90 weight %, excellent
Being selected as 45~90 weight % is, for example, 45~80 weight % or 45~65 weight % or 55~75 weight %.
Optionally, the light hydrocarbons are at least partially from the separation product of the product separation system.This
In the case of kind, the separation system also isolates light hydrocarbons separation product, and the light hydrocarbons and the heavy hydrocarbon oil
The weight ratio of raw material is (0.01~0.6): 1, preferably (0.05~0.3): 1.
Optionally, first catalytic cracking catalyst and the second catalytic cracking catalyst are respectively less than containing average pore size
0.7 nanometer of shape-selective zeolite, the shape-selective zeolite be selected from MFI structure zeolite, ferrierite, chabasie, dachiardite,
At least one of erionite, type A zeolite, epistilbite and laumontite.
Optionally, it is described first catalysis reaction operating condition include: reaction temperature be 480~600 DEG C be, for example, 500~
550 DEG C or 510~540 DEG C；Reaction time is such as 1~5 second or 2~4 seconds 0.5~10 second；Agent oil weight ratio is (5~15): 1
Such as 6~10:1；Water oil weight ratio is (0.05~1): 1 such as (0.08~0.5): 1 or (0.1~0.3): 1.
Optionally, it is described second catalysis reaction operating condition include: reaction temperature be 520~750 DEG C be, for example, 520~
600 DEG C or 520~550 DEG C；It is, for example, 1~3 second or 1.4~3 seconds that reaction time, which is 0.1~3 second,；Agent oil weight ratio be (6~
40): 1 is, for example, (8~25): 1 or (10~20): 1 or (10~17): 1；Water oil weight ratio is (0.1~1): 1 is, for example, (0.1
~0.5): 1 or (0.1~0.25): 1 or (0.1~0.3): 1.
Optionally, it is anti-to be respectively selected from riser reactor, down pipe for the first reactor and the second reactor
Answer device, fluidized-bed reactor, riser and down pipe compound reactor, riser and fluidized bed compound reactor, down pipe with
One of fluidized bed compound reactor.
Optionally, the third reactor is fluidized-bed reactor, the operating condition of the third reactor are as follows: reaction temperature
Degree is, for example, 500~600 DEG C or 510~550 DEG C, preferably 510~560 DEG C for 450~750 DEG C；Weight (hourly) space velocity (WHSV) is 1~30h-1
For example, 3~20 or 5~15h-1；The absolute pressure of settler is 0.15~0.40MPa.
The catalyst cracking method that the disclosure provides overcomes catalyst liter in prior art route and regenerator configuration design
Mild catalyst burns the problem that two processes are strictly bound, can not be separated, and high-temperature regenerated catalyst circulation-heavy is respectively configured
Hydrocarbon ils reacts route, high temperature carbon deposited catalyst circulation-light hydrocarbons and reacts route, can reduce dry gas and coke yield.Pass through
It establishes to the special reproduction reaction process of the carbon deposited catalyst, overcomes prior art carbon deposited catalyst directly and light hydrocarbon oil
So that alkene is generated coke when reaction, causes coke yield high, the low critical issue of light hydrocarbons conversion ratio.With prior art phase
Than, the disclosure can in heavy hydrocarbon oil catalyzed conversion low-carbon olefines high-output, while dry gas and coke yield are lower.
Specifically, the disclosure has following compared with the method for traditional heavy hydrocarbon oil catalyzed conversion low-carbon olefines high-output
Any one or more beneficial effect has the effect of under preferable case all following:
1. regenerator in the prior art has two functions: first is that the carbon deposit under aerobic environment on burning-off catalyst,
Second is that increasing the temperature of catalyst to carry the required heat of reaction, two function bindings, therefore regenerative process can only provide
Dryout the high temperature catalyst of net carbon deposit.Oxygen-containing fluidization regions and anaerobic fluidization regions, oxygen-containing fluidization regions are arranged in the disclosure in a regenerator
Still have the carbon distribution on burning-off catalyst and make two functions of catalyzer temperature-elevating, high temperature is provided and dryouies the catalyst of net carbon deposit,
Anaerobic fluidization regions establish new anaerobic regenerative response process, do not burn up carbon deposit while retaining makes the function of catalyzer temperature-elevating
In carbon, and be only greatly reduced the hydrogen mass fraction in carbon deposit, the property of carbon deposit on catalyst changed, to provide high temperature
Specific reactivity can carbon deposited catalyst.Regenerator in the disclosure realizes catalyzer temperature-elevating and catalyst burning-off carbon deposit two
A function it is relatively independent, therefore can flexibly for reaction process provide multiplicity catalyst.
2. in existing publication, participating in petroleum hydrocarbon reaction by introducing carbon deposited catalyst to be generated, there are some reductions
The effect of dry gas and coke yield, but the effect for reducing dry gas and coke yield is general, also results in the production of the high added values such as propylene
Product yield declines, and the hydrogen mass fraction of carbon deposit is higher on untreated carbon deposited catalyst, between 0.55~0.85%, these
Carbon deposit has chemical reactivity, and hydrogen transfer activity easily occurs with light hydrocarbons such as alkene, hinders cracking of olefins reaction, or even make
Alkene generates coke, plays negative effect, causes coke yield high, conversion ratio is low.The disclosure passes through anaerobic fluidization regions reaction regeneration
Process thoroughly changes the property of carbon deposit on catalyst, and the hydrogen mass fraction of carbon deposit significantly reduces, treated carbon deposited catalyst
With the second catalytic cracking catalyst Returning reactor, then with include alkene light hydrocarbons react when, to the obstruction of cracking of olefins
Effect is also greatly reduced, and the selectivity that alkene is converted into low-carbon alkene can be improved.Light hydrocarbons including alkene will occur more
More cracking reactions generate the low-carbon alkenes such as propylene, reduce and generate coke and dry gas.
3. the method that the disclosure provides is reacted with the carbon deposited catalyst of the specific reactivity energy of high temperature with light hydrocarbons, both protected
Dry gas and coke yield are greatly reduced when having demonstrate,proved the required heat of light hydrocarbons reaction, and light hydrocarbons being reacted.
4. the design of regenerator and catalyst circulation route in the disclosure can flexible modulation enter light hydrocarbons reaction zone
The initial temperature of middle carbon deposited catalyst, so that making the adjusting of oil ratio in reactor need not be wanted by reactor outlet reaction temperature
The limitation asked can also equally reduce the problem of light hydrocarbons directly contact the heat cracking reaction of initiation with high-temperature regenerated catalyst.
5. anaerobic fluidization regions remove the partial heat in regenerator, drop by heating up to carbon deposited catalyst in regenerator
The low temperature of regenerator, reduces the generation of second-time burning in regenerator dilute phase space (also referred to as tail combustion), has regenerator and take
The partial function of hot equipment, it might even be possible to cancel regenerator interior heat collecting device, reduce investment outlay.
6. the method that the disclosure provides, compared with the conventional method, coke selectivity is low, and dry gas selectivity is low, productivity of propylene
It is higher.
Other feature and advantage of the disclosure will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
Attached drawing is and to constitute part of specification for providing further understanding of the disclosure, with following tool
Body embodiment is used to explain the disclosure together, but does not constitute the limitation to the disclosure.In the accompanying drawings:
Fig. 1 is the flow diagram for the catalyst cracking method for reducing dry gas and coke yield that the disclosure provides.
Fig. 2 is the structural schematic diagram of the anaerobic fluidization regions in regenerator.
Description of symbols
1 first reactor
2 second reactors
3 third reactors
7 strippers
8 settlers
9 regenerators
11 first catalytic cracking catalyst feed-lines
12 second catalytic cracking catalyst feed-lines
17 reclaimable catalyst feed-lines
18 reclaimable catalyst feed-lines
19 reclaimable catalyst feed-lines
21 pipelines (injection heavy hydrocarbon oil raw material)
22 pipelines (injection light hydrocarbons)
28 pipelines (conveying reaction oil gas)
30 pipelines (conveying dry gas)
31 pipelines (transportation of liquefied gas)
32 pipelines (gasoline feed)
33 pipelines (conveying diesel oil)
34 pipelines (conveying heavy oil)
41 pipelines (injection atomizing steam)
42 pipelines (injection atomizing steam)
47 pipelines (injection stripped vapor)
51 pipelines (injection pre-lift medium)
52 pipelines (injection pre-lift medium)
53 pipelines (injecting lift medium)
58 pipelines (injection air)
59 pipelines (conveying regenerated flue gas)
70 product separation systems
The oxygen-containing fluidization regions of 91 regenerators
92 regenerator anaerobic fluidization regions
921 low temperature catalyst delivery pipes
922 gas-solid separators
923 catalyst distributors
924 take hot comb
925 deaeration pipes
926 high temperature catalyst delivery pipes
927 fluidized gas entrances
Specific embodiment
It is described in detail below in conjunction with specific embodiment of the attached drawing to the disclosure.It should be understood that this place is retouched
The specific embodiment stated is only used for describing and explaining the disclosure, is not limited to the disclosure.
The disclosure provides a kind of catalysis conversion method for reducing dry gas and coke yield, this method comprises:
Heavy hydrocarbon oil raw material is set to contact progress the first catalysis reaction with the first catalytic cracking catalyst in the first reactor,
Reaction gained mixture is separated in settler into qi-promoting prescription, the first carbon deposited catalyst and the first product are obtained；
Light hydrocarbons are made to contact progress the second catalysis reaction with the second catalytic cracking catalyst in the second reactor, by institute
It states the reaction mixture introducing third reactor comprising catalyst that second reactor obtains and continues third catalysis reaction, it will
Reaction mixture obtained by third reactor produces in the settler into isolated second carbon deposited catalyst of qi-promoting prescription and second
Object, the boiling range of the light hydrocarbons are 8~253 DEG C；
First carbon deposited catalyst and the second carbon deposited catalyst are introduced into the stripper below settler and stripped,
The oxygen-containing fluidization regions that catalyst of the first part after stripping introduces regenerator are subjected to aerobic regeneration, obtain the first regeneration catalyzing
Agent is sent into first regenerated catalyst in first reactor as first catalytic cracking catalyst；
The anaerobic fluidization regions that catalyst of the second part after stripping introduces regenerator are subjected to nothing at 600~800 DEG C
Oxygen regeneration, obtains the second regenerated catalyst, is sent into second regenerated catalyst as second catalytic cracking catalyst
In second reactor；
First product and the second product are introduced into product separation system and carry out product separation, obtains including low-carbon alkene
Product, gasoline product, the separation product of heavy oil product and optional light hydrocarbons product.
In existing catalytic cracking unit, after regenerator regenerates, the temperature of catalyst is increased to catalytic cracking catalyst
600~700 DEG C, then after reacting with heavy hydrocarbon oil, the temperature of carbon deposited catalyst is reduced to 480~600 DEG C, at this time carbon deposited catalyst
Entrained shortage of heat provides adequate reaction heat, therefore carbon deposited catalyst to react cracking low-carbon olefines high-output for light hydrocarbons
It must return in regenerator and regenerate to improve temperature, burning-off catalyst upper surface carbon distribution in oxygen containing environment in regenerator；Regeneration
The catalyst for dryouting net coke afterwards is reacted with light hydrocarbons again, and can be formed more carbon deposit on a catalyst and be generated more dry
Gas, so product selectivity declines.The design of the prior art and device will be provided with active due to the requirement of process reaction heat
Carbon deposited catalyst carries out unnecessary burn, it has to select regenerated catalyst directly to react with light hydrocarbons, cause final
Coke and dry gas yied are higher in product.
On the other hand, the inventor of the disclosure is the study found that if straight by the carbon deposited catalyst after reacting with heavy hydrocarbon oil
It connects and is reacted again with light hydrocarbons, even if these carbon deposited catalysts by stripping, in the composition of carbon deposit or contain a large amount of band alkane
The polycyclic aromatic hydrocarbon of base side chain, hydrogen mass fraction is higher in carbon deposit, in the reaction process of carbon deposited catalyst and light hydrocarbons, light hydrocarbon
The cracking reaction of class is susceptible to the obstruction of hydrogen transfer reaction, and is easily formed new coke.
The inventor of the disclosure is by laboratory research discovery, catalytic cracking catalyst and heavy containing shape-selective molecular sieve
After hydrocarbon ils is reacted under suitable condition, stripped, carbon deposited catalyst is formed, which is heated up and carries out anaerobic regeneration
Processing, obtains through the regenerated catalyst of anaerobic.It compares and is reacted in the regenerated catalyst for dryouting net coke with light hydrocarbons,
The oil inlet of light hydrocarbons continuous several times is reacted on through treated carbon deposited catalyst, the production of low-carbon alkene in products therefrom
Rate does not reduce, and dry gas and coke yield significantly reduce.
According to the disclosure, first catalytic cracking catalyst and second catalytic cracking catalyst can be this field
It is conventional use of to carry out catalytic cracking reaction, can be identical catalytic cracking catalyst, or different catalytic cracking
Catalyst, preferably identical catalytic cracking catalyst.
The disclosure does not have the specific type of first catalytic cracking catalyst and second catalytic cracking catalyst
Special limitation.Preferably, first catalytic cracking catalyst and the second catalytic cracking catalyst respectively contain average pore size
Shape-selective zeolite less than 0.7 nanometer, the shape-selective zeolite can be for selected from the zeolite with MFI structure, ferrierite, water chestnut boilings
At least one of stone, dachiardite, erionite, type A zeolite, epistilbite and laumontite.Wherein, the zeolite of the MFI structure can
Think one of ZSM-5 and ZRP series zeolite or a variety of, it can also be for through RE, P, Fe, Co, Ni, Cu, Zn, Mo, Mn, Ga and Sn
At least one of one of element modified ZSM-5 and ZRP series zeolite or a variety of.Optionally implement in disclosure one kind
In mode, on the basis of the dry weight (weight of 800 DEG C of roastings 1 hour) of catalytic cracking catalyst, the catalytic cracking
Catalyst includes the clay of in terms of butt 15~50 weight %, the molecular sieve of in terms of butt 15~50 weight % and in terms of butt 10
The binder of~35 weight %, the molecular sieve is for the zeolite of MFI structure or by 25~100 weight %MFI structural zeolites and 0
Other zeolites composition other than~75 weight %MFI structural zeolites；The MFI structure zeolite be preferably phosphorus and selected from RE, P, Fe,
At least one of Co, Ni, Cu, Zn, Mo, Mn, Ga and Sn element modified ZSM-5 molecular sieve and/or HZSM-5 molecular sieve.Institute
One of other zeolites stated such as y-type zeolite, β zeolite are a variety of.The clay is for example preferably selected from kaolin, more
Hydrokaolinite, montmorillonite, diatomite, galapectite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and swollen
Moisten one of soil or a variety of.The binder such as acidification pseudo-boehmite, Aluminum sol, silica solution, magnalium colloidal sol, zirconium is molten
One of glue, titanium colloidal sol are a variety of, preferably acidification pseudo-boehmite and Aluminum sol etc..
According to the disclosure, the first reactor and second reactor can be catalysis well-known to those skilled in the art
Conversion reactor, for example, the first reactor and the second reactor are respectively, to be selected from riser reactor, down pipe anti-
Answer device, fluidized-bed reactor, riser and down pipe compound reactor, riser and fluidized bed compound reactor, down pipe with
One of fluidized bed compound reactor.The fluidized-bed reactor can be for selected from fixed fluidized-bed reactor, particulate fluidization
In bed reactor, bubbling bed reactor, turbulent bed reactor, fast bed reactor, transport bed reactor and dense-phase fluidized bed
It is a kind of.Wherein riser reactor, downer reactor and fluidized-bed reactor can be isodiametric riser reactor, under
Row pipe reactor and fluidized-bed reactor are also possible to the riser reactor, downer reactor and fluidisation of various variable diameters
Bed reactor.
According to the disclosure, heavy hydrocarbon oil raw material is in the first reactor with the first catalytic cracking catalyst under fluidized state
Contact carries out the first catalysis reaction.It is 480~600 DEG C that the operating condition of the first catalysis reaction, which may include: reaction temperature,
For example, 500~550 DEG C or 510~540 DEG C；Reaction time is such as 1~5 second or 2~4 seconds 0.5~10 second；Agent oil weight ratio
For (5~15): 1 such as 6~10:1；Water oil weight ratio is (0.05~1): 1 such as (0.08~0.5): 1 or (0.1~0.3):
1。
According to the disclosure, the heavy hydrocarbon oil raw material can be for selected from petroleum hydrocarbon oil, synthetic oil, liquefied coal coil, tar sand oil
At least one of with shale oil.The synthetic oil can synthesize obtained distillate by Fischer-Tropsch (F-T) for coal, natural gas.
Preferably, the heavy hydrocarbon oil raw material be petroleum hydrocarbon oil, for example, selected from AGO (atmospheric gas oil), vacuum gas oil (VGO), coker gas oil,
At least one of deasphalted oil, hydrogenation tail oil, reduced crude, decompression residuum and crude oil.
According to the disclosure, in order to reach the optimal carbon deposit effect of catalyst surface, the average phase of the heavy hydrocarbon oil raw material
200 are preferably not lower than to molecular mass.Heavy hydrocarbon oil raw material with above-mentioned relative molecular mass both can guarantee enough products
Carbon content, meanwhile, the heavy hydrocarbon oil raw material of macromolecular will not enter the micropore of catalyst, and carbon deposit be deposited on catalyst surface and big
Mesoporous does not influence the secondary response effect of carbon deposited catalyst.The average molecular mass refers to average opposite point of hydro carbons
Son amount, i.e., the summation of the relative atomic mass of each atom in petroleum hydrocarbon chemical formula are a basic physics ginsengs of petroleum hydrocarbon
Number, industry measuring method are as follows: hydro carbons relative molecular weight measuring method SH/T 0583.
According to the disclosure, light hydrocarbons contact under fluidized state with the second catalytic cracking catalyst in the second reactor
Carry out the second catalysis reaction.It is described second catalysis reaction operating condition may include: reaction temperature be 520~750 DEG C for example
It is 520~600 DEG C or 520~550 DEG C；It is, for example, 1~3 second or 1.4~3 seconds that reaction time, which is 0.1~3 second,；Agent oil weight ratio
It is, for example, (8~25): 1 or (10~20): 1 or (10~17): 1 for (6~40): 1；Water oil weight ratio is (0.1~1): 1 for example
For (0.1~0.5): 1 or (0.1~0.25): 1 or (0.1~0.3): 1.
According to the disclosure, the specific type of the light hydrocarbons does not have special limitation, if meet its boiling range 8~
253 DEG C, such as may include C4 hydrocarbon-fraction, direct steaming gasoline, catalytic cracked naphtha, catalytic cracking stable gasoline, coking
Gasoline, Fischer-Tropsch (F-T) synthetic gasoline, all kinds of diesel oil light fractions etc., it is self-produced that above-mentioned fraction can come from device described in the disclosure,
It can be from other devices.In order to further increase the yield of premium, the boiling range of the light hydrocarbons is preferably 9~
160 DEG C, further preferably 9~60 DEG C.On the basis of the total weight of the light hydrocarbons, the olefin(e) centent of the light hydrocarbons
It can be 30~90 weight %, preferably 45~90 weight % are, for example, 45~80 weight % or 45~65 weight % or 55~75
Weight %.
According to the disclosure, the light hydrocarbons can be produced at least partially from the separation of the product separation system
In object, in such cases, the separation system also isolates light hydrocarbons separation product, and the light hydrocarbons with it is described heavy
The weight ratio of matter hydrocarbon oil crude material can be (0.01~0.6): 1, preferably (0.05~0.3): 1.
According to the disclosure, the third reactor is preferably fluidized-bed reactor, and the fluidized-bed reactor can be choosing
It is self-retaining fluidized-bed reactor, dispersion fluidized bed reactor, bubbling bed reactor, turbulent bed reactor, fast bed reactor, defeated
Send one of a reactor and dense-phase fluidized bed.The fluidized-bed reactor can be isodiametric fluidized-bed structure, can also
To be variable diameters fluidized-bed structure.The operating condition of the third reactor can be with are as follows: reaction temperature be 450~750 DEG C for example
For 500~600 DEG C or 510~550 DEG C, preferably 510~560 DEG C；Weight (hourly) space velocity (WHSV) is 1~30h-1For example, 3~20 or 5~
15h-1。
According to the disclosure, mixture obtained by the reaction in first reactor is separated in settler into qi-promoting prescription, is obtained
First carbon deposited catalyst is introduced into the stripper below settler and is stripped；And reaction mixture obtained by third reactor is existed
It is separated in the settler into qi-promoting prescription, obtains the second carbon deposited catalyst and be also introduced into stripper to be stripped；In settler
Absolute pressure can be 0.1~0.40MPa.
According to the disclosure, the oxygen-containing fluidization regions progress that catalyst of the first part after stripping is introduced regenerator is aerobic again
It is raw, obtain the first regenerated catalyst.The temperature of first regenerated catalyst can be, for example, 620~720 for 560~800 DEG C
DEG C, on the basis of the dry weight of the first regenerated catalyst, the carbon deposit content of first regenerated catalyst can for 0.01~
0.1 weight %.
According to the disclosure, the anaerobic fluidization regions that catalyst of the second part after stripping introduces regenerator are subjected to anaerobic again
It is raw, accelerate the carbon deposit on the carbon deposited catalyst of the part after anaerobic regeneration occurs, obtains the second regenerated catalyst.Described second
The temperature of regenerated catalyst can be, for example, 600~780 DEG C or 620~720 DEG C or 650~710 DEG C or 630 for 560~800 DEG C
~700 DEG C, on the basis of the dry weight of the second regenerated catalyst, the carbon deposit content of second regenerated catalyst can be
0.5~1.9 weight %, preferably 0.9~1.3 weight %, further preferably 0.91~0.99 weight %.Further, with
On the basis of the weight of carbon deposit in second regenerated catalyst, the hydrogen content in the carbon deposit of second regenerated catalyst can be
0.1~0.65 weight %, preferably 0.1~0.5 weight %.
According to the disclosure, this method can also include: the fluidisation by oxygen content less than 3 volume % (at standard conditions)
Gas is introduced into anaerobic fluidization regions, and the fluidized gas includes inert gas, and the inert gas can be for example nitrogen and rare
Gas helium, neon, argon, krypton, xenon etc..Such as the fluidized gas at standard conditions contains 0-3 volume % or 0.5~2.5 body
Accumulate the oxygen of %, the inert gas of 97~100 volume % or 97.5~99.5 volume %.Fluidized gas containing a small amount of oxygen is drawn
Enter the hydrogen that can be burnt up in catalyst carbon deposit, further decrease the mass fraction of the hydrogen in carbon deposit, accelerates polycyclic aromatic hydrocarbon in carbon deposit
It is converted into the coke graphitizing process of graphite, and quickly improves the temperature of catalyst.
According to the disclosure, the structure of the anaerobic fluidization regions can be the form that arbitrarily can be realized the purpose of the disclosure.
In a kind of optional embodiment of the disclosure, as shown in Fig. 2, the anaerobic fluidization regions of the regenerator may include: low temperature
Catalyst transport 921, catalyst distributor 923, takes hot comb 924, deaeration pipe 925 and high-temperature catalytic at gas-solid separator 922
Agent delivery pipe 926.One end of the low temperature catalyst delivery pipe 921 is connected to the stripper 7, and the other end is connected with gas-solid point
From device 922.The lower section of the gas-solid separator 922 has catalyst distributor 923 and is connected to the catalyst distributor 923
Take hot comb 924.It is described to take the pipeline that hot comb 924 is arranged in vertical for multiple groups and bottom end is connected to, the catalyst
Distributor 923 has the multiple distribution mouths being connected with the multiple groups pipeline for taking hot comb 924, and catalyst enters the catalysis
It is evenly distributed in the multiple groups pipeline for taking hot comb 924 by gravity by multiple distribution mouth after agent distributor 923.It is described de-
Tracheae 925 takes the lower end of hot comb 924 and offers fluidized gas entrance 927, the deaeration pipe 925 in junction described in being connected to
For the standpipe that lower end is connected with the high temperature catalyst delivery pipe 926, the high temperature catalyst delivery pipe 926 and described second anti-
Device 2 is answered to be connected to.The regenerated temperature of the anaerobic (600~800 DEG C) in the disclosure refers to the temperature in deaeration pipe 925.
According to the disclosure, first product and the second product are introduced into product separation system and carry out product separation, is obtained
Separation product including dry gas product, liquefied gas product, gasoline product, diesel product and heavy oil product etc., wherein liquefied gas passes through
Further product the purpose of isolated ethylene, propylene.
Method provided by 1 pair of disclosure is further described with reference to the accompanying drawing, but the disclosure not therefore by
To any restrictions.
In Fig. 1, first reactor 1 is riser reactor, and second reactor 2 is riser reactor, third reactor 3
For fluidized-bed reactor.First catalytic cracking catalyst (hot regenerated catalyst) is urged by the oxygen-containing fluidization regions 91 of regenerator through first
Fluidized cracking catalysts feed-line 11 enters 1 bottom of riser of first reactor, and is situated between in the pre-lift injected by pipeline 51
Accelerate to flow up under the action of matter.Heavy hydrocarbon oil raw material after preheating is mixed through pipeline 21 with the atomizing steam from pipeline 41
The weight ratio of injecting lift pipe 1 afterwards, water vapour and hydrocarbon oil crude material is (0.05~1): 1, the outlet temperature of riser reactor 1 is
480~600 DEG C, the reaction time in riser reactor 1 is 0.5~10 second, and the weight ratio of catalyst and hydrocarbon oil crude material is 5
~15, the absolute pressure in settler 8 is 0.1~0.40MPa.The mixture of reaction oil gas and catalyst is through going out in riser 1
Mouthful fast separating device gas agent separation, the first carbon deposited catalyst introduces stripper 7, the reaction oil gas isolated through settler 8 and its
The pipeline 28 at top is sent into subsequent product separation system 70 and carries out product separation, and dry gas, liquefied gas, gasoline, bavin are obtained after separation
The products such as oil, heavy oil (are drawn through pipeline 30,31,32,33,34) respectively, and wherein liquefied gas is through further isolated ethylene, third
The purpose of alkene product, while can further the isolated light hydrocarbons (being drawn through pipeline 22) for freshening.Light hydrocarbons warp
After pipeline 22 is mixed with the atomizing steam from pipeline 42 in injected in second reactor 2, the weight ratio of water vapour and hydrocarbon oil crude material
For (0.1~1): 1,2 outlet temperature of riser reactor is 520~750 DEG C, and the reaction time in riser 2 is 0.1~3
Second, the weight ratio of catalyst and hydrocarbon oil crude material is 6~40.The reaction oil gas of riser reactor 2 and the mixture warp of catalyst
Leg outlet, which is further introduced into 3 fluidized bed of third reactor, to be continued to react, and the reaction temperature of fluidized bed 3 is 450~
750 DEG C, weight (hourly) space velocity (WHSV) is 1~30h-1, the reclaimable catalyst of oil gas and a part of carbon deposit enters through fluidized-bed reactor 3 after reaction
Separation, isolates the second carbon deposited catalyst and enters stripper 7 in settler 8.Stripped vapor injects in stripper 7 through pipeline 47,
With the reclaimable catalyst counter current contacting of carbon deposit, reaction oil gas entrained by reclaimable catalyst is stripped as much as possible clean.Regeneration
Device 9 includes oxygen-containing fluidization regions 91 and anaerobic fluidization regions 92.Carbon deposited catalyst after stripping introduces spent agent feed-line 17, portion
Carbon deposited catalyst is divided further to be delivered to through reclaimable catalyst feed-line 19 under the promotion medium effect injected by pipeline 53
In anaerobic fluidization regions 92 in regenerator 9, gas-solid separator is first passed through at the top of anaerobic fluidization regions by a small amount of gas of entrainment from upper
Portion separates, and is introduced into the multiple of anaerobic fluidization regions through catalyst distributor through gravity and takes in hot comb, and will be a part of
Oxygen content is introduced into anaerobic fluidization regions less than the fluidized gas of 3 volume %, is reacted, is heated up under hot environment in regenerator, makes
Carbon deposit on carbon deposited catalyst accelerates after coke graphitizing process occurs, and the hydrogen mass fraction of carbon deposit significantly reduces, to ask for heat
Carbon deposited catalyst in comb finally imports deaeration pipe, removes the gas carried secretly on a small quantity, completes reaction process, obtains the second regeneration
Catalyst makes it return to second reactor through the second catalytic cracking catalyst feed-line 12 as the second catalytic cracking catalyst
It is recycled in 2.Remaining carbon deposited catalyst is sent into the oxygen-containing fluidization regions 91 of regenerator 9, air warp through spent agent feed-line 18
Pipeline 58 injects oxygen-containing fluidization regions 91, and catalyst is contacted with heated air in regenerator and (taken off at 600 DEG C~800 DEG C
Tracheae temperature) under regenerated, obtain the first regenerated catalyst, make its as the first catalytic cracking catalyst through first catalysis split
Change and is recycled in the return first reactor of catalyst transport pipeline 11.Regenerated flue gas is drawn through pipeline 59.
The method that the disclosure provides is further illustrated below by embodiment, but the disclosure is not therefore by any limit
System.
Catalyst employed in embodiment is that the trade names of Sinopec catalyst asphalt in Shenli Refinery production are MMC-2
Cracking catalyst, specific nature is shown in Table 1, which is less than the shape-selective zeolite of 0.7nm containing average pore size.
Embodiment 1
Embodiment l illustrates that the method that the disclosure provides reduces the effect of dry gas and coke yield during hydrocarbon oil catalytic conversion
Fruit.
Using tool, there are three successive reaction-regenerative operation middle- scale devices of reactor to be tested, wherein the first reaction
Device is riser, and it is highly 3800 millimeters that the internal diameter of riser reactor, which is 16 millimeters,.Second reactor is to promote tube reaction
Device, internal diameter are 16 millimeters, are highly 3200 millimeters.The outlet of second riser reactor introduces fluidized-bed reactor as third reaction
The internal diameter of device, fluidized-bed reactor is 64 millimeters, is highly 300 millimeters.
The first regenerated catalyst that first catalytic cracking catalyst is 680 DEG C of temperature, it is oblique through the first catalytic cracking catalyst
Pipe enters the bottom of the riser reactor of first reactor, and flows up under the action of pre-lift steam.Heavy hydrocarbon oil
Raw material (main character is shown in Table 2) preheated stove heating passes through feed nozzle penetrating the to after mix after 350 DEG C with atomization water vapour
In one reactor, is contacted with the first regenerated catalyst of heat and carry out catalytic conversion reaction.Reaction oil gas (the first product) and first
Carbon deposited catalyst enters from first reactor leg outlet carries out quick separating in settler, the first carbon deposited catalyst enters
Stripper is stripped.Second catalytic cracking catalyst is treated graphited carbon deposited catalyst (the second regeneration catalyzing
Agent), the temperature of the second catalytic cracking catalyst is 680 DEG C, enters second reactor through the second catalytic cracking catalyst inclined tube
The bottom of riser reactor, and flowed up under the action of pre-lift steam.(9~57 DEG C) of light hydrocarbon feedstock enter the
It is contacted in two reactors with the second regenerated catalyst of heat and carries out catalysis reaction.The weight ratio of light hydrocarbons and heavy hydrocarbon oil raw material
For 0.2:1.Reaction oil agent mixture from second reactor is further in leg outlet introducing third reactor fluidized bed
Reaction, oil gas (the second product), which enters in settler with the second carbon deposited catalyst through fluidized-bed reactor, after reaction separates, separation
The second carbon deposited catalyst out enters stripper by gravity and is stripped.From first reactor and third reactor
Reaction oil gas is drawn from settler together, is introduced product separation system and is carried out product separation, obtains gaseous product and various liquid
Body product, while being partially separated to obtain light hydrocarbons.The carbon deposited catalyst of stripper is after stripping, and a part is through spent agent all the way
Delivery pipe enters in the anaerobic fluidization regions of regenerator, and (the laboratory selection of a part of fluidized gas is introduced in anaerobic fluidization regions
High pure nitrogen, nitrogen content >=99.99 volume % at standard conditions, oxygen content≤0.01 volume %) at 695 DEG C
Anaerobic regeneration, carbon deposit accelerates that coke graphitizing process occurs, while the hydrogen mass fraction of carbon deposit significantly reduces, and second obtained is again
Raw catalyst, which returns in second reactor, to be recycled；Rest part enters the oxygen-containing stream of regenerator through spent agent delivery pipe
Change and contacted in area with heated air and carry out aerobic regeneration at 700 DEG C, the first regenerated catalyst for obtaining heat returns to
It is recycled in first reactor.The first catalytic cracking catalyst (the first regenerated catalyst) is detected during continuous operation
The hydrogen mass fraction of the carbon deposit content and carbon deposit of carbon deposit content and the second catalytic cracking catalyst (the second regenerated catalyst).
Prevailing operating conditions and result are listed in table 3.
Comparative example l
Comparative example l illustrates that regenerator only has oxygen-containing fluidization regions, and the regeneration catalyzing that the second catalytic cracking catalyst is 680 DEG C
The effect of hydrocarbon oil catalytic conversion process when agent.
Using tool, there are three successive reaction-regenerative operation middle- scale devices of reactor to be tested, wherein the first reaction
Device is riser, and it is highly 3800 millimeters that the internal diameter of riser reactor, which is 16 millimeters,.Second reactor is to promote tube reaction
Device, internal diameter are 16 millimeters, are highly 3200 millimeters.The outlet of second riser reactor introduces fluidized-bed reactor as third reaction
The internal diameter of device, fluidized-bed reactor is 64 millimeters, is highly 300 millimeters.
The first regenerated catalyst that first catalytic cracking catalyst is 680 DEG C of temperature, it is oblique through the first catalytic cracking catalyst
Pipe enters the bottom of the riser reactor of first reactor, and flows up under the action of pre-lift steam.Heavy hydrocarbon oil
Raw material (main character is shown in Table 2) preheated stove heating passes through feed nozzle penetrating the to after mix after 350 DEG C with atomization water vapour
In one reactor, is contacted with the first regenerated catalyst of heat and carry out catalytic conversion reaction.Reaction oil gas (the first product) and first
Carbon deposited catalyst enters from first reactor leg outlet carries out quick separating in settler, the first carbon deposited catalyst enters
Stripper is stripped.The second regenerated catalyst that second catalytic cracking catalyst is 680 DEG C of temperature, is urged through the second catalytic cracking
Agent inclined tube enters the bottom of the riser reactor of second reactor, and flows up under the action of pre-lift steam.Gently
(9~57 DEG C) of matter hydrocarbon raw material enter second reactor in heat the second regenerated catalyst contact progress catalytic conversion reaction.
The weight ratio of light hydrocarbons and heavy hydrocarbon oil raw material is 0.2:1.Reaction oil agent mixture from second reactor is in riser
Outlet introduces third reactor fluidized bed and further reacts, and oil gas (the second product) is with the second carbon deposited catalyst through fluidizing after reaction
Bed reactor enters to be separated in settler, and the second carbon deposited catalyst isolated enters stripper by gravity and carries out vapour
It mentions.Reaction oil gas from first reactor and third reactor is drawn from settler together, introduce product separation system into
The separation of row product, obtains gaseous product and various product liquids, while being partially separated to obtain light hydrocarbons.The carbon deposit of stripper is urged
Agent all returns to after stripping through spent agent delivery pipe in the oxygen-containing fluidization regions of regenerator, contacts simultaneously with heated air
Aerobic regeneration is carried out at 700 DEG C, the regenerated catalyst for obtaining heat, which returns in first reactor and second reactor to recycle, to be made
With.Regenerator adds outside heat removing equipment and takes superfluous heat, control reaction thermal balance and regenerator regeneration temperature away.Continuously transporting
The carbon deposit content of detection the first catalytic cracking catalyst (the first regenerated catalyst) and the second catalytic cracking catalysis during row
The carbon deposit content of agent (the second regenerated catalyst) and the hydrogen mass fraction of carbon deposit.Prevailing operating conditions and result are listed in table 3.Mainly
Operating condition and result are listed in table 3.
Comparative example 2
Comparative example 2 illustrates that regenerator only has the effect of the hydrocarbon oil catalytic conversion process of oxygen-containing fluidization regions, the second catalytic cracking
Catalyst is directly from the carbon deposited catalyst in stripper, and carbon deposited catalyst quickly heats up to 680 DEG C by electric heating.
Using tool, there are three successive reaction-regenerative operation middle- scale devices of reactor to be tested, wherein the first reaction
Device is riser, and it is highly 3800 millimeters that the internal diameter of riser reactor, which is 16 millimeters,.Second reactor is to promote tube reaction
Device, internal diameter are 16 millimeters, are highly 3200 millimeters.The outlet of second riser reactor introduces fluidized-bed reactor as third reaction
The internal diameter of device, fluidized-bed reactor is 64 millimeters, is highly 300 millimeters.
First catalytic cracking catalyst is 680 DEG C of temperature of regenerated catalyst, through the first catalytic cracking catalyst inclined tube into
Enter the bottom of the riser reactor of first reactor, and is flowed up under the action of pre-lift steam.Heavy hydrocarbon oil raw material
(main character is shown in Table 2) preheated stove heating sprays into first instead to after mix after 350 DEG C with atomization water vapour, through feed nozzle
It answers in device, is contacted with the regenerated catalyst of heat and carry out catalytic conversion reaction.Reaction oil gas (the first product) and the catalysis of the first carbon deposit
Agent enters from first reactor leg outlet carries out quick separating in settler, the first carbon deposited catalyst enter stripper into
Row stripping.Second catalytic cracking catalyst is the carbon deposited catalyst directly from stripper.Stripper bottom is through the second spent agent
Delivery pipe is connected with the bottom of the riser reactor of second reactor, and electric heating is arranged in the second spent agent delivery pipe
Facility, by 500 DEG C of carbon deposited catalysts in stripper quickly heat up to 680 DEG C and be fed directly to second reactor riser it is anti-
The bottom of device is answered, and is flowed up under the action of pre-lift steam.(9~57 DEG C) of light hydrocarbon feedstock enter second reactor
In contacted with the carbon deposited catalyst from stripper carry out catalytic conversion reaction.The weight ratio of light hydrocarbons and heavy hydrocarbon oil raw material
For 0.2:1.Reaction oil agent mixture from second reactor is further introduced into third reactor fluidized bed in leg outlet
Further reaction, oil gas (the second product) and the second carbon deposited catalyst enter through fluidized-bed reactor after reaction divides in settler
From the second carbon deposited catalyst isolated enters stripper by gravity and stripped.From first reactor and third
The reaction oil gas of reactor is drawn from settler together, is introduced product separation system and is carried out product separation, obtains gaseous product
With various product liquids, while being partially separated to obtain light hydrocarbons.It is catalyzed from the carbon deposit of first reactor and second reactor
Agent is in stripper after stripping, and a part is directly returned and is recycled in second reactor, remaining is conveyed through the first spent agent
Pipe returns in the oxygen-containing fluidization regions of regenerator, and whole carbon deposited catalysts are contacted with heated air and 700 in regenerator
Aerobic regeneration is carried out at DEG C, the regenerated catalyst for obtaining heat, which returns in first reactor, to be recycled.Regenerator adds outer take
Hot equipment takes superfluous heat, control reaction thermal balance and regenerator regeneration temperature away.First is detected during continuous operation
The carbon deposit content and the second catalytic cracking catalyst (the second regeneration catalyzing of catalytic cracking catalyst (the first regenerated catalyst)
Agent) carbon deposit content and carbon deposit hydrogen mass fraction.Prevailing operating conditions and result are listed in table 3.Prevailing operating conditions and result
It is listed in table 3.
Embodiment 2
Embodiment 2 illustrates that the method that the disclosure provides reduces the effect of dry gas and coke yield during hydrocarbon oil catalytic conversion
Fruit.
The reaction unit of use is the same as embodiment l.Raw material, major experimental step are with embodiment l, except that selects is light
Matter hydro carbons boiling range is 9~205 DEG C.The weight ratio of light hydrocarbons and heavy hydrocarbon oil raw material is 0.25:1.Prevailing operating conditions and knot
Fruit is listed in table 3.In the anaerobic fluidization regions of regenerator, introducing a part of fluidized gas, (ordinary nitrogen is selected in laboratory, in standard shape
Nitrogen content >=99.5 volume % under condition, oxygen content≤0.5 volume %).
Comparative example 3
Comparative example 3 illustrates that regenerator only has oxygen-containing fluidization regions, and the second catalytic cracking catalyst is in stripper
Hydrocarbon oil catalytic conversion mistake when 500 DEG C of carbon deposited catalysts are mixed with the regenerated catalyst from 680 DEG C of regenerator by the weight ratio of 1:1
The effect of journey.
Using tool, there are three successive reaction-regenerative operation middle- scale devices of reactor to be tested, wherein the first reaction
Device is riser, and it is highly 3800 millimeters that the internal diameter of riser reactor, which is 16 millimeters,.Second reactor is to promote tube reaction
Device, internal diameter are 16 millimeters, are highly 3200 millimeters.The outlet of second riser reactor introduces fluidized-bed reactor, and fluidized bed is anti-
The internal diameter for answering device is 64 millimeters, is highly 300 millimeters.
First catalytic cracking catalyst is 680 DEG C of temperature of regenerated catalyst, through the first catalytic cracking catalyst inclined tube into
Enter the bottom of the riser reactor of first reactor, and is flowed up under the action of pre-lift steam.Heavy hydrocarbon oil raw material
(main character is shown in Table 2) preheated stove heating sprays into first instead to after mix after 350 DEG C with atomization water vapour, through feed nozzle
It answers in device, is contacted with the regenerated catalyst of heat and carry out catalytic conversion reaction.Reaction oil gas (the first product) and the catalysis of the first carbon deposit
Agent enters from first reactor leg outlet carries out quick separating in settler, the first carbon deposited catalyst enters stripper.
Second catalytic cracking catalyst presses 1:1 for the carbon deposited catalyst from stripper and from 680 DEG C of regenerator of regenerated catalyst
Weight ratio mixing.The bottom of riser reactor of the stripper bottom through the second reclaimable catalyst delivery pipe and second reactor
It is connected, and electric heating facility is set in the second spent agent delivery pipe, 500 DEG C of carbon deposited catalysts in stripper is quickly heated
To 520 DEG C and be fed directly to second reactor riser reactor bottom, while by regenerated catalyst through second catalysis
Cracking catalyst inclined tube is also delivered to the bottom of the riser reactor of second reactor, and under the action of pre-lift steam to
Upper flowing.(9~57 DEG C) of light hydrocarbon feedstock enter in second reactor and contact and be catalyzed with the second catalytic cracking catalyst
Conversion reaction.The weight ratio of light hydrocarbons and heavy hydrocarbon oil raw material is 0.25:1.Reaction finish mixing from second reactor
Object is further introduced into third reactor fluidized bed in leg outlet and further reacts, oil gas (the second product) and second after reaction
Carbon deposited catalyst enters through fluidized-bed reactor to be separated in settler, the second carbon deposited catalyst isolated by gravity into
Enter to stripper.Reaction oil gas from first reactor and third reactor is drawn from settler together, introduces product point
Product separation is carried out from system, obtains gaseous product and various product liquids, while being partially separated to obtain light hydrocarbons.From
One reactor and the carbon deposited catalyst of second reactor in stripper after stripping, in a part directly return second reactor
It is recycled, remaining is returned to through the first spent agent delivery pipe in the oxygen-containing fluidization regions of regenerator, and whole carbon deposits are urged in regenerator
Agent is contacted with heated air and is regenerated at 700 DEG C, obtains the regenerated catalyst of heat, regenerated catalyst a part
It is mixed with the first carbon deposited catalyst from stripper and is sent into second reactor recycling, remaining is returned in first reactor
It is recycled.Regenerator adds outside heat removing equipment and takes superfluous heat, control reaction thermal balance and regenerator regeneration temperature away.?
The carbon deposit content and the second catalysis that the first catalytic cracking catalyst (the first regenerated catalyst) is detected during continuous operation are split
Change the carbon deposit content of catalyst (the second regenerated catalyst) and the hydrogen mass fraction of carbon deposit.Prevailing operating conditions and result are listed in table
3.Prevailing operating conditions and result are listed in table 3.
Embodiment 3
Embodiment illustrates that method provided by the invention reduces the effect of dry gas and coke yield during hydrocarbon oil catalytic conversion
Fruit.
The reaction unit of use is the same as embodiment l.Raw material, major experimental step are with embodiment l, except that selects is light
Matter hydro carbons boiling range is 145~235 DEG C.The weight ratio of light hydrocarbons and heavy hydrocarbon oil raw material is respectively 0.2:1.Prevailing operating conditions
Table 3 is listed in result.In the anaerobic fluidization regions of regenerator, introducing a part of fluidized gas, (ordinary nitrogen is selected in laboratory, is being marked
Nitrogen content >=99.9 volume % under quasi- situation, oxygen content≤0.1 volume %).
Table 1
Table 2
| Feedstock oil title | Reduced crude |
| Density (20 DEG C), kg/m3 | 891.6 |
| Element composition, % | |
| C | 86.20 |
| H | 13.06 |
| S | 0.28 |
| N | 0.29 |
| Basic nitrogen | 922 |
| Race's composition, % | |
| Saturated hydrocarbons | 59.0 |
| Aromatic hydrocarbons | 22.3 |
| Colloid | 18.3 |
| Asphalitine | 0.4 |
| Carbon residue, % | 5.44 |
| Kinematic viscosity, mm2/s | |
| 80℃ | 32.65 |
| 100℃ | 18.77 |
| Freezing point, DEG C | >50 |
| Refractive index, 70 DEG C | 1.4848 |
| Total acid number, mgKOH/g | 0.44 |
| Average molecular mass | 528 |
| Tenor, mg/kg | |
| Fe | 4.2 |
| Ni | 17.9 |
| Cu | <0.1 |
| V | 0.2 |
| Na | 0.3 |
| Ca | 0.7 |
| Zn | 0.9 |
| Volume boiling range is depressurized, DEG C | |
| IBP | 258.0 |
| 5% | 365.9 |
| 10% | 388.7 |
| 30% | 435.7 |
| 50% | 489.0 |
| 66.5% | 569.4 |
Table 3
Seen from table 3, the method that embodiment 1 is provided using the disclosure, the yield that propylene is produced in catalytic cracking is 18.89 weights
% is measured, and compared with comparative example 1,3.17 weight % of dry gas and the total reduction of coke yield.
Second catalytic cracking catalyst is using the carbon deposited catalyst after heating in comparative example 2, the hydrogen mass fraction of carbon deposit compared with
Height, although dry gas and coke yield decrease, productivity of propylene only has 15.92 weight %.And the second catalysis in embodiment 1
The hydrogen mass fraction of carbon deposit significantly reduces in Cracking catalyst, and compared with comparative example 2, dry gas and coke yield decline 1.60 weights
% is measured, productivity of propylene increases by 2.97 weight %.
Second catalytic cracking catalyst is that carbon deposited catalyst and regenerated catalyst after heating mix in comparative example 3, with
Comparative example 3 is compared, and the method that embodiment 2 is provided using the disclosure, the yield of preparing propylene through catalytic conversion is up to 18.72 weight %
When, dry gas and coke yield amount to reduction to 1.91 weight %.
In embodiment 3, using the reaction condition of opposite mitigation, when productivity of propylene is up to 17.11 weight %, dry gas yied is only
There are 4.22 heavy %, coke yield only has 8.04 weight %.
The preferred embodiment of the disclosure is described in detail in conjunction with attached drawing above, still, the disclosure is not limited to above-mentioned reality
The detail in mode is applied, in the range of the technology design of the disclosure, a variety of letters can be carried out to the technical solution of the disclosure
Monotropic type, these simple variants belong to the protection scope of the disclosure.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the disclosure to it is various can
No further explanation will be given for the combination of energy.
In addition, any combination can also be carried out between a variety of different embodiments of the disclosure, as long as it is without prejudice to originally
Disclosed thought equally should be considered as disclosure disclosure of that.
Claims (16)
1. a kind of catalysis conversion method for reducing dry gas and coke yield, which is characterized in that this method comprises:
Heavy hydrocarbon oil raw material is set to contact progress the first catalysis reaction with the first catalytic cracking catalyst in the first reactor, it will be anti-
It answers gained mixture to separate in settler into qi-promoting prescription, obtains the first carbon deposited catalyst and the first product；
Light hydrocarbons are made to contact progress the second catalysis reaction with the second catalytic cracking catalyst in the second reactor, by described the
The reaction mixture comprising catalyst that two reactors obtain introduces third reactor and continues third catalysis reaction, by third
Reaction mixture obtained by reactor is in the settler into isolated second carbon deposited catalyst of qi-promoting prescription and the second product, institute
The boiling range for stating light hydrocarbons is 8~253 DEG C；
First carbon deposited catalyst and the second carbon deposited catalyst are introduced into stripper and are stripped, by first part through stripping
The oxygen-containing fluidization regions that rear catalyst introduces regenerator carry out aerobic regeneration, obtain the first regenerated catalyst, make described first again
Raw catalyst is sent into first reactor as first catalytic cracking catalyst；
The anaerobic fluidization regions that catalyst of the second part after stripping introduces regenerator are subjected to anaerobic again at 600~800 DEG C
It is raw, the second regenerated catalyst is obtained, second regenerated catalyst is made to be sent into second as second catalytic cracking catalyst
In reactor；
First product and the second product are introduced into product separation system and carry out product separation, obtains including that low-carbon alkene produces
Object, gasoline product, the separation product of diesel product and heavy oil product.
2. according to the method described in claim 1, wherein, this method further include: the fluidized gas by oxygen content less than 3 volume %
It is introduced into anaerobic fluidization regions, the fluidized gas contains the inert gas not less than 97 volume %, and the inert gas is selected from nitrogen
At least one of gas, helium, neon, argon, krypton and xenon.
3. according to the method described in claim 1, wherein, the anaerobic fluidization regions of the regenerator include: low temperature catalyst conveying
Pipe (921), catalyst distributor (923), takes hot comb (924), deaeration pipe (925) and high-temperature catalytic at gas-solid separator (922)
Agent delivery pipe (926)；
One end of the low temperature catalyst delivery pipe (921) is connected to the stripper (7), and the other end is connected with gas-solid separator
(922), the lower section of the gas-solid separator (922) have catalyst distributor (923) and with the catalyst distributor (923)
Connection takes hot comb (924), described to take the pipeline that hot comb (924) are arranged in vertical for multiple groups and bottom end is connected to, institute
It states deaeration pipe (925) and is connected to and described take the lower end of hot comb (924) and offer fluidized gas entrance (927), institute in junction
Stating deaeration pipe (925) is the standpipe that lower end is connected with the high temperature catalyst delivery pipe (926), the high temperature catalyst delivery pipe
(926) it is connected to the second reactor (2).
4. the temperature of first regenerated catalyst is 560~800 DEG C according to the method described in claim 1, wherein, with the
On the basis of the dry weight of one regenerated catalyst, the carbon deposit content of first regenerated catalyst is 0.01~0.1 weight %.
5. the temperature of second regenerated catalyst is 560~800 DEG C according to the method described in claim 1, wherein, with the
On the basis of the dry weight of two regenerated catalysts, the carbon deposit content of second regenerated catalyst is 0.5~1.9 weight %, excellent
It is selected as 0.9~1.3 weight %, further preferably 0.91~0.99 weight %.
6. described on the basis of the weight of the carbon deposit in the second regenerated catalyst according to the method described in claim 5, wherein
Hydrogen content in the carbon deposit of second regenerated catalyst is 0.1~0.65 weight %, preferably 0.1~0.5 weight %.
7. according to the method described in claim 1, wherein, the heavy hydrocarbon oil raw material is selected from petroleum hydrocarbon oil, synthetic oil, coal liquid
At least one of carburetion, tar sand oil and shale oil, preferably petroleum hydrocarbon oil, the petroleum hydrocarbon oil be selected from AGO (atmospheric gas oil),
At least one of vacuum gas oil (VGO), coker gas oil, deasphalted oil, hydrogenation tail oil, reduced crude, decompression residuum and crude oil.
8. according to the method described in claim 7, wherein, the average molecular mass of the heavy hydrocarbon oil raw material is not less than
200。
9. according to the method described in claim 1, wherein, the light hydrocarbons are 9~160 DEG C, further preferably 9~60
℃；
On the basis of the total weight of the light hydrocarbons, the olefin(e) centent of the light hydrocarbons is 30~90 weight %, preferably
45~90 weight %.
10. according to the method described in claim 1, wherein, the light hydrocarbons are at least partially from the product segregative line
In the separation product of system.
11. according to the method described in claim 1, wherein, the weight ratio of the light hydrocarbons and the heavy hydrocarbon oil raw material is
(0.01~0.6): 1, preferably (0.05~0.3): 1.
12. according to the method described in claim 1, wherein, first catalytic cracking catalyst and the second catalytic cracking are catalyzed
The respective shape-selective zeolite containing average pore size less than 0.7 nanometer of agent, the shape-selective zeolite be selected from MFI structure zeolite,
At least one of ferrierite, chabasie, dachiardite, erionite, type A zeolite, epistilbite and laumontite.
13. according to the method described in claim 1, wherein, the operating condition of the first catalysis reaction includes: that reaction temperature is
480~600 DEG C；Reaction time is 0.5~10 second；Agent oil weight ratio is (5~15): 1；Water oil weight ratio is (0.05~1): 1.
14. according to the method described in claim 1, wherein, the operating condition of the second catalysis reaction includes: that reaction temperature is
520~750 DEG C；Reaction time is 0.1~3 second；Agent oil weight ratio is (6~40): 1；Water oil weight ratio is (0.1~1): 1.
15. according to method described in claim l, wherein the first reactor and the second reactor are respectively and are selected from
Riser reactor, downer reactor, fluidized-bed reactor, riser and down pipe compound reactor, riser and fluidisation
One of bed compound reactor, down pipe and fluidized bed compound reactor.
16. the third is reacted according to the method described in claim 1, wherein, the third reactor is fluidized-bed reactor
The operating condition of device are as follows: reaction temperature is 450~750 DEG C, preferably 510~560 DEG C；Weight (hourly) space velocity (WHSV) is 1~30h-1；Settler
Absolute pressure be 0.15~0.40MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| US11401475B2 (en) | 2020-03-13 | 2022-08-02 | Lummus Technology Llc | Production of light olefins from crude oil via fluid catalytic cracking process and apparatus |
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