CN103769199A - Preparation method of sulfuration type hydro-cracking catalyst - Google Patents
Preparation method of sulfuration type hydro-cracking catalyst Download PDFInfo
- Publication number
- CN103769199A CN103769199A CN201210409561.8A CN201210409561A CN103769199A CN 103769199 A CN103769199 A CN 103769199A CN 201210409561 A CN201210409561 A CN 201210409561A CN 103769199 A CN103769199 A CN 103769199A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- solution
- ammonium
- carrier component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a sulfuration type hydro-cracking catalyst. The preparation method comprises the following steps: selecting a carrier component of a hydro-cracking catalyst, wherein the carrier component comprises at least an acidic cracking component, adding water into the carrier component powder, pulping so as to obtain slurry (d), then adding an ammonium molybdate and/or ammonium tungstate solution (a), an ammonium sulfide solution (b), and a nickel salt and/or cobalt salt solution (c) into the slurry (d) to carry out reactions, filtering, washing and drying the reaction product in the protection of inert gas, adding an adhesive into the reaction product, kneading, forming, drying, and burning in the protection of inert gas so as to obtain the sulfurization type hydro-cracking catalyst. The preparation method makes the active metal be evenly distributed on the carrier so as to generate more II type Ni(Co)Mo(W)S active phases with a higher activity; thus the catalyst has a high sulfurization degree and a high utilization rate of active metal, so that the hydrogenation performance of the catalyst is improved.
Description
Technical field
The present invention relates to a kind of preparation method of sulfurized hydrogenation Cracking catalyst.
Background technology
In recent years, along with the minimizing day by day of petroleum reserves, international oil price climbs up and up, and the trend of crude oil heaviness, in poor quality is more and more serious, and market constantly increases the demand of high-quality middle cut oil product.Therefore, volume increase intermediate oil, improves diesel and gasoline ratio, improves this imbalance between supply and demand and seems particularly important, and the key that solves this contradiction is to develop the selective high hydrocracking catalyst of midbarrel oil type.Current industrialized hydrocracking catalyst, its metal active constituent major part is all to exist with oxide form, and reactive metal oxides on catalyst need to be converted into sulfide when actual use, therefore, catalyst needs before use through over cure or claims presulfurization.
Conventional catalyst vulcanization process adopts " in device " sulfuration or claims " original position " sulfuration, first the catalyst of oxidation state is packed in hydrogenation reactor, then in the process constantly heating up to passing into hydrogen in reactor and vulcanizing agent carries out presulfurization, this method is brought following problem: (1) will set up special presulfurization equipment on hydrogenation plant; (2) water that the vulcanizing agent adding in sulfidation and reaction generate and hydrogen sulfide very easily cause the corrosion of high-pressure reactor and relevant devices, cause device damage and potential safety hazard; (3) sulfidation is longer, incurs loss through delay on-stream time.(4) vulcanizing agent used is inflammable, poisonous, in sulfidation to environment; (5) in device, the cost of presulfurization is higher.
For this reason, there is pre-curing technology outside scene simple, efficient, pollution-free and that cost is low (or claiming " device is outer " presulfurization), being transferred to by the presulfurization of catalyst the catalyst carrying out on special vulcanization reaction device or make has been the catalyst of sulphided state, thereby catalyst is packed in hydrogenation reactor can be used, need not vulcanize, this technology has become the development trend of hydrocracking catalyst technology of preparing in recent years again.
At present, the hydrocracking catalyst of open report " device is outer " pre-curing technology mainly contains two kinds of technology paths:
(1) the first technology path is first vulcanizing agent to be adopted the method for distillation, melting or dipping to be incorporated in the space of hydrocracking catalyst of oxidation state, then under existing, inert gas makes catalyst member presulfurization through hyperthermic treatment, finally catalyst is packed in hydrogenation reactor, in temperature-rise period, under the existence at hydrogen, complete the presulfurization of catalyst going into operation;
(2) the second technology path is in special prevulcanisation-devices, completes the presulfurization of catalyst under the existence of hydrogen and hydrogen sulfide or labile organic sulfurizing agent, then makes non-hypergolic presulfurization type catalyst through oxygen-containing gas Passivation Treatment.
CN85107953 discloses a kind of method of processing hydrogenation catalyst, wherein mainly comprise first with petroleum solvent dissolve and the elementary sulfur of dilution, multiple organic polysulfide at 50～150 ℃ of impregnation process hydrocracking catalysts, then in the atmosphere of no hydrogen, at lower than 275 ℃, process, reactive metal oxides is vulcanized, finally under the existence of hydrogen, at the temperature higher than 275 ℃, activate.CN91101805.7 discloses a kind of method in hole of sulphur being mixed to hydrocarbon processing catalysts, and its feature is: first adopt solvent dilution vulcanizing agent process catalyst, then steam exist under, vulcanizing treatment at the temperature higher than 250 ℃.The organosulfur compound that vulcanizing agent used easily decomposites hydrogen sulfide by elementary sulfur with under hydrogen exists forms, and solvent used is the solvent naphtha that contains olefine fraction or vegetable oil.US 6,365,542 discloses a kind of hydrocracking catalyst device method of sulfuration outward, is characterized in first processing catalyst with the oil containing elementary sulfur, alkene at 100～120 ℃, then process inert gas treatment at the temperature of 100～300 ℃.US 6,417,134 disclose a kind of outer method for pre-sulphuration of device of hydrotreating catalyst, be characterized in first with the elementary sulfur of solvent dilution, organic sulfur compound, organic polysulfide, containing the oil of alkene, containing component impregnation process catalyst at the temperature of 300 ℃ of ethylene linkage, then at the temperature of 250～600 ℃, use hydrogen treat, finally use oxygen-containing gas passivation.Said method is all that ready-made oxidized catalyst is carried out to presulfurization processing, has the following disadvantages like this in preparation process: the oxide M oO of hydrocracking catalyst active metal Mo, W, Co, Ni
3, WO
3, there is strong interaction in CoO, NiO and carrier surface, causes active metal component sulfuration difficulty and not exclusively, the hydrogenation activity of catalyst is reduced, and can cause serious environmental pollution in sulfidation.
CN200410039449.5 discloses a kind of preparation method of sulfide type catalyst, it is that mode by incipient impregnation is by the molybdenum dithiophosphate of solubility (tungsten) hydrochlorate and Co(Ni) atom substep or a step load on the carrier of catalyst, and in inert gas through heat treated, have the sulfide type catalyst of metal sulfide thereby make load.Because Thiomolybdate and thiqtung state etc. are water insoluble, obtain solution need to add organic solvent, and complicated process of preparation is unsuitable for large-scale industrial production.In addition, the method, in high-temperature process, due to the volatilization of organic solvent, has been strengthened the interaction of hydrogenation component and carrier, has affected the sulfuration of catalyst, and sulphidity is relatively low, and the activity and selectivity of catalyst declines.
The impact of the reactivity worth of sintering temperature on sulfur-bearing precursor hydrocracking catalyst has been studied in " petroleum refining and chemical industry " (2011,42 (6): 50-56).Mode by kneading loads on ammonium thiomolybdate and nickel nitrate on the carrier of catalyst, and in inert gas through heat treated, obtain the sulfide type catalyst of sulfur-bearing metal sulfide.The method technique is simple, state of cure (vulcanization) is high, makes the sulfurized hydrogenation Cracking catalyst making have higher activity and selectivity, but the catalyst metals dispersing uniformity of preparing due to kneading method is poor, using rate of metal is low, has affected activity and the product property of catalyst.
Summary of the invention
For overcoming above-mentioned the deficiencies in the prior art part, the invention provides the preparation method of the sulfurized hydrogenation Cracking catalyst that a kind of metal is uniformly dispersed, state of cure (vulcanization) is high, activity is high and product is of fine quality.
The preparation method of sulfurized hydrogenation Cracking catalyst of the present invention, comprising:
(l) preparation dimolybdate salt and/or ammonium tungstate salting liquid a, formulating vulcanization ammonium salt solution b, preparation nickel salt and/or cobalt salt solution c;
(2) selective hydrocracking catalyst carrier component, carrier component at least comprises a kind of acid cracking component, by the making beating that adds water of carrier component powder, obtains slurries d;
(3) solution a, solution b and solution c are passed into slurries d, control reaction temperature at 50 ~ 80 ℃, the time of passing into is 0.5 ~ 2 hour;
(4) material of step (3) gained filtered, wash, under the protection of inert gas, be dried, obtain catalyst intermediate;
(5) catalyst intermediate is added to adhesive kneading, through extruded moulding, dry under the protection of inert gas, roasting, makes sulfurized hydrogenation Cracking catalyst.
In step (1), in ammonium molybdate and/or ammonium tungstate solution, every 100 ml contain 5 ~ 30gMo and/or W, are preferably 5 ~ 10gMo and/or W.The concentration of ammonium sulfide solution is 5wt% ~ 30wt%, is preferably 10wt% ~ 15wt%.In nickel salt and/or cobalt salt slurries, every 100 ml contain 5 ~ 20gNi and/or Co, are preferably 5 ~ 10gNi and/or Co.Described nickel salt and/or cobalt salt are selected from one or more in nitrate, carbonate, subcarbonate, acetate, chloride.
In step (2), described carrier of hydrocracking catalyst component at least comprises a kind of acid cracking component, acid cracking component comprises molecular sieve or amorphous acidic components, and molecular sieve generally comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve etc.Amorphous acidic components are generally one or more in amorphous aluminum silicide, amorphous silicon magnesium etc.Required molecular sieve can require to carry out suitable modification according to serviceability.In hydrocracking catalyst, carrier component can also comprise acid weak inorganic refractory oxide, is generally aluminium oxide or contains auxiliary agent aluminium oxide.Take the weight of final catalyst as benchmark, the general content of acid cracking component is 10wt% ~ 60wt%, Mo and/or W be take the content of element as 10wt%～30wt%, and Co and/or Ni, simultaneously can also salic 0 ~ 50 wt % take the content of element as 2wt%～10wt%.
In step (2), the volume ratio of carrier component powder and water is 1:5 ~ 1:30, is preferably 1:10 ~ 1:20.Described carrier component powder is hydroxide and/or the oxide powder that can generate carrier component.Such as amorphous acidic components adopt contained amorphous silica-alumina dry glue powder and/or amorphous silicon magnesium dry glue powder, aluminium oxide adopts aluminum oxide dry glue powder, and molecular sieve adopts molecular sieve powder etc.The active metal component of hydrocracking catalyst of the present invention is W and/or Mo and Ni and/or Co, can contain auxiliary agent simultaneously.The selection of carrier of hydrocracking catalyst component, active metal component and auxiliary agent and consumption can specifically be determined according to the needs of application according to this area general knowledge.
The ratio of controlling Mo and/or the molal quantity of W and the molal quantity of ammonium sulfide in step (3) is 1:10 ~ 1:2.
In step (4), described inert gas is preferably nitrogen, and described drying condition is as follows: 90 ~ 140 ℃ are dried at 4 ~ 10 o'clock.
In step (5), binding agent is generally the little porous aluminum oxide through peptization.Moulding can be determined according to the shape of final catalyst, as extrusion etc.Described drying condition is as follows: be dried 4 ~ 14 hours at 100 ~ 130 ℃, roasting condition was as follows: 450 ~ 600 ℃ of roastings 3 ~ 10 hours.
In the preparation method of sulfurized hydrogenation Cracking catalyst of the present invention, the imbibition ability of carrier powder is very strong, after making beating is processed, carrier powder is through fully water suction, be present in slurries d with graininess, as ammonium molybdate and/or ammonium tungstate solution a, when ammonium sulfide solution b and solution c pass into slurries d, ammonium molybdate or ammonium tungstate react the water-fast particle tiny and uniform Thiomolybdate or the thiqtung state that generate with ammonium sulfide, because carrier component powder does not substantially have capillary absorption ability after making beating, so Thiomolybdate and/or thiqtung state are deposited on the surface of carrier powder equably, in subsequent processes, be decomposed to form MoS tiny and lower valency that be evenly distributed at carrier surface
2and WS
2plates, form more corner angle, be conducive to molybdenum and/cobalt is adsorbed onto edges and corners, form active higher II type Ni(Co with Mo or W) Mo(W) the active phase of S, make the state of cure (vulcanization) of catalyst high, improved the utilization ratio of active metal, thereby improved the Hydrogenation of catalyst.And in the inventive method, the active metallic content of catalyst can be adjusted flexibly, avoid low the brought difficulty of Thiomolybdate and/or thiqtung state solubility.In addition, pore volume, aperture and the specific area impact of the inventive method on carrier component is less, and therefore, pore volume, the specific area of gained hydrocracking catalyst are larger.
Hydrocracking catalyst prepared by the inventive method, the Thiomolybdate and/or the thiqtung state decomposes that generate due to reaction are molybdenum sulfide and/or tungsten sulfide, nickel salt and/or cobalt salt are converted into the sulfide of nickel and/or cobalt after follow-up heat treated, therefore, the hydrocracking catalyst of gained itself is sulphided state, in use without vulcanizing again.Result of study proves, load have the catalyst of the lower valency sulfide of Mo, W, Co, Ni in room temperature and drier air, be safe, not self-heating with diergolic, therefore, according to the prepared catalyst of the method for this invention, as long as through inert gas treatment, and adopt the airtight and lucifuge of room temperature packing, can guarantee the security of catalyst stores, transportation and filling process.
The sulfurized hydrogenation Cracking catalyst of the inventive method gained is applicable to need sulphided state hydrocracking catalyst catalytic process.
The sulfurized hydrogenation Cracking catalyst that the inventive method makes is for hydrocracking process, be suitable for treatment of heavy hydrocarbon material, comprise one or more in vacuum gas oil (VGO), coker gas oil, deasphalted oil, thermal cracking gas oil, catalytic gas oil, the various hydrocarbon-type oils of catalytic cracking circulation wet goods, raw material is generally the hydro carbons containing 300～600 ℃ of boiling points, and nitrogen content can be at 50～2500 μ g/g.
The specific embodiment
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail.In the present invention, wt% is mass fraction, and v% is volume fraction.
Embodiment 1
Catalyst catA involved in the present invention.
Preparation Ammoniun Heptamolybdate Solution 250 ml(a), in solution, containing 10g molybdenum 100ml, prepare 10wt% ammonium sulfide solution 500ml(b), preparation nickel nitrate solution 40ml(c), in slurries, containing 5g nickel/100ml, take 120g contained amorphous silica-alumina dry glue powder, 30gY molecular sieve powder (SiO
2/ Al
2o
3mol ratio is 40, lattice constant is 2.432nm, infrared acidity 0.19mmol/g, specific area 866m
2/ g, pore volume 0.52ml/g); join and in 1500g water, be beaten into slurries (d); by (a) and (b) and (c) slowly adding in slurries (d); stir; 65 ℃ of hierarchy of control temperature; react after 1 hour filter, washing, by gained material under the protection of inert gas 100 ℃ dry 6 hours dry, obtain catalyst intermediate.After catalyst intermediate is put into roller and evenly mixed, then the adhesive that adds 180g to be made up of nitric acid and SB aluminium oxide peptization, kneading, rolls, make can extrusion paste, extruded moulding.Under the protection of nitrogen, 120 ℃ dry 6 hours, 500 ℃ of roastings 4 hours, make catalyst catA.
Embodiment 2
Catalyst catB involved in the present invention.
Preparation ammonium tetramolybdate solution 400 ml(a), in solution, containing 5g molybdenum 100/ml, prepare 15wt% ammonium sulfide solution 300ml(b), preparation nickel nitrate solution 30ml(c), in slurries, containing 8 nickel/100ml, take 110g contained amorphous silica-alumina dry glue powder, 28g beta-molecular sieve powder (SiO
2/ A1
2o
3=28(molecular proportion), lattice constant is 1.198nm, relative crystallinity is 95%, infrared acidity 0.174mmol/g, specific area 894m
2/ g, pore volume 0.54lml/g); join and in 1500g water, be beaten into slurries (d); by (a) and (b) and (c) slowly adding in slurries (d); stir; 65 ℃ of hierarchy of control temperature; react after 1 hour filter, washing, by gained material under the protection of inert gas 110 ℃ dry 5 hours dry, obtain catalyst intermediate.After catalyst intermediate is put into roller and evenly mixed, then the adhesive that adds 180g to be made up of nitric acid and SB aluminium oxide peptization, kneading, rolls, make can extrusion paste, extruded moulding.Under the protection of nitrogen, 120 ℃ dry 6 hours, 500 ℃ of roastings 4 hours, make catalyst catB.
Embodiment 3
Catalyst catC involved in the present invention.
Preparation ammonium metatungstate solution 250 ml(a), in solution, containing 10g tungsten 100ml, prepare 10wt% ammonium sulfide solution 500ml(b), preparation nickel nitrate solution 40ml(c), in slurries, containing 5g nickel/100ml, take 120g contained amorphous silica-alumina dry glue powder, 30gY molecular sieve powder (SiO
2/ Al
2o
3mol ratio is 40, lattice constant is 2.432nm, infrared acidity 0.19mmol/g, specific area 866m
2/ g, pore volume 0.52ml/g); join and in 1500g water, be beaten into slurries (d); by (a) and (b) and (c) slowly adding in slurries (d); stir; hierarchy of control temperature 60 C; react after 1 hour filter, washing, by gained material under the protection of inert gas 100 ℃ dry 6 hours dry, obtain catalyst intermediate.After catalyst intermediate is put into roller and evenly mixed, then the adhesive that adds 180g to be made up of nitric acid and SB aluminium oxide peptization, kneading, rolls, make can extrusion paste, extruded moulding.Under the protection of nitrogen, 120 ℃ dry 6 hours, 500 ℃ of roastings 4 hours, make catalyst catC.
Comparative example 1
Reference catalyst D preparation.Take 106g amorphous aluminum silicide, 33gY molecular sieve (character is with embodiment 1), after putting into roller and evenly mixing, then the adhesive that adds 180g to be made up of nitric acid and SB aluminium oxide peptization, kneading, rolls, make can extrusion paste, extruded moulding.110 ℃ dry 6 hours, be then placed in Muffle furnace, be roasting 4 hours in the air of 500 ℃ in temperature, obtain reference agent carrier D.
Take four thio ammonium molybdate 56.9g, add 30ml monoethanolamine and 20ml distilled water, stir lower dissolving, obtain sanguine settled solution A.Take nickel oxide powder 6.5g, add 20ml monoethanolamine and 5.0g tartaric acid, add under thermal agitation and dissolve, obtain blue-green settled solution B.Solution A and solution B are mixed to get to solution C.At room temperature place and dry for 24 hours with this solution impregnation 100g reference agent carrier D.Catalyst after drying is placed in to tube furnace, and at 350 ℃, logical nitrogen treatment 4 hours, obtains reference catalyst catD.
Comparative example 2
With 200ml Mo-Ni co-impregnated solution (MoO
3be respectively 36g/100ml and 10g/100ml with the concentration of NiO) excessive dipping 100g reference agent carrier D 2 hours, 100 ℃ dry 6 hours, 500 ℃ of roastings 4 hours, make reference catalyst catE.
It is sulfurized oil that reference catalyst catEization adopts containing the kerosene of carbon disulfide.Presulfurization condition is as follows: hydrogen dividing potential drop 14.7MPa, 370 ℃ of curing temperatures, vulcanizing agent content 2wt%, volume space velocity 1.0h
-1, hydrogen to oil volume ratio 1000.
Comparative example 3
In " petroleum refining and chemical industry " (2011,42 (6): 50-56), the preparation method of catalyst prepares reference catalyst F.Take 116g amorphous aluminum silicide, 32gY molecular sieve (character is with embodiment 1), 55.0g ammonium thiomolybdate, 42g nickel nitrate, after putting into roller and evenly mixing, then the adhesive that adds 180g to be made by nitric acid and SB aluminium oxide peptization, kneading, roll, make can extrusion paste, extruded moulding.Under the protection of nitrogen, 110 ℃ dry 6 hours, be then placed in Muffle furnace roasting 4 hours at 500 ℃, make catalyst catF.
The physico-chemical property of table 1 embodiment and comparative example gained catalyst
| Catalyst numbering | catA | catB | catC | catD | catE | catF |
| Catalyst composition, in element, wt% | ? | ? | ? | ? | ? | ? |
| Mo | 15.9 | 14.9 | － | 17.4 | 16.8 | 16.7 |
| W | － | ? | 16.3 | － | － | － |
| Ni | 4.3 | 3.8 | 3.6 | 4.5 | 4.7 | 4.1 |
| Catalyst property | ? | ? | ? | ? | ? | ? |
| Specific area, m 2/g | 271 | 380 | 268 | 194 | 197 | 241 |
| Pore volume, ml/g | 0.49 | 0.51 | 0.48 | 0.33 | 0.34 | 0.42 |
The invention described above catalyst catA, catB, catC and comparative example catalyst catD, catE, catF are carried out to active evaluation test.Test is carried out on 200ml small hydrogenation device, and raw materials used oil nature is in table 2.Operating condition is as follows: hydrogen dividing potential drop 14.7MPa, hydrogen to oil volume ratio 1500:1, volume space velocity 1.5h when liquid
-1.Catalyst activity result of the test is in table 3.
Table 2 evaluation is used feedstock oil character
| Feedstock oil | Iran VGO |
| Density (20 ℃)/gcm -3 | 0.9025 |
| Boiling range/℃ | ? |
| IBP/10%/50% | 308/369/430 |
| 90%/95%/EBP | 50/3526/560 |
| Carbon residue, wt% | 0.2 |
| S，wt% | 1.5 |
| N，wt% | 0.11 |
| BMCI value | 41.5 |
Table 3 catalyst activity evaluation result
| Catalyst numbering | catA | catB | catC | catD | catE | catF |
| Reaction temperature, ℃ | 368 | 369 | 369 | 382 | 380 | 375 |
| Product distributes | ? | ? | ? | ? | ? | ? |
| < 370 ℃ of conversion ratios, wt% | 64.0 | 64.3 | 64.2 | 64.6 | 65.1 | 63.8 |
| Middle distillates oil selectivity, wt%(132～370 ℃) | 85.7 | 85.8 | 85.4 | 81.9 | 83.1 | 84.2 |
| Major product character | ? | ? | ? | ? | ? | ? |
| Heavy naphtha (82～132 ℃) | ? | ? | ? | ? | ? | ? |
| Virtue is dived, wt% | 60.1 | 59.9 | 61.4 | 59.6 | 59.5 | 59.8 |
| Jet fuel (132 ~ 282 ℃) | ? | ? | ? | ? | ? | ? |
| Freezing point, ℃ | <-60 | <-60 | <-60 | <-60 | <-60 | <-60 |
| Aromatic hydrocarbons, wt% | 3.7 | 3.7 | 3.6 | 3.9 | 4.0 | 4.1 |
| Smoke point, mm | 28 | 27 | 28 | 27 | 28 | 27 |
| Diesel oil (282 ~ 350 ℃) | ? | ? | ? | ? | ? | ? |
| Cetane number | 64 | 64 | 62 | 59 | 61 | 59 |
| Condensation point, ℃ | -10 | -16 | -11 | -9 | -8 | -8 |
| 370 ℃ of tail oils (>) | ? | ? | ? | ? | ? | ? |
| BMCI | 8.7 | 9.3 | 8.9 | 10.6 | 10.7 | 10.5 |
Claims (13)
1. a preparation method for sulfurized hydrogenation Cracking catalyst, comprising:
(l) preparation dimolybdate salt and/or ammonium tungstate salting liquid a, formulating vulcanization ammonium salt solution b, preparation nickel salt and/or cobalt salt solution c;
(2) selective hydrocracking catalyst carrier component, carrier component at least comprises a kind of acid cracking component, by the making beating that adds water of carrier component powder, obtains slurries d;
(3) solution a, solution b and solution c are passed into slurries d, control reaction temperature at 50 ~ 80 ℃, the time of passing into is 0.5 ~ 2 hour;
(4) material of step (3) gained filtered, wash, under the protection of inert gas, be dried, obtain catalyst intermediate;
(5) catalyst intermediate is added to adhesive kneading, through extruded moulding, dry under the protection of inert gas, roasting, makes sulfurized hydrogenation Cracking catalyst.
2. in accordance with the method for claim 1, it is characterized in that in step (1), in ammonium molybdate and/or ammonium tungstate solution, every 100 ml contain 10 ~ 30gMo and/or W; The concentration of ammonium sulfide solution is 5wt% ~ 30wt%; In nickel salt and/or cobalt salt slurries, every 100 ml contain 5 ~ 20gNi and/or Co.
3. in accordance with the method for claim 1, it is characterized in that in step (1), in ammonium molybdate and/or ammonium tungstate solution, every 100 ml contain 5 ~ 10gMo and/or W; The concentration of ammonium sulfide solution is 10wt% ~ 15wt%; In nickel salt and/or cobalt salt slurries, every 100 ml contain 5 ~ 10gNi and/or Co.
4. according to the preparation method of catalyst claimed in claim 1, it is characterized in that, in step (2), acid cracking component comprises one or more in molecular sieve and amorphous acidic components.
5. according to the preparation method of catalyst claimed in claim 4, it is characterized in that described molecular sieve comprises one or more in Y zeolite, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieve; Amorphous acidic components are one or more in amorphous aluminum silicide, amorphous silicon magnesium.
6. according to the preparation method of catalyst claimed in claim 1, it is characterized in that: in hydrocracking catalyst, in carrier component, contain aluminium oxide or contain auxiliary agent aluminium oxide.
7. according to the preparation method of catalyst claimed in claim 1, it is characterized in that: take the weight of final catalyst as benchmark, acid cracking constituent content is 10wt% ~ 60wt%, Mo and/or W are take the content of element as 10wt%～30wt%, Co and/or Ni are take the content of element as 2wt%～10wt%, and the content of aluminium oxide is 0 ~ 50 wt %.
8. according to the preparation method of catalyst claimed in claim 1, it is characterized in that: in step (2), the volume ratio of carrier component powder and water is 1:5 ~ 1:30.
9. according to the preparation method of catalyst claimed in claim 1, it is characterized in that: in step (2), the volume ratio of carrier component powder and water is 1:10 ~ 1:20.
10. the ratio that in accordance with the method for claim 1, it is characterized in that controlling in step (3) Mo and/or the molal quantity of W and the molal quantity of ammonium sulfide is 1:10 ~ 1:2.
11. according to the preparation method of catalyst claimed in claim 1, it is characterized in that: described nickel salt and/or cobalt salt are selected from one or more in nitrate, carbonate, subcarbonate, acetate, chloride.
12. according to the preparation method of catalyst claimed in claim 1, it is characterized in that: in step (4), described drying condition is as follows: 90 ~ 140 ℃ are dried at 4 ~ 10 o'clock.
13. according to the preparation method of catalyst claimed in claim 1, it is characterized in that: in step (5), described drying condition is as follows: be dried 4 ~ 14 hours at 100 ~ 130 ℃, roasting condition was as follows: 450 ~ 600 ℃ of roastings 3 ~ 10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409561.8A CN103769199B (en) | 2012-10-24 | 2012-10-24 | The preparation method of sulfurized hydrogenation Cracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210409561.8A CN103769199B (en) | 2012-10-24 | 2012-10-24 | The preparation method of sulfurized hydrogenation Cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769199A true CN103769199A (en) | 2014-05-07 |
| CN103769199B CN103769199B (en) | 2015-09-30 |
Family
ID=50562233
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210409561.8A Active CN103769199B (en) | 2012-10-24 | 2012-10-24 | The preparation method of sulfurized hydrogenation Cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769199B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944126A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | hydrocracking catalyst intermediate, hydrocracking catalyst and preparation method thereof |
| CN110270360A (en) * | 2018-03-14 | 2019-09-24 | 赢创德固赛有限公司 | The method for preparing oligomerisation catalyst |
| CN114433203A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrocracking catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394684A (en) * | 2002-04-10 | 2003-02-05 | 中国科学院大连化学物理研究所 | Preparation method of transition metal carbide catalyst and its catalytic performance |
| CN101722055A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for preparing sulfide type catalyst |
| EP2264129A2 (en) * | 2009-04-27 | 2010-12-22 | Petroleo Brasileiro S.A. | Process for hydrotreating biomass oil diluted in a refinery stream of petroleum hydrocarbons |
-
2012
- 2012-10-24 CN CN201210409561.8A patent/CN103769199B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1394684A (en) * | 2002-04-10 | 2003-02-05 | 中国科学院大连化学物理研究所 | Preparation method of transition metal carbide catalyst and its catalytic performance |
| CN101722055A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Method for preparing sulfide type catalyst |
| EP2264129A2 (en) * | 2009-04-27 | 2010-12-22 | Petroleo Brasileiro S.A. | Process for hydrotreating biomass oil diluted in a refinery stream of petroleum hydrocarbons |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106944126A (en) * | 2016-01-07 | 2017-07-14 | 中国石油化工股份有限公司 | hydrocracking catalyst intermediate, hydrocracking catalyst and preparation method thereof |
| CN110270360A (en) * | 2018-03-14 | 2019-09-24 | 赢创德固赛有限公司 | The method for preparing oligomerisation catalyst |
| CN110270360B (en) * | 2018-03-14 | 2023-04-28 | 赢创运营有限公司 | Process for preparing oligomerization catalysts |
| CN114433203A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Preparation method of vulcanization type hydrocracking catalyst |
| CN114433203B (en) * | 2020-10-19 | 2023-09-01 | 中国石油化工股份有限公司 | Preparation method of vulcanized hydrocracking catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769199B (en) | 2015-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103769198B (en) | A kind of preparation method of sulfurized hydrogenation Cracking catalyst | |
| CN103769200B (en) | A kind of method preparing sulfurized hydrogenation Cracking catalyst | |
| CN103769197B (en) | A kind of method for making of sulfurized hydrogenation Cracking catalyst | |
| CN102836736B (en) | A kind of preparation method of sulfurized hydrogenation catalyst | |
| CN104646034B (en) | A kind of preparation method of sulfurized hydrogenation catalyst for refining | |
| CN104646010A (en) | Process improvement method of vulcanized hydrogenation refining catalyst | |
| CN112844416A (en) | Hydrogenation catalyst and preparation method thereof | |
| CN105521791B (en) | The preparation method of vulcanization type catalyst for selective hydrodesulfurizationof of gasoline | |
| CN106179414B (en) | A kind of sulfurized hydrogenation catalyst for refining and preparation method thereof | |
| CN103769169B (en) | A kind of preparation method of sulfurized hydrogenation process catalyst | |
| CN103769170B (en) | A kind of method preparing sulfurized hydrogenation process catalyst | |
| CN1283361C (en) | In situ outer prevulcanization method for hydrogenation catalyst | |
| CN109304183A (en) | Handle the hydrotreating catalyst and the preparation method and application thereof of inferior oil material | |
| CN103769199B (en) | The preparation method of sulfurized hydrogenation Cracking catalyst | |
| CN103769168B (en) | A kind of method for making of sulfurized hydrogenation process catalyst | |
| CN103769171B (en) | The preparation method of sulfurized hydrogenation process catalyst | |
| CN108097329A (en) | A kind of hydrocracking catalyst and preparation method thereof and start-up method | |
| JP5825572B2 (en) | Method for regenerating hydrotreating catalyst | |
| CN105582963B (en) | A kind of preparation method of vulcanization type catalyst for selective hydrodesulfurizationof of gasoline | |
| CN106944126B (en) | Hydrocracking catalyst intermediate, hydrocracking catalyst and preparation method thereof | |
| CN103801333B (en) | The preparation method of a kind of year sulfur type hydrogenation catalyst | |
| CN102836725B (en) | Preparation method for hydrorefining catalyst | |
| CN102836727A (en) | Preparation method for hydrogenation catalyst with high denitrogenation activity and high dearomatization activity | |
| CN109304213A (en) | A kind of hydrocracking catalyst and the preparation method and application thereof | |
| CN115337939B (en) | Sulfurized aromatic saturated catalyst, preparation method thereof and distillate oil hydrofining method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |