CN103769196B - A kind of residual oil hydrocatalyst, its preparation method and application thereof - Google Patents
A kind of residual oil hydrocatalyst, its preparation method and application thereof Download PDFInfo
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Abstract
A kind of residual hydrocracking catalyst, on the basis of catalyst total amount, contains the hydrated ferric oxide of 2wt%～20wt%, the molecular sieve of 27wt%～55wt%, the heat-resistant inorganic oxide carrier of 30wt%～70wt% in this catalyst.Preferably described catalyst is made up of hydrated ferric oxide and catalytic cracking spent catalyst.This catalyst can use coprecipitation method to prepare, and this catalyst is when residual hydrocracking is reacted, and in terms of Fe, the addition of catalyst is 0.1wt%～1.0wt% of residual oil raw material.The catalyst that the present invention provides is suitable for asphalitine and the high super-viscous oil of tenor, the hydrocracking process of poor residuum, has preparation method simple, without noble metal, low cost, the advantage that yield of light oil is high.
Description
Technical field
The present invention relates to the residual hydrocracking catalyst of a kind of fecund light Fuel, the preparation of this catalyst
Method, and use the residual oil hydrocracking process of this catalyst.
Background technology
Oil is produced by the heaviness day by day of world petroleum resource and in poor quality problem and economic quickly increasing
The contradiction that the demand of product grows with each passing day so that heavy oil lighting technology is increasingly paid close attention to, wherein by each refinery
Slurry bed system resid hydrocracking process because of its can process high carbon residue, the inferior raw material of high tenor and have
Stronger competitiveness and preferable development prospect.Catalyst be resid hydrocracking process core technology it
One, for reducing reaction severity, improve reaction efficiency, improve oil yield, reduce coking yield, from
And reduce Residual cracking cost, improving its economic competitiveness has very important effect.
The catalyst that slurry bed system Residue Hydrotreating Technology uses is divided into pressed powder, oil-soluble Organometallic compounds
Thing, water soluble compound etc..Oil-soluble organo-metallic catalyst has preferable dispersibility and catalysis is lived
Property, yield of light oil can be effectively improved, but oil-soluble organo-metallic catalyst is the most poisonous, and organic
In metallic compound, the content of metal active constituent is low, and when measuring with metal, usage amount is big, and cost is high.Water
Compound containing active metal generally need to be distributed to alcohols or alcohol/aqueous mixtures by solube metallic catalyst
In solution, reach homodisperse purpose in oil, but need moisture removal before processing, to reduce
Reaction stagnation pressure or the reduction water corrosion to reaction unit.
Solid powder th-1 catalyst is a kind of to apply more residual oil slurry bed system hydrocracking catalyst, such as residual oil
Slurry bed system is hydrocracked in prior art employing ferrous sulfate, mineral powder or coal dust and makees additive, and these are solid
Body fine catalyst has good load Jiao's performance, but it is big to there is addition, bad dispersibility in the feed,
The shortcoming serious to equipment attrition.
Fluid catalytic cracking is one of commonly used light materialization of heavy oil processing technique of oil plant.Used by it
Catalyst be a kind of catalyst that in oil refining process, application amount is maximum, the every annual consumption of China 80～
90kt.Catalytic cracking catalyst in use activity reduces, and needs supplement fresh periodically, quantitatively
Catalyst, draws off the dead catalyst inactivated simultaneously.Along with catalytic cracking process processes raw material residue ratio
The raising of example, the raising of the residual refining residual oil ratio of catalytic cracking spent catalyst, produce the amount of dead catalyst very
Greatly, the dead catalyst of upper kiloton is produced every year such as the device of year treating capacity 1,000,000 tons.Dead catalyst activity
Low, containing a certain amount of heavy metal, the most rationally dispose dead catalyst and be always what insider was paid close attention to
Problem.
CN101543783A proposes with the catalytic cracking spent catalyst through calcination process as carrier, load
Mo oxide or Mo Yu Ni, Fe compounding oxide as residual hydrocracking catalyst, described in urge
Agent uses incipient impregnation, then dry, high-temperature roasting, and active component is the unitary containing Mo or many
Unit's oxide, and Mo is expensive, if reclaiming, relatively costly.
Summary of the invention
One of the technical problem to be solved in the present invention is on the basis of prior art, it is provided that a kind of new residual oil
Hydrocracking catalyst.
The two of the technical problem to be solved in the present invention are to provide above-mentioned new residual hydrocracking catalyst
Preparation method.
The three of the technical problem to be solved in the present invention are on the basis of existing technology, it is provided that a kind of fecund is light
The residual oil hydrocracking process of matter hydrocarbon ils.
A kind of residual hydrocracking catalyst, on the basis of catalyst total amount, contains in this catalyst
The hydrated ferric oxide of 2wt%～20wt%, the molecular sieve of 27wt%～55wt%, 30wt%～70wt%
Heat-resistant inorganic oxide carrier.
Preferably, described catalyst is possibly together with the transition metal oxide of 0.2wt%～3wt%；Institute
Stating transition metal is one or more in nickel, vanadium and ferrum.
In the catalyst that the present invention provides, the molecular formula of described hydrated ferric oxide is FeOOH, also known as
For FeOOH, selected from goethitum (alpha-feooh), lepidocrocite (γ-FeOOH) and akaganeite
One or more in (β-FeOOH).Described molecular sieve is selected from Y type molecular sieve and/or has MFI
One or more in the molecular sieve of structure, described heat-resistant inorganic oxide carrier is selected from aluminium oxide, oxygen
One or more in SiClx, Kaolin and kieselguhr.
The residual oil hydrocatalyst that the present invention provides, can be by molecular sieve and heat-resistant inorganic oxide and transition
Metallic compound is prepared as pressed powder through making beating, spray drying and impregnating method, then with hydration oxygen
Change ferrum pressed powder mix homogeneously, presented in two kinds of pressed powder physical mixed.Can also be by water
Close ferrum oxide to be carried on the pressed powder containing molecular sieve and heat-resistant inorganic oxide, with loaded catalyst
Presented in.The hydrated ferric oxide individually existed with powdery uses the sedimentation method to prepare, and is carried on solid powder
Coprecipitation is used to prepare during end.
Preferably, the residual oil hydrocatalyst that the present invention provides is by the useless catalysis of hydrated ferric oxide and catalytic cracking
Agent forms.Described catalytic cracking spent catalyst is the catalytic cracking of the inactivation discharged in catalytic cracking unit
Catalyst or industry poising agent.Usually, catalytic cracking spent catalyst is containing Y type molecular sieve and/or tool
There is the catalyst of the molecular sieve of MFI structure, also can be containing heat-resistant inorganic oxide or the change containing transition metal
Compound.
Described catalytic cracking spent catalyst preferably comprises one or more metals in nickel, vanadium and ferrum,
Under preferable case, on the basis of total catalyst weight, in terms of metal, in described catalytic cracking spent catalyst
Total metal content is 1wt%～5wt%, more preferably 1wt% ~ 3wt%.Preferably described catalytic cracking is given up
The pore volume of catalyst is 0.05 ~ 0.5ml/g, more preferably 0.08 ~ 0.2ml/g.The most described catalytic cracking
On dead catalyst, coke content is less than 0.5wt%.
In the method that the present invention provides, micro-reactivity of described catalytic cracking spent catalyst is 20～70,
Preferably 30～60.Wherein said micro-activity refers to that placing 5.0g in micro fixed-bed reactor treats
Surveying catalyst, using 235 ~ 337 DEG C of huge port light diesel fuel is standard raw materials, reaction temperature be 460 DEG C,
Weight space velocity 16h-1, oil ratio be 3.2 reaction condition under carry out react 70s, in gained product
(< 204 DEG C of gasoline+gas+coke) quality accounts for the percent of combined feed.
The present invention provide method in, described catalytic cracking spent catalyst through roasting, flour, sieve,
Particle diameter is less than 150 μm, preferably 100 μm.Catalytic cracking spent catalyst roasting is to reduce catalyst
On carbon deposit, expose more active sites, sintering temperature 450～750 DEG C, preferably 500～650 DEG C.
In the catalyst that the present invention provides, on the basis of total catalyst weight, in terms of ferrum, described hydration
The content of ferrum oxide is 0.5wt%～20wt%, preferably 1wt%～15wt%, more preferably 2wt%～
10wt%.
In the catalyst that the present invention provides, described residual oil hydrocatalyst is aqua oxidation iron powder and urge
Change the mixture of cracking dead catalyst.Or for loading the shape of hydrated ferric oxide on catalytic cracking spent catalyst
Formula.
Wherein, the residual oil hydrocatalyst provided as the present invention is that aqua oxidation iron powder is given up with catalytic cracking
During the mixture of catalyst, the preparation method of residual oil hydrocatalyst comprises the following steps:
(1) water solublity iron containing compounds is dissolved in water, adds appropriate dispersion aids, mix homogeneously；
(2) mixed solution that step (1) obtains adds alkali compounds；
(3) in step (2) gained mixture, it is passed through oxygen-containing gas；
(4) step (3) gained mixture through filtering, washing, dried, pulverize and obtain aqua oxidation
Iron powder；
(5) aqua oxidation iron powder and catalytic cracking spent catalyst are mixed in proportion obtain residual hydrogenation
Cracking catalyst.
The present invention provide method for preparing catalyst in, described dispersion aids selected from ethylenediamine, glutamic acid,
Mixing of one or more in ethylenediaminetetraacetic acid (EDTA), tartaric acid, diammonium phosphate and citric acid
Compound；Dispersion aids is 1:500 ~ 1:100 with the mol ratio of Fe.
In the method for preparing catalyst that the present invention provides, described dispersion aids is selected from ethylenediaminetetraacetic acid
And/or diammonium phosphate (EDTA)；Dispersion aids is 1:300 ~ 1:100 with the mol ratio of Fe.
In the method for preparing catalyst that the present invention provides, described water solublity iron containing compounds is selected from sulphuric acid
One or more in ferrum, ferrous sulfate, Ferrous acetate, ferric nitrate and ferrous chloride.
The present invention provide method for preparing catalyst in, described alkali compounds selected from ammonia, ammonia,
One or more in sodium hydroxide solution, sodium carbonate liquor, alkali compounds with the mol ratio of Fe is
1.8~2.5。
In the method for preparing catalyst that the present invention provides, in described oxygen-containing gas, the volume content of oxygen is
20% ~ 100%, preferably air, it is 5 ~ 60 minutes that oxygen-containing gas is passed through the time.
In the preparation method that the present invention provides, the operation temperature of described step (1) ~ (3) is 15 ~ 40
℃.The dry drying means that this area can be used conventional in step (4), as dry at 80～120 DEG C
Dry at least 2 hours.
In the preparation method that the present invention provides, described catalytic cracking spent catalyst and water soluble iron compound
Use ratio so that the residual oil hydrocatalyst prepared meet, on the basis of total catalyst weight,
In terms of ferrum, the content of described hydrated ferric oxide is 0.5wt%～20wt%, preferably 1wt%～15wt
%, more preferably 2wt%～10wt%.
The present invention provide containing hydrated ferric oxide and the residual oil hydrocatalyst of catalytic cracking spent catalyst
Preparation method two, use coprecipitation to prepare on catalytic cracking spent catalyst load hydrated ferric oxide slag
Oil hydrogenation catalysts.Comprise the following steps:
(1) iron containing compounds is dissolved in water, adds appropriate dispersion aids, mix homogeneously；
(2) catalytic cracking spent catalyst is added in the mixed solution of step (1), be simultaneously introduced alkalescence
Compound；
(3) in step (2) gained mixture, it is passed through oxygen-containing gas；
(4) step (3) gained mixture through filtering, after washing, dried, obtain residual hydrogenation and urge
Agent.
Wherein, the dispersion aids described in step (1) is selected from ethylenediamine, glutamic acid, ethylenediamine tetrem
The mixture of one or more in acid, tartaric acid, diammonium phosphate and citric acid；Dispersion aids with
The mol ratio of Fe is 1:500 ~ 100.
Water solublity iron containing compounds described in step (1) is selected from iron sulfate, ferrous sulfate, acetic acid Asia
One or more in ferrum, ferric nitrate and ferrous chloride.
Alkali compounds described in step (2) is selected from ammonia, ammonia, sodium hydroxide solution and carbonic acid
One or more in sodium solution, alkali compounds is (1.8 ~ 2.5) with the mol ratio of Fe: 1.
Described in step (3), in oxygen-containing gas, the volume content of oxygen is 20% ~ 100%, oxygen-containing gas
The time of being passed through is 5 ~ 60 minutes.
The presoma of iron containing compounds dissolves and mixes employing coprecipitation, temperature with catalytic cracking spent catalyst
Control to 20～90 DEG C, preferably 30 DEG C～60 DEG C.
Being dried in step (4) can use drying means conventional in the art, and this is not had by the present invention
Restricted, such as baking temperature is 80～120 DEG C, and drying time is 1～24 hour, preferably 1 ~ 2 little
Time.
Described catalytic cracking spent catalyst and the use ratio of water soluble iron compound so that prepare
Residual oil hydrocatalyst meet, on the basis of total catalyst weight, in terms of ferrum, described aqua oxidation
The load capacity of ferrum is 0.5wt%～20wt%, preferably 1wt%～15wt%, more preferably 2wt%～
10wt%。
Present invention additionally comprises the catalyst prepared according to above-mentioned method for preparing catalyst.
A kind of residual oil hydrocracking process, mixes any of the above-described kind of residual hydrocracking catalyst and auxiliary agent
After be scattered in residual oil raw material, carry out hydrocracking reaction in presence of hydrogen, reaction product is separated
After obtain product oil；Wherein, described described auxiliary agent is Cosan and/or sulfur-containing compound.
In the method for hydrogen cracking that the present invention provides, the addition of described residual oil hydrocatalyst is by wherein
Fe meter, for 0.1wt%～5.0wt% of residual oil raw material；Described auxiliary agent based on S therein, S/Fe
Molar ratio be 1～2.
In the method for hydrogen cracking that the present invention provides, described residual oil is direct selected from petroleum refining process, coal
Liquefaction and oil coal face initial boiling point that the hydrogen process of refining altogether the obtains heavy hydrocarbon more than 350 DEG C.
The present invention provide method for hydrogen cracking in, described heavy hydrocarbon selected from reduced crude, decompression residuum,
In heavy catalytic cycle oil, catalytic cracked oil pulp, Aromatics Extractive Project oil, visbreaker tar and coking heavy oil
One or more.
In the method for hydrogen cracking that the present invention provides, described residual hydrocracking reaction is divided into two rank
Section, first stage reaction condition is: temperature 300～380 DEG C, pressure 8～20MPa, the response time 5～
60 minutes, preferably 10～30 minutes；Second stage reaction condition is: temperature 380～470 DEG C, preferably
420～460 DEG C, pressure 8～22MPa, preferably 12～20MPa, response time 10～90 minutes, excellent
Select 15～60 minutes.
Compared with prior art, the residual oil hydrocatalyst that the present invention provides contains hydrated ferric oxide, molecule
Sieve and transition metal oxide, can be catalyzed residual hydrocracking, fecund light hydrocarbon oil.Preferably by being hydrated
Ferrum oxide and the catalyst of catalytic cracking spent catalyst composition, can recycle the useless of catalytic cracking unit
Catalyst, cheap.Further, since catalytic cracking catalyst has certain faintly acid, be conducive to
Colloid, the cracking of asphalitine macromole in residual oil, in product, light ends oil yield is high, and catalysis simultaneously is split
Change also deposition on dead catalyst and have the heavy metals such as a certain amount of Ni, V and Fe, in hydrocracking process
Active component can be partially converted into, improve hydrogenation activity, suppression asphalitine green coke.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further illustrated, but the most therefore makes the present invention be subject to
Any restriction.
Tahe oil plant taken from by residual oil, and character is shown in Table 1.Catalytic cracking spent catalyst (trade name
MLC-500, is produced by catalyst asphalt in Shenli Refinery of China Petrochemical Corp.), catalytic cracking is given up
(trade name ARC-1S is divided public affairs by Sinopec Group's catalyst Shandong to catalyst
Department produces), through 500 DEG C of roastings 2 hours, grind passing-screen size into powder less than 150 μm, be designated as respectively FCC～
1、FCC~2.Character is shown in Table 2.
The preparation method of the residual oil hydrocatalyst that the embodiment 1～5 explanation present invention provides.
Embodiment 1
50.0g ferrous sulfate heptahydrate and 0.20gEDTA being dissolved in 400g deionized water, stirring is all
Even, separately take 25.0g ammonia and instill above-mentioned solution while stirring, be passed through air and continue to stir 20min,
Then carry out sucking filtration, washing, obtain filter cake and be dried 2 hours in 105 DEG C, pulverize and sieve and obtain powdery
Iron containing compounds, is designated as Fe～1.Prepared Fe ~ 1 and FCC-1 are mixed with the ratio of 1:5
To residual oil hydrocatalyst A1.
Embodiment 2
Weigh 35g ferrous sulfate heptahydrate and 0.12g ammonium dihydrogen phosphate and put into beaker, add 200g go from
Sub-water is stirred continuously dissolving, weighs FCC～1 dose of 50.0g and adds in above-mentioned solution, while stirring will
Be added dropwise over 17g ammonia, drip complete, be passed through air and continue stir 20min, then sucking filtration,
Washing, obtains filter cake and is dried 3 hours in 105 DEG C, pulverize and sieve and obtain residual oil hydrocatalyst A2.
In A2, the content of hydrated ferric oxide is 18.2wt%, and the content of catalytic cracking spent catalyst is 81.8wt
%。
Embodiment 3
Weigh 9.4g Ferrous acetate and 0.05gEDTA puts into beaker, add 100g deionized water continuous
Stirring and dissolving, weighs FCC～1 dose of 50.0g and adds in copperas solution, while stirring will dropwise
Add 7.0g ammonia, drip complete, be passed through air and continue to stir 30min, then sucking filtration, washing,
Obtain filter cake to be dried 2 hours in 105 DEG C, pulverize and sieve and obtain residual oil hydrocatalyst and be designated as A3.
In A3, the content of hydrated ferric oxide is 8.5wt%, and the content of catalytic cracking spent catalyst is 91.5wt
%。
Embodiment 4
Weigh 27.50g ferrous sulfate heptahydrate and 0.08g citric acid and put into beaker, add 150g go from
Sub-water is stirred continuously dissolving, weighs FCC～2 doses of 50.0g and adds in copperas solution, and limit is stirred
Limit will be added dropwise over 14g ammonia, drip complete, be passed through air and continues to stir 20min, then take out
Filter, washing, obtain filter cake and be dried 3 hours in 105 DEG C, and the residual hydrogenation obtained that pulverizes and sieves is catalyzed
Agent A4.In A4, the content of hydrated ferric oxide is 15wt%, and the content of catalytic cracking spent catalyst is
85wt%。
Embodiment 5
Weigh 5.8g iron chloride and 0.02g ethylenediamine puts into beaker, add 100g deionized water continuous
Stirring and dissolving, weighs FCC～2 doses of 50.0g and adds in copperas solution, while stirring will dropwise
Add 5g ammonia, drip complete, be passed through air and continue to stir 20min, then sucking filtration, washing,
Obtaining filter cake to be dried 2 hours in 105 DEG C, the residual oil hydrocatalyst obtained is designated as A5.Water in A5
The content closing ferrum oxide is 6wt%, and the content of catalytic cracking spent catalyst is 94wt%.
The residual oil hydrocracking process of the embodiment 6～10 explanation present invention, and the residual hydrogenation of the present invention
Catalyst is for the effect of residual hydrocracking.
Embodiment 6
The residual oil by 400g residual oil, being calculated as residual oil raw material weight 0.3% with Fe and catalyst A1 and
1.0g sulfur adds in High Temperature High Pressure stirred tank, stirs, sealing, hydrogen first pressing 9.0MPa,
350 DEG C, react 15min；It is continuously heating to 430 DEG C, reacts 30min.React complete on 180 DEG C of left sides
Right release, simultaneously meter gaseous amount sampling analysis gas composition, bottom product extracts through normal hexane, returns
Send simulation distillation after receiving solvent, then obtain Colophonium and Jiao after toluene extracting normal hexane insoluble matter.Residual oil
Matter is shown in Table 1, and reaction result is shown in Table 3.
Using distillate yield and bottoms conversion as the leading indicator of catalyst performance evaluation.
Computational methods are as follows:
Yield of light oil=less than 350 DEG C of fraction section quality/raw oil quality × 100%
Distillate yield=less than 524 DEG C of fraction section quality/raw oil quality × 100%
Liquid yield=liquid product mass/raw oil quality × 100%
Bottoms conversion=less than 524 DEG C of constituent mass (gassiness)/raw oil quality × 100%
Coking yield=(toluene insolubles quality～catalyst)/raw oil quality × 100%
Embodiment 7
Testing according to method same as in Example 6, except for the difference that prepared by catalyst embodiment 2
A2, addition is calculated as the 1.0% of residual oil raw material weight with Fe.The results are shown in Table 3.
Embodiment 8
Testing according to method same as in Example 6, except for the difference that prepared by catalyst embodiment 3
A3, addition is calculated as the 0.5% of residual oil raw material weight with Fe.The results are shown in Table 3.
Embodiment 9
Testing according to method same as in Example 6, except for the difference that prepared by catalyst embodiment 4
A4, addition is calculated as the 0.3% of residual oil raw material weight, reaction temperature 450 DEG C with Fe.The results are shown in Table
3。
Embodiment 10
Testing according to method same as in Example 6, except for the difference that prepared by catalyst embodiment 5
A5, addition is calculated as the 0.3% of residual oil raw material weight, response time 60min with Fe.The results are shown in Table
3。
Comparative example 1
Test according to method same as in Example 6, except for the difference that use catalyst only to use embodiment
The Fe～1 of 1 preparation, is not added with waste acetic acid, and addition is calculated as residual oil raw material weight with Fe
0.3%.The results are shown in Table 3.
Comparative example 2
Test according to method same as in Example 6, except for the difference that use catalyst only with FCC～
1, addition is the 3% of residual oil raw material weight.The results are shown in Table 3.
Table 1
| Analysis project | Residual oil |
| Density (20 DEG C)/(g/cm3) | 1.0101 |
| Kinematic viscosity, mm2/s | |
| 80℃ | >5000 |
| 100℃ | 1069 |
| Carbon residue, w% | 18.8 |
| Metal analysis, μ g/g | |
| Fe | 11.2 |
| Ni | 54.1 |
| V | 310 |
| Elementary analysis/weight % | |
| C | 85.78 |
| H | 10.37 |
| S | 3.1 |
| N | 0.58 |
| O | 0.17 |
| Four components/weight % | |
| Saturated point | 26.6 |
| Aromatic hydrocarbons | 37.8 |
| Colloid | 20.6 |
| Asphalitine | 15.0 |
Table 2
| Analysis project | FCC～1 | FCC～2 |
| Specific surface area/(m2/ g) | 135 | 105 |
| Pore volume/(ml/g) | 0.16 | 0.11 |
| Bulk density/(g/cm3) | 0.77 | 0.75 |
| Fe content/(μ g/g) | 3500 | 8200 |
| Ni content/(μ g/g) | 5400 | 2100 |
| V content/(μ g/g) | 4000 | 6100 |
| Micro-activity/% | 60 | 55.5 |
| Molecular sieve content/% | 29.1 | 40.2 |
| Heat-resistant inorganic oxide content/% | 69.6 | 58.1 |
Table 3
By embodiment in table 3 6～10 compared with comparative example, it can be seen that use of the present invention
Catalyst and residual oil hydrocracking process, bottoms conversion at least improves 3.5 percentage points, and liquid is received
Rate improve more than 5 percentage points, and the product slates of liquid yield be improved significantly, distillate receive
Rate significantly improves, and the yield of light oil less than 350 DEG C is more than 49%, and coking yield also decreases,
Illustrate that catalyst of the present invention has the good performance that is hydrocracked to residual oil, and can light oil with high yield.
Claims (23)
1. a residual hydrocracking catalyst, it is characterised in that described catalyst is by aqua oxidation
Ferrum and catalytic cracking spent catalyst composition, on the basis of catalyst total amount, in this catalyst containing 2wt%～
The hydrated ferric oxide of 20wt%, the molecular sieve of 27wt%～55wt%, 30wt%'s～70wt% is heat-resisting
Inorganic oxide carrier；Micro-reactivity of described catalytic cracking spent catalyst is 20～70.
2. according to the catalyst of claim 1, it is characterised in that described catalytic cracking spent catalyst
Particle diameter less than 150 μm.
3. according to the catalyst of claim 1, it is characterised in that described catalytic cracking spent catalyst
Pore volume be 0.05～0.5ml/g.
4. according to the catalyst of claim 1, it is characterised in that on described catalytic cracking spent catalyst
Coke content is less than 0.5wt%.
5. according to the catalyst of any one in claim 1-4, it is characterised in that described residual hydrogenation
Cracking catalyst is the mixture of aqua oxidation iron powder and catalytic cracking spent catalyst.
6. according to the catalyst of any one in claim 1-4, it is characterised in that described residual hydrogenation
Cracking catalyst is load hydrated ferric oxide on catalytic cracking spent catalyst.
7. the preparation method of claim 5 catalyst, it is characterised in that comprise the following steps:
(1) water solublity iron containing compounds is dissolved in water, adds appropriate dispersion aids, mix homogeneously；
(2) mixed solution that step (1) obtains adds alkali compounds；
(3) in step (2) gained mixture, it is passed through oxygen-containing gas；
(4) step (3) gained mixture through filtering, washing, dried, pulverize and obtain aqua oxidation
Iron powder；
(5) aqua oxidation iron powder is mixed with catalytic cracking spent catalyst.
8. according to the method for claim 7, it is characterised in that described dispersion aids selected from ethylenediamine,
One or more in glutamic acid, ethylenediaminetetraacetic acid, tartaric acid, diammonium phosphate and citric acid
Mixture；Dispersion aids is 1:500～1:100 with the mol ratio of Fe.
9. according to the method for claim 8, it is characterised in that described dispersion aids is selected from ethylenediamine
Tetraacethyl and/or diammonium phosphate；Dispersion aids is 1:300～1:100 with the mol ratio of Fe.
10. according to the method for claim 7, it is characterised in that described water solublity iron containing compounds choosing
One or more in iron sulfate, ferrous sulfate, Ferrous acetate, ferric nitrate and ferrous chloride.
11. according to the method for claim 7, it is characterised in that described alkali compounds selected from ammonia,
One or more in sodium hydroxide and sodium carbonate, alkali compounds with the mol ratio of Fe is
(1.8～2.5): 1.
12. according to the method for claim 10, it is characterised in that in described oxygen-containing gas, oxygen content is
20%～100%, it is 5～60 minutes that oxygen-containing gas is passed through the time.
The preparation method of 13. claim 6 catalyst, it is characterised in that comprise the following steps:
(1) water solublity iron containing compounds is dissolved in water, adds appropriate dispersion aids, mix homogeneously；
(2) catalytic cracking spent catalyst is added in the mixed solution of step (1), be simultaneously introduced alkalescence
Compound；
(3) in step (2) gained mixture, it is passed through oxygen-containing gas；
(4) step (3) gained mixture through filtering, washing, dried, obtain residual hydrocracking
Catalyst.
14. according to the method for claim 13, it is characterised in that described dispersion aids is selected from second two
One or several in amine, glutamic acid, ethylenediaminetetraacetic acid, tartaric acid, diammonium phosphate and citric acid
The mixture planted；Dispersion aids is 1:500～100 with the mol ratio of Fe.
15. according to the method for claim 13, it is characterised in that described water solublity iron containing compounds
One or more in iron sulfate, ferrous sulfate, Ferrous acetate, ferric nitrate and ferrous chloride.
16. according to the method for claim 13, it is characterised in that described alkali compounds selected from ammonia,
One or more in sodium hydroxide and sodium carbonate, alkali compounds with the mol ratio of Fe is
(1.8～2.5): 1.
17. according to the method for claim 13, it is characterised in that in described oxygen-containing gas, oxygen content is
20%～100%, it is 5～60 minutes that oxygen-containing gas is passed through the time.
18. 1 kinds of residual oil hydrocracking process, it is characterised in that by any one in claim 1-4
It is scattered in residual oil raw material after residual hydrocracking catalyst and auxiliary agent mixing, adds in presence of hydrogen
Hydrogen cracking reaction, obtains product oil after reaction product is separated；Wherein said auxiliary agent be Cosan and
/ or sulfur-containing compound.
19. according to the method for hydrogen cracking of claim 18, it is characterised in that described residual hydrogenation
The addition of Cracking catalyst is based on Fe therein, for 0.1wt%～5.0wt% of residual oil raw material；Institute
The auxiliary agent stated is based on S therein, and the molar ratio of S/Fe is 1～2.
20. according to the method for hydrogen cracking of claim 19, it is characterised in that described residual oil is selected from
Petroleum refining process, DCL/Direct coal liquefaction and oil coal face initial boiling point that the hydrogen process of refining altogether obtains more than 350 DEG C of weights
Matter hydrocarbon.
21. according to the method for hydrogen cracking of claim 20, it is characterised in that described heavy hydrocarbon choosing
From reduced crude, decompression residuum, heavy catalytic cycle oil, catalytic cracked oil pulp, Aromatics Extractive Project oil,
One or more in visbreaker tar and coking heavy oil.
22. according to the method for hydrogen cracking of claim 18, it is characterised in that described residual hydrogenation
Cracking reaction is divided into two stages, and first stage reaction condition is: temperature 300～380 DEG C, pressure 8～
20MPa, response time 5～60 minutes；Second stage reaction condition is: temperature 380～470 DEG C, pressure
Power 8～22MPa, response time 10～90 minutes.
23. according to the method for hydrogen cracking of claim 22, it is characterised in that first stage reaction bar
Part: response time 10～30 minutes；Second stage reaction condition: temperature 420～460 DEG C, pressure 12～
20MPa, response time 15～60 minutes.
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| CN104437661B (en) * | 2014-12-29 | 2016-08-31 | 山东利丰达生物科技有限公司 | A kind of catalyst for dreg-oil suspension bed hydrogenation cracking and preparation method thereof |
| CN107709525B (en) * | 2015-09-30 | 2021-09-07 | 环球油品公司 | Slurry hydrocracking process using iron and particulate carbon catalyst |
| CN107670699B (en) * | 2016-08-01 | 2021-04-13 | 北京华石联合能源科技发展有限公司 | Heavy oil suspension bed hydrogenation catalyst adopting composite carrier |
| CN108067242B (en) * | 2016-11-15 | 2019-10-15 | 中国石油化工股份有限公司 | A kind of recycling and reusing method of hydrogenation catalyst dead meal |
| CN108620083B (en) * | 2017-03-24 | 2019-10-11 | 中国石油化工股份有限公司 | A kind of recycling and reusing method of hydrogenation catalyst dead meal |
| CN108311168B (en) * | 2017-12-13 | 2021-03-16 | 煤炭科学技术研究院有限公司 | Composite catalyst and preparation method and application thereof |
| CN108587675B (en) * | 2018-03-29 | 2020-06-09 | 南京大学连云港高新技术研究院 | Heavy oil viscosity reducing method |
| US10619110B2 (en) * | 2018-04-11 | 2020-04-14 | Saudi Arabian Oil Company | Hydrocracking and hydrotreating catalytic compositions comprising a zeolite and regenerated, spent catalyst and uses thereof |
| CN111111771A (en) * | 2019-12-25 | 2020-05-08 | 陕西延长石油（集团）有限责任公司 | Recycling method and application of catalytic cracking waste catalyst |
| CN115739070A (en) * | 2022-11-02 | 2023-03-07 | 润和科华催化剂(上海)有限公司 | Catalyst for residual oil hydrogenation in slurry bed and application method thereof |
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