CN106475119A - The preparation method of hydrocracking catalyst and utilize its slurry bed system hydrogenation technique - Google Patents
The preparation method of hydrocracking catalyst and utilize its slurry bed system hydrogenation technique Download PDFInfo
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- CN106475119A CN106475119A CN201610777289.7A CN201610777289A CN106475119A CN 106475119 A CN106475119 A CN 106475119A CN 201610777289 A CN201610777289 A CN 201610777289A CN 106475119 A CN106475119 A CN 106475119A
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- hydrocracking
- hydrocracking catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
- B01J37/105—Hydropyrolysis
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/06—Sulfides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention provides a kind of preparation method of hydrocracking catalyst and utilize its slurry bed system hydrocracking process, described preparation method is with molybdenum concntrate as raw material, after mixed gas activation through vapor and hydrogen, anaerobic ageing, described hydrocracking catalyst is obtained, the preparation method of the present invention is drawn materials inexpensively, and economy is high, and simple process is quick, and do not produce any garbage, environmental protection.In addition slurry bed system hydrocracking process of the present invention, can with high yield by crude conversion be high-quality light-end products, be particularly suited for process carbon residue be more than 18% residual oil.
Description
Technical field
The present invention relates to catalyst technical field was and in particular to a kind of preparation method of hydrocracking catalyst and utilization should
The slurry bed system hydrogenation technique that catalyst is carried out.
Background technology
In recent years, petroleum refining industry both domestic and external is faced with petroleum resources heaviness in poor quality in short supply, crude oil, oil product
Demand structure change etc. increasingly serious situation so that market is continuously increased to the demand of high-quality middle cut oil product,
Therefore, increase production intermediate oil, improve diesel and gasoline ratio, improve imbalance between supply and demand and be particularly important.Heavy oil is extremely important as one kind
The energy, successful development and utilization heavy oil resources are very crucial for the future of petrochemical industry, especially with to midbarrel
The increase of oily demand, the deep hydrogenation of heavy charge changes into high-quality light-end products becomes more and more meaningful.
During actual industrial production, have been carried out industrialized scale using hydrogenation plant have fixed bed, moving bed
And fluidized-bed reactor, wherein fixed bed and moving bed be higher for the requirement of raw material, is not suitable for processing heavy, inferior raw material,
Although fluidized-bed hydrogenation technology can process inferior raw material, its operating condition is harsh, and plant investment is relatively costly, and current
The slurry bed system hydrogenation technique not yet realizing industrialization large-scale application but can process various inferior raw materials, such as high metal (nickel and vanadium
Mass content in more than 100 μ g/g), high carbon residue (mass content of carbon residue be more than 15%), (mass content of sulfur is more than high-sulfur
2.0%) inferior heavy oil, and light oil yield is high, especially diesel oil distillate high income, good product quality, thus receive people
Increasing pay close attention to.In the factor of numerous impact slurry bed system hydrocracking process effects, hydrocracking catalyst is undoubtedly
It is a vital influence factor.
Industrialized hydrocracking catalyst at present, its metal active constituent major part is all to exist in the form of an oxide,
Need for the reactive metal oxides on catalyst to be converted into sulfide when actually used, therefore, catalyst needs before use
Through over cure or presulfurization is claimed to process.But the defect of above-mentioned processing mode is, the active metal oxygen of hydrocracking catalyst
Compound MoO3、WO3, CoO, NiO and carrier surface there is very strong interaction, cause active metal component to be difficult to vulcanize or sulfur
Change not exclusively, thus leading to the hydrogenation activity of catalyst to reduce, and sulfidation also can cause serious environmental pollution.
For overcoming the drawbacks described above of prior art presence, Chinese patent literature CN103769198A provides a kind of directly system
The method of the standby hydrocracking catalyst with metal sulfide as active component, specifically includes：Select carrier component, it at least wraps
Include a kind of acidic cracking components, carrier component powder body is added water making beating, obtains serosity, then by Thiomolybdate and/or thio
Tungstates serosity, nickel salt and/or cobalt salt solution are passed through in above-mentioned serosity and stir, and after filtering, wash, being dried, add viscous
Mixture kneading, molding, and drying and roasting under inert gas shielding, prepared sulfurized hydrogenation Cracking catalyst.Above-mentioned technology is led to
Cross and carrier component is carried out with making beating process so that carrier does not possess capillary absorption ability substantially, be conducive to active metal dispersed
In carrier surface, generation more II type Mo (W) S activity phase thus can be decomposed in follow-up roasting process, thus improve
The Hydrogenation of catalyst.
But the complicated process of preparation of above-mentioned technology, sewage load is big, the prepared catalyst poor resistance to impurity, and
And it is still not ideal using this catalyst residual oil to be carried out with the yield of the light-end products of gained and quality after hydrotreating, thus
It is not suitable for large-scale industrial production.Therefore, how the preparation method of hydrocracking catalyst is improved so as to technique is simple
List, no waste produce, hydrogenation activity is high, the quality better high income of light-end products, remain this area skill urgently to be resolved hurrily
Art problem.
Content of the invention
The technical problem to be solved in the present invention is to overcome slurry bed system hydrocracking catalyst of the prior art because of activity
Not high and lead to the yield of light-end products and the defect of insufficient quality, so provide a kind of process is simple, no waste produce, hydrogenation
Activity is high, the preparation method of slurry bed system hydrocracking catalyst of the quality better high income of light-end products and being entered using this catalyst
The technique that row slurry bed system is hydrocracked.
For this reason, the technical scheme that the present invention realizes above-mentioned purpose is：
A kind of preparation method of hydrocracking catalyst, including,
Activation step：Under conditions of pressure no more than 0.2Mpa, temperature are 200-500 DEG C, using vapor and hydrogen
Mixed gas activation processing is carried out to molybdenum concntrate, obtain catalyst precursor；
Aging step：Described catalyst precursor is placed in 150-300 DEG C of oxygen-free environment and carries out ripening, cold
But, obtain final product described hydrocracking catalyst.
In described mixed gas, vapor and the volume ratio of hydrogen are (85-95)：(5-15).
After described mixed gas are preheated to more than 300 DEG C, then contact with described molybdenum concntrate.
Described activation step is carried out in a fluidized bed reactor, and the volume space velocity of fluid bed bed is 2-5h-1.
The granularity of described molybdenum concntrate is 20-120 μm；The quality of described molybdenum concntrate meets People's Republic of China's non-ferrous metal
Industry standard YS/T235-2007 or the regulation of standard GB/T 3200-89.
The time of described activation processing is the 10-120 second；The 4-10h of the time of described ripening.
In terms of the gross mass of described hydrocracking catalyst, molybdenum content is more than 45wt%.
A kind of slurry bed system hydrocracking process, including,
Hydrogenation step：In the presence of the hydrocracking catalyst being obtained by above-mentioned preparation method, high carbon residue residual oil is in temperature
Spend for 400-460 DEG C, hydrogen dividing potential drop be 12-20MPa, hydrogen-oil ratio be 500-1000Nm3/ t, liquid hourly space velocity (LHSV) are 0.5-2h-1Condition
Under carry out hydrocracking reaction；
Separating step：The product of described hydrocracking reaction is carried out separating, collects liquid phase, as light-end products.
Described hydrocracking catalyst mix homogeneously with described high carbon residue residual oil after together with pump in response system, or will
Described hydrocracking catalyst is individually added into response system；
Described hydrocracking catalyst is (0.06-0.7) with the mass ratio of described high carbon residue residual oil：100.
It has been additionally added additive while adding described hydrocracking catalyst, described additive is hydrocracked with described
The mass ratio of catalyst is (0.05-0.2)：1；Described additive is sulfur.
High carbon residue residual oil in the present invention be normal slag formed in heavy crude, viscous crude and/or petroleum refining process and/
Or subtracting slag, its carbon residue is 15-25%.
Technical scheme has the advantage that：
1st, the preparation method of hydrocracking catalyst of the present invention, by adopting with molybdenum bisuphide as main component
Molybdenum concntrate, it is contemplated that molybdenum concntrate particle surface in its course of processing can form small amounts molybdenum that is, exists as preparing raw material
MoS2Particle surface embeds a little oxygen atom, thus reducing the hydrogenation activity of molybdenum concntrate, this also exactly molybdenum concntrate directly as
Activity when hydrocracking catalyst uses and all relatively low problem of utilization rate are located, for this reason, the present invention adopts vapor and hydrogen
The mixed gas of gas carry out activation processing to molybdenum concntrate, the oxygen atom of molybdenum concntrate particle surface is removed, is allowed to catalysis activity
It is restored, thus can directly obtain sulfurized hydrogenation Cracking catalyst.
And, the main active component of the hydrocracking catalyst that the preparation method of the present invention is obtained is molybdenum bisuphide, by
It is presented in lower valency sulfide in Mo, it is safe, not self-heating sum in room temperature and relatively dry in the air
Diergolic, therefore, molybdenum concntrate after activation only need to through anaerobic ripening, then using room temperature is airtight and lucifuge packaging so that it may
To ensure safety during storage, transport and filling for the catalyst.As can be seen here, the hydrogenation that the method for the invention is obtained
Cracking catalyst need not through presulfurization process just can be used directly, not only reduce the use cost of catalyst it is often more important that
The existing hydrocracking catalyst with metal oxide form presence also can be overcome to vulcanize because being difficult to or vulcanize not exclusively and lead
The low defect of activation.
In addition, the preparation method of the present invention is drawn materials inexpensively, economy is high, and simple process is quick, and does not produce any discarded
Thing, environmental protection.
2nd, the slurry bed system hydrocracking process that the present invention provides, by being hydrocracked of being obtained using the method for the invention
Catalyst, and high carbon residue residual oil is carried out adding under the hydroconversion conditions such as specific reaction temperature, hydrogen pressure, hydrogen-oil ratio, liquid hourly space velocity (LHSV)
Hydrogen is processed, thus the light-end products such as gasoline, diesel oil can be translated into.The hydrocracking catalyst of the present invention is to high carbon residue residual oil
In more than 524 DEG C components conversion ratio up to more than 85%, and be obtained light-end products quality better, that is to say, by this
The activity of the hydrocracking catalyst that bright methods described is obtained is good, the high income of thus obtained light-end products and good quality.
Specific embodiment
Urge to the preparation method of hydrocracking catalyst provided by the present invention and using this with reference to specific embodiment
The slurry bed system hydrocracking process of agent is described in detail.In the following embodiments, wt% represents weight/mass percentage composition.
Embodiment 1
The preparation method of the hydrocracking catalyst described in the present embodiment, including：
(1) by volume ratio be 85:15 vapor and the mixed gas of hydrogen are heated to 300 DEG C, be then sent to
It is filled with the fluidized-bed reactor of molybdenum concntrate, the body that control reaction pressure is 0.2Mpa, temperature is 500 DEG C and fluid bed bed
Long-pending air speed is 2h-1Activation processing is carried out to molybdenum concntrate, after 60s, obtains catalyst precursor；
Wherein, the granularity of molybdenum concntrate is 90-120 μm, and its quality meets the regulation of standard GB/T 3200-89；
(2) catalyst precursor is placed in the ripening entering 7h during behavior in 150 DEG C of oxygen-free environment, is cooled to room temperature
Afterwards, airtight lucifuge packaging, obtains final product described hydrocracking catalyst；In terms of the gross mass of this catalyst, molybdenum content is 45.5wt%.
The slurry bed system hydrocracking process being carried out using the catalyst that the present embodiment is obtained, including：
A () is 100 according to mass ratio：0.06 ratio, by the normal slag formed in the viscous crude course of processing, (its carbon residue is
15%) hydrocracking catalyst being obtained with the present embodiment mix homogeneously and together with pump in paste state bed reactor, controlling instead
Answer temperature to be 400 DEG C, hydrogen dividing potential drop be 20MPa, hydrogen-oil ratio be 500Nm3/ t, liquid hourly space velocity (LHSV) are 2h-1Under conditions of carry out hydrogenation and split
Change reaction；
B () carries out to the product of above-mentioned hydrocracking reaction separating, collect liquid phase, as light-end products.
After testing, in raw material, the conversion ratio of more than 524 DEG C components is 85%.
Embodiment 2
The preparation method of the hydrocracking catalyst described in the present embodiment, including：
(1) by volume ratio be 90:10 vapor and the mixed gas of hydrogen are heated to 350 DEG C, be then sent to
It is filled with the fluidized-bed reactor of molybdenum concntrate, control reaction pressure is 0.15Mpa, temperature is 350 DEG C and fluid bed bed
Volume space velocity is 5h-1Activation processing is carried out to molybdenum concntrate, after 10s, obtains catalyst precursor；
Wherein, the granularity of molybdenum concntrate is 20-100 μm, and its quality meets the regulation of standard GB/T 3200-89；
(2) catalyst precursor is placed in the ripening entering 10h during behavior in 200 DEG C of oxygen-free environment, is cooled to room
Wen Hou, airtight lucifuge packaging, obtain final product described hydrocracking catalyst；In terms of the gross mass of this catalyst, molybdenum content is 48wt%.
The slurry bed system hydrocracking process being carried out using the catalyst that the present embodiment is obtained, including：
A () is 100 according to mass ratio：0.1 ratio, will subtract slag (its carbon residue formed in the heavy crude course of processing
Be worth for 18%) with the present embodiment be obtained hydrocracking catalyst mix homogeneously and together with pump in paste state bed reactor, controlling
Reaction temperature processed is 430 DEG C, hydrogen dividing potential drop is 12MPa, hydrogen-oil ratio is 750Nm3/ t, liquid hourly space velocity (LHSV) are 1h-1Under conditions of carry out plus
Hydrogen cracking reaction；
B () carries out to the product of above-mentioned hydrocracking reaction separating, collect liquid phase, as light-end products.
After testing, in raw material, the conversion ratio of more than 524 DEG C components is 89%.
Embodiment 3
The preparation method of the hydrocracking catalyst described in the present embodiment, including：
(1) by volume ratio be 88:12 vapor and the mixed gas of hydrogen are heated to 400 DEG C, be then sent to
It is filled with the fluidized-bed reactor of molybdenum concntrate, control reaction pressure is 0.16Mpa, temperature is 450 DEG C and fluid bed bed
Volume space velocity is 3.5h-1Activation processing is carried out to molybdenum concntrate, after 120s, obtains catalyst precursor；
Wherein, the granularity of molybdenum concntrate is 50-80 μm, and its quality meets the regulation of standard GB/T 3200-89；
(2) catalyst precursor is placed in the ripening entering 4h during behavior in 250 DEG C of oxygen-free environment, is cooled to room temperature
Afterwards, airtight lucifuge packaging, obtains final product described hydrocracking catalyst；In terms of the gross mass of this catalyst, molybdenum content is 50wt%.
The slurry bed system hydrocracking process being carried out using the catalyst that the present embodiment is obtained, including：
A () is 100 according to mass ratio：0.4 ratio, by the slag that subtracts formed in petroleum refining process, (its carbon residue is
25%) hydrocracking catalyst being obtained with the present embodiment mix homogeneously and together with pump in paste state bed reactor, controlling instead
Answer temperature to be 450 DEG C, hydrogen dividing potential drop be 16MPa, hydrogen-oil ratio be 1000Nm3/ t, liquid hourly space velocity (LHSV) are 0.5h-1Under conditions of be hydrogenated with
Cracking reaction；
B () carries out to the product of above-mentioned hydrocracking reaction separating, collect liquid phase, as light-end products.
After testing, in raw material, the conversion ratio of more than 524 DEG C components is 86%.
Embodiment 4
The preparation method of the hydrocracking catalyst described in the present embodiment, including：
(1) by volume ratio be 90:10 vapor and the mixed gas of hydrogen are heated to 300 DEG C, be then sent to
It is filled with the fluidized-bed reactor of molybdenum concntrate, control reaction pressure is 0.16Mpa, temperature is 400 DEG C and fluid bed bed
Volume space velocity is 4.5h-1Activation processing is carried out to molybdenum concntrate, after 30s, obtains catalyst precursor；
Wherein, the granularity of molybdenum concntrate is 50-120 μm, and its quality meets the regulation of standard GB/T 3200-89；
(2) catalyst precursor is placed in the ripening entering 5h during behavior in 280 DEG C of oxygen-free environment, is cooled to room temperature
Afterwards, airtight lucifuge packaging, obtains final product described hydrocracking catalyst；In terms of the gross mass of this catalyst, molybdenum content is 50wt%.
The slurry bed system hydrocracking process being carried out using the catalyst that the present embodiment is obtained, including：
A () is 100 according to mass ratio：0.3 ratio, by the normal slag formed in petroleum refining process, (its carbon residue is
24%) hydrocracking catalyst being obtained with the present embodiment mix homogeneously and together with pump in paste state bed reactor, controlling instead
Answer temperature to be 440 DEG C, hydrogen dividing potential drop be 14MPa, hydrogen-oil ratio be 850Nm3/ t, liquid hourly space velocity (LHSV) are 1.5h-1Under conditions of be hydrogenated with
Cracking reaction；
B () carries out to the product of above-mentioned hydrocracking reaction separating, collect liquid phase, as light-end products.
After testing, in raw material, the conversion ratio of more than 524 DEG C components is 90%.
Embodiment 5
The preparation method of the hydrocracking catalyst described in the present embodiment, including：
(1) by volume ratio be 93:7 vapor and the mixed gas of hydrogen be fed through be filled with molybdenum concntrate fluid bed anti-
Answer in device, control reaction pressure is the volume space velocity that 0.18Mpa, temperature are 200 DEG C and fluid bed bed is 4h-1Molybdenum concntrate is entered
Row activation processing, obtains catalyst precursor after 100s；
Wherein, the granularity of molybdenum concntrate is 50-100 μm, and its quality meets the regulation of standard GB/T 3200-89；
(2) catalyst precursor is placed in the ripening entering 6h during behavior in 300 DEG C of oxygen-free environment, is cooled to room temperature
Afterwards, airtight lucifuge packaging, obtains final product described hydrocracking catalyst；In terms of the gross mass of this catalyst, molybdenum content is 47wt%.
The slurry bed system hydrocracking process being carried out using the catalyst that the present embodiment is obtained, including：
A () pumps into the normal slag (its carbon residue is 20%) formed in the viscous crude course of processing in paste state bed reactor, then
Add the prepared hydrocracking catalyst of the present embodiment and appropriate sulfur, and guarantee that residual oil is 100 with the mass ratio of catalyst：
0.5, sulfur is 0.05 with the mass ratio of catalyst：1；Controlling reaction temperature be 460 DEG C, hydrogen dividing potential drop be that 18MPa, hydrogen-oil ratio are
600Nm3/ t, liquid hourly space velocity (LHSV) are 1.5h-1Under conditions of carry out hydrocracking reaction；
B () carries out to the product of above-mentioned hydrocracking reaction separating, collect liquid phase, as light-end products.
After testing, in raw material, the conversion ratio of more than 524 DEG C components is 90%.
Embodiment 6
The preparation method of the hydrocracking catalyst described in the present embodiment, including：
(1) by volume ratio be 95:5 vapor and the mixed gas of hydrogen are heated to 300 DEG C, are then fed through and are filled with
The volume sky that in the fluidized-bed reactor of molybdenum concntrate, control reaction pressure is 0.19Mpa, temperature is 300 DEG C and fluid bed bed
Speed is 3h-1Activation processing is carried out to molybdenum concntrate, after 80s, obtains catalyst precursor；
Wherein, the granularity of molybdenum concntrate is 80-120 μm, and its quality meets China's non-ferrous metal industry standard YS/T235-
2007 regulation；
(2) catalyst precursor is placed in the ripening entering 8h during behavior in 230 DEG C of oxygen-free environment, is cooled to room temperature
Afterwards, airtight lucifuge packaging, obtains final product described hydrocracking catalyst；In terms of the gross mass of this catalyst, molybdenum content is 52wt%.
The slurry bed system hydrocracking process being carried out using the catalyst that the present embodiment is obtained, including：
A () pumps into normal slag formed in the heavy crude course of processing in paste state bed reactor (its carbon residue is
22%), add hydrocracking catalyst and the appropriate sulfur that the present embodiment is obtained, and guarantee the mass ratio of residual oil and catalyst
For 100：0.7, sulfur is 0.2 with the mass ratio of catalyst：1；Controlling reaction temperature be 420 DEG C, hydrogen dividing potential drop be 15MPa, hydrogen
Oil ratio is 900Nm3/ t, liquid hourly space velocity (LHSV) are 2h-1Under conditions of carry out hydrocracking reaction；
B () carries out to the product of above-mentioned hydrocracking reaction separating, collect liquid phase, as light-end products.
After testing, in raw material, the conversion ratio of more than 524 DEG C components is 93%.
Comparative example 1
The preparation method of the hydrocracking catalyst described in this comparative example, including：
(1) 300 DEG C of vapor is fed through in the fluidized-bed reactor being filled with molybdenum concntrate, control reaction pressure is
0.16Mpa, temperature are the volume space velocity of 400 DEG C and fluid bed bed is 4.5h-1Activation processing is carried out to molybdenum concntrate, after 30s
Obtain catalyst precursor；
Wherein, the granularity of molybdenum concntrate is 50-120 μm, and its quality meets the regulation of standard GB/T 3200-89；
(2) catalyst precursor is placed in the ripening entering 5h during behavior in 280 DEG C of oxygen-free environment, is cooled to room temperature
Afterwards, airtight lucifuge packaging, obtains final product described hydrocracking catalyst；In terms of the gross mass of this catalyst, molybdenum content is 50wt%.
Using this comparative example be obtained catalyst with the embodiment of the present invention 4 identical under the conditions of high carbon residue residual oil is carried out
Slurry bed system hydrocracking process is processed, prepared light-end products.After testing, in raw material, the conversion ratio of more than 524 DEG C components is 72%.
Comparative example 2
The preparation method of the hydrocracking catalyst described in this comparative example, including：
Volume ratio is 90:10 vapor and the mixed gas of hydrogen are heated to 300 DEG C, are then sent to filling
Have that granularity is 50-120 μm and quality meets in the fluidized-bed reactor of the molybdenum concntrate that standard GB/T 3200-89 specifies, control
Reaction pressure is the volume space velocity that 0.16Mpa, temperature are 400 DEG C and fluid bed bed is 4.5h-1Molybdenum concntrate is entered with 30s during behavior
Activation processing, be then cooled to room temperature, airtight lucifuge packaging, obtain final product described hydrocracking catalyst；Total with this catalyst
Quality meter, molybdenum content is 50wt%.
Using this comparative example be obtained catalyst with the embodiment of the present invention 4 identical under the conditions of high carbon residue residual oil is carried out
Slurry bed system hydrocracking process is processed, prepared light-end products.After testing, in raw material, the conversion ratio of more than 524 DEG C components is 80%.
Experimental example
The physicochemical property of the light-end products that above-described embodiment 4 and comparative example 1-2 are obtained is tested, result such as table 1 institute
Show, residual oil property is shown in Table 2.
The physicochemical property of the light-end products that table 1 embodiment 4 and comparative example 1-2 are obtained
Table 2 residual oil property
| Density (20 DEG C, g/cm3) | 0.9012 |
| Boiling range/DEG C (IBP/EBP) | 360/523 |
| Sulfur content, μ g g-1 | 218.9 |
| Nitrogen content, μ g g-1 | 1347 |
| Carbon left | 21% |
As it can be seen from table 1 compared with comparative example 1-2, the slurry bed system hydrocracking process institute that the embodiment of the present invention 4 provides
Prepared light-end products have more preferable quality, thus illustrate, the preparation method of the present invention is passed through under given conditions to molybdenum essence
Ore deposit is activated and ripening, is conducive to improving the catalysis activity of catalyst, thus being favorably improved the quality of light-end products.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.Right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (10)
1. a kind of preparation method of hydrocracking catalyst, including,
Activation step：Under conditions of pressure no more than 0.2Mpa, temperature are 200-500 DEG C, mixed using vapor and hydrogen
Close gas and activation processing is carried out to molybdenum concntrate, obtain catalyst precursor；
Aging step：Described catalyst precursor is placed in 150-300 DEG C of oxygen-free environment and carries out ripening, cooling, that is,
Obtain described hydrocracking catalyst.
2. the preparation method of hydrocracking catalyst according to claim 1 is it is characterised in that water in described mixed gas
Steam is (85-95) with the volume ratio of hydrogen：(5-15).
3. the preparation method of hydrocracking catalyst according to claim 1 and 2 is it is characterised in that described mixed gas
After being preheated to more than 300 DEG C, then contact with described molybdenum concntrate.
4. the preparation method of the hydrocracking catalyst according to any one of claim 1-3 is it is characterised in that described activation
Step is carried out in a fluidized bed reactor, and the volume space velocity of fluid bed bed is 2-5h-1.
5. the preparation method of the hydrocracking catalyst according to any one of claim 1-4 is it is characterised in that described molybdenum is smart
The granularity of ore deposit is 20-120 μm；
The quality of described molybdenum concntrate meets People's Republic of China's non-ferrous metal industry standard YS/T235-2007 or national standard
The regulation of GB3200-89.
6. the preparation method of the hydrocracking catalyst according to any one of claim 1-5 is it is characterised in that described activation
The time processing is the 10-120 second；The 4-10h of the time of described ripening.
7. the preparation method of the hydrocracking catalyst according to any one of claim 1-6 is it is characterised in that added with described
The gross mass meter of hydrogen Cracking catalyst, molybdenum content is more than 45wt%.
8. a kind of slurry bed system hydrocracking process, including,
Hydrogenation step：In the presence of the hydrocracking catalyst that the preparation method described in claim 1-7 is obtained, high carbon residue
Residual oil temperature be 400-460 DEG C, hydrogen dividing potential drop be 12-20MPa, hydrogen-oil ratio be 500-1000Nm3/ t, liquid hourly space velocity (LHSV) are 0.5-2h-1Under conditions of carry out hydrocracking reaction；
Separating step：The product of described hydrocracking reaction is carried out separating, collects liquid phase, as light-end products.
9. slurry bed system hydrocracking process according to claim 8 is it is characterised in that described hydrocracking catalyst and institute
Pump in response system together after stating high carbon residue residual oil mix homogeneously, or described hydrocracking catalyst is individually added into anti-
Answer in system；
Described hydrocracking catalyst is (0.06-0.7) with the mass ratio of described high carbon residue residual oil：100.
10. the slurry bed system hydrocracking process according to any one of claim 9-11 is it is characterised in that adding described in addition
It has been additionally added additive, described additive with the mass ratio of described hydrocracking catalyst is while hydrogen Cracking catalyst
(0.05-0.2)：1；Described additive is sulfur.
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| CN115475622A (en) * | 2022-08-24 | 2022-12-16 | 宁波中金石化有限公司 | Preparation method and application of slurry bed hydrogenation catalyst based on waste porcelain powder carrier |
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| CN103080279A (en) * | 2010-07-06 | 2013-05-01 | 道达尔炼油与销售部 | Hydroconversion process for heavy hydrocarbonaceous feedstock |
| WO2015192788A1 (en) * | 2014-06-19 | 2015-12-23 | 北京中科诚毅科技发展有限公司 | Residual oil slurry bed hydrocracking method and device |
| WO2016056330A1 (en) * | 2014-10-08 | 2016-04-14 | 株式会社神戸製鋼所 | Method for hydrocracking, method for producing hydrocracked oil, hydrocracking device, and device for producing hydrocracked oil |
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| CN103080279A (en) * | 2010-07-06 | 2013-05-01 | 道达尔炼油与销售部 | Hydroconversion process for heavy hydrocarbonaceous feedstock |
| WO2015192788A1 (en) * | 2014-06-19 | 2015-12-23 | 北京中科诚毅科技发展有限公司 | Residual oil slurry bed hydrocracking method and device |
| WO2016056330A1 (en) * | 2014-10-08 | 2016-04-14 | 株式会社神戸製鋼所 | Method for hydrocracking, method for producing hydrocracked oil, hydrocracking device, and device for producing hydrocracked oil |
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| CN115475622A (en) * | 2022-08-24 | 2022-12-16 | 宁波中金石化有限公司 | Preparation method and application of slurry bed hydrogenation catalyst based on waste porcelain powder carrier |
| CN115475622B (en) * | 2022-08-24 | 2023-08-25 | 宁波中金石化有限公司 | Preparation method and application of slurry bed hydrogenation catalyst based on waste porcelain powder carrier |
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