CN107051467A - A kind of preparation method of additive modification ternary metal unsupported catalyst - Google Patents
A kind of preparation method of additive modification ternary metal unsupported catalyst Download PDFInfo
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- CN107051467A CN107051467A CN201611133616.1A CN201611133616A CN107051467A CN 107051467 A CN107051467 A CN 107051467A CN 201611133616 A CN201611133616 A CN 201611133616A CN 107051467 A CN107051467 A CN 107051467A
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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
- B01J23/888—Tungsten
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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
- C10G2300/1048—Middle distillates
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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
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °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
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The present invention relates to a kind of preparation method of additive modification ternary metal unsupported catalyst, it is two kinds of different auxiliary agents of introducing during coprecipitation prepares unsupported catalyst, active component, auxiliary agent are combined, i.e., the polyethylene glycol of different molecular weight is added in nickel molybdate and ammonium metatungstate mixed solution（PEG）With diatomite respectively as dispersant surfactants（Wherein PEG molecular weight be 100 10000 between）And dispersant.Modified unsupported catalyst preparation method of the present invention, the dispersiveness of active metal component and the Hydrogenation of catalyst can be effectively improved, the mechanical strength of unsupported catalyst is significantly improved, while ensure that modified catalyst meets strict demand of the national standard to diesel deep desulfurization after the hydrogenation reaction.
Description
Technical field
The present invention relates to a kind of preparation method of additive modification ternary metal unsupported catalyst, the catalyst can be extensive
Hydrofinishing applied to diesel oil.
Background technology
With the continuous development of China's economy, the scale of vehicle fuel usage amount is increasing, and the pollution to environment is continuous
Aggravation, the people increasingly improves to the cry of environmental protection.Therefore, the domestic research and development to clean fuel for vehicle correlation technique are got over
More to pay attention to, the sulfur content standard to clean fuel for vehicle is increasingly strict.Have begun to use state's V standard at present, sulfur content is tight
Lattice requirement reaches below 10ppm.
Current two kinds of Hydrobon catalyst basic load type catalyst and unsupported catalyst；Wherein supported catalyst
Active component industrially using more, is often carried on γ-Al by agent2O3Or on the carrier such as molecular sieve, then through drying, roasting
Burn, the step such as shaping produces loaded catalyst, but loaded catalyst has the shortcomings that itself can not overcome, such as catalyst by
The limitation of active metal load capacity and the influence of carrier, active metal density are smaller, activated centre not enough collects medium, hydrogenation activity
By a definite limitation.Therefore, the concern in recent years to non-supported hydrogenation desulphurization catalyst increasingly increases, and research deepens continuously,
The many gratifying achievements obtained.This kind of unsupported catalyst is described in US6299760B1 using solid surface reaction skill
Art prepares the composite oxide of metal with suitable specific surface area, meso-hole structure, through presulfurization, prepares unsupported metal sulphur
Compound hydrogenation catalyst.A kind of preparation method of loaded catalyst is described in EP0469675, the carrier used is porous
The mixture of aluminum oxide, porous molecular screen and amorphous aluminum silicate, gained catalyst pores gap structure is more flourishing.
CN101255356 describes a kind of preparation method of the unsupported catalyst for intermediate base distillate oil deep hydrofinishing,
Reacted by urea melting, obtain a kind of catalyst particles itself with nano pore and high specific surface area, the catalysis
Agent has abundant catalytic hydrogenation activity position.
But above-mentioned catalyst also all has some shortcomings of itself, such as catalytic mechanical intensity is poor, gold in preparation process
Belong to the rate of recovery low, on the high side etc..Therefore, it is necessary to a kind of new preparation method be developed, so as to improve unsupported catalyst
Performance.
The content of the invention
It is an object of the invention to improve catalyst metals active component point in existing unsupported catalyst technology of preparing
Scattered property is poor, pore structure is not flourishing enough, the shortcoming of bad mechanical strength.Increase catalytic metal utilization rate, improve its hydrogenation reaction
Activity.
Its specific solution is as follows：
It is activearm sub-material from two kinds of group vib metallic compounds, is dissolved in a certain amount of deionized water wiring solution-forming A, and with
It is 8-11 that precipitating reagent, which adjusts solution A to appropriate pH value range,；From former for co-catalysis component with certain water miscible nickel salt
Material, is dissolved in a certain amount of deionized water wiring solution-forming B；Solution B is added into solution A, it is seen that there is precipitation to generate；Stirred at 70-100 DEG C
Mix and polyethylene glycol (PEG) and diatomite are added in the suspension 3-8h containing precipitation, whipping process, be combined active component
Entirely, constant temperature stands solution after the completion of stirring, and burin-in process 4-168h is carried out to it；Ageing process terminates rear suction filtration suspension, and
Filter cake is washed with deionized water, filter cake is placed in constant temperature infrared drying oven and dries 4-32h, catalyst precursor is obtained；Fired,
Reduction produces the unsupported catalyst with good hydrodesulfurization activity in device.
Selected water-soluble nickel source can be one kind in nickel nitrate, nickel acetate, nickel chloride, nickel sulfate, two kinds of group vibs
Metallic compound is Mo, W or Cr ammonium salt.
The metal molar proportioning of co-catalysis component Ni and two kinds of group vib active components is 1:1:1-4:1:1.
Selected precipitating reagent is one kind in ammoniacal liquor, sodium carbonate, sodium acid carbonate and sodium hydroxide.
The mode that solution B adds solution A is to be added dropwise or disposably add, when being added dropwise, using equality of temperature or different temperature
It is added dropwise；The mode that polyethylene glycol adds solution is to be slowly added into or disposably add, and when being slowly added into, is fallen using equality of temperature or different temperature
Enter；The mode that diatomite adds solution is to be slowly added into or disposably add, and when being slowly added into, is poured into using equality of temperature or different temperature.
The time of described hydrothermal aging is 6-10h.
Calcination process is carried out to catalyst precursor, sintering temperature is 300-500 DEG C, and roasting time is 2-6h, roasting knot
Corresponding oxidized catalyst is obtained after beam；Reversion in device is carried out to oxidized catalyst, reduction pressure is 2-4MPa, temperature
Spend for 200-400 DEG C, air speed is 1-4h-1, hydrogen to oil volume ratio is 200-700, and the recovery time is 4-24h, after reduction process terminates
Obtain corresponding sulphided state catalyst.
The molecular weight of described polyethylene glycol is 100-10000.
Described diatomaceous addition accounts for the 10%-30% of catalyst gross mass.
Advantages of the present invention effect is as follows：
The specific surface area of ternary metal unsupported catalyst prepared by the present invention is 70-120m2/ g, pore volume is 0.15-
0.19cm3/ g, average pore size is 5.6-6.7nm.The catalyst particle size is fine, and rate of metal is high, adds with preferable
Hydrogen desulphurization reaction activity.The preparation process of catalyst is simple, easy to operate, and preparation condition is gentle, beneficial to industrialized production and application.
Non-loading type Ni bases catalyst prepared by the present invention reacts for diesel hydrogenation for removal sulphur, improves sulfide in diesel oil
Removal efficiency.The sulfide molecules in diesel oil is at utmost changed into hydrogen sulfide by catalytic hydrogenation reaction, significantly improve diesel oil
Desulfurization degree, meets increasingly strict diesel oil sulfur content national standard.
Brief description of the drawings
Fig. 1 is the pattern schematic diagram of addition auxiliary agent rear catalyst.
Embodiment
The present invention is deeply illustrated below in conjunction with example.
Embodiment 1
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs nickel acetate tetrahydrate 9.954g, ammonium heptamolybdate
5.071g, ammonium metatungstate 3.531g.Ammonium heptamolybdate 5.071g, ammonium metatungstate 3.531g are poured into the there-necked flask of 500ml capacity,
It is completely dissolved with 300ml deionized water at 50 DEG C, obtains solution A.The pH=of solution A is adjusted by precipitating reagent of ammoniacal liquor
9, heating water bath solution A temperature is to 90 DEG C.Nickel acetate tetrahydrate is poured into beaker with 20ml deionized water dissolvings, solution B is obtained.
Solution B is changed into slow instill in solution A under equality of temperature, it is seen that there is precipitation to increasingly generate.After after completion of dropping, stir molten at 90 DEG C
Liquid 5h, makes active component fully be combined.In whipping process polyethylene glycol C 1.856g, diatomite D1.523g are separately added into molten
Liquid, it is to be mixed finish after, stand suspension to carry out hydrothermal aging processing, ageing time 2h to it.Aging terminates rear suction filtration and hanged
Supernatant liquid, washs filter cake.Filter cake is placed in infrared drying oven, 12h is dried at 120 DEG C, catalyst precursor is made.To forerunner
Body is calcined, and 450 DEG C of sintering temperature, roasting time 4h obtains oxidized catalyst.Tabletting, mistake are carried out to calcined catalyst
Sieve, chooses 20-40 mesh particle and loads reactor.In 4MPa, 350 DEG C, 2h-1, device is carried out to catalyst under conditions of G/L=500
Interior reversion, gained specific surface area of catalyst is 79m2/ g, pore volume 0.14cm3/ g, average pore size 5.5nm.
Embodiment 2
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs Nickelous nitrate hexahydrate 11.632g, ammonium heptamolybdate
5.071g, ammonium metatungstate 3.531g.In the there-necked flask that Mo, W compound are poured into 500ml capacity, existed with 300ml deionized water
It is completely dissolved at 50 DEG C, obtains solution A.The pH=9 of solution A, heating water bath solution A temperature are adjusted by precipitating reagent of ammoniacal liquor
To 90 DEG C.Nickelous nitrate hexahydrate is poured into beaker with 20ml deionized water dissolvings, solution B is obtained.Solution B is changed slowly under equality of temperature
Instill in solution A, it is seen that there is precipitation to increasingly generate.After after completion of dropping, agitating solution 5h, makes active component abundant at 90 DEG C
It is compound.By polyethylene glycol C 2.023g in whipping process, diatomite D 4.047g are separately added into solution, it is to be mixed finish after, it is quiet
Suspension is put to carry out it hydrothermal aging processing, ageing time 2h.Aging terminates rear suction filtration suspension, washs filter cake.Will filter
Cake is placed in infrared drying oven, and 12h is dried at 110 DEG C, and catalyst precursor is made.Presoma is calcined, roasting temperature
450 DEG C of degree, roasting time 4h obtains oxidized catalyst.Tabletting, sieving are carried out to calcined catalyst, 20-40 mesh particles are chosen
Load reactor.In 4MPa, 360 DEG C, 2h-1, reversion in device, gained catalysis are carried out under conditions of G/L=500 to catalyst
Agent specific surface area is 86m2/ g, pore volume 0.15cm3/ g, average pore size 5.8nm.
Embodiment 3
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs Nickel dichloride hexahydrate 9.520g, ammonium heptamolybdate
5.071g, ammonium metatungstate 3.531g.In the there-necked flask that Mo, W compound are poured into 500ml capacity, existed with 300ml deionized water
It is completely dissolved at 50 DEG C, obtains solution A.The pH=9 of solution A, heating water bath solution A temperature are adjusted by precipitating reagent of ammoniacal liquor
To 90 DEG C.Nickel dichloride hexahydrate is poured into beaker with 20ml deionized water dissolvings, solution B is obtained.Solution B is changed slowly under equality of temperature
Instill in solution A, it is seen that there is precipitation to increasingly generate.After after completion of dropping, agitating solution 5h, makes active component abundant at 90 DEG C
It is compound.By polyethylene glycol C 1.812g in whipping process, diatomite D 3.624g are separately added into solution, it is to be mixed finish after, it is quiet
Suspension is put to carry out it hydrothermal aging processing, ageing time 2h.Aging terminates rear suction filtration suspension, washs filter cake.Will filter
Cake is placed in infrared drying oven, and 12h is dried at 110 DEG C, and catalyst precursor is made.Presoma is calcined, roasting temperature
450 DEG C of degree, roasting time 4h obtains oxidized catalyst.Tabletting, sieving are carried out to calcined catalyst, 20-40 mesh particles are chosen
Load reactor.In 4MPa, 360 DEG C, 2h-1, reversion in device, gained catalysis are carried out under conditions of G/L=500 to catalyst
Agent specific surface area is 95m2/ g, pore volume 0.15cm3/ g, average pore size 6.0nm.
Embodiment 4
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs Nickel dichloride hexahydrate 9.520g, ammonium heptamolybdate
5.071g, ammonium metatungstate 3.531g.In the there-necked flask that Mo, W compound are poured into 500ml capacity, existed with 300ml deionized water
It is completely dissolved at 50 DEG C, obtains solution A.The pH=9 of solution A, heating water bath solution A temperature are adjusted by precipitating reagent of ammoniacal liquor
To 90 DEG C.Nickel dichloride hexahydrate is poured into beaker with 20ml deionized water dissolvings, solution B is obtained.Solution B is changed slowly under equality of temperature
Instill in solution A, it is seen that there is precipitation to increasingly generate.After after completion of dropping, agitating solution 5h, makes active component abundant at 90 DEG C
It is compound.By polyethylene glycol C 1.812g in whipping process, diatomite D 3.624g are separately added into solution, it is to be mixed finish after, it is quiet
Suspension is put to carry out it hydrothermal aging processing, ageing time 4h.Aging terminates rear suction filtration suspension, washs filter cake.Will filter
Cake is placed in infrared drying oven, and 12h is dried at 110 DEG C, and catalyst precursor is made.Presoma is calcined, roasting temperature
450 DEG C of degree, roasting time 4h obtains oxidized catalyst.Tabletting, sieving are carried out to calcined catalyst, 20-40 mesh particles are chosen
Load reactor.In 4MPa, 360 DEG C, 2h-1, reversion in device, gained catalysis are carried out under conditions of G/L=500 to catalyst
Agent specific surface area is 108m2/ g, pore volume 0.17cm3/ g, average pore size 6.4nm.
Embodiment 5
This example illustrates the preparation method of comparative catalyst.
According to Ni:Mo:W=2:1:1 metal molar proportioning weighs nickel acetate tetrahydrate 9.954g, ammonium heptamolybdate
5.071g, ammonium metatungstate 3.531g.In the there-necked flask that Mo, W compound are poured into 500ml capacity, existed with 300ml deionized water
It is completely dissolved at 50 DEG C, obtains solution A.The pH=9 of solution A, heating water bath solution A temperature are adjusted by precipitating reagent of ammoniacal liquor
To 90 DEG C.Nickel acetate tetrahydrate is poured into beaker to dissolve with appropriate amount of deionized water, solution B is obtained.Solution B is changed slowly under equality of temperature
Instill in solution A, it is seen that there is precipitation to increasingly generate.Polyethylene glycol C 1.856g, diatomite D3.711g are distinguished in whipping process
Solution is added, after after after completion of dropping, the agitating solution 5h at 90 DEG C makes active component fully be combined.Stirring finishes rear suction filtration
Suspension, washs filter cake.Filter cake is placed in infrared drying oven, 12h is dried at 110 DEG C, catalyst precursor is made.To preceding
Drive body to be calcined, 450 DEG C of sintering temperature, roasting time 4h obtains oxidized catalyst.To calcined catalyst carry out tabletting,
Sieving, chooses 20-40 mesh particle and loads reactor.In 4MPa, 360 DEG C, 2h-1, catalyst is carried out under conditions of G/L=500
Reversion in device, gained specific surface area of catalyst is 72m2/ g, pore volume 0.13cm3/ g, average pore size 5.2nm.
Embodiment 6
This example illustrates the evaluation method of catalyst of the present invention
The activity rating of catalyst is carried out on the miniature hydrogenation reaction device of 20ml high pressures.It is that Dalian west is urged very much to evaluate raw material
Change cracked diesel oil, raw material is pumped into using gear pump, product is after cold high score and low pressure separator gas-liquid separation, product liquid access
Gather tank.After pre-vulcanization process terminates, reduction temperature is pumped into evaluation raw material to 280 DEG C.Stable reaction 6h is followed by sample, sample
Gathered once per 3h.The Activity evaluation of several addition different molecular weight PEG catalyst is as shown in table 1.
Embodiment 7
The metal molar proportioning of co-catalysis component Ni and two kinds of group vib active components is 1:1:1.Selected precipitating reagent is
Sodium acid carbonate, it is 11 that precipitating reagent, which adjusts solution A to appropriate pH value range,.The mode that solution B adds solution A is disposable adds
Enter；The mode that polyethylene glycol adds solution is disposable adds；The mode that diatomite adds solution is disposably added.Described water
The time of heat ageing is 6h.Calcination process is carried out to catalyst precursor, sintering temperature is 300 DEG C, and roasting time is 2h, roasting
Corresponding oxidized catalyst is obtained after end；Reversion in device is carried out to oxidized catalyst, reduction pressure is 2MPa, temperature
Spend for 200 DEG C, air speed is 1h-1, hydrogen to oil volume ratio is 200:1, the recovery time is 4h, and reduction process obtains corresponding sulphur after terminating
Change state catalyst.The molecular weight of described polyethylene glycol is 100-10000.Described diatomaceous addition accounts for the total matter of catalyst
The 10% of amount.Other step be the same as Examples 1.
Embodiment 8
The metal molar proportioning of co-catalysis component Ni and two kinds of group vib active components is 4:1:1.Selected precipitating reagent is
Sodium carbonate, it is 8 that precipitating reagent, which adjusts solution A to appropriate pH value,.The mode that solution B adds solution A is added dropwise using equality of temperature；
The mode that polyethylene glycol adds solution is slowly added into using equality of temperature；The mode that diatomite adds solution is slowly added using equality of temperature
Enter.The time of described hydrothermal aging is 10h.Calcination process is carried out to catalyst precursor, sintering temperature is 500 DEG C, roasting
Time is 6h, and roasting obtains corresponding oxidized catalyst after terminating；Reversion in device, reduction are carried out to oxidized catalyst
Pressure is 4MPa, and temperature is 400 DEG C, and air speed is 4h-1, hydrogen to oil volume ratio is 700：1, the recovery time is 24h, and reduction process terminates
After obtain corresponding sulphided state catalyst.The molecular weight of described polyethylene glycol is 100-10000.Described diatomaceous addition
Amount accounts for the 30% of catalyst gross mass.Other step be the same as Examples 1.
Embodiment 9
Suspension 3h of the stirring containing precipitation, burin-in process 4h is carried out to it at 70 DEG C；Filter cake is placed in constant temperature infrared
4h is dried in drying box；Other step be the same as Examples 1.
Embodiment 10
Suspension 8h of the stirring containing precipitation, burin-in process 18h is carried out to it at 100 DEG C；Filter cake is placed in constant temperature red
32h is dried in outer drying box.Other step be the same as Examples 1.Other step be the same as Examples 1.
Invention effect：
Existing conventional unsupported catalyst preparation method is contrasted, the significant technical characteristic of the present invention is in coprecipitation
Prepare and select suitable nickel source during unsupported catalyst, and introduce two kinds of auxiliary agents respectively.Pass through adding for two kinds of auxiliary agents
Plus make it that prepared unsupported catalyst particle is uniform, arrangement regulation is neat, pore structure is more flourishing, rate of metal
Corresponding increase, hydrodesulfurization activity is significantly improved, and desulfurization degree is close to 100%.Meanwhile, operability of the present invention is very strong, prepares bar
Part is gentle, suitable for batch amplification production and industrial applications.
Table 1 adds the heap density and desulfurization degree of different molecular weight PEG Ni-Mo-W unsupported catalysts
Claims (9)
1. a kind of preparation method of additive modification ternary metal unsupported catalyst, it is characterized in that comprising the following steps：
It is activearm sub-material from two kinds of group vib metallic compounds, is dissolved in a certain amount of deionized water wiring solution-forming A, and to precipitate
It is 8-11 that agent, which adjusts solution A to appropriate pH value range,；It is molten from being co-catalysis component raw material with certain water miscible nickel salt
In a certain amount of deionized water wiring solution-forming B；Solution B is added into solution A, it is seen that there is precipitation to generate；Stir and contain at 70-100 DEG C
Have and polyethylene glycol (PEG) and diatomite are added in the suspension 3-8 h of precipitation, whipping process, make active component compound complete, stir
Constant temperature stands solution after the completion of mixing, and burin-in process 4-18 h are carried out to it；Ageing process terminates rear suction filtration suspension, and with go from
Sub- water washing filter cake, is placed in drying 4-32 h in constant temperature infrared drying oven by filter cake, obtains catalyst precursor；In fired, device
Reduction produces the unsupported catalyst with good hydrodesulfurization activity.
2. preparation method according to claim 1, it is characterised in that selected water-soluble nickel source can be nickel nitrate,
One kind in nickel acetate, nickel chloride, nickel sulfate, two kinds of group vib metallic compounds are Mo, W or Cr ammonium salt.
3. preparation method according to claim 1, it is characterised in that co-catalysis component Ni and two kinds of group vib active components
Metal molar proportioning be 1:1:1-4:1:1.
4. preparation method according to claim 1, it is characterised in that selected precipitating reagent is ammoniacal liquor, sodium carbonate, carbonic acid
One kind in hydrogen sodium and sodium hydroxide.
5. preparation method according to claim 1, it is characterised in that the mode that solution B adds solution A be added dropwise or
It is disposable to add, when being added dropwise, it is added dropwise using equality of temperature or different temperature；The mode that polyethylene glycol adds solution is to be slowly added into or one
Secondary property is added, and when being slowly added into, is poured into using equality of temperature or different temperature；The mode that diatomite adds solution is to be slowly added into or disposably
Add, when being slowly added into, poured into using equality of temperature or different temperature.
6. preparation method according to claim 1, it is characterised in that the time of described hydrothermal aging is 6-10 h.
7. preparation method according to claim 1, it is characterised in that calcination process, roasting are carried out to catalyst precursor
Temperature is 300-500 DEG C, and roasting time is 2-6 h, and roasting obtains corresponding oxidized catalyst after terminating；Oxidation state is urged
Agent carries out reversion in device, and reduction pressure is 2-4 MPa, and temperature is 200-400 DEG C, and air speed is 1-4 h-1, hydrogen oil volume
Than for 200-700：1, the recovery time is 4-24 h, and reduction process obtains corresponding sulphided state catalyst after terminating.
8. preparation method according to claim 1, it is characterised in that the molecular weight of described polyethylene glycol is 100-
10000。
9. preparation method according to claim 1, it is characterised in that described diatomaceous addition accounts for the total matter of catalyst
The 10%-30% of amount.
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