CN107930648B - A kind of heavy oil floating bed hydrocracking catalyst and preparation method thereof - Google Patents
A kind of heavy oil floating bed hydrocracking catalyst and preparation method thereof Download PDFInfo
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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8873—Zinc, cadmium or mercury
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
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- 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
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1077—Vacuum residues
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Abstract
The present invention discloses a kind of heavy oil floating bed hydrocracking catalyst and preparation method thereof, catalyst includes the ore composition powder after Zinc oxide powder and vulcanization, ore composition powder after vulcanization includes nickel-containing ore, containing tungsten ore, and/or iron-stone, and wherein the content of zinc oxide is 10~56wt%.Ore composition powder and zinc oxide after vulcanization is dry-mixed, and obtained catalyst coking yield is low, liquid yield is high, desulfurization degree is high, and the impurity ability such as sulfur resistive, anti-metal, nitrogen, carbon residue is strong, the slurry-bed hydrocracking for inferior heavy oil.
Description
Technical field
The present invention relates to its a kind of heavy oil floating bed hydrocracking catalyst and preparation method thereof.
Background technique
Inferior heavy oil floating bed hydrogenation technological development emphasis is mainly the improvement of catalyst and its technique.Floating bed hydrogenation is split
Changing catalyst is mainly one or more of supported V IB and/or VIII group metal using substances such as siliceous, aluminium as carrier.Such as
CN201610832248.3, CN201610516189.9, CN201510417279.8.Hydrocracking catalyst for suspension bed, which exists, lives
Property is low, coking rate is high, reaction temperature is easy to the problems such as rising violently.Suspension bed hydrogenation process is by the finely grained catalyst of high dispersive or adds
Add object to pass through reactor together with feedstock oil and hydrogen, is a kind of invest and the lower inferior heavy oil deep processing side of operating cost
Method has the characteristics that strong adaptability to raw material, simple process, conversion ratio and its demetallization per height, light oil yield are high.Such as
CN01114169.7, CN201610258622.3, CN201480021127.X.Inferior heavy oil hydrogenation technique also has residue fixed-bed
Add hydrogen and floating bed hydrogenation combination technology, such as CN00110715.1, contains group vib metal and/or group VIII metal group first
In the presence of divided catalyst, colloid, the asphalitine of the easy green coke in charging are effectively taken off, then in suspension bed or similar reaction
Make pretreated charging hydro-conversion in device.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide, a kind of high conversion rate, coking yield be low, desulfurization degree
High, distillate high income heavy oil floating bed hydrocracking catalyst, the slurry-bed hydrocracking for inferior heavy oil.
For achieving the above object, the present invention adopts the following technical scheme that；
Scheme one, a kind of heavy oil floating bed hydrocracking catalyst, by the ore composition powder after Zinc oxide powder and vulcanization
End composition, wherein the content of Zinc oxide powder is 10~56wt%, and the mineral constituent powder after the vulcanization includes nickeliferous mine
Stone contains one or more of tungsten ore, iron-stone.
Scheme two, a kind of heavy oil floating bed hydrocracking catalyst, by the ore composition powder after Zinc oxide powder, vulcanization
With micro- mesoporous cadmium ferrite composition after vulcanization, wherein the content of Zinc oxide powder is 10~56wt%, micro- mesoporous ferrous acid after vulcanization
Lanthanum content is 0.2 ~ 12wt%, and the mineral constituent powder after the vulcanization includes nickel-containing ore, containing in tungsten ore, iron-stone
One or more.Micro- mesoporous cadmium ferrite content after vulcanization is preferably 0.5 ~ 6.0wt%.
In scheme one and scheme two, it is preferred that the content of Zinc oxide powder is 10 ~ 45wt% in the catalyst.
In scheme one and scheme two, it is preferred that the Zinc oxide powder is nano zine oxide.
In scheme one and scheme two, it is preferred that the zinc oxide is the zinc oxide of the structure containing gahnite.
Preferably, in the catalyst, including the nickel-containing ore powder and/or 5 ~ 35wt% sulphur after 10 ~ 34wt% vulcanization
The iron-stone powder after tungstenic mineral dust and/or 5 ~ 45 wt% vulcanization after change.
A method of preparing the heavy oil floating bed hydrocracking catalyst as described in scheme one: by the ore of 50 ~ 180 mesh
Component powders carry out vulcanizing treatment with vulcanizing agent, then dry-mixed with Zinc oxide powder, are sufficiently stirred, are catalyzed after mixing
Agent, the catalyst of preparation can effectively facilitate the progress of inferior heavy oil hydrocracking reaction, improve inferior heavy oil hydrogenation activity, reduce
Green coke amount, desulfurization effect are good.
A method of it preparing the heavy oil floating bed hydrocracking catalyst as described in scheme two: micro- mesoporous cadmium ferrite is used
Vulcanizing agent carries out vulcanizing treatment, and Zinc oxide powder is dry-mixed obtains mixed-powder；Then again by the ore composition powder of 50 ~ 180 mesh
End carries out vulcanizing treatment with vulcanizing agent, dry-mixed with mixed-powder, is sufficiently stirred, obtains catalyst after mixing.
According to preparation method as described above, the ore composition powder is before carrying out vulcanizing treatment, first 400 ~ 500
2 ~ 10 h are roasted under conditions of DEG C, remove impurity, obtain 50 ~ 180 mesh powder using crushing, sieving after removal of impurities；The sulphur
Agent includes one or more of carbon disulfide, dimethyl disulfide, sulphur, and the additional amount of vulcanizing agent is heavy oil weight
0.05%~1.2%。
The preferred nano zine oxide of zinc oxide of the present invention, is uniformly mixed with mineral dust, and catalyst is not easy to coalesce, dispersibility
It is good.It is highly preferred that zinc oxide is the zinc oxide of the structure containing gahnite, after the zinc oxide of the structure containing gahnite and vulcanization
Mineral dust mixing.The preparation method of the zinc oxide of the structure containing gahnite is simultaneously without restriction.
Mineral dust is uniformly mixed after cure, and vulcanization process is without restriction, and vulcanizing agent can be carbon disulfide, dimethyl
The one or more such as two sulphur, sulphur.The additional amount of vulcanizing agent is the 0.05% ~ 1.2% of oily weight, preferably 0.08% ~ 1.0%.This hair
Bright catalyst need not vulcanize when reacting for floating bed hydrogenation, directly react.
Inferior heavy oil of the present invention can be residual oil, shale oil, tar sand oil, again (thick) oil, extra heavy oil, deep layer stone
Oil, pitch, coal tar etc..
Mineral dust of the present invention is 50 ~ 180 mesh, and Zinc oxide powder is 50 ~ 180 mesh.
Ore of the present invention can be natural crystal, also without restriction to nickel, tungsten, iron equal size, can be contained according to ore
Some nickel, tungsten, iron equal size height adjustment ore additional amount.Zinc oxide preferably carries out calcination process, in 450 ~ 550 DEG C of condition
2 ~ 10h of lower roasting obtains 50 ~ 180 mesh powder using crushing etc..
Preparation process of the invention be it is dry-mixed, preparation process is simple, and hydrogenation activity is high, desulfurization effect is good, inhibits coking energy
Power is strong.
Inferior heavy oil sulfur content, carbon residue, nitrogen and tenor are relatively high, and the easily green coke substance such as asphalitine, colloid, aromatic hydrocarbons contains
Amount is also high, and difficulty of processing is big.Hydrocracking catalyst for suspension bed of the present invention, hydrogenation activity is high, desulfurization effect is good, inhibits knot
It is burnt.The zinc oxide of the especially structure containing gahnite is mixed with the mineral dust after vulcanization, the catalyst sulfur resistive of preparation, anti-gold
The impurity ability such as category, nitrogen, carbon residue is strong, and activity is higher, carries out to heavy components such as asphalitine, colloid, aromatic hydrocarbons in inferior heavy oil
Effective hydro-conversion inhibits coking ability strong, improves inferior heavy oil conversion ratio and desulfurization degree.
Inferior heavy oil hydrogenation reaction temperature is relatively high, generally tens degree higher than set temperature, the high slag oil crack of reaction temperature
While rate increases, gas yield is also increased with it, and fraction oil yield reduces, and reaction pressure increases, and coking yield obviously increases,
The normal operation of catalyst and equipment, or even parking are influenced when serious.
In response to the above problems, catalyst is improved, catalyst of the present invention further includes micro- mesoporous cadmium ferrite (LaFeO3 )
Compound.The preparation method of the micro- mesoporous cadmium ferrite of the present invention is simultaneously without restriction, such as can prepare with the following method, lemon
Acid is dissolved in stirring and dissolving in deionized water, then lanthanum nitrate and ferric nitrate is added in citric acid, stirring and dissolving, and polypropylene is added
The additional amount of sour sodium or polyacrylic acid, Sodium Polyacrylate or polyacrylic acid is the 0.1-9wt%, preferably 0.1-6.0wt% of cadmium ferrite.
Stirring, after reaction, obtains finished product through drying, roasting, grinding.The micro- mesoporous cadmium ferrite of the present invention is mixed with other components after preferably vulcanizing
It closes, it is highly preferred that micro- mesoporous cadmium ferrite after vulcanization is first mixed with zinc oxide, is then mixed again with other components, is catalyzed in this way
Agent good dispersion, activity are high.
Cadmium ferrite prepared by the present invention have it is micro- mesoporous, be used for suspension bed inferior heavy oil hydrogenation reaction, on the one hand, catalyst
The burnt ability of load is strong, so that the coke that reaction generates is not bonded on the inner wall of reaction kettle and its in-line coking, is conducive to fill
Set long period steady running.On the other hand, with the introducing of micro- mesoporous cadmium ferrite, inferior heavy oil is made to be hydrocracked desulphurization reaction phase
To mitigation, effective the problem of inhibiting rapid cleavage reaction temperature to rise violently, and micro- mesoporous cadmium ferrite and zinc oxide and its other groups
Dividing has mutual synergistic effect, and then improves and be hydrocracked desulphurization reaction activity, reduces coking yield；Improve liquid yield,
Light oil yield and desulfurization degree.
The preferred bauxite of mineral constituent of the present invention, bauxite are bauxite after vulcanization, and bauxite powder and zinc oxide are dry-mixed.
It is highly preferred that the dead catalyst containing cobalt, molybdenum is first added in bauxite, if bauxite and the dead catalyst containing cobalt, molybdenum are dry-mixed, contain
Cobalt, molybdenum dead catalyst account for the 1 ~ 50% of bauxite quality, preferably 3~42wt%, more preferable 5~32 wt%, bauxite with contain
Cobalt, molybdenum dead catalyst mixing after vulcanize again.The dead catalyst cobalt molybdenum content of present invention molybdenum containing cobalt is without restriction, can be effective
Utilize the dead catalyst of the molybdenum containing cobalt.Bauxite and the dead catalyst mixing after cure containing cobalt, molybdenum, it is then dry-mixed with zinc oxide again,
The catalyst of preparation can effectively facilitate the progress of inferior heavy oil hydrocracking reaction, improve inferior heavy oil hydrogenation activity, reduce life
Jiao Liang, desulfurization effect are good.
Another embodiment of the present invention, the preferred kaolin powder of mineral constituent and iron-stone powder, kaolin powder
With kaolin powder and iron-stone powder that iron-stone powder is after vulcanization, Zinc oxide powder content is 15.0~50.0
Wt%, kaolin powder content after vulcanization are 15.0~60.0wt%, the iron-stone content of powder after vulcanization is 15.0~
55.0wt%, kaolin powder are dry-mixed with zinc oxide.The content of zinc oxide is preferably 20~45 wt% in catalyst, and more preferable 30
~45wt%, preferably 25~55wt% of kaolin content, more preferable 30~45 wt% of kaolin content, preferably iron-stone 15~45
Wt%, more preferable 15~35 wt% of iron-stone.Further preferably, catalyst of the present invention further includes ZSM-5 molecular sieve, catalyst
Middle ZSM-5 molecular sieve is also possible to useless ZSM-5 molecular sieve, and ZSM-5 molecular sieve content is 0.2 ~ 15 wt%, and ZSM-5 molecular sieve is most
It is mixed again with other components after being mixed with zinc oxide well, is conducive to give full play to catalyst hydrogenation cracking desulfurization activity in this way.
ZSM-5 molecular sieve is also possible to useless ZSM-5 molecular sieve.
Certainly, mineral dust of the present invention may be nickel compound containing, Tungstenic compound, and/or iron containing compounds, contain
Molybdenum compound, containing aluminium and/or siliceous molecular sieve, such as Y molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve, super steady USY molecule
Sieve, beta-molecular sieve etc..Another embodiment of the present invention, the preferred kaolin powder of mineral constituent, after in catalyst further including vulcanization
Molybdate compound powder, kaolin powder content is 15.0~55.0wt% after vulcanization, and zinc oxide is 10.0 ~ 65.0wt%, vulcanization
Molybdate compound is 1.0~25.0wt% afterwards, and kaolin powder, molybdenum compound and zinc oxide are dry-mixed.Kaolin powder after vulcanization
Content preferably 15.0 ~ 45.0wt%, more preferable 15.0 ~ 40.0wt%, molybdenum compound is 0.2~25.0wt% after Containing Sulfur, preferably
1.0~20.0 wt%, more preferable 1.5~18.0wt%.
The present invention also provides a kind of inferior heavy oil floating bed hydrocracking sulfur methods, include the following steps:
(1) above-mentioned inferior heavy oil suspension bed hydrogenation catalyst is mixed with inferior heavy oil；Catalyst amount be 90 ~
1800ppm；
(2) it being warming up to reaction temperature and carries out hydrogenation reaction, the temperature of hydrogenation reaction is 340 ~ 450 DEG C, reaction pressure is 5 ~
20MPa, reaction time are 0.5 ~ 4h.
The temperature of hydrogenation reaction of the present invention is preferably 350 ~ 400 DEG C.
Reaction pressure of the present invention is preferably 7 ~ 17MPa, more preferable 10 ~ 15MPa；Reaction time is 0.5 ~ 4h；Hydrogen oil
Volume ratio is preferably 500~1500, and air speed is preferably 0.5~3.5h-1。
The beneficial effects of the present invention are:
The method of the present invention is adaptable to different material, and inferior heavy oil high conversion rate, coking yield are low, desulfurization degree is high, evaporate
Divide oil yield high.
Specific embodiment
The present invention is described in further detail by the following examples, but these embodiments are not considered as to limit of the invention
System.
Prepare primary raw material source used in catalyst: source chemicals used in the present invention are commercial product.With distillate
The primary evaluation index of yield, inferior heavy oil conversion ratio, desulfurization degree and coking yield as catalyst catalytic performance.
Embodiment 1
After mixing containing tungsten ore, 25.00g iron-stone (being all 60 mesh) by 20.00g nickel-containing ore, 30.00g, it uses
Vulcanizing agent carries out vulcanizing treatment, and vulcanizing agent is carbon disulfide, then dry-mixed with the 25.00g Zinc oxide powder of 60 mesh, sufficiently stirs
It mixes, obtains catalyst 1 after mixing.
Embodiment 2
After three kinds of 450 DEG C of ore roastings, take 30.00g nickel-containing ore, 22.00g containing tungsten ore, 30.00g iron-stone
(being all 80 mesh) carries out vulcanizing treatment after mixing, with vulcanizing agent, and vulcanizing agent is carbon disulfide, then contains zinc-aluminium with 18.00g
The Zinc oxide powder of spinel structure is dry-mixed, is sufficiently stirred, and obtains catalyst 2 after mixing.
Embodiment 3
After three kinds of ores and 450 DEG C of zinc oxide roastings, take 22.00g nickel-containing ore, 18.00g containing tungsten ore, 15.00g
Iron-stone (being all 100 mesh) after mixing, carries out vulcanizing treatment with vulcanizing agent, and vulcanizing agent is carbon disulfide, then with
The Zinc oxide powder of 45.00g structure containing gahnite is dry-mixed, is sufficiently stirred, and obtains catalyst 3 after mixing.
Embodiment 4
15.00g nickel-containing ore, 26.00g is taken after mixing, to use containing tungsten ore, 29.00g iron-stone (being all 70 mesh)
Vulcanizing agent carries out vulcanizing treatment, and vulcanizing agent is sulphur powder, then dry-mixed with 30.00g nano-zinc oxide powder, is sufficiently stirred, and mixes
Catalyst 4 is obtained after uniformly.
Embodiment 5
27.00g nickel-containing ore, 23.00g is taken after mixing, to be vulcanized with vulcanizing agent containing tungsten ore (being all 120 mesh)
Processing, vulcanizing agent is sulphur powder, then dry-mixed with the Zinc oxide powder of 50.00g structure containing gahnite, is sufficiently stirred, and is mixed
Catalyst 5 is obtained after uniformly.
Embodiment 6
Under stirring condition, by 0.25mol La (NO3)3It is dissolved in 100mL water, citric acid stirring and dissolving is added；It adds
0.5 mol Fe(NO3)3, 18g Sodium Polyacrylate is then added, continues stirring 30min and obtains reaction solution, be fired, grind
To micro- mesoporous cadmium ferrite.
After three kinds of 450 DEG C of ore roastings, take 30.00g nickel-containing ore, 22.00g containing tungsten ore, 30.00g iron-stone
(being all 80 mesh) carries out vulcanizing treatment after mixing, with vulcanizing agent, and vulcanizing agent is carbon disulfide, obtains ore mix.1g
Micro- mesoporous cadmium ferrite powder and the Zinc oxide powder of 18.00g structure containing gahnite are dry-mixed after vulcanization, then mixed with ore again
Object mixing is closed, obtains catalyst 6 after mixing.The evaluation condition of catalyst is converted with embodiment 2, the inferior heavy oil of catalyst
Rate 93.18%, 83.46 wt% of fraction oil yield, 92.62 % of liquid yield, coking yield 0.26%, desulfurization degree 91.1%, reaction temperature rising
42℃。
Embodiment 7
15.00g nickel-containing ore, 26.00g is taken after mixing, to use containing tungsten ore, 29.00g iron-stone (being all 70 mesh)
Vulcanizing agent carries out vulcanizing treatment, and vulcanizing agent is sulphur powder, obtains ore mix.3g vulcanization after micro- mesoporous cadmium ferrite powder with
30.00g nano-zinc oxide powder is dry-mixed and then mixes again with ore mix, obtains catalyst 7 after mixing.Catalyst
Evaluation condition is the same as embodiment 2, the inferior heavy oil conversion ratio 93.06% of catalyst, 82.23 wt% of fraction oil yield, liquid yield
92.14 %, coking yield 0.27%, desulfurization degree 91.6%, 43 DEG C of reaction temperature rising.
Comparative example 1
The preparation of catalyst is with embodiment 2, except that do not vulcanize after three kinds of ore miberal powder ends mixing, then with
18.00g Zinc oxide powder is dry-mixed, is sufficiently stirred, and vulcanizes again after obtaining comparative catalyst 1 after mixing.Reaction raw materials oil and
For its process conditions with embodiment 1, reaction result is shown in Table 2.
Comparative example 2
The preparation of catalyst is with embodiment 3, except that do not vulcanize after three kinds of ore miberal powder ends mixing, then with
45.00g nano-zinc oxide powder is dry-mixed, is sufficiently stirred, and obtains comparative catalyst 2 after mixing, and then comparative catalyst 2 is again
Vulcanization, with embodiment 1, reaction result is shown in Table 2 for reaction raw materials oil and its process conditions.
Using decompression residuum as reaction raw materials, residual oil property such as table 1, as can be seen from Table 1, residual oil arene content, colloid, drip
Green matter, carbon residue content are higher, and tenor, sulfur content are also higher.60.00g is added into the autoclave that volume is 0.3L
The catalyst of decompression residuum, 800ppm above-described embodiment 1 ~ 5 and its comparative example, reaction pressure 12MPa；Reaction temperature is 380 DEG C,
Reaction time is 2h, after reaction, is down to room temperature to temperature, and the liquid oil of taking-up is weighed, and reaction result is shown in Table 2.
1 Vacuum Residue Properties of table
2 evaluating catalyst result of table
It can be seen that by 2 evaluating catalyst result of table in residual oil arene content 30.7%, gum level 27.1%, pitch
In the case where matter 11.5%, carbon left 25.42%, sulfur content 4.8%, the inferior heavy oil conversion ratio of catalyst in 90wt% or more,
Distillate yield is higher than 80.21 wt%, liquid yield, that is, 90.12 wt% or more of light oil constituents yield, and coking yield is below
0.45wt%, 89.6% or more desulfurization degree.Wherein embodiment 2 and 4 reaction temperature rising of embodiment are respectively 46 DEG C and 48 DEG C.Catalyst is anti-
The impurity ability such as sulphur, anti-metal, nitrogen, carbon residue is strong, has to heavy components such as asphalitine, colloid, aromatic hydrocarbons in inferior heavy oil
Hydro-conversion is imitated, inhibits coking, inferior heavy oil conversion ratio and desulfurization degree are high, and activity is higher.
Embodiment 8
The bauxite powder of 60 mesh of 60.00g is subjected to vulcanizing treatment with vulcanizing agent, vulcanizing agent is carbon disulfide, then with
The 15.00g Zinc oxide powder of 80 mesh is dry-mixed, is sufficiently stirred, and obtains catalyst 8 after mixing.
Embodiment 9
After the bauxite powder of 80 mesh of 40.00g and 80 purpose powder containing spent Mo-Co catalyst of 8.00g are mixed, sulphur is used
Agent carries out vulcanizing treatment, and vulcanizing agent is carbon disulfide, then dry-mixed with 20.57g nano-zinc oxide powder, is sufficiently stirred, and mixes
Catalyst 9 is obtained after closing uniformly.
Embodiment 10
By bauxite powder and the 8.00g powder containing spent Mo-Co catalyst (being all 120 mesh) of 40.00g, with vulcanizing agent into
Row vulcanizing treatment, vulcanizing agent are carbon disulfide, then dry-mixed with the Zinc oxide powder of 20.57g structure containing gahnite, sufficiently
Stirring, obtains catalyst 10 after mixing.
Embodiment 11
By 60.00g bauxite powder and 10.59g, powder containing spent Mo-Co catalyst (being all 140 mesh), is carried out with vulcanizing agent
Vulcanizing treatment, vulcanizing agent are sulphur powders, then dry-mixed with the Zinc oxide powder of 5.31g structure containing gahnite, are sufficiently stirred, and are mixed
Catalyst 11 is obtained after closing uniformly.
Embodiment 12
By bauxite powder and the 4.52g powder containing spent Mo-Co catalyst (being all 100 mesh) of 60.00g, with vulcanizing agent into
Row vulcanizing treatment, vulcanizing agent are carbon disulfide, then dry-mixed with the Zinc oxide powder of 12.29g structure containing gahnite, sufficiently
Stirring, obtains catalyst 12 after mixing.
Comparative example 3
The preparation of catalyst is with embodiment 9, except that bauxite powder and the 8.00g molybdenum containing cobalt of 40.00g is given up
After catalyst fines mixing, do not vulcanize, it is then dry-mixed with 20.57g Zinc oxide powder, it is sufficiently stirred, obtains after mixing pair
Than vulcanizing again after catalyst 3.
Comparative example 4
The preparation of catalyst is with embodiment 10, except that bauxite powder and the 8.00g molybdenum containing cobalt of 40.00g is given up
Do not vulcanize after catalyst fines mixing, it is then dry-mixed with the Zinc oxide powder of 20.57g structure containing gahnite, it is sufficiently stirred,
Comparative catalyst 4 is obtained after mixing, and then comparative catalyst 4 vulcanizes again, and reaction raw materials oil and its process conditions are the same as implementation
Example 8, reaction result is shown in Table 4.
Using decompression residuum as reaction raw materials, residual oil property such as table 3, as can be seen from Table 3, residual oil arene content, colloid, drip
Green matter, carbon residue content are higher, and tenor, sulfur content are also higher.60.00g is added into the autoclave that volume is 0.3L
Decompression residuum, the catalyst of 700ppm above-described embodiment 8 ~ 12 and its comparative catalyst 3,4, reaction pressure 11MPa；Reaction temperature
It is 400 DEG C, reaction time 2h, after reaction, is down to room temperature to temperature, the liquid oil of taking-up is weighed, reaction result is shown in
Table 4.
3 Vacuum Residue Properties of table
4 evaluating catalyst result of table
It can be seen that by 4 evaluating catalyst result of table in residual oil arene content 34.3%, gum level 25.7%, pitch
In the case where matter 15.6%, carbon left 23.96%, sulfur content 5.2%, the inferior heavy oil conversion ratio of catalyst in 91wt% or more,
Distillate yield is higher than 80.34 wt%, liquid yield, that is, 90.03 wt% of light oil constituents yield, and coking yield is below 0.42
Wt%, 88.2% or more desulfurization degree.Wherein embodiment 9 and 11 reaction temperature rising of embodiment are respectively 50 DEG C and 47 DEG C.Catalyst sulfur resistive,
The impurity ability such as anti-metal, nitrogen, carbon residue is strong, to the heavy components such as asphalitine, colloid, aromatic hydrocarbons in inferior heavy oil carry out effectively plus
Hydrogen conversion inhibits coking, and inferior heavy oil conversion ratio and desulfurization degree are high, and activity is higher.
Embodiment 13
After the bauxite powder of 80 mesh of 40.00g and 80 purpose powder containing spent Mo-Co catalyst of 8.00g are mixed, sulphur is used
Agent carries out vulcanizing treatment, obtains the mixture of the aluminium of molybdenum containing cobalt, vulcanizing agent is carbon disulfide, the micro- mesoporous cadmium ferrite powder of 1.41g
It is dry-mixed with 20.57g nano-zinc oxide powder, it is sufficiently stirred, then the mixture again with the aluminium of molybdenum containing cobalt is urged after mixing
Agent 13.The evaluation condition of catalyst is the same as embodiment 9, the inferior heavy oil conversion ratio 92.28t% of catalyst, fraction oil yield
81.22 wt%, liquid yield 92.33 wt%, coking yield 0.29wt%, desulfurization degree 90.2%, 44 DEG C of reaction temperature rising.
Embodiment 14
By bauxite powder and the 4.52g powder containing spent Mo-Co catalyst (being all 100 mesh) of 60.00g, with vulcanizing agent into
Row vulcanizing treatment, obtains the mixture of the molybdenum of cobalt containing aluminium, and vulcanizing agent is carbon disulfide.The micro- mesoporous cadmium ferrite powder of 2.38 g with
The Zinc oxide powder of 12.29g structure containing gahnite is dry-mixed, is sufficiently stirred, and then mixes again with the mixture of the molybdenum of cobalt containing aluminium
Uniformly, catalyst 14 is obtained.The evaluation condition of catalyst is evaporated with embodiment 12, the inferior heavy oil conversion ratio 92.94t% of catalyst
Point 82.12 wt% of oil yield, liquid yield 93.08 wt%, coking yield 0.24wt%, desulfurization degree 91.5%, 42 DEG C of reaction temperature rising.
Embodiment 15
After mixing by 35.00g kaolin powder and 33.00g iron-stone (being all 90 mesh), sulphur is carried out with vulcanizing agent
Change processing, vulcanizing agent is carbon disulfide, then dry-mixed with the 32.00g Zinc oxide powder of 90 mesh, is sufficiently stirred, after mixing
Obtain catalyst 15.
Embodiment 16
After kaolin powder and 430 DEG C of iron-stone powder roastings, by 40.00g kaolin powder and 30.00g iron content
Ore (being all 60 mesh) carries out vulcanizing treatment after mixing, with vulcanizing agent, and vulcanizing agent is sulphur powder, micro- mesoporous ferrous acid after 5g vulcanization
The Zinc oxide powder of lanthanum powder and the 30.00g structure containing gahnite is dry-mixed, then mixed with kaolin powder and iron-stone powder
It closes, is sufficiently stirred, obtains catalyst 16 after mixing.
Embodiment 17
After kaolin powder and 450 DEG C of iron-stone powder roastings, by 20.00g kaolin powder and 55.00g iron content
Ore (being all 80 mesh) carries out vulcanizing treatment after mixing, with vulcanizing agent, and vulcanizing agent is carbon disulfide, and 25.00g is containing zinc-aluminium point
The Zinc oxide powder of spinel structure is mixed with the useless ZSM-5 of 5g, then dry-mixed with micro- mesoporous cadmium ferrite powder after 7g vulcanization again, is mixed
It is uniformly mixed again with kaolin powder and iron-stone mixture after closing uniformly, obtains catalyst 17.
Embodiment 18
30.00g kaolin powder and 52.00g iron-stone (being all 80 mesh) are subjected to sulphur with vulcanizing agent after mixing
Change processing, vulcanizing agent are sulphur powders, and micro- mesoporous cadmium ferrite powder and 18.00g nano-zinc oxide powder are dry-mixed after 5g vulcanization, sufficiently stir
It mixes, then obtains catalyst 18 after mixing with kaolin powder and iron-stone again.
Embodiment 19
By kaolin and 450 DEG C of zinc oxide roasting after, take the micro- mesoporous cadmium ferrite powder of 40.00g kaolin, 4.00g and
7.00g molybdenum oxide (being all 50 mesh) after mixing, carries out vulcanizing treatment with vulcanizing agent, and vulcanizing agent is sulphur powder, then with 50 mesh
49.00g structure containing gahnite Zinc oxide powder it is dry-mixed, be sufficiently stirred, obtain catalyst 19 after mixing.To subtract
Pressure residual oil is reaction raw materials, and residual oil property such as table 1, as can be seen from Table 1, residual oil arene content, colloid, asphalitine, carbon residue contain
Amount is higher, and tenor, sulfur content are also higher.To volume be 0.3L autoclave in be added 50.00g decompression residuum,
The catalyst of 720ppm above-described embodiment 19, reaction pressure 10MPa；Reaction temperature is 370 DEG C, reaction time 2.5h, reaction
After, it is down to room temperature to temperature, the liquid oil of taking-up is weighed, reaction result is shown in Table 6.
Comparative example 5
The preparation of catalyst is with embodiment 16, except that after kaolin powder and the mixing of iron-stone powder, not sulphur
Change, it is then dry-mixed with 30.00g Zinc oxide powder, it is sufficiently stirred, vulcanizes again after obtaining comparative catalyst 5 after mixing.Reaction
With embodiment 15, reaction result is shown in Table 6 for feedstock oil and its process conditions.
Using decompression residuum as reaction raw materials, residual oil property such as table 5, as can be seen from Table 5, residual oil arene content, colloid, drip
Green matter, carbon residue content are higher, and tenor, sulfur content are also higher.60.00g is added into the autoclave that volume is 0.3L
The catalyst 5 of decompression residuum, 800ppm above-described embodiment 15 ~ 18 and its comparative example, reaction pressure 12MPa；Reaction temperature is 390
DEG C, reaction time 2h is down to room temperature to temperature after reaction, and the liquid oil of taking-up is weighed, and reaction result is shown in Table 6.
5 Vacuum Residue Properties of table
6 evaluating catalyst result of table
It can be seen that by 6 evaluating catalyst result of table in residual oil arene content 27.5%, gum level 29.5%, pitch
In the case where matter 12.1%, carbon left 22.69%, sulfur content 3.7%, the inferior heavy oil conversion ratio of catalyst in 91wt% or more,
Distillate yield is higher than 80.96 wt%, liquid yield, that is, 90.13 wt% or more of light oil constituents yield, and coking yield is below
0.42wt%, 90.4% or more desulfurization degree.Wherein 15 ~ 19 reaction temperature rising of embodiment is respectively 52 DEG C, 47 DEG C, 44 DEG C, 48 DEG C, 42
℃.The impurity ability such as catalyst sulfur resistive, anti-metal, nitrogen, carbon residue is strong, to heavys such as asphalitine, colloid, aromatic hydrocarbons in inferior heavy oil
Component carries out effective hydro-conversion, inhibits coking, inferior heavy oil conversion ratio and desulfurization degree are high, and activity is higher.Catalyst 16 ~ 19 is anti-
It opposite should mitigate, coking yield is low.
Certainly, the present invention can also have other various embodiments, without departing substantially from spirit of that invention and its its essence,
Those skilled in the art can make various corresponding changes and modifications, but these corresponding changes and change according to the present invention
Shape all should belong to protection scope of the present invention.
Claims (11)
1. a kind of heavy oil floating bed hydrocracking catalyst, it is characterised in that: after the catalyst is by Zinc oxide powder and vulcanization
Ore composition powder constituent, wherein the content of Zinc oxide powder be 10~56wt%, the ore composition powder after the vulcanization
For nickel-containing ore, contain one or more of tungsten ore, iron-stone.
2. a kind of heavy oil floating bed hydrocracking catalyst, it is characterised in that: after the catalyst is by Zinc oxide powder, vulcanization
Micro- mesoporous cadmium ferrite composition after ore composition powder and vulcanization, wherein the content of Zinc oxide powder is 10~56wt%, after vulcanization
Micro- mesoporous cadmium ferrite content be 0.2 ~ 12wt%, ore composition content of powder after vulcanization is 40 ~ 80wt%, after the vulcanization
Ore composition powder be nickel-containing ore, contain one or more of tungsten ore, iron-stone.
3. heavy oil floating bed hydrocracking catalyst according to claim 1 or 2, it is characterised in that: in the catalyst
The content of Zinc oxide powder is 10 ~ 45wt%.
4. heavy oil floating bed hydrocracking catalyst according to claim 1 or 2, it is characterised in that: the oxide powder and zinc
End is nano zine oxide.
5. heavy oil floating bed hydrocracking catalyst according to claim 1 or 2, it is characterised in that: the catalyst
In, including the nickel-containing ore powder after 10 ~ 34wt% vulcanization and/or the tungstenic mineral dust and/or 5 ~ 45 after 5 ~ 35wt% vulcanization
Iron-stone powder after wt% vulcanization.
6. a kind of method for preparing heavy oil floating bed hydrocracking catalyst as described in claim 1, it is characterised in that: by 50
The ore composition powder of ~ 180 mesh carries out vulcanizing treatment with vulcanizing agent, then dry-mixed with Zinc oxide powder, is sufficiently stirred, and mixing is equal
Catalyst is obtained after even.
7. a kind of method for preparing heavy oil floating bed hydrocracking catalyst as claimed in claim 2, it is characterised in that: will be micro-
Mesoporous cadmium ferrite carries out vulcanizing treatment with vulcanizing agent, and Zinc oxide powder is dry-mixed obtains mixed-powder；Then again by 50 ~ 180 mesh
Ore composition powder carry out vulcanizing treatment with vulcanizing agent, it is dry-mixed with mixed-powder, be sufficiently stirred, be catalyzed after mixing
Agent.
8. the preparation method of heavy oil floating bed hydrocracking catalyst according to claim 6 or 7, it is characterised in that: institute
The ore composition powder stated first roasts 2 ~ 10 h before carrying out vulcanizing treatment under conditions of 400 ~ 500 DEG C, removes impurity, removes
50 ~ 180 mesh powder are obtained using crushing, sieving after miscellaneous.
9. the preparation method of heavy oil floating bed hydrocracking catalyst according to claim 6 or 7, it is characterised in that: oxygen
Change zinc powder with other components carry out it is dry-mixed before, first under conditions of 450 ~ 550 DEG C roast 2 ~ 10h, using crush, sieving
Obtain 50 ~ 180 mesh powder.
10. the preparation method of heavy oil floating bed hydrocracking catalyst according to claim 8, which is characterized in that the sulphur
Agent is carbon disulfide, one or more of dimethyl disulfide and sulphur.
11. heavy oil floating bed hydrocracking catalyst according to claim 1 or 2, which is characterized in that in the catalyst
Containing 10~35wt% of 10~25wt% of tungsten ore and/or iron-stone.
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