CN106732636B - 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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- CN106732636B CN106732636B CN201611055022.3A CN201611055022A CN106732636B CN 106732636 B CN106732636 B CN 106732636B CN 201611055022 A CN201611055022 A CN 201611055022A CN 106732636 B CN106732636 B CN 106732636B
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- 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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- 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 using houghite as carrier predecessor, using the product of roasting of houghite as carrier.In the hydrodemetallization of residual oil and coal tar, hydrodesulfurization, hydrodenitrogeneration and add catalytic activity in hydrogen priming reaction high in sulphided state poor quality oil hydrogenation catalysts provided by the invention, and is not easy coking.
Description
Technical field
The invention belongs to the technical fields of poor oil suspension bed hydrogenation catalyst, and in particular to before using houghite as carrier
Object is driven, using its product of roasting as the poor oil suspension bed hydrogenation catalyst of carrier.
Background technique
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 range, the yield of coal tar is also increasing year by year
It is more.Wherein between 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 growing day by day for also resulting in people
Depending on.Therefore effectively processing these poor oils is just particularly important, and Hydrofining Technology is to make most having for poor oil lighting
One of efficacious prescriptions case.If can will be worth low poor oil " eating dry squeeze only " deep processing to make up at the fuel oil and chemicals of high-quality
The deficiency of oil product, then poor oil industry can then show biggish development potentiality.
Due to containing a large amount of sulphur, nitrogen, metal impurities in this kind of poor oil, and containing the charcoal for being easy to coking, and these
Impurity will cause the catalyst poisoning in treatment process, to impact to Catalytic processes and stabilization of equipment performance, therefore right
Poor oil carries out impurity removal.This requires such catalyst to have good hydrodesulfurization, hydrodenitrogeneration and plus the de- charcoal of hydrogen
Activity will also have certain hydrogenation cracking activity at the same time.
Currently, industrial general oil hydrogenation catalysts inferior using aluminium oxide as carrier, are added suitable according to different requirements
The auxiliary agent of amount can also improve the hydrofinishing effect of catalyst by adjusting the acid-base property of alumina support at the same time.
Chinese patent literature CN104998693A discloses a kind of preparation method and application of oil hydrogenation catalysts inferior, the prior art
Natural bauxite is subjected to high-temperature process in air atmosphere, then immerses acid solution and carries out sour processing, thus purifying natural alumina
The ingredients such as aluminium oxide, silica and iron oxide in mine, and its crystallization degree is improved, after processing in the surface acidity of bauxite
Heart redistribution, specific surface area and Kong Rong are significantly increased, and are handled obtained catalyst and are conducive to improve catalyst to poor quality
The macromoleculars such as oily studies on asphaltene and colloid add hydrogen activity function, to improve its high light fraction yield.However since this is urged
Agent uses aluminium oxide for carrier, and the acid centre on surface makes active component be not easy to disperse, and is being used for coal so as to cause it
Activity is lower when hydrogenation of tar removes metal, hydrodesulfurization and hydrodenitrogeneration, and there are problems that easy coking, and then lead to coal
The conversion ratio of tar or residual oil is low.
Summary of the invention
Therefore, technical problem to be solved by the present invention lies in overcoming in existing oil hydrogenation catalysts inferior in residual oil and
The hydrodemetallization of coal tar, hydrodesulfurization, hydrodenitrogeneration are low with catalytic activity in hydrogen priming reaction is added, and are easy lacking for coking
It falls into, 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 adopts the following technical scheme:
A kind of sulphided state poor quality oil hydrogenation catalysts are produced using houghite as carrier predecessor with the roasting of houghite
Object is carrier.
It further include active component and sublimed sulfur, the active component is Co, Ni, Fe, the group of Mo, one or both of W
It closes.
The carrier is the MMgA1-LDO (M=Co, Ni and Fe) that houghite is fired.
It further include sublimed sulfur, each component weight of the catalyst are as follows: 5~20 parts by weight of carrier；Active component,
0.2~1.2 parts by weight are measured by its oxide；1.8~7.2 parts by weight of sublimed sulfur.
The active component is Mo and/or W.
The carrier is with NaOH and Na2CO3For precipitating reagent, the mixing using coprecipitation precipitating metal cation salt is molten
Metal cation in liquid, and by heating aging, centrifugation, dry carrier predecessor, then roast 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 of O or a variety of；
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 includes the following steps:
(1) houghite carrier predecessor is prepared: after the mixed solution of metal cation salt is instilled in precipitating reagent, heating
To 60-100 DEG C, pH=8-11 is then adjusted, continues to stand 8-24h after stirring 1-3h, it is so dry that carry through centrifuge washing to neutrality
Body predecessor MMgAl-LDHs (M=Co, Ni and Fe)；
(2) prepare carrier: the resulting carrier predecessor of calcination steps (1) obtain carrier MMgAl-LDO (M=Co, Ni and
Fe)；
(3) it prepares oxidized catalyst: dipping solution is impregnated by carrier MMgAl-LDO (M=using equi-volume impregnating
Co, Ni and Fe) on, then roast to obtain oxidized catalyst Mo (W)/MMgAl-LDO (M=Co, Ni and Fe), the dipping solution
For (NH4)6Mo7O24·4H2O or (NH4)10W12O41·XH2The aqueous solution of O；
(4) it prepares sulphided state catalyst: being carried out at vulcanization after oxidized catalyst obtained by step (3) is mixed with sublimed sulfur
Reason, obtains sulphided state poor quality oil hydrogenation catalysts.
Drying temperature in step (1) is 80-120 DEG C, drying time 6-24h；
The maturing temperature of the roasting carrier predecessor is 500~800 DEG C, and calcining time is 2~4h；
Maturing temperature described in step (3) is 450~650 DEG C, and calcining time is 2~4h；
It is 250-350 DEG C that vulcanizing treatment described in step (4), which 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 are 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 substance of O
Sum and Al (NO3)3·9H2The ratio between amount of substance of O is 3:1~1:3.
The substance withdrawl syndrome of the NaOH is 0.32mol/L, the anhydrous Na2CO3Substance amount and Al (NO3)3·
9H2The amount of the substance of O is identical.
The equi-volume impregnating carries out at normal temperatures and pressures.
Application of the above-mentioned catalyst in the reaction of poor oil hydrogenation catalyst, reaction initial hydrogen pressure are 12.5MPa, stirring rate
500r/min, curing temperature are respectively 190 DEG C and 250 DEG C, and vulcanization time is 30min, and 430 DEG C of reaction temperature, the reaction time
90min。
Technical solution of the present invention has the advantages that
1, sulphided state poor quality oil hydrogenation catalysts provided by the invention are using houghite as carrier predecessor, with houghite
Product of roasting be carrier, wherein carrier be houghite product of roasting, compare table by high-temperature roasting is still with higher
Area can easily be accommodated the acid-base property of carrier surface, and auxiliary agent can be introduced directly into houghite, obtained after roasting containing auxiliary agent
Composite oxide carrier, and auxiliary agent is uniformly dispersed, and good interaction is formed between auxiliary agent and active component.In lower work
Property component load capacity under its catalytic activity be obviously improved than similar catalyst, and have good anticoking capability.
2, the magnesia-alumina hydrotalcite of sulphided state poor quality oil hydrogenation catalysts provided by the invention prepares water using coprecipitation
Talcum simple process, it is easily operated, it is cheap, it can be mass-produced, have broad application prospects.
3, sulphided state poor quality oil hydrogenation catalysts catalytic activity provided by the invention is high, and metal, sulphur, nitrogen removal efficiency are high and not
Easy coking.
Specific embodiment
There is provided following embodiments is to preferably further understand the present invention, it is not limited to the best embodiment party
Formula is not construed as limiting the contents of the present invention and protection scope, anyone under the inspiration of the present invention or by the present invention and its
The feature of his prior art is combined and any and identical or similar product of the present invention for obtaining, all falls within of the invention
Within protection scope.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.
Embodiment 1
The concentration for weighing the amount of 3.2g substance is NaOH the and 2.65g anhydrous Na of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, is poured into three-necked flask after stirring 20min and continue to stir 1h.By (Co2++Mg2+)/(Al3+) molar ratio be 1:1 and Co2 +/(Co2++Mg2+) molar ratio is the 0.03 corresponding nitrate solution of proportion, 0.2182gCo (NO is weighed respectively3)2·6H2O、
6.2179g Mg(NO3)2·6H2O and 9.3783g Al (NO3)3·9H2O is dissolved in 250ml deionized water, ultrasound point after dissolution
10min is dissipated, mixed solution is obtained.The mixed solution of cobalt magnalium is slowly dropped into precipitating reagent with peristaltic pump with the speed of 5ml/min
In the three-necked flask at place, and it is vigorously stirred.PH=9 or so is adjusted during dropwise addition, is warming up to after being added dropwise
90 DEG C, continue to stand for 24 hours after stirring 2h.It is centrifuged after standing and finishing, washing to pH=7.Then in 100 DEG C of dry 12h,
To obtain CoMgAl-LDHs.It is placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, obtain CoMgAl-
LDO is denoted as carrier 1.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous solution of O is impregnated on CoMgAl-LDO, it
Be placed in Muffle furnace, in 450 DEG C of roasting 2h, to obtain Mo/CoMgAl-LDO, wherein the mass fraction of Mo be 7% (with
MoO3Meter).It is denoted as oxidized catalyst A.
Embodiment 2
The concentration for weighing the amount of 3.2g substance is NaOH the and 7.95g anhydrous Na of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, is poured into three-necked flask after stirring 20min and continue to stir 1h.By (Ni2++Mg2+)/(Al3+) molar ratio be 1:3 and Ni2 +/(Ni2++Mg2+) molar ratio is the 0.03 corresponding salting liquid of proportion, 0.2181g Ni (NO is weighed respectively3)2·6H2O、
6.2179Mg(NO3)2·6H2O and 28.1349g Al (NO3)3·9H2O is dissolved in 250ml deionized water, ultrasonic disperse after dissolution
10min obtains mixed solution.The mixed solution of cobalt magnalium is slowly dropped into precipitating reagent institute with peristaltic pump with the speed of 5ml/min
Three-necked flask in, and be vigorously stirred.PH=9 or so is adjusted during dropwise addition, and 90 are warming up to after being added dropwise
DEG C, continue to stand for 24 hours after stirring 2h.Be centrifuged after standing and finishing, washing to pH=7. then in 100 DEG C of dry 12h, from
And obtain NiMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, obtain NiMgAl-
LDO is denoted as carrier 2.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous solution of O is impregnated on NiMgAl-LDO, it
Be placed in Muffle furnace, in 450 DEG C of roasting 2h, to obtain Mo/NiMgAl-LDO, wherein the mass fraction of Mo be 9% (with
MoO3Meter).It is denoted as oxidized catalyst B.
Embodiment 3
The concentration for weighing the amount of 3.2g substance is NaOH the and 0.88g anhydrous Na of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, is poured into three-necked flask after stirring 20min and continue to stir 1h.By (Fe2++Mg2+)/(Al3+) molar ratio be 3:1 and Fe2 +/(Fe2++Mg2+) molar ratio is the 0.03 corresponding salting liquid of proportion, 0.2160Fe (NO is weighed respectively3)2·6H2O、6.2179gMg
(NO3)2·6H2O and 3.1261g Al (NO3)3·9H2O is dissolved in 250ml deionized water, and ultrasonic disperse 10min after dissolution is obtained
To mixed solution.The three mouthfuls mixed solution of cobalt magnalium is slowly dropped into the speed of 6ml/min with peristaltic pump where precipitating reagent
In flask, and it is vigorously stirred.PH=9 or so is adjusted during dropwise addition, and 90 DEG C are warming up to after being added dropwise, continues to stir
2h is mixed to stand later for 24 hours.It is centrifuged after standing and finishing, washing to pH=7.Then in 100 DEG C of dry 12h, to obtain
FeMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, obtain FeMgAl-LDO, remember
For carrier 3.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous solution of O is impregnated on CoMgAl-LDO, be placed on
In Muffle furnace, in 450 DEG C of roasting 2h, to obtain Mo/FeMgAl-LDO, wherein the mass fraction of Mo is 13% (with MoO3
Meter).It is denoted as oxidized catalyst C.
Embodiment 4
The concentration for weighing the amount of 3.2g substance is NaOH the and 1.325g anhydrous Na of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, is poured into three-necked flask after stirring 20min and continue to stir 1h.By (Ni2++Mg2+)/(Al3+) molar ratio be 2:1 and Ni2 +/(Ni2++Mg2+) molar ratio is the 0.03 corresponding salting liquid of proportion, 0.2181g Co (NO is weighed respectively3)2·6H2O、6.2179g
Mg(NO3)2·6H2O and 4.6891g Al (NO3)39H2O is dissolved in 250ml deionized water, ultrasonic disperse 10min after dissolution,
Obtain mixed solution.The three mixed solution B of cobalt magnalium is slowly dropped into the speed of 5ml/min with peristaltic pump where precipitating reagent
In mouth flask, and it is vigorously stirred.PH=9 or so is adjusted during dropwise addition, 90 DEG C are warming up to after being added dropwise, and is continued
2h is stirred to stand later for 24 hours.It is centrifuged after standing and finishing, washing to pH=7.Then in 100 DEG C of dry 12h, to obtain
NiMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, obtain NiMgAl-LDO, remember
For carrier 4.Using equi-volume impregnating (NH4)10W12O41·XH2The ammonia spirit of O is impregnated on NiMgAl-LDO, postposition
In Muffle furnace, in 450 DEG C of roasting 2h, to obtain W/NiMgAl-LDO, wherein the mass fraction of W is 5% (with WO3Meter).
It is denoted as oxidized catalyst D.
Embodiment 5
The concentration for weighing the amount of 3.2g substance is NaOH the and 2.65g anhydrous Na of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, is poured into three-necked flask after stirring 20min and continue to stir 1h.By (Co2++Mg2+)/(Al3+) molar ratio be 1:1 and Co2 +/(Co2++Mg2+) molar ratio is the 0.03 corresponding nitrate solution of proportion, 0.2182gCo (NO is weighed respectively3)2·6H2O、
6.2179g Mg(NO3)2·6H2O and 9.3783g Al (NO3)3·9H2O is dissolved in 250ml deionized water, ultrasound point after dissolution
10min is dissipated, mixed solution is obtained.The mixed solution of cobalt magnalium is slowly dropped into precipitating reagent with peristaltic pump with the speed of 5ml/min
In the three-necked flask at place, and it is vigorously stirred.PH=9 or so is adjusted during dropwise addition, is warming up to after being added dropwise
90 DEG C, continue to stand for 24 hours after stirring 2h.It is centrifuged after standing and finishing, washing to pH=7.Then in 100 DEG C of dry 12h,
To obtain CoMgAl-LDHs.It is placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, obtain CoMgAl-
LDO is denoted as carrier 1.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous solution of O is impregnated on CoMgAl-LDO, it
It is placed in Muffle furnace, in 450 DEG C of roasting 2h, to obtain Mo/CoMgAl-LDO, wherein the mass fraction of Mo and Co is 6%
(with MoO3It is counted with CoO).It is denoted as oxidized catalyst E.
Embodiment 6
The concentration for weighing the amount of 3.2g substance is NaOH the and 7.95g anhydrous Na of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, is poured into three-necked flask after stirring 20min and continue to stir 1h.By (Ni2++Mg2+)/(Al3+) molar ratio be 1:3 and Ni2 +/(Ni2++Mg2+) molar ratio is the 0.03 corresponding salting liquid of proportion, 0.2181g Ni (NO is weighed respectively3)2·6H2O、
6.2179Mg(NO3)2·6H2O and 28.1349g Al (NO3)3·9H2O is dissolved in 250ml deionized water, ultrasonic disperse after dissolution
10min obtains mixed solution.The mixed solution of cobalt magnalium is slowly dropped into precipitating reagent institute with peristaltic pump with the speed of 5ml/min
Three-necked flask in, and be vigorously stirred.PH=9 or so is adjusted during dropwise addition, and 90 are warming up to after being added dropwise
DEG C, continue to stand for 24 hours after stirring 2h.Be centrifuged after standing and finishing, washing to pH=7. then in 100 DEG C of dry 12h, from
And obtain NiMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, obtain NiMgAl-
LDO is denoted as carrier 2.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous solution of O is impregnated on NiMgAl-LDO, it
It is placed in Muffle furnace, in 450 DEG C of roasting 2h, to obtain Mo/NiMgAl-LDO, wherein the mass fraction of Ni and Mo is 10%
(with NiO and MoO3Meter).It is denoted as oxidized catalyst F.
Embodiment 7
The concentration for weighing the amount of 3.2g substance is NaOH the and 0.88g anhydrous Na of 0.32mol/l2CO3Be dissolved in 250ml go from
In sub- water, is poured into three-necked flask after stirring 20min and continue to stir 1h.By (Fe2++Mg2+)/(Al3+) molar ratio be 3:1 and Fe2 +/(Fe2++Mg2+) molar ratio is the 0.03 corresponding salting liquid of proportion, 0.2160Fe (NO is weighed respectively3)2·6H2O、6.2179gMg
(NO3)2·6H2O and 3.1261g Al (NO3)3·9H2O is dissolved in 250ml deionized water, and ultrasonic disperse 10min after dissolution is obtained
To mixed solution.The three mouthfuls mixed solution of cobalt magnalium is slowly dropped into the speed of 6ml/min with peristaltic pump where precipitating reagent
In flask, and it is vigorously stirred.PH=9 or so is adjusted during dropwise addition, and 90 DEG C are warming up to after being added dropwise, continues to stir
2h is mixed to stand later for 24 hours.It is centrifuged after standing and finishing, washing to pH=7.Then in 100 DEG C of dry 12h, to obtain
FeMgAl-LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, obtain FeMgAl-LDO, remember
For carrier 3.Using equi-volume impregnating (NH4)6Mo7O24·4H2The aqueous solution of O is impregnated on CoMgAl-LDO, be placed on
In Muffle furnace, in 450 DEG C of roasting 2h, to obtain Mo/FeMgAl-LDO, wherein the mass fraction of Fe and NiO be 11% (with
NiO and Fe3O4Meter).It is denoted as oxidized catalyst G.
Embodiment 8
The application method of oxidized catalyst prepared by embodiment 1-7, the specific steps are as follows:
First by 60g reduced crude, 1.85g catalyst fines (embodiment 1-7) and 0.586g sublimed sulfur in high-speed homogenization
2h is stirred evenly in machine.Then about 44g said mixture is taken to be added in autoclave for active testing, being passed through hydrogen makes
Reacting kettle inner pressure reaches 24MPa and hunts leak.Said mixture is first being warming up to 190 DEG C of holdings before active testing
Then 0.5h is warming up to 250 DEG C of holding 0.5h again and carries out vulcanizing treatment, finally obtains sulphided state catalyst.To sulfidation knot
Shu Hou is warming up to 450 DEG C of reaction temperature, stops heating and stirring after reacting 90min under stirring rate is 500r/min, uses
Temperature in the kettle is rapidly decreased to room temperature to terminate reaction by water-cooling pattern.
Comparative example 1
Weigh 3.2g NaOH and 2.65g anhydrous Na2CO3It is dissolved in 250ml deionized water, pours into three mouthfuls after stirring 20min
Continue to stir 1h in flask.It is that 2:1 matches corresponding salting liquid by the molar ratio of magnesium and aluminium.6.4102g Mg is weighed respectively
(NO3)2·6H2O and 9.37825g Al (NO3)3·9H2O is dissolved in 250ml deionized water, and ultrasonic disperse 10min after dissolution is obtained
To mixed solution.The three mouthfuls of burnings mixed solution of magnalium being slowly dropped into the speed of 5ml/min with peristaltic pump where precipitating reagent
In bottle, and it is vigorously stirred.PH=9 or so is adjusted during dropwise addition, and 90 DEG C are warming up to after being added dropwise, continues to stir
It is stood for 24 hours after 2h.It is centrifuged after standing and finishing, washing to pH=7. is then in 100 DEG C of dry 12h, to obtain MgAl-
LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, MgAl-LDO is obtained, is denoted as carrier 5.
Using equi-volume impregnating Ni (NO3)2·6H2O and (NH4)6Mo7O24·4H2The ammonium hydroxide mixed solution of O is impregnated into MgAl-LDO
On, be placed in Muffle furnace, in 450 DEG C of roasting 2h, to obtain NiMo/MgAl-LDO as reference, the wherein matter of Mo
Measuring score is to be respectively 7% (with MoO3Meter), it is denoted as oxidized catalyst H.
Comparative example 2
Weigh 3.2g NaOH and 2.65g anhydrous Na2CO3It is dissolved in 250ml deionized water, pours into three mouthfuls after stirring 20min
Continue to stir 1h in flask.It is that 2:1 matches corresponding salting liquid by the molar ratio of magnesium and aluminium.6.4102g Mg is weighed respectively
(NO3)2·6H2O and 9.37825g Al (NO3)3·9H2O is dissolved in 250ml deionized water, and ultrasonic disperse 10min after dissolution is obtained
To mixed solution.The three mouthfuls of burnings mixed solution of magnalium being slowly dropped into the speed of 5ml/min with peristaltic pump where precipitating reagent
In bottle, and it is vigorously stirred.PH=9 or so is adjusted during dropwise addition, and 90 DEG C are warming up to after being added dropwise, continues to stir
It is stood for 24 hours after 2h.It is centrifuged after standing and finishing, washing to pH=7. is then in 100 DEG C of dry 12h, to obtain MgAl-
LDHs.It is subsequently placed in Muffle furnace, 600 DEG C of roasting 4h is risen to the rate of 3 DEG C/min, MgAl-LDO is obtained, is denoted as carrier 5.
Using equi-volume impregnating (NH4)6Mo7O24·4H2The ammonium hydroxide mixed solution of O is impregnated on MgAl-LDO, be placed on Muffle
In furnace, in 450 DEG C of roasting 2h, to obtain Mo/MgAl-LDO as reference, wherein the mass fraction of Mo is 7% (with MoO3
Meter).It is denoted as oxidized catalyst I.
Illustrate: catalyst obtained by above embodiments 1-7 and comparative example 1-2 is oxidized catalyst, and entire
Really play catalytic action in hydrogenation process is sulphided state catalyst, but sulphided state catalyst is very unstable in air
It is fixed, it is easy to which that desulfurication, which occurs, leads to catalyst inactivation.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, so that oxidized catalyst is become sulphided state catalyst, then
Carry out hydrogenation reaction.It due to the no longer ingress of air after vulcanization, but is directly reacted, so as to avoid the hair of devulcanization
It is raw, be conducive to being stabilized for active phase.
The oxidation state of application method and embodiment the 1-7 preparation of oxidized catalyst H and I prepared by comparative example 1 and 2 is catalyzed
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, design pressure of Chemical Equipment Co., Ltd.'s production
430 DEG C of 35MPa, design temperature) and by Shanghai Changji Geological Instrument Co., Ltd. produce vacuum distillation analyzer (SYD-
Activity rating is carried out to above-mentioned catalyst on 0165A).
Activity rating specific experiment is as follows:
60g reduced crude, 1.85g catalyst fines and 0.586g sublimed sulfur are stirred in high-speed homogenization machine first
It is even, then take about 44g said mixture to be added in autoclave for active testing, being first passed through hydrogen reaches pressure in kettle
It hunts leak to 24MPa, while air in kettle is discharged, being re-filled with hydrogen makes to reach certain pressure in kettle, it is warming up to reaction temperature,
It is reacted under certain stirring rate and stops heating and stirring after a certain period of time, temperature in the kettle is rapidly decreased to by room using water-cooling pattern
Temperature is to terminate reaction.Wherein, active testing condition: initial hydrogen pressure 12.5MPa, stirring rate 500r/min, curing temperature difference
It is 190 and 250 DEG C, vulcanization time is 30min, and 450 DEG C of reaction temperature, reaction time 90min.Reaction is collected after the reaction was completed
Product in kettle carries out vacuum distillation test, with the residual oil (> 500 DEG C) in toluene supersound washing distilling flask after distillation,
It is burnt that liquid phase is obtained after centrifugation, drying.Finally obtained bottoms conversion, fraction oil yield, coking yield, liquid yield and gas
Yield is as catalyst activity evaluation index.
The catalytic activity of catalyst is evaluated with following index:
Total recovery=(obtained distillate+gas recovery ratio)/raw material oil quality × 100%
Fraction oil yield=500 DEG C of boiling point or less liquid oil quality/raw material oil quality × 100%
Metal removal rate=(tenor in tenor/feedstock oil in 1- liquid oil) × 100%
Coking rate (toluene insolubles)=solid residue/raw material oil quality × 100%
The evaluation index of 1 poor oil suspension bed hydrogenation catalyst of table
Table 1 is that the poor oil suspension bed of the catalyst in embodiment 1-7 and comparative example 1,2 using the method for the present invention preparation adds
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 higher total recovery, wherein the total recovery of sample B may be up to 97.81%, and boiling point is reachable in 500 DEG C of fraction oil yields below
86.39, at the same time, 96.9% also may be up to the removal efficiency of metal component, and there is lower coking rate, to present
Higher hydrogenation activity out.It is compared with comparative sample, nickel active component of cobalt is directly carried on hydrotalcite product of roasting surface, is obtained
To poor oil total recovery only have 81.14%, hydrogenation activity is poor.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (6)
1. a kind of sulphided state poor quality oil hydrogenation catalysts, which is characterized in that the component including following parts by weight:
5~20 parts of carrier
Active component, based on its oxide, 0.2~1.2 part
1.8~7.2 parts of sublimed sulfur
The carrier is the product of roasting of houghite；The active component is Mo and/or W；
The preparation method of above-mentioned sulphided state poor quality oil hydrogenation catalysts, includes the following steps:
(1) it prepares houghite carrier predecessor: after the mixed solution of metal cation salt is instilled in precipitating reagent, being warming up to
60-100 DEG C, pH=8-11 is then adjusted, continues to stand 8-24h after stirring 1-3h, through centrifuge washing to neutrality, in 80-120 DEG C
Lower dry 6-24h obtains carrier predecessor MMgAl-LDHs, M=Co, Ni or Fe；
(2) prepare carrier: calcination steps (1) 2~4h of resulting carrier predecessor at 500~800 DEG C obtains carrier MMgAl-
LDO, M=Co, Ni or Fe；
(3) it prepares oxidized catalyst: dipping solution being impregnated on carrier MMgAl-LDO using equi-volume impregnating, then is roasted
Burning obtains oxidized catalyst, and the dipping solution is (NH4)6Mo7O24·4H2O or (NH4)10W12O41·XH2The aqueous solution of O；
(4) it prepares sulphided state catalyst: carrying out vulcanizing treatment after oxidized catalyst obtained by step (3) is mixed with sublimed sulfur,
The temperature of vulcanizing treatment is 250-350 DEG C, and the time is 2~4h, obtains sulphided state poor quality oil hydrogenation catalysts.
2. catalyst according to claim 1, which is characterized in that the precipitating reagent is NaOH and Na2CO3Aqueous solution；
The metal cation salt is selected from nitrate, Mg (NO3)2·6H2O and Al (NO3)3·9H2O, wherein the nitrate is
Co(NO3)2·6H2O、Ni(NO3)2·6H2O or Fe (NO3)2·6H2Any one of O；
The houghite is cobalt magnesia-alumina hydrotalcite, nickel magnesia-alumina hydrotalcite or iron magnesia-alumina hydrotalcite.
3. the preparation method of catalyst described in claim 2, which comprises the steps of:
(1) it prepares houghite carrier predecessor: after the mixed solution of metal cation salt is instilled in precipitating reagent, being warming up to
60-100 DEG C, pH=8-11 is then adjusted, continues to stand 8-24h after stirring 1-3h, through centrifuge washing to neutrality, dry carrier
Predecessor MMgAl-LDHs, M=Co, Ni or Fe；
(2) prepare carrier: the resulting carrier predecessor of calcination steps (1) obtains carrier MMgAl-LDO, M=Co, Ni or Fe；
(3) it prepares oxidized catalyst: dipping solution being impregnated on carrier MMgAl-LDO using equi-volume impregnating, then is roasted
Burning obtains oxidized catalyst, and the dipping solution is (NH4)6Mo7O24·4H2O or (NH4)10W12O41·XH2The aqueous solution of O；
(4) it prepares sulphided state catalyst: carrying out vulcanizing treatment after oxidized catalyst obtained by step (3) is mixed with sublimed sulfur,
Obtain sulphided state poor quality oil hydrogenation catalysts.
4. preparation method according to claim 3, which is characterized in that the drying temperature in step (1) is 80-120 DEG C, is done
The dry time is 6-24h；
The maturing temperature of the roasting carrier predecessor is 500~800 DEG C, and calcining time is 2~4h；
Maturing temperature described in step (3) is 450~650 DEG C, and calcining time is 2~4h；
The temperature of vulcanizing treatment described in step (4) is 250-350 DEG C, and the time is 2~4h.
5. the preparation method according to claim 4, which is characterized in that the Co in the mixed solution of the metal cation salt
(NO3)2·6H2O and Mg (NO3)2·6H2The sum of the amount of the substance of O and Al (NO3)3·9H2The ratio between amount of substance of O be 3:1~
1:3；
The substance withdrawl syndrome of NaOH is 0.32mol/L, the Na in the precipitating reagent2CO3Substance amount and Al (NO3)3·
9H2The amount of the substance of O is identical；
The equi-volume impregnating carries out at normal temperatures and pressures.
6. application of any catalyst of claim 1-2 in the reaction of poor oil hydrogenation catalyst, which is characterized in that reaction is just
Beginning hydrogen pressure is 12.5MPa, and stirring rate 500r/min, curing temperature is respectively 190 DEG C and 250 DEG C, and vulcanization time is
30min, 430 DEG C of reaction temperature, reaction time 90min.
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| 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 |
| CN109158120B (en) * | 2018-08-01 | 2020-04-14 | 东北大学 | CO based on adsorption enhancement effect2Hydrogenation catalyst and preparation method thereof |
| 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 |
| 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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