CN106732636A - A kind of sulphided state poor oil suspension bed hydrogenation catalyst and its preparation method and application - Google Patents
A kind of sulphided state poor oil suspension bed hydrogenation catalyst and its preparation method and application Download PDFInfo
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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
- 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
- B01J23/8872—Alkali or alkaline earth metals
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
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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
- 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
- B01J23/78—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 alkali- or alkaline earth metals
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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
- 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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- 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
- B01J37/20—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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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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
- C10G2300/1037—Hydrocarbon fractions
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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
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
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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 present invention discloses a kind of sulphided state poor quality oil hydrogenation catalysts and its preparation method and application, belongs to the technical field of poor oil suspension bed hydrogenation catalyst.Catalyst of the present invention is carrier predecessor with houghite, and the product of roasting with houghite is as carrier.In the HDM of residual oil and coal tar, hydrodesulfurization, hydrodenitrogeneration and catalysis activity is high in hydrogenation priming reaction in the sulphided state poor quality oil hydrogenation catalysts that the present invention is provided, and it is not easy coking.
Description
Technical field
The invention belongs to the technical field of poor oil suspension bed hydrogenation catalyst, and in particular to before with houghite as carrier
Drive thing, the poor oil suspension bed hydrogenation catalyst with its product of roasting as carrier.
Background technology
It is well known that with increasingly deficient, the heaviness of crude oil and the in poor quality day in world wide of world energy sources resource
Become serious.At the same time, with the increasingly consumption of Coal Energy Source in Chinese scope, the yield of its coal tar is also increasing year by year
It is many.Between wherein 2005-2013, Chinese coal tar total output is increased with average annual 9.9% speed, coal tar total output in 2013
Go up 16% to 20,000,000 ton on year-on-year basis.And in world wide the yield of residual oil and heavy oil the weight that also result in people growing day by day
Depending on.Therefore these poor oils are effectively processed just to be particularly important, and Hydrofining Technology is to make most having for poor oil lighting
One of efficacious prescriptions case.If low poor oil " eating dry squeezing only " deep processing can be worth to be made up into the fuel oil and chemicals of high-quality
The deficiency of oil product, then poor oil industry can then show larger development potentiality.
Due to containing substantial amounts of sulphur, nitrogen, metal impurities in this kind of poor oil, and containing being easy to the charcoal of coking, and these
Impurity can cause the catalyst poisoning in processing procedure, so as to be impacted to Catalytic processes and stabilization of equipment performance therefore right
Poor oil carries out impurity removal.This requires that such catalyst has good hydrodesulfurization, hydrodenitrogeneration and the de- charcoal of hydrogenation
Activity, at the same time, will also have certain hydrogenation cracking activity.
At present, industrial general oil hydrogenation catalysts inferior are added suitable with aluminum oxide as carrier according to different requirements
The auxiliary agent of amount, at the same time, it is also possible to improve the hydrofinishing effect of catalyst by adjusting the acid-base property of alumina support.
Chinese patent literature CN104998693A discloses a kind of preparation method and application of oil hydrogenation catalysts inferior, the prior art
Natural bauxite is carried out into high-temperature process in air atmosphere, then immerses acid solution to carry out acid treatment, so that purifying natural alum clay
The compositions such as aluminum oxide, silica and iron oxide in ore deposit, and its crystallization degree is improved, after treatment in the surface acidity of bauxite
The heart is redistributed, and specific surface area and pore volume are significantly increased, and is conducive to improving catalyst to poor quality through the catalyst obtained by treatment
The hydrogenation activity function of the macromolecular such as oily studies on asphaltene and colloid, so as to improve its light fraction yield high.Urged yet with this
It is carrier that agent uses aluminum oxide, and the acid centre on its surface causes that active component is difficult dispersion, so as to cause it for coal
Activity is relatively low when hydrogenation of tar removing metal, hydrodesulfurization and hydrodenitrogeneration, and there is a problem of easy coking, and then causes coal
The conversion ratio of tar or residual oil is low.
The content of the invention
Therefore, the technical problems to be solved by the invention be overcome in existing oil hydrogenation catalysts inferior in residual oil and
The HDM of coal tar, hydrodesulfurization, hydrodenitrogeneration and catalysis activity is low in hydrogenation priming reaction, and easily coking lacks
Fall into, so as to provide a kind of sulphided state poor quality oil hydrogenation catalysts and its preparation method and application.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of sulphided state poor quality oil hydrogenation catalysts, are carrier predecessor with houghite, are produced with the roasting of houghite
Thing is carrier.
Also include active component and sublimed sulfur, the active component is Co, Ni, Fe, Mo, one or two the group in W
Close.
The carrier is the fired MMgA1-LDO (M=Co, Ni and Fe) for obtaining of houghite.
Also include sublimed sulfur, each component weight of the catalyst is：The weight portion of carrier 5~20；Active component,
0.2~1.2 weight portion is measured by its oxide；The weight portion of sublimed sulfur 1.8~7.2.
The active component is Mo and/or W.
The carrier is with NaOH and Na2CO3It is precipitating reagent, the mixing using coprecipitation precipitation metal cation salt is molten
Metal cation in liquid, and by aging, centrifugation, dry the carrier predecessor of heating up, then it is calcined to obtain carrier；
The metal cation salt is selected from Co (NO3)2·6H2O、Ni(NO3)2·6H2O、Fe(NO3)2·6H2O、Mg
(NO3)2·6H2O and Al (NO3)3·9H2One or more in O；
The carrier predecessor is magnesia-alumina hydrotalcite, cobalt magnesia-alumina hydrotalcite, nickel magnesia-alumina hydrotalcite and/or iron magnalium
Houghite.
The preparation method of above-mentioned catalyst comprises the following steps：
(1) houghite carrier predecessor is prepared：After in the mixed solution instillation precipitating reagent of metal cation salt, heat up
To 60-100 DEG C, pH=8-11 is then adjusted, continue to stand 8-24h after stirring 1-3h, it is dry to carry through centrifuge washing to neutrality
Body predecessor MMgAl-LDHs (M=Co, Ni and Fe)；
(2) carrier is prepared：Carrier predecessor obtained by calcination stepses (1) obtain carrier MMgAl-LDO (M=Co, Ni and
Fe)；
(3) oxidized catalyst is prepared：Dipping solution is impregnated into by carrier MMgAl-LDO (M=using equi-volume impregnating
Co, Ni and Fe) on, then be calcined and obtain oxidized catalyst Mo (W)/MMgAl-LDO (M=Co, Ni and Fe), the dipping solution
It is (NH4)6Mo7O24·4H2O or (NH4)10W12O41·XH2The aqueous solution of O；
(4) sulphided state catalyst is prepared：Carried out at vulcanization after step (3) gained oxidized catalyst is mixed with sublimed sulfur
Reason, obtains sulphided state poor quality oil hydrogenation catalysts.
Drying temperature in step (1) is 80-120 DEG C, and drying time is 6-24h；
The sintering temperature of the roasting carrier predecessor is 500~800 DEG C, and roasting time is 2~4h；
Sintering temperature described in step (3) is 450~650 DEG C, and roasting time is 2~4h；
It is 250-350 DEG C that vulcanizing treatment described in step (4) obtains temperature, and the time is 2~4h.
The mixed solution of the metal cation salt is Co (NO3)2·6H2O、Ni(NO3)2·6H2O、Fe(NO3)2·
6H2O、Mg(NO3)2·6H2O and/or Al (NO3)3·9H2The mixed solution of O, the precipitating reagent is NaOH and anhydrous Na2CO3。
Co (NO in the mixed solution of the metal cation salt3)2·6H2O and Mg (NO3)2·6H2The amount of the material of O
And with Al (NO3)3·9H2The ratio between amount of material of O is 3：1~1：3.
The substance withdrawl syndrome of the NaOH is 0.32mol/L, the anhydrous Na2CO3Material amount and Al (NO3)3·
9H2The amount of the material of O is identical.
The equi-volume impregnating is carried out at normal temperatures and pressures.
Application of the above-mentioned catalyst in the reaction of poor oil hydrogenation catalyst, reaction initial hydrogen pressure is 12.5MPa, stir speed (S.S.)
500r/min, curing temperature is respectively 190 DEG C and 250 DEG C, and cure time is 30min, 430 DEG C of reaction temperature, reaction time
90min。
Technical solution of the present invention, has the following advantages that：
1st, the present invention provide sulphided state poor quality oil hydrogenation catalysts with houghite be carrier predecessor, with houghite
Product of roasting be carrier, wherein carrier for houghite product of roasting, by high-temperature roasting still have ratio table higher
Area, it is easy to adjust the soda acid property of carrier surface, can be introduced directly into houghite by auxiliary agent, obtain containing auxiliary agent after roasting
Composite oxide carrier, and auxiliary agent is uniformly dispersed, and good interaction is formed between auxiliary agent and active component.In relatively low work
Its catalysis activity is obviously improved than similar catalyst under property component load capacity, and with good anticoking capability.
The magnesia-alumina hydrotalcite of the sulphided state poor quality oil hydrogenation catalysts that the 2nd, the present invention is provided prepares water using coprecipitation
Talcum process is simple, it is easy to operate, it is cheap, can be mass-produced, have broad application prospects.
3rd, the sulphided state poor quality oil hydrogenation catalysts catalysis activity that the present invention is provided is high, and metal, sulphur, nitrogen removal efficiency are high and not
Easy coking.
Specific embodiment
It is to preferably further understand the present invention to provide following embodiments, it is not limited to the optimal embodiment party
Formula, is not construed as limiting to present disclosure and protection domain, anyone under enlightenment of the invention or by the present invention and its
The feature of his prior art be combined and draw it is any with the present invention it is same or like as product, all fall within of the invention
Within protection domain.
Unreceipted specific experiment step or condition person in embodiment, according to the normal experiment described by document in the art
The operation of step or condition can be carried out.Agents useful for same or the unreceipted production firm person of instrument, be can by city available from
Conventional reagent product.
Embodiment 1
The concentration for weighing the amount of 3.2g materials is NaOH the and 2.65g anhydrous Nas of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, poured into after stirring 20min in there-necked flask and continue to stir 1h.By (Co2++Mg2+)/(Al3+) mol ratio be 1:1 and Co2 +/(Co2++Mg2+) mol ratio is the 0.03 corresponding nitrate solution of proportioning, and 0.2182gCo (NO are weighed respectively3)2·6H2O、
6.2179g Mg(NO3)2·6H2O and 9.3783g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasound point after dissolving
10min is dissipated, mixed solution is obtained.The mixed solution peristaltic pump of cobalt magnalium is slowly dropped into precipitating reagent with the speed of 5ml/min
In the there-necked flask at place, and it is stirred vigorously.PH=9 or so is adjusted during dropwise addition, is warming up to after completion of dropping
90 DEG C, continue to stand 24h after stirring 2h.It is centrifuged after standing is finished, washing to pH=7.Then 12h is dried at 100 DEG C,
So as to obtain CoMgAl-LDHs.It is placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtains CoMgAl-
LDO, is designated as carrier 1.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous impregnation of O on CoMgAl-LDO, it
After be placed in Muffle furnace, be calcined 2h at 450 DEG C, so as to obtain Mo/CoMgAl-LDO, wherein the mass fraction of Mo be 7% (with
MoO3Meter).It is designated as oxidized catalyst A.
Embodiment 2
The concentration for weighing the amount of 3.2g materials is NaOH the and 7.95g anhydrous Nas of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, poured into after stirring 20min in there-necked flask and continue to stir 1h.By (Ni2++Mg2+)/(Al3+) mol ratio be 1:3 and Ni2 +/(Ni2++Mg2+) mol ratio is the 0.03 corresponding salting liquid of proportioning, and 0.2181g Ni (NO are weighed respectively3)2·6H2O、
6.2179Mg(NO3)2·6H2O and 28.1349g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasonic disperse after dissolving
10min, obtains mixed solution.The mixed solution peristaltic pump of cobalt magnalium is slowly dropped into precipitating reagent institute with the speed of 5ml/min
There-necked flask in, and be stirred vigorously.PH=9 or so is adjusted during dropwise addition, 90 are warming up to after completion of dropping
DEG C, continue to stand 24h after stirring 2h.It is centrifuged after standing is finished, then washing to pH=7. dries 12h at 100 DEG C, from
And obtain NiMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtains NiMgAl-
LDO, is designated as carrier 2.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous impregnation of O on NiMgAl-LDO, it
After be placed in Muffle furnace, be calcined 2h at 450 DEG C, so as to obtain Mo/NiMgAl-LDO, wherein the mass fraction of Mo be 9% (with
MoO3Meter).It is designated as oxidized catalyst B.
Embodiment 3
The concentration for weighing the amount of 3.2g materials is NaOH the and 0.88g anhydrous Nas of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, poured into after stirring 20min in there-necked flask and continue to stir 1h.By (Fe2++Mg2+)/(Al3+) mol ratio be 3:1 and Fe2 +/(Fe2++Mg2+) mol ratio is the 0.03 corresponding salting liquid of proportioning, and 0.2160Fe (NO are weighed respectively3)2·6H2O、6.2179gMg
(NO3)2·6H2O and 3.1261g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasonic disperse 10min after dissolving, is obtained
To mixed solution.Three mouthfuls where the mixed solution peristaltic pump of cobalt magnalium is slowly dropped into precipitating reagent with the speed of 6ml/min
In flask, and it is stirred vigorously.PH=9 or so is adjusted during dropwise addition, 90 DEG C are warming up to after completion of dropping, continue to stir
Mix and stand 24h after 2h.It is centrifuged after standing is finished, washing to pH=7.Then 12h is dried at 100 DEG C, so as to obtain
FeMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtain FeMgAl-LDO, remembers
It is carrier 3.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous impregnation of O is placed in afterwards on CoMgAl-LDO
In Muffle furnace, 2h is calcined at 450 DEG C, so as to obtain Mo/FeMgAl-LDO, the wherein mass fraction of Mo is 13% (with MoO3
Meter).It is designated as oxidized catalyst C.
Embodiment 4
The concentration for weighing the amount of 3.2g materials is NaOH the and 1.325g anhydrous Nas of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, poured into after stirring 20min in there-necked flask and continue to stir 1h.By (Ni2++Mg2+)/(Al3+) mol ratio be 2:1 and Ni2 +/(Ni2++Mg2+) mol ratio is the 0.03 corresponding salting liquid of proportioning, and 0.2181g Co (NO are weighed respectively3)2·6H2O、6.2179g
Mg(NO3)2·6H2O and 4.6891g Al (NO3)39H2O is dissolved in 250ml deionized waters, ultrasonic disperse 10min after dissolving,
Obtain mixed solution.Where the mixed solution B peristaltic pumps of cobalt magnalium are slowly dropped into precipitating reagent with the speed of 5ml/min three
In mouth flask, and it is stirred vigorously.PH=9 or so is adjusted during dropwise addition, 90 DEG C are warming up to after completion of dropping, continued
24h is stood after stirring 2h.It is centrifuged after standing is finished, washing to pH=7.Then 12h is dried at 100 DEG C, so as to obtain
NiMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtain NiMgAl-LDO, remembers
It is carrier 4.Using equi-volume impregnating (NH4)10W12O41·XH2The ammonia spirit of O is impregnated on NiMgAl-LDO, it is rearmounted
In Muffle furnace, 2h is calcined at 450 DEG C, so as to obtain W/NiMgAl-LDO, the wherein mass fraction of W is 5% (with WO3Meter).
It is designated as oxidized catalyst D.
Embodiment 5
The concentration for weighing the amount of 3.2g materials is NaOH the and 2.65g anhydrous Nas of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, poured into after stirring 20min in there-necked flask and continue to stir 1h.By (Co2++Mg2+)/(Al3+) mol ratio be 1:1 and Co2 +/(Co2++Mg2+) mol ratio is the 0.03 corresponding nitrate solution of proportioning, and 0.2182gCo (NO are weighed respectively3)2·6H2O、
6.2179g Mg(NO3)2·6H2O and 9.3783g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasound point after dissolving
10min is dissipated, mixed solution is obtained.The mixed solution peristaltic pump of cobalt magnalium is slowly dropped into precipitating reagent with the speed of 5ml/min
In the there-necked flask at place, and it is stirred vigorously.PH=9 or so is adjusted during dropwise addition, is warming up to after completion of dropping
90 DEG C, continue to stand 24h after stirring 2h.It is centrifuged after standing is finished, washing to pH=7.Then 12h is dried at 100 DEG C,
So as to obtain CoMgAl-LDHs.It is placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtains CoMgAl-
LDO, is designated as carrier 1.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous impregnation of O on CoMgAl-LDO, it
After be placed in Muffle furnace, be calcined 2h at 450 DEG C, so as to obtain Mo/CoMgAl-LDO, the mass fraction of wherein Mo and Co is 6%
(with MoO3Counted with CoO).It is designated as oxidized catalyst E.
Embodiment 6
The concentration for weighing the amount of 3.2g materials is NaOH the and 7.95g anhydrous Nas of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, poured into after stirring 20min in there-necked flask and continue to stir 1h.By (Ni2++Mg2+)/(Al3+) mol ratio be 1:3 and Ni2 +/(Ni2++Mg2+) mol ratio is the 0.03 corresponding salting liquid of proportioning, and 0.2181g Ni (NO are weighed respectively3)2·6H2O、
6.2179Mg(NO3)2·6H2O and 28.1349g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasonic disperse after dissolving
10min, obtains mixed solution.The mixed solution peristaltic pump of cobalt magnalium is slowly dropped into precipitating reagent institute with the speed of 5ml/min
There-necked flask in, and be stirred vigorously.PH=9 or so is adjusted during dropwise addition, 90 are warming up to after completion of dropping
DEG C, continue to stand 24h after stirring 2h.It is centrifuged after standing is finished, then washing to pH=7. dries 12h at 100 DEG C, from
And obtain NiMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtains NiMgAl-
LDO, is designated as carrier 2.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous impregnation of O on NiMgAl-LDO, it
After be placed in Muffle furnace, be calcined 2h at 450 DEG C, so as to obtain Mo/NiMgAl-LDO, the mass fraction of wherein Ni and Mo is 10%
(with NiO and MoO3Meter).It is designated as oxidized catalyst F.
Embodiment 7
The concentration for weighing the amount of 3.2g materials is NaOH the and 0.88g anhydrous Nas of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, poured into after stirring 20min in there-necked flask and continue to stir 1h.By (Fe2++Mg2+)/(Al3+) mol ratio be 3:1 and Fe2 +/(Fe2++Mg2+) mol ratio is the 0.03 corresponding salting liquid of proportioning, and 0.2160Fe (NO are weighed respectively3)2·6H2O、6.2179gMg
(NO3)2·6H2O and 3.1261g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasonic disperse 10min after dissolving, is obtained
To mixed solution.Three mouthfuls where the mixed solution peristaltic pump of cobalt magnalium is slowly dropped into precipitating reagent with the speed of 6ml/min
In flask, and it is stirred vigorously.PH=9 or so is adjusted during dropwise addition, 90 DEG C are warming up to after completion of dropping, continue to stir
Mix and stand 24h after 2h.It is centrifuged after standing is finished, washing to pH=7.Then 12h is dried at 100 DEG C, so as to obtain
FeMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtain FeMgAl-LDO, remembers
It is carrier 3.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous impregnation of O is placed in afterwards on CoMgAl-LDO
In Muffle furnace, 2h are calcined at 450 DEG C, so as to obtain Mo/FeMgAl-LDO, the mass fraction of wherein Fe and NiO for 11% (with
NiO and Fe3O4Meter).It is designated as oxidized catalyst G.
Embodiment 8
The application method of the oxidized catalyst prepared by embodiment 1-7, comprises the following steps that：
First by 60g reduced crudes, 1.85g catalyst fineses (embodiment 1-7) and 0.586g sublimed sulfurs in high-speed homogenization
Stir 2h in machine.Then taking during about 44g said mixtures are added to autoclave is used for active testing, and being passed through hydrogen makes
Reacting kettle inner pressure reaches 24MPa and is hunted leak.Said mixture had first been warming up to 190 DEG C of holdings before active testing
0.5h, 250 DEG C of holding 0.5h are then warming up to again carries out vulcanizing treatment, finally gives sulphided state catalyst.Treat sulfidation knot
Shu Hou, is warming up to 450 DEG C of reaction temperature, heating is stopped after 90min is reacted under stir speed (S.S.) is 500r/min and is stirred, and uses
Temperature in the kettle is rapidly decreased to room temperature with terminating reaction by water-cooling pattern.
Comparative example 1
Weigh 3.2g NaOH and 2.65g anhydrous Nas2CO3It is dissolved in 250ml deionized waters, three mouthfuls is poured into after stirring 20min
Continue to stir 1h in flask.It is 2 by the mol ratio of magnesium and aluminium:The corresponding salting liquid of 1 proportioning.6.4102g Mg are weighed respectively
(NO3)2·6H2O and 9.37825g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasonic disperse 10min after dissolving, is obtained
To mixed solution.Three mouthfuls of burnings where the mixed solution peristaltic pump of magnalium is slowly dropped into precipitating reagent with the speed of 5ml/min
In bottle, and it is stirred vigorously.PH=9 or so is adjusted during dropwise addition, 90 DEG C are warming up to after completion of dropping, continue to stir
24h is stood after 2h.It is centrifuged after standing is finished, then washing to pH=7. dries 12h at 100 DEG C, so as to obtain MgAl-
LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtain MgAl-LDO, is designated as carrier 5.
Using equi-volume impregnating Ni (NO3)2·6H2O and (NH4)6Mo7O24·4H2The ammoniacal liquor mixed solution of O is impregnated into MgAl-LDO
On, it is placed in Muffle furnace afterwards, 2h is calcined at 450 DEG C, so as to obtain NiMo/MgAl-LDO as reference, the wherein matter of Mo
Amount fraction is respectively 7% (with MoO3Meter), it is designated as oxidized catalyst H.
Comparative example 2
Weigh 3.2g NaOH and 2.65g anhydrous Nas2CO3It is dissolved in 250ml deionized waters, three mouthfuls is poured into after stirring 20min
Continue to stir 1h in flask.It is 2 by the mol ratio of magnesium and aluminium:The corresponding salting liquid of 1 proportioning.6.4102g Mg are weighed respectively
(NO3)2·6H2O and 9.37825g Al (NO3)3·9H2O is dissolved in 250ml deionized waters, ultrasonic disperse 10min after dissolving, is obtained
To mixed solution.Three mouthfuls of burnings where the mixed solution peristaltic pump of magnalium is slowly dropped into precipitating reagent with the speed of 5ml/min
In bottle, and it is stirred vigorously.PH=9 or so is adjusted during dropwise addition, 90 DEG C are warming up to after completion of dropping, continue to stir
24h is stood after 2h.It is centrifuged after standing is finished, then washing to pH=7. dries 12h at 100 DEG C, so as to obtain MgAl-
LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the speed of 3 DEG C/min, obtain MgAl-LDO, is designated as carrier 5.
Using equi-volume impregnating (NH4)6Mo7O24·4H2The ammoniacal liquor mixed solution of O is impregnated on MgAl-LDO, and Muffle is placed in afterwards
In stove, 2h is calcined at 450 DEG C, so as to obtain Mo/MgAl-LDO as reference, the wherein mass fraction of Mo is 7% (with MoO3
Meter).It is designated as oxidized catalyst I.
Explanation：Catalyst obtained by above example 1-7 and comparative example 1-2 is oxidized catalyst, and whole
Really play catalytic action in hydrogenation process is sulphided state catalyst, but sulphided state catalyst is very unstable in atmosphere
It is fixed, it is easy to which that desulfurication occurs causes catalyst to inactivate.Therefore the vulcanization measure that we take is, by residual oil, oxidation state
Catalyst and sublimed sulfur are added in reactor, then elevated temperature cure, oxidized catalyst is changed into sulphided state catalyst, then
Carry out hydrogenation reaction.Due to the no longer ingress of air after vulcanization, but directly reacted, so as to avoid the hair of devulcanization
It is raw, be conducive to the stable existence of active phase.
The oxidation state catalysis that the application method of oxidized catalyst H and I prepared by comparative example 1 and 2 is prepared with embodiment 1-7
Agent is identical, is all the application method of embodiment 8.
Experimental example 1.
The catalyst number consecutively that embodiment 1-7 and comparative example 1-2 are prepared is A-I, using by Yantai Pine Ridge
Autoclave (KCFD02-03, volume 0.2L, heating power 3kW, the design pressure of Chemical Equipment Co., Ltd.'s production
430 DEG C of 35MPa, design temperature) and by the vacuum distillation analyzer (SYD- of Shanghai Changji Geological Instrument Co., Ltd.'s production
Activity rating is carried out to above-mentioned catalyst on 0165A).
Activity rating specific experiment is as follows：
Stirred in high-speed homogenization machine first by 60g reduced crudes, 1.85g catalyst fineses and 0.586g sublimed sulfurs
Even, then taking during about 44g said mixtures are added to autoclave is used for active testing, and being first passed through hydrogen reaches pressure in kettle
Hunted leak to 24MPa, while discharging air in kettle, being re-filled with hydrogen makes to reach certain pressure in kettle, is warming up to reaction temperature,
Stop heating after reacting certain hour under certain stir speed (S.S.) and stir, temperature in the kettle is rapidly decreased to by room using water-cooling pattern
Temperature is with terminating reaction.Wherein, active testing condition：Initial hydrogen pressure 12.5MPa, stir speed (S.S.) 500r/min, curing temperature difference
It it is 190 and 250 DEG C, cure time is 30min, 450 DEG C of reaction temperature, reaction time 90min.Reaction is collected after the completion of reaction
Product in kettle carries out vacuum distillation test, distillation terminate after with toluene supersound washing distilling flask residual oil (>500 DEG C),
It is burnt liquid phase to be obtained after centrifugation, drying.Finally bottoms conversion, cut oil yield, coking yield, liquid yield and the gas for obtaining
Yield is used as catalyst activity evaluation index.
The catalysis activity of catalyst is evaluated with following index：
Total recovery=(distillate+gas recovery ratio for obtaining)/raw material oil quality × 100%
Liquid oil quality/raw material oil quality × 100% below cut oil yield=500 DEG C of boiling point
Metal removal rate=(tenor in tenor/feedstock oil in 1- liquid oils) × 100%
Coking rate (toluene insolubles)=solid residue/raw material oil quality × 100%
The evaluation index of the poor oil suspension bed hydrogenation catalyst of table 1
Table 1 is embodiment 1-7 and comparative example 1, and the poor oil suspension bed of the catalyst prepared using the inventive method in 2 is added
The evaluation index of hydrogen catalyst.
As it can be seen from table 1 poor oil suspension bed hydrogenation catalyst (sample A-G) poor oil of the present invention can reach
To total recovery higher, the total recovery of wherein sample B may be up to 97.81%, and cut oil yield of the boiling point below 500 DEG C is reachable
86.39, at the same time, the removal efficiency to metal component also may be up to 96.9%, and with relatively low coking rate, so as to present
Go out hydrogenation activity higher.Compared with control sample, nickel active component of cobalt is directly carried on hydrotalcite product of roasting surface, it is obtained
To poor oil total recovery only have 81.14%, hydrogenation activity is poor.
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is 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 and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of sulphided state poor quality oil hydrogenation catalysts, it is characterised in that with houghite be carrier predecessor, with houghite
Product of roasting be carrier.
2. catalyst according to claim 1, it is characterised in that also including active component and sublimed sulfur, the activearm
It is divided into Co, Ni, Fe, Mo, one or two the combination in W.
3. catalyst according to claim 2, it is characterised in that the carrier is that houghite is fired to be obtained
MMgA1-LDO (M=Co, Ni and Fe).
4. catalyst according to claim 3, it is characterised in that also including sublimed sulfur, each component weight of the catalyst
Amount part matches and is：The weight portion of carrier 5~20；Active component, 0.2~1.2 weight portion is measured by its oxide；Sublimed sulfur 1.8~
7.2 weight portions.
5. catalyst according to claim 6, it is characterised in that the active component is Mo and/or W.
6. catalyst according to claim 5, it is characterised in that the carrier is with NaOH and Na2CO3It is precipitating reagent, adopts
The metal cation in the mixed solution of metal cation salt is precipitated with coprecipitation, and by the aging, centrifugation that heats up, dry
Carrier predecessor, is then calcined to obtain carrier；
The metal cation salt is selected from Co (NO3)2·6H2O、Ni(NO3)2·6H2O、Fe(NO3)2·6H2O、Mg(NO3)2·
6H2O and Al (NO3)3·9H2One or more in O；
The carrier predecessor is magnesia-alumina hydrotalcite, cobalt magnesia-alumina hydrotalcite, nickel magnesia-alumina hydrotalcite and/or iron magnesia-alumina water
Talcum.
7. the preparation method of any catalyst of claim 1-6, it is characterised in that comprise the following steps：
(1) houghite carrier predecessor is prepared：After in the mixed solution instillation precipitating reagent of metal cation salt, it is warming up to
60-100 DEG C, then adjust pH=8-11, continue to stand 8-24h after stirring 1-3h, through centrifuge washing to neutrality, dry carrier
Predecessor MMgAl-LDHs (M=Co, Ni and Fe)；
(2) carrier is prepared：Carrier predecessor obtained by calcination stepses (1) obtains carrier MMgAl-LDO (M=Co, Ni and Fe)；
(3) oxidized catalyst is prepared：Using equi-volume impregnating by dipping solution be impregnated into carrier MMgAl-LDO (M=Co,
Ni and Fe) on, then be calcined and obtain oxidized catalyst Mo (W)/MMgAl-LDO (M=Co, Ni and Fe), the dipping solution is
(NH4)6Mo7O24·4H2O or (NH4)10W12O41·XH2The aqueous solution of O；
(4) sulphided state catalyst is prepared：Vulcanizing treatment is carried out after step (3) gained oxidized catalyst is mixed with sublimed sulfur,
Obtain sulphided state poor quality oil hydrogenation catalysts.
8. according to any described preparation methods of claim 1-7, it is characterised in that the drying temperature in step (1) is 80-
120 DEG C, drying time is 6-24h；
The sintering temperature of the roasting carrier predecessor is 500~800 DEG C, and roasting time is 2~4h；
Sintering temperature described in step (3) is 450~650 DEG C, and roasting time is 2~4h；
It is 250-350 DEG C that vulcanizing treatment described in step (4) obtains temperature, and the time is 2~4h.
9. preparation method according to claim 8, it is characterised in that the mixed solution of the metal cation salt is Co
(NO3)2·6H2O、Ni(NO3)2·6H2O、Fe(NO3)2·6H2O、Mg(NO3)2·6H2O and/or Al (NO3)3·9H2The mixing of O
Solution, the precipitating reagent is NaOH and anhydrous Na2CO3。
Co (NO in the mixed solution of the metal cation salt3)2·6H2O and Mg (NO3)2·6H2The sum of the amount of the material of O
With Al (NO3)3·9H2The ratio between amount of material of O is 3：1~1：3.
The substance withdrawl syndrome of the NaOH is 0.32mol/L, the anhydrous Na2CO3Material amount and Al (NO3)3·9H2O
Material amount it is identical.
The equi-volume impregnating is carried out at normal temperatures and pressures.
10. application of any catalyst of claim 1-9 in the reaction of poor oil hydrogenation catalyst, it is characterised in that reaction
Initial hydrogen pressure is 12.5MPa, and stir speed (S.S.) 500r/min, curing temperature is respectively 190 DEG C and 250 DEG C, and cure time is
30min, 430 DEG C of reaction temperature, reaction time 90min.
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| CN107486193A (en) * | 2017-07-18 | 2017-12-19 | 福州大学化肥催化剂国家工程研究中心 | A kind of hydrogenation catalyst and preparation method thereof |
| CN108704633A (en) * | 2018-05-07 | 2018-10-26 | 郑州东旺矿业有限公司 | A kind of activation method of bauxite, bauxite catalyst and preparation method thereof |
| CN109158120A (en) * | 2018-08-01 | 2019-01-08 | 东北大学 | A kind of CO based on absorption humidification2Hydrogenation catalyst and preparation method thereof |
| CN109453781A (en) * | 2018-09-26 | 2019-03-12 | 上海智冠高分子材料有限公司 | A kind of hydrotalcite catalyst and its preparation method and application |
| CN111185195A (en) * | 2020-03-20 | 2020-05-22 | 北京工业大学 | Preparation method and application of platinum-supported catalyst taking hydrotalcite as precursor gadolinium terbium nickel magnesium aluminum composite |
| CN113441188A (en) * | 2021-06-11 | 2021-09-28 | 中科合成油技术有限公司 | Pre-sulfurization method of inferior and/or heavy oil slurry bed hydrogenation iron-based catalyst |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107486193A (en) * | 2017-07-18 | 2017-12-19 | 福州大学化肥催化剂国家工程研究中心 | A kind of hydrogenation catalyst and preparation method thereof |
| CN107486193B (en) * | 2017-07-18 | 2020-09-08 | 福州大学化肥催化剂国家工程研究中心 | Hydrogenation catalyst and preparation method thereof |
| CN108704633A (en) * | 2018-05-07 | 2018-10-26 | 郑州东旺矿业有限公司 | A kind of activation method of bauxite, bauxite catalyst and preparation method thereof |
| CN109158120A (en) * | 2018-08-01 | 2019-01-08 | 东北大学 | A kind of CO based on absorption humidification2Hydrogenation catalyst and preparation method thereof |
| CN109158120B (en) * | 2018-08-01 | 2020-04-14 | 东北大学 | CO based on adsorption enhancement effect2Hydrogenation catalyst and preparation method thereof |
| CN109453781A (en) * | 2018-09-26 | 2019-03-12 | 上海智冠高分子材料有限公司 | A kind of hydrotalcite catalyst and its preparation method and application |
| CN109453781B (en) * | 2018-09-26 | 2022-02-08 | 上海智冠高分子材料有限公司 | Hydrotalcite catalyst and preparation method and application thereof |
| CN111185195A (en) * | 2020-03-20 | 2020-05-22 | 北京工业大学 | Preparation method and application of platinum-supported catalyst taking hydrotalcite as precursor gadolinium terbium nickel magnesium aluminum composite |
| CN111185195B (en) * | 2020-03-20 | 2022-07-19 | 北京工业大学 | Preparation method and application of platinum-supported catalyst taking hydrotalcite as precursor gadolinium terbium nickel magnesium aluminum compound |
| CN113441188A (en) * | 2021-06-11 | 2021-09-28 | 中科合成油技术有限公司 | Pre-sulfurization method of inferior and/or heavy oil slurry bed hydrogenation iron-based catalyst |
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