CN103769196A - Residual oil hydrogenation catalyst, as well as preparation method and application thereof - Google Patents
Residual oil hydrogenation catalyst, as well as preparation method and application thereof Download PDFInfo
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Abstract
A residual oil hydrocracking catalyst is benchmarked against the total quantity of catalysts, and comprises 2 wt%-20 wt% of a ferric oxide hydrate, 27 wt%-55 wt% of a molecular sieve, and 30 wt%-70 wt% of a heat-proof inorganic oxide carrier. Preferably, the catalyst comprises the ferric oxide hydrate and a catalytic cracking spent catalyst. The catalyst can be prepared in a coprecipitation method, and according to Fe, the adding amount of the catalyst is 0.1 wt%-1.0 wt% of the amount of the residual oil raw material. The catalyst provided by the invention is suitable for hydrocracking asphaltene super heavy oil with high metallic content and inferior residual oil, has the advantages of simple preparation method, low cost, and high light oil yield, and does not contain noble metals.
Description
Technical field
The present invention relates to a kind of residual hydrocracking catalyst of voluminous light Fuel, the preparation method of this catalyst, and use the residual oil hydrocracking process of this catalyst.
Background technology
The contradiction that the heaviness day by day of world petroleum resource and in poor quality problem and economic rapid growth grow with each passing day to the demand of oil product, each refinery is more and more paid close attention to heavy oil lighting technology, wherein starch state bed residual hydrocracking technique and there is stronger competitiveness and good development prospect because of its inferior raw material that can process high carbon residue, high tenor.Catalyst is one of core technology of residual hydrocracking technique, for reducing reaction severity, improves reaction efficiency, improves oily yield, reduces coking yield, thereby reduces residual oil processing cost, and improving its economic competitiveness has very important effect.
The catalyst that slurry state bed Residue Hydrotreating Technology is used is divided into pressed powder, oil-soluble organo-metallic compound, water soluble compound etc.Oil-soluble organo-metallic catalyst has good dispersibility and catalytic activity, can effectively improve yield of light oil, but oil-soluble organo-metallic catalyst is conventionally poisonous, and in organo-metallic compound, the content of metal active constituent is low, while metering with metal, use amount is large, and cost is high.Water soluble metal catalyst need be distributed to the compound that contains active metal in alcohols or alcohol/aqueous mixtures solution conventionally, reach homodisperse object in oil, but before processing, need to remove moisture, to reduce reaction stagnation pressure or to reduce the corrosion of water to reaction unit.
Solid powder th-1 catalyst is a kind of more residual oil slurry state bed hydroprocessing Cracking catalyst of applying, as residual oil slurry state bed hydroprocessing cracking available technology adopting ferrous sulfate, mineral powder or coal dust are made additive, these solid powder th-1 catalysts have the good burnt performance of carrying, but exist addition large, bad dispersibility in raw material, the shortcoming serious to equipment attrition.
Fluid catalytic cracking is one of light materialization of heavy oil processing technology of generally adopting of oil plant.Its catalyst used is a kind of catalyst of application quantity maximum in oil refining process, and the every annual consumption of China is at 80～90kt.Catalytic cracking catalyst is activity decreased in use, needs regularly, fresh makeup catalyst quantitatively, draws off the dead catalyst of inactivation simultaneously.Along with the process raw material raising of residue ratio of catalytic cracking process, the raising of the residual refining residual oil ratio of catalytic cracking spent catalyst, the amount that produces dead catalyst is very large, as the annual dead catalyst that produces upper kiloton of device of year 1000000 tons for the treatment of capacities.Dead catalyst activity is low, contains a certain amount of heavy metal, and how rationally to dispose dead catalyst is the problem that insider pays close attention to always.
CN101543783A proposes take the catalytic cracking spent catalyst through calcination process as carrier, the composite oxide of load Mo oxide or Mo and Ni, Fe is as residual hydrocracking catalyst, described catalyst adopts incipient impregnation, then dry, high-temperature roasting, active component is monobasic or the multivariant oxide containing Mo, and Mo is expensive, if reclaim, cost is higher.
Summary of the invention
One of the technical problem to be solved in the present invention is on prior art basis, and a kind of new residual hydrocracking catalyst is provided.
Two of the technical problem to be solved in the present invention is to provide the preparation method of above-mentioned new residual hydrocracking catalyst.
Three of the technical problem to be solved in the present invention is on the basis of existing technology, and a kind of residual oil hydrocracking process of voluminous light hydrocarbon oil is provided.
A kind of residual hydrocracking catalyst, take catalyst total amount as benchmark, 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 also contains the transition metal oxide of 0.2wt%～3wt%; Described transition metal is one or more in nickel, vanadium and iron.
In catalyst provided by the invention, the molecular formula of described hydrated ferric oxide is FeOOH, also be called FeOOH, be selected from one or more in goethite (alpha-feooh), lepidocrocite (γ-FeOOH) and akaganeite (β-FeOOH).Described molecular screening is from Y zeolite and/or have one or more in the molecular sieve of MFI structure, and described heat-resistant inorganic oxide carrier is selected from one or more in aluminium oxide, silica, kaolin and diatomite.
Residual oil hydrocatalyst provided by the invention, can by molecular sieve and heat-resistant inorganic oxide and transistion metal compound, through making beating, spraying, dry and impregnating method be prepared into pressed powder, then mix with hydrated ferric oxide pressed powder, exist with the form of two kinds of pressed powder physical mixed.Also hydrated ferric oxide can be carried on the pressed powder containing molecular sieve and heat-resistant inorganic oxide, exist with the form of loaded catalyst.The hydrated ferric oxide existing with powdery separately adopts precipitation method preparation, adopts coprecipitation preparation while being carried on pressed powder.
Preferably, residual oil hydrocatalyst provided by the invention is made up of hydrated ferric oxide and catalytic cracking spent catalyst.Described catalytic cracking spent catalyst is catalytic cracking catalyst or the industrial poising agent of the inactivation of discharging in catalytic cracking unit.Usually, catalytic cracking spent catalyst is the catalyst that contains Y zeolite and/or have the molecular sieve of MFI structure, also can contain heat-resistant inorganic oxide or the compound containing transition metal.
In described catalytic cracking spent catalyst, preferably contain one or more metals in nickel, vanadium and iron, under preferable case, take total catalyst weight as benchmark, in metal, in described catalytic cracking spent catalyst, total metal content is 1wt%～5wt%, more preferably 1wt% ~ 3wt%.Preferably the pore volume of described catalytic cracking spent catalyst is 0.05 ~ 0.5ml/g, more preferably 0.08 ~ 0.2ml/g.On preferred described catalytic cracking spent catalyst, coke content is less than 0.5wt%.
In method provided by the invention, micro-reactivity of described catalytic cracking spent catalyst is 20～70, preferably 30～60.Wherein said micro-activity refers to places 5.0g catalyst to be measured in micro fixed-bed reactor, and adopting 235 ~ 337 ℃, huge port light diesel fuel is standard raw materials, is 460 ℃, weight space velocity 16h in reaction temperature
-1, react 70s under the oil ratio reaction condition that is 3.2, in gained product, (<204 ℃ of gasoline+gas+coke) quality accounts for the percentage of combined feed.
In method provided by the invention, described catalytic cracking spent catalyst through roasting, flour, sieve, particle diameter is less than 150 μ m, preferred 100 μ m.Catalytic cracking spent catalyst roasting is in order to reduce the carbon deposit on catalyst, exposes more active sites, 450～750 ℃ of sintering temperatures, preferably 500～650 ℃.
In catalyst provided by the invention, take total catalyst weight as benchmark, in iron, the content of described hydrated ferric oxide is 0.5wt%～20wt%, preferably 1wt%～15wt%, more preferably 2wt%～10wt%.
In catalyst provided by the invention, described residual oil hydrocatalyst is the mixture of aqua oxidation iron powder and catalytic cracking spent catalyst.Or be the form of load hydrated ferric oxide on catalytic cracking spent catalyst.
Wherein, in the time that residual oil hydrocatalyst provided by the invention is the mixture of aqua oxidation iron powder and catalytic cracking spent catalyst, the preparation method of residual oil hydrocatalyst comprises the following steps:
(1) by water-soluble water-soluble iron containing compounds, add appropriate dispersion aids, mix;
(2) in the mixed solution that step (1) obtains, add alkali compounds;
(3) in step (2) gained mixture, pass into oxygen-containing gas;
(4) step (3) gained mixture after filtration, washing, dry after, pulverize and obtain aqua oxidation iron powder;
(5) aqua oxidation iron powder and catalytic cracking spent catalyst are mixed to get to residual hydrocracking catalyst in proportion.
In method for preparing catalyst provided by the invention, described dispersion aids is selected from one or more the mixture in ethylenediamine, glutamic acid, ethylenediamine tetra-acetic acid (EDTA), tartaric acid, diammonium hydrogen phosphate and citric acid; The mol ratio of dispersion aids and Fe is 1:500 ~ 1:100.
In method for preparing catalyst provided by the invention, described dispersion aids is selected from ethylenediamine tetra-acetic acid (EDTA) and/or diammonium hydrogen phosphate; The mol ratio of dispersion aids and Fe is 1:300 ~ 1:100.
In method for preparing catalyst provided by the invention, described water-soluble iron containing compounds is selected from one or more in ferric sulfate, ferrous sulfate, ferrous acetate, ferric nitrate and frerrous chloride.
In method for preparing catalyst provided by the invention, described alkali compounds is selected from one or more in ammoniacal liquor, ammonia, sodium hydroxide solution, sodium carbonate liquor, and the mol ratio of alkali compounds and Fe is 1.8 ~ 2.5.
In method for preparing catalyst provided by the invention, in described oxygen-containing gas, the volume content of oxygen is 20% ~ 100%, preferably air, and it is 5 ~ 60 minutes that oxygen-containing gas passes into the time.
In preparation method provided by the invention, the operating temperature of described step (1) ~ (3) is 15 ~ 40 ℃.The dry drying means that can adopt this area routine in step (4), as being dried at least 2 hours at 80～120 ℃.
In preparation method provided by the invention, the usage ratio of described catalytic cracking spent catalyst and water-soluble iron compound, the residual oil hydrocatalyst preparing is met, take total catalyst weight as benchmark, in iron, the content of described hydrated ferric oxide is 0.5wt%～20wt%, preferably 1wt%～15wt%, more preferably 2wt%～10wt%.
The preparation method's of the residual oil hydrocatalyst that contains hydrated ferric oxide and catalytic cracking spent catalyst provided by the invention two, adopts coprecipitation to prepare load hydrated ferric oxide residual oil hydrocatalyst on catalytic cracking spent catalyst.Comprise the following steps:
(1) iron containing compounds is water-soluble, add appropriate dispersion aids, mix;
(2) catalytic cracking spent catalyst is added in the mixed solution of step (1), add alkali compounds simultaneously;
(3) in step (2) gained mixture, pass into oxygen-containing gas;
(4) step (3) gained mixture after filtration, after washing, dry after, obtain residual oil hydrocatalyst.
Wherein, the dispersion aids described in step (1) is selected from one or more the mixture in ethylenediamine, glutamic acid, ethylenediamine tetra-acetic acid, tartaric acid, diammonium hydrogen phosphate and citric acid; The mol ratio of dispersion aids and Fe is 1:500 ~ 100.
Water-soluble iron containing compounds described in step (1) is selected from one or more in ferric sulfate, ferrous sulfate, ferrous acetate, ferric nitrate and frerrous chloride.
Alkali compounds described in step (2) is selected from one or more in ammoniacal liquor, ammonia, sodium hydroxide solution and sodium carbonate liquor, and the mol ratio of alkali compounds and Fe is (1.8 ~ 2.5): 1.
Described in step (3), in oxygen-containing gas, the volume content of oxygen is 20% ~ 100%, and it is 5 ~ 60 minutes that oxygen-containing gas passes into the time.
The presoma of iron containing compounds dissolves to mix with catalytic cracking spent catalyst and adopts coprecipitation, and temperature controls to 20～90 ℃, preferably 30 ℃～60 ℃.
The dry drying means that can adopt routine in this area in step (4), the present invention is not limited in this respect, and for example baking temperature is 80～120 ℃, and be 1～24 hour, preferably 1 ~ 2 hour drying time.
The usage ratio of described catalytic cracking spent catalyst and water-soluble iron compound, the residual oil hydrocatalyst preparing is met, take total catalyst weight as benchmark, in iron, the load capacity of described hydrated ferric oxide is 0.5wt%～20wt%, preferably 1wt%～15wt%, more preferably 2wt%～10wt%.
The present invention also comprises the catalyst preparing according to above-mentioned method for preparing catalyst.
A kind of residual oil hydrocracking process by being scattered in residual oil raw material after above-mentioned any residual hydrocracking catalyst and auxiliary agent mixing, carries out hydrocracking reaction under hydrogen exists, and reaction product obtains product oil after separating; Wherein, described described auxiliary agent is Cosan and/or sulfur-containing compound.
In method for hydrogen cracking provided by the invention, the addition of described residual oil hydrocatalyst, by Fe wherein, is the 0.1wt%～5.0wt% of residual oil raw material; Described auxiliary agent is by S wherein, and the molar ratio of S/Fe is 1～2.
In method for hydrogen cracking provided by the invention, described residual oil is selected from petroleum refining process, DCL/Direct coal liquefaction and oily coal and faces the heavy hydrocarbon that initial boiling point that hydrogen refining process altogether obtains is greater than 350 ℃.
In method for hydrogen cracking provided by the invention, described heavy hydrocarbon is selected from one or more in reduced crude, decompression residuum, heavy catalytic cycle oil, catalytic cracked oil pulp, Aromatics Extractive Project oil, visbreaker tar and coking heavy oil.
In method for hydrogen cracking provided by the invention, described residual hydrocracking reaction is divided into two stages, and first stage reaction condition is: 300～380 ℃ of temperature, pressure 8～20MPa, 5～60 minutes reaction time, preferably 10～30 minutes; Second stage reaction condition is: 380～470 ℃ of temperature, preferably 420～460 ℃, pressure 8～22MPa, preferred 12～20MPa, 10～90 minutes reaction time, preferably 15～60 minutes.
Compared with prior art, residual oil hydrocatalyst provided by the invention contains hydrated ferric oxide, molecular sieve and transition metal oxide, can catalysis residual hydrocracking, and voluminous light hydrocarbon oil.The catalyst being preferably made up of hydrated ferric oxide and catalytic cracking spent catalyst, can recycle the dead catalyst of catalytic cracking unit, cheap.In addition, because catalytic cracking catalyst has certain faintly acid, be conducive to colloid in residual oil, the macromolecular cracking of asphalitine, in product, light ends oil yield is high, on catalytic cracking spent catalyst, also deposit the heavy metals such as a certain amount of Ni, V and Fe simultaneously, in hydrocracking process, can Partial Conversion be active component, improve hydrogenation activity, suppress asphalitine green coke.
The specific embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but therefore do not make the present invention be subject to any restriction.
Residual oil is taken from Tahe oil plant, and character is in table 1.Catalytic cracking spent catalyst (trade name MLC-500, produced by catalyst asphalt in Shenli Refinery of China Petrochemical Corp.), catalytic cracking spent catalyst (trade name ARC-1S, produced by catalyst asphalt in Shenli Refinery of Sinopec Group), through 500 ℃ of roastings 2 hours, grind passing-screen size into powder and be less than 150 μ m, be designated as respectively FCC～1, FCC ~ 2.Character is in table 2.
The preparation method of embodiment 1～5 explanation residual oil hydrocatalyst provided by the invention.
Embodiment 1
50.0g ferrous sulfate heptahydrate and 0.20gEDTA are dissolved in 400g deionized water, stir, separately get 25.0g ammoniacal liquor and splash into while stirring above-mentioned solution, pass into air and continue to stir 20min, then carry out suction filtration, washing, obtain filter cake in 105 ℃ dry 2 hours, pulverize and sieve and obtain powdery iron-containing compound, be designated as Fe～1.Fe ~ 1 making and FCC-1 are mixed to get to residual oil hydrocatalyst A1 with the ratio of 1:5.
Embodiment 2
Weigh 35g ferrous sulfate heptahydrate and 0.12g ammonium dihydrogen phosphate (ADP) and put into beaker, add the continuous stirring and dissolving of 200g deionized water, weighing a FCC～1 dose 50.0g adds in above-mentioned solution, to dropwise add while stirring 17g ammoniacal liquor, dropwise, pass into air and continue to stir 20min, then suction filtration, washing, obtain filter cake in 105 ℃ dry 3 hours, 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 and put into beaker, add the continuous stirring and dissolving of 100g deionized water, weighing a FCC～1 dose 50.0g adds in copperas solution, to dropwise add while stirring 7.0g ammoniacal liquor, dropwise, pass into air and continue to stir 30min, then suction filtration, washing, obtain filter cake in 105 ℃ dry 2 hours, 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 the continuous stirring and dissolving of 150g deionized water, weighing a FCC～2 dose 50.0g adds in copperas solution, to dropwise add while stirring 14g ammoniacal liquor, dropwise, pass into air and continue to stir 20min, then suction filtration, washing, obtain filter cake in 105 ℃ dry 3 hours, pulverize and sieve the residual oil hydrocatalyst A4 obtaining.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 and put into beaker, add the continuous stirring and dissolving of 100g deionized water, weighing a FCC～2 dose 50.0g adds in copperas solution, to dropwise add while stirring 5g ammoniacal liquor, dropwise, pass into air and continue to stir 20min, then suction filtration, washing, obtain filter cake in 105 ℃ dry 2 hours, the residual oil hydrocatalyst obtaining is designated as A5.In A5, the content of hydrated ferric oxide is 6wt%, and the content of catalytic cracking spent catalyst is 94wt%.
Embodiment 6～10 explanation residual oil hydrocracking process of the present invention, and residual oil hydrocatalyst of the present invention is for the effect of residual hydrocracking.
Embodiment 6
By 400g residual oil, count the residual oil of residual oil raw material weight 0.3% and catalyst A 1 and 1.0g sulphur with Fe and add in HTHP stirred tank, stir, sealing, hydrogen first pressing 9.0MPa, at 350 ℃, reaction 15min; Continue to be warming up to 430 ℃, reaction 30min.React complete 180 ℃ of left and right releases, measure gas flow sampling analysis gas composition simultaneously, still bottom product, through n-hexane extracting, send simulation distil after recovery solvent, then obtain pitch and Jiao after toluene extracting n-hexane insoluble matter.Residual oil character is in table 1, and reaction result is in table 3.
Leading indicator using distillate yield and bottoms conversion as catalyst performance evaluation.
Computational methods are as follows:
350 ℃ of cut section quality/feedstock oil quality × 100% of yield of light oil=be less than
524 ℃ of cut section quality/feedstock oil quality × 100% of distillate yield=be less than
Liquid yield=fluid product quality/feedstock oil quality × 100%
Bottoms conversion=be less than 524 ℃ of constituent masses (gassiness)/feedstock oil quality × 100%
Coking yield=(toluene insoluble amount～catalyst)/feedstock oil quality × 100%
Embodiment 7
Test according to the method identical with embodiment 6, that different is A2 prepared by catalyst embodiment 2, and addition is counted 1.0% of residual oil raw material weight with Fe.The results are shown in Table 3.
Embodiment 8
Test according to the method identical with embodiment 6, that different is A3 prepared by catalyst embodiment 3, and addition is counted 0.5% of residual oil raw material weight with Fe.The results are shown in Table 3.
Embodiment 9
Test according to the method identical with embodiment 6, that different is A4 prepared by catalyst embodiment 4, and addition is counted 0.3% of residual oil raw material weight with Fe, 450 ℃ of reaction temperatures.The results are shown in Table 3.
Embodiment 10
Test according to the method identical with embodiment 6, that different is A5 prepared by catalyst embodiment 5, and addition is counted 0.3% of residual oil raw material weight with Fe, reaction time 60min.The results are shown in Table 3.
Comparative example 1
Test according to the method identical with embodiment 6, different is Fe～1 that adopts catalyst only to prepare with embodiment 1, does not add useless catalytic cracking catalyst, and addition is counted 0.3% of residual oil raw material weight with Fe.The results are shown in Table 3.
Comparative example 2
Test according to the method identical with embodiment 6, different is to adopt catalyst only to use FCC～1, and addition is 3% of residual oil raw material weight.The results are shown in Table 3.
Table 1
| Analysis project | Residual oil |
| Density (20 ℃)/(g/cm 3） | 1.0101 |
| Kinematic viscosity, mm 2/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/% by weight | ? |
| C | 85.78 |
| H | 10.37 |
| S | 3.1 |
| N | 0.58 |
| O | 0.17 |
| Four components/% by weight | ? |
| Saturated point | 26.6 |
| Aromatic hydrocarbons | 37.8 |
| Colloid | 20.6 |
| Asphalitine | 15.0 |
Table 2
| Analysis project | FCC～1 | FCC～2 |
| Specific area/(m 2/g） | 135 | 105 |
| Pore volume/(ml/g) | 0.16 | 0.11 |
| Bulk density/(g/cm 3） | 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, can find out, use catalyst of the present invention and residual oil hydrocracking process, bottoms conversion at least improves 3.5 percentage points, and liquid yield improves more than 5 percentage points, and the product of liquid yield distribute be improved significantly, distillate yield obviously improves, and the yield of light oil that is less than 350 ℃ is greater than 49%, and coking yield also decreases, illustrate that catalyst of the present invention has good hydrocracking performance to residual oil, and can light oil with high yield.
Claims (27)
1. a residual hydrocracking catalyst, is characterized in that, take catalyst total amount as benchmark, contains the hydrated ferric oxide of 2wt%～20wt% in this catalyst, the molecular sieve of 27wt%～55wt%, the heat-resistant inorganic oxide carrier of 30wt%～70wt%.
2. according to the catalyst of claim 1, it is characterized in that, described catalyst also contains the transition metal oxide of 0.2wt%～3wt%; Described transition metal is one or more in nickel, vanadium and iron.
3. according to the catalyst of claim 1 or 2, it is characterized in that, described catalyst is made up of hydrated ferric oxide and catalytic cracking spent catalyst.
4. according to the catalyst of claim 3, it is characterized in that, take catalyst total amount as benchmark, in metal, described catalytic cracking spent catalyst contains one or more in nickel, vanadium and iron, and total metal contents in soil is 1wt%～5wt%.
5. according to the catalyst of claim 3, it is characterized in that, the particle diameter of described catalytic cracking spent catalyst is less than 150 μ m.
6. according to the catalyst of claim 3, it is characterized in that, the pore volume of described catalytic cracking spent catalyst is 0.05 ~ 0.5ml/g.
7. according to the catalyst of claim 3, it is characterized in that, on described catalytic cracking spent catalyst, coke content is less than 0.5wt%.
8. according to any catalyst in claim 3-7, it is characterized in that, described residual hydrocracking catalyst is the mixture of aqua oxidation iron powder and catalytic cracking spent catalyst.
9. according to any catalyst in claim 3-7, it is characterized in that, described residual hydrocracking catalyst is load hydrated ferric oxide on catalytic cracking spent catalyst.
10. the preparation method of claim 7 catalyst, is characterized in that, comprises the following steps:
(1) by water-soluble water-soluble iron containing compounds, add appropriate dispersion aids, mix;
(2) in the mixed solution that step (1) obtains, add alkali compounds;
(3) in step (2) gained mixture, pass into oxygen-containing gas;
(4) step (3) gained mixture after filtration, washing, dry after, pulverize and obtain aqua oxidation iron powder;
(5) aqua oxidation iron powder is mixed with catalytic cracking spent catalyst.
11. according to the method for claim 10, it is characterized in that, described dispersion aids is selected from one or more the mixture in ethylenediamine, glutamic acid, ethylenediamine tetra-acetic acid, tartaric acid, diammonium hydrogen phosphate and citric acid; The mol ratio of dispersion aids and Fe is 1:500 ~ 100.
12. according to the method for claim 11, it is characterized in that, described dispersion aids is selected from ethylenediamine tetra-acetic acid and/or diammonium hydrogen phosphate; The mol ratio of dispersion aids and Fe is 1:300 ~ 1:100.
13. according to the method for claim 10, it is characterized in that, described water-soluble iron containing compounds is selected from one or more in ferric sulfate, ferrous sulfate, ferrous acetate, ferric nitrate and frerrous chloride.
14. according to the method for claim 10, it is characterized in that, described alkali compounds is selected from one or more in ammoniacal liquor, ammonia, sodium hydroxide solution and sodium carbonate liquor, and the mol ratio of alkali compounds and Fe is (1.8 ~ 2.5): 1.
15. according to the method for claim 10, it is characterized in that, in described oxygen-containing gas, oxygen content is 20% ~ 100%, and it is 5 ~ 60 minutes that oxygen-containing gas passes into the time.
The preparation method of 16. claim 9 catalyst, is characterized in that, comprises the following steps:
(1) by water-soluble water-soluble iron containing compounds, add appropriate dispersion aids, mix;
(2) catalytic cracking spent catalyst is added in the mixed solution of step (1), add alkali compounds simultaneously;
(3) in step (2) gained mixture, pass into oxygen-containing gas;
(4) step (3) gained mixture after filtration, washing, dry after, obtain residual oil hydrocatalyst.
17. according to the method for claim 16, it is characterized in that, described dispersion aids is selected from one or more the mixture in ethylenediamine, glutamic acid, ethylenediamine tetra-acetic acid, tartaric acid, diammonium hydrogen phosphate and citric acid; The mol ratio of dispersion aids and Fe is 1:500 ~ 100.
18. according to the method for claim 16, it is characterized in that, described water-soluble iron containing compounds is selected from one or more in ferric sulfate, ferrous sulfate, ferrous acetate, ferric nitrate and frerrous chloride.
19. according to the method for claim 16, it is characterized in that, described alkali compounds is selected from one or more in ammoniacal liquor, ammonia, sodium hydroxide solution and sodium carbonate liquor, and the mol ratio of alkali compounds and Fe is (1.8 ~ 2.5): 1.
20. according to the method for claim 16, it is characterized in that, in described oxygen-containing gas, oxygen content is 20% ~ 100%, and it is 5 ~ 60 minutes that oxygen-containing gas passes into the time.
21. 1 kinds of residual oil hydrocracking process, it is characterized in that, by being scattered in residual oil raw material after any residual oil hydrocatalyst in claim 1-9 and auxiliary agent mixing, under existing, hydrogen carries out hydrocracking reaction, and reaction product obtains product oil after separating; Wherein said auxiliary agent is Cosan and/or sulfur-containing compound.
22. according to the method for hydrogen cracking of claim 21, it is characterized in that, the addition of described residual oil hydrocatalyst, by Fe wherein, is the 0.1wt%～5.0wt% of residual oil raw material; Described auxiliary agent is by S wherein, and the molar ratio of S/Fe is 1～2.
23. according to the method for hydrogen cracking of claim 22, it is characterized in that, described residual oil is selected from petroleum refining process, DCL/Direct coal liquefaction and oily coal and faces the initial boiling point that hydrogen refining process altogether obtains and be greater than 350 ℃ of heavy hydrocarbons.
24. according to the method for hydrogen cracking of claim 23, it is characterized in that, described heavy hydrocarbon is selected from one or more in reduced crude, decompression residuum, heavy catalytic cycle oil, catalytic cracked oil pulp, Aromatics Extractive Project oil, visbreaker tar and coking heavy oil.
25. according to the method for hydrogen cracking of claim 21, it is characterized in that, described residual hydrocracking reaction is divided into two stages, and first stage reaction condition is: 300～380 ℃ of temperature, pressure 8～20MPa, 5～60 minutes reaction time; Second stage reaction condition is: 380～470 ℃ of temperature, pressure 8～22MPa, 10～90 minutes reaction time.
26. according to the method for hydrogen cracking of claim 25, it is characterized in that first stage reaction condition: 10～30 minutes reaction time; Second stage reaction condition: 420～460 ℃ of temperature, pressure 12～20MPa, 15～60 minutes reaction time.
27. catalyst of preparing according to the method for claim 10-20.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104437661A (en) * | 2014-12-29 | 2015-03-25 | 山东利丰达生物科技有限公司 | Catalyst for residual oil suspended bed hydro-cracking and preparing method thereof |
| CN107670699A (en) * | 2016-08-01 | 2018-02-09 | 北京华石联合能源科技发展有限公司 | A kind of heavy oil floating bed hydrogenation catalyst using complex carrier |
| CN107709525A (en) * | 2015-09-30 | 2018-02-16 | 环球油品公司 | Slurry hydrocracking method is carried out using iron and granular carbon catalyst |
| CN108067242A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of recycling method of hydrogenation catalyst dead meal |
| CN108311168A (en) * | 2017-12-13 | 2018-07-24 | 煤炭科学技术研究院有限公司 | A kind of composite catalyst and its preparation method and application |
| CN108587675A (en) * | 2018-03-29 | 2018-09-28 | 南京大学连云港高新技术研究院 | A kind of method of heavy oil visbreaking |
| CN108620083A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of recycling method of hydrogenation catalyst dead meal |
| 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 |
| CN112154028A (en) * | 2018-04-11 | 2020-12-29 | 沙特阿拉伯石油公司 | Hydrocracking and hydrotreating catalyst composition comprising zeolite and regenerated spent catalyst and use thereof |
| WO2024093339A1 (en) * | 2022-11-02 | 2024-05-10 | 润和科华催化剂(上海)有限公司 | Catalyst for slurry reactor residual oil hydrogenation, and application method therefor |
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| CN104437661A (en) * | 2014-12-29 | 2015-03-25 | 山东利丰达生物科技有限公司 | Catalyst for residual oil suspended bed hydro-cracking and preparing method thereof |
| CN107709525A (en) * | 2015-09-30 | 2018-02-16 | 环球油品公司 | Slurry hydrocracking method is carried out using iron and granular carbon catalyst |
| 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 |
| CN107670699A (en) * | 2016-08-01 | 2018-02-09 | 北京华石联合能源科技发展有限公司 | A kind of heavy oil floating bed hydrogenation catalyst using complex carrier |
| CN108067242A (en) * | 2016-11-15 | 2018-05-25 | 中国石油化工股份有限公司 | A kind of recycling method of hydrogenation catalyst dead meal |
| 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 |
| CN108620083A (en) * | 2017-03-24 | 2018-10-09 | 中国石油化工股份有限公司 | A kind of recycling 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 |
| CN108311168A (en) * | 2017-12-13 | 2018-07-24 | 煤炭科学技术研究院有限公司 | A kind of composite catalyst and its preparation method and application |
| 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 |
| CN108587675A (en) * | 2018-03-29 | 2018-09-28 | 南京大学连云港高新技术研究院 | A kind of method of heavy oil visbreaking |
| CN112154028A (en) * | 2018-04-11 | 2020-12-29 | 沙特阿拉伯石油公司 | Hydrocracking and hydrotreating catalyst composition comprising zeolite and regenerated spent catalyst and use 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 |
| WO2024093339A1 (en) * | 2022-11-02 | 2024-05-10 | 润和科华催化剂(上海)有限公司 | Catalyst for slurry reactor residual oil hydrogenation, and application method therefor |
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