CN104549328A - Method for preparing residual oil hydro-demetallization catalyst - Google Patents
Method for preparing residual oil hydro-demetallization catalyst Download PDFInfo
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Abstract
The invention discloses a method for preparing a residual oil hydro-demetallization catalyst. The method comprises the following steps: (1) utilizing a polyhydric alcohol and/or a monosaccharide water solution for impregnation of an alumina carrier, carrying out hydrothermal carbonization treatment in a sealed vessel after the impregnation, and carrying out drying; (2) utilizing hydrogen peroxide for surface modification treatment of the alumina carrier which is hydrothermally carbonized in step (1), carrying out drying, loading the modified alumina carrier with active constituents, and carrying out drying again; (3) utilizing the alumina carrier which is loaded with the active constituents in step (2) for calcination in a nitrogen atmosphere or an inertia atmosphere, and then for calcination again in an oxygen-containing atmosphere to obtain the residual oil hydro-demetallization catalyst. The prepared residual oil hydro-demetallization catalyst is characterized in that the functions of the active constituents and a carrier are relatively poor, and the active constituents are uniformly distributed on the carrier, so that the active constituents are easy to vulcanize, and the demetallization activity and the desulfurization activity of the residual oil hydro-demetallization catalyst are obviously improved.
Description
Technical field
The invention belongs to field of catalyst preparation, relate in particular to a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst.
Background technology
Hydrogenation catalyst the most common is generally with aluminium oxide, silica etc. for carrier at present, the loaded catalyst being active component with metals such as Co, Ni, Mo, W.Active component adopts the method for dipping or kneading to load on carrier, then obtains catalyst through super-dry, roasting.In roasting process, active metal component is easily had an effect with alumina support and is formed very strong M-O-Al key, causes active component formation Spinel and loses activity, or makes active component cannot complete cure thus reduction catalyst activity.
CN101439289A discloses a kind of preparation method of hydrogenation catalyst.This catalyst metal components is made up of one or both metal ingredients in one or both and Mo, W of comprising in Co, Ni, with urea or ammoniacal liquor for reaction promoter, the method of reaction in-situ in carrier hole is adopted to make metal active constituent generate nickel molybdate (cobalt) or nickel tungstate (cobalt) compounds, thus the reaction of metal and carrier can be avoided, make metal active constituent more easily cure simultaneously, the activity of hydrogenation catalyst can be improved.But catalyst different activities component interphase interaction prepared by the method defines new compound, be unfavorable for that active component is dispersed on carrier and improve further with activity, in addition, preparation process is more complicated.
CN102451704A discloses a kind of preparation method of hydrocracking catalyst, and this catalyst is with amorphous aluminum silicide and aluminium oxide for carrier, and group VIII and group vib metal are hydrogenation active component, preferably containing active material B
2o
3.Catalyst of the present invention is by after amorphous aluminum silicide and aluminium oxide mixed-forming, drying process, then infusion process supported active metals, then drying and roasting and obtain.The method is compared with the infusion process of routine, and shaping carrier, without roasting, simplifies preparation process, and the strong interaction decreased between active metal and carrier, be conducive to Active components distribution, be more conducive to the performance of metal active, it also avoid the specific area loss because multistep roasting causes.But because shaping carrier is without calcination process, the mechanical strength of catalyst is undesirable.
Summary of the invention
For existing technical deficiency, the invention provides a kind of preparation method of residuum hydrogenating and metal-eliminating catalyst, catalyst activity component prepared by the method and carrier function more weak, active component is evenly distributed on carrier, easy complete cure, significantly improves the demetalization of catalyst and desulphurizing activated.
The preparation method of residuum hydrogenating and metal-eliminating catalyst of the present invention, comprises following content:
(1) adopt polyalcohol and/or monose aqueous impregnation alumina support, in airtight container, after dipping terminates, carry out hydro-thermal charing process, dry;
(2) alumina support after the charing of step (1) hydro-thermal being processed is through hydrogen peroxide surface modification treatment, dry, and then load active component is dry;
(3) aluminium oxide of load active component step (2) obtained, first roasting under nitrogen or inert atmosphere, and then roasting under an oxygen-containing atmosphere, obtain residuum hydrogenating and metal-eliminating catalyst.
In the inventive method, the polyalcohol described in step (1) comprises one or more in xylitol, sorbierite, sweet mellow wine or arabite etc.; Described monose comprises one or more in glucose, ribose or fructose etc.Described dipping adopts equi-volume impregnating or crosses volume impregnation method.Polyalcohol and/or monose and Al in maceration extract
3+mol ratio be 0.1 ~ 1:1.Described dip time is 60 ~ 120 minutes.
In the inventive method, hydro-thermal charing treatment temperature described in step (1) is 180-250 DEG C, preferred 200-230 DEG C, hydrothermal conditions is 6-12 hour, preferred 8-10 hour, hydrothermal treatment consists pressure is self-generated pressure, can ensure that polyalcohol and/or monose carbonize completely under this hydro-thermal carbonization condition.Wherein, self-generated pressure is relevant with treatment temperature, and when temperature is 100 DEG C, the general 0.1MPa of force value (gauge pressure), when 150 DEG C, force value is generally 0.43MPa, and when 250 DEG C, force value is generally 1.95 MPa.
In the inventive method, the alumina support after the dipping in step (1) is preferably before charing process, and carry out sealing heat treatment, heat-treat condition is: 80 ~ 130 DEG C process 0.5 ~ 2 hour.
In the inventive method, the alumina support described in step (1) can be spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape or granulated, is best with bar shaped.Alumina support can adopt commercially available, conventional method also can be adopted to obtain, be suitable for the aluminium oxide of residuum hydrogenating and metal-eliminating catalyst carrier.
In the inventive method, the mass concentration of step (2) described hydrogen peroxide is 10%-30%, detailed process is: the alumina support taken after appropriate charing is placed in beaker, then in beaker, add hydrogen peroxide solution make the complete submergence of carrier, beaker is placed in water-bath in 40-60 DEG C of process 1-5 hour, finally by carrier filtration, drying.
In the inventive method, described active component is one or more in Mo, W, Ni or Co, is preferably Mo and Ni.
In the inventive method, the load active component described in step (2) adopted volume impregnation, incipient impregnation, spray impregnating method, and dip time is 1-5 hour, preferred volume impregnation excessively.Wherein, the soluble compound of active component is chosen in the preparation of maceration extract, as nickel chloride, nickel nitrate, nickelous sulfate, nickel acetate, cobalt chloride, cobalt nitrate, cobaltous sulfate, cobalt acetate, phosphomolybdic acid, ammonium molybdate, ammonium metatungstate and ammonium tungstate etc., in maceration extract, the concentration of active component is counted with corresponding oxide content: MoO
3and/or WO
310 ~ 80g/100ml, NiO and/or CoO 2 ~ 20g/100ml, the concrete concentration of maceration extract can be determined according to the active metallic content on final catalyst.
In the inventive method, described drying condition is dry 6-10 hour at 80-120 DEG C.
In the inventive method, the nitrogen in step (3) or the sintering temperature under inert atmosphere are 400-600 DEG C, and roasting time is 3-6 hour, and wherein inert atmosphere is one or more in helium, neon or argon gas; Sintering temperature under oxygen-containing atmosphere is 350-450 DEG C, roasting time is 1-6 hour, wherein oxygen-containing atmosphere is the one in the mixture of purity oxygen, air, oxygen and nitrogen or the mixture of oxygen and inert gas, and oxygen volume fraction is in the gas phase 50% ~ 100%.
The inventive method is with containing polyalcohol and/or monose aqueous impregnation shaped alumina alumina supporter, by hydro-thermal charing process, the surface of alumina support and the inwall in duct form uniform layer of charcoal, layer of charcoal increases through the content of the oxy radical of Activation of Hydrogen Peroxide Solution process rear surface, polarity strengthens, and facilitates being uniformly distributed of active component; Charcoal precursor charing before to flood after carrier carry out certain sealing heat treatment, facilitate charcoal precursor and be uniformly distributed on carrier, make the layer of charcoal of carrier surface evenly; In roasting process under nitrogen or inert atmosphere, existence due to alumina carrier surface layer of charcoal effectively prevents the strong interaction between metal component and alumina support, thus avoid active component formation Spinel, under low temperature oxygen-containing atmosphere during roasting, layer of charcoal generation oxidation reaction is removed, metal active constituent loads on alumina support, namely the suitable interaction force had between metal active constituent and carrier maintains active component being uniformly distributed at oxidized surface, make again active component be easy to sulfuration, improve the reactivity of catalyst.
Detailed description of the invention
further illustrate the effect of the inventive method below in conjunction with embodiment, but be not limited to following examples.The commercially available shaped alumina alumina supporter adopted in embodiment, the pore volume of alumina support is 0.7-1.5ml/g, and specific area is 150-300m
2/ g, bore dia is the 70%-90% that the hole of 10-20nm accounts for total pore volume, and crushing strength is 130-160N/cm.
Take appropriate above-mentioned alumina support and proceeded in autoclave polytetrafluoroethyllining lining, add appropriate containing polyalcohol and/or the monose aqueous solution in above-mentioned alumina support, dipping 60-120 minute, dipping terminates autoclave to proceed in baking oven in 80-130 DEG C of hydrothermal treatment consists 0.5-2 hour, then temperature is increased to 180-250 DEG C of sealing hydro-thermal charing process 6-12 hour, then room temperature is naturally cooled to, alumina support after hydrothermal treatment consists is dry 1-3 hour (directly can carry out drying when liquid is less, without the need to filtering) at 90-130 DEG C.Carrier after charing is that the hydrogen peroxide of 10%-30% activates 1-5 hour in 40-60 DEG C, the carrier drying after activation through mass concentration, then contains 10-80g/100mlMoO with appropriate
3the above-mentioned carrier 1-5 hour of impregnation fluid of 2-20g/100mlNiO, filter redundant solution, dry 6-10 hour at 80-120 DEG C, the first roasting 3-6 hour at 400-600 DEG C in a nitrogen atmosphere of dried material, then roasting 1-6 hour at 350-450 DEG C under an oxygen-containing atmosphere, obtained Hydrodemetalation catalyst.
Embodiment 1
Taking pore volume is 0.9ml/g, and specific area is 220m
2the γ phase cylinder bar shaped alumina support 100 grams of/g joins in autoclave polytetrafluoroethyllining lining, adds the aqueous solution (xylitol and Al that 150ml is dissolved with 228 grams of xylitols wherein
3+mol ratio is 1:1) flood 60 minutes, after dipping, autoclave to proceed in baking oven in 80 DEG C of sealing heat treatments 120 minutes through sealing, is then warming up to 180 DEG C, carbonizes process 9 hours under self-generated pressure, naturally cool to room temperature.Alumina support after hydrothermal treatment consists at 120 DEG C dry 3 hours.Dried carrier is in the hydrogen peroxide of 15wt%, and 50 DEG C activate 3 hours, contains MoO after drying with 150ml
3105 grams (molybdenum source is from ammonium molybdate), the above-mentioned carrier of impregnation fluid of NiO15 gram (nickel source is from nickel chloride) 3 hours, filter redundant solution, drying 8 hours at 110 DEG C, dried material is roasting 5 hours at 550 DEG C in a nitrogen atmosphere first, then be 40% at oxygen purity, volume of air mark is roasting 4 hours at 400 DEG C under the mixed atmosphere of 60%.Obtained residuum hydrogenating and metal-eliminating catalyst C1 of the present invention.
Embodiment 2
With embodiment 1, just alumina support 150ml is dissolved with the aqueous solution (sorbierite and the Al of 136.5 grams of sorbierites
3+mole for 0.5:1) to flood 120 minutes, heat treatment temperature is 130 DEG C, and heat treatment time is 60 minutes.During charing process, temperature is 200 DEG C, and carbonization time is 8 hours.During activation, the concentration of hydrogen peroxide is 20wt%, and activation temperature is 55 DEG C, and soak time is 2 hours.MoO is contained with 150ml in activity component impregnation process
385 grams (molybdenum source is from ammonium molybdate), NiO10 gram of (nickel source is from nickel nitrate) impregnation fluid.Obtained residuum hydrogenating and metal-eliminating catalyst C2 of the present invention.
Embodiment 3
With embodiment 1, just alumina support 150ml is dissolved with the aqueous solution (sweet mellow wine and the Al of 81.9 grams of sweet mellow wine
3+mole for 0.3:1) flood 60 minutes.Heat treatment temperature is 100 DEG C, and heat treatment time is 90 minutes.During charing process, temperature is 240 DEG C, and carbonization time is 12 hours.During activation, the concentration of hydrogen peroxide is 10wt%, and activation temperature is 60 DEG C, and soak time is 4 hours.MoO is contained with 150ml in activity component impregnation process
3115 grams (molybdenum source is from ammonium molybdate), NiO15 gram of (nickel source is from basic nickel carbonate) impregnation fluid.Obtained residuum hydrogenating and metal-eliminating catalyst C3 of the present invention.
Embodiment 4
With embodiment 1, just alumina support 150ml is dissolved with the aqueous solution (arabite and the Al of 159.6 grams of arabites
3+mole be 0.7:1) dipping, carbonization temperature is 250 DEG C, and carbonization time is 6 hours.During activation, the concentration of hydrogen peroxide is 30wt%, and activation temperature is 45 DEG C, and soak time is 1 hour, obtained residuum hydrogenating and metal-eliminating catalyst C4 of the present invention.
Embodiment 5
With embodiment 1, just alumina support 150ml is dissolved with mixed alcohol aqueous impregnation (alcohol and the Al of 22.8 grams of xylitols, 22.8 grams of arabites, 27.3 sorbierites and 27.3 grams of sweet mellow wine
3+mole be 0.1:1), during charing process, temperature is 220 DEG C, and the processing time is 10 hours.During activation, the concentration of hydrogen peroxide is 25wt%, and activation temperature is 40 DEG C, and soak time is 5 hours, obtained residuum hydrogenating and metal-eliminating catalyst C5 of the present invention.
Embodiment 6
With embodiment 1, just alumina support 150ml is dissolved with aqueous impregnation (glucose and the Al of 162 grams of glucose
3+mole be 0.6:1), during charing process, temperature is 230 DEG C, and the processing time is 9 hours.During activation, the concentration of hydrogen peroxide is 20wt%, and activation temperature is 40 DEG C, and soak time is 4 hours, obtained residuum hydrogenating and metal-eliminating catalyst C6 of the present invention.
Embodiment 7
With embodiment 1, just alumina support 150ml is dissolved with aqueous impregnation (ribose and the Al of 180 grams of ribose
3+mole be 0.8:1), during charing process, temperature is 190 DEG C, and the processing time is 6 hours.During activation, the concentration of hydrogen peroxide is 30wt%, and activation temperature is 45 DEG C, and soak time is 2 hours, obtained residuum hydrogenating and metal-eliminating catalyst C7 of the present invention.
Embodiment 8
With embodiment 1, just alumina support 150ml is dissolved with 54 grams of glucose, 54 grams of fructose, and the aqueous impregnation of 22.8 grams of xylitols, 27.3 sorbierites, during charing process, temperature is 240 DEG C, and the processing time is 9 hours.During activation, the concentration of hydrogen peroxide is 10wt%, and activation temperature is 60 DEG C, and soak time is 4 hours, obtained residuum hydrogenating and metal-eliminating catalyst C8 of the present invention.
Comparative example 1
With embodiment 1, just flood and hydrothermal treatment consists without alcohol and/or sugar juice before the impregnated activated component of alumina support, obtained comparative catalyst C9.
Comparative example 2
With embodiment 1, just before the impregnated activated component of alumina support without alcohol and/or sugar juice dipping, in autoclave, carry out hydrothermal treatment consists, obtained comparative catalyst C10 with deionized water dipping.
Comparative example 3
With embodiment 1, the alumina support just after charing, without hydrogen peroxide oxidation process, obtains comparative catalyst C11.
With electron probe instrument, embodiment 1-8 and comparative example 1-3 catalyst sample are analyzed, measure active component distribution situation in the carrier, concrete method of testing is as follows: radial symmetric cutting catalyst, measure catalyst kernel of section position and be 1/4,1/2,3/4 and catalyst external surface place tenor with center relative distance, in test process respectively under the condition that relative distance is identical, measure the active component content of 10 different directions positions and average, the relative ratio of each relative distance place tenor and central metal content is in table 1.
The relative ratio of table 1 relative distance tenor and central metal content.
Table 1 result shows, catalyst metals active component prepared by the inventive method is even along catalyst granules radial distribution.
Embodiment 9
The following examples illustrate the catalytic performance of heavy resid Hydrodemetalation catalyst provided by the invention and comparative catalyst.
With decompression residuum listed by table 2 for raw material, the catalytic performance of catalyst C9-C11 prepared by the catalyst C1-C8 that on the hydrogenation reaction device of 200 milliliters prepared by evaluation example 1-8 and comparative example 1-3, the bar that catalyst is long 2 ~ 3 millimeters, catalyst loading amount is 100 milliliters, reaction temperature is 390 DEG C, hydrogen dividing potential drop is 15MPa, and liquid hourly space velocity (LHSV) is 1.0 hours
-1, hydrogen to oil volume ratio is 900, reacts the content measuring after 200 hours and generate each impurity in oil, and calculate removal efficiency, evaluation result is in table 3.
Table 2 feedstock oil character.
Table 3 catalyst hydrogenation performance comparison.
| C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | C9 | C10 | C11 | |
| Nickel removal, wt% | 67.1 | 65.2 | 65.6 | 65.9 | 68.4 | 68.1 | 67.3 | 66.8 | 38.7 | 46.4 | 53.6 |
| Vanadium removal, wt% | 74.9 | 74.4 | 74.2 | 75.9 | 77.3 | 76.8 | 74.5 | 74.7 | 54.2 | 58.7 | 65.9 |
| Desulfurization, wt% | 52.5 | 50.4 | 50.3 | 53.0 | 53.8 | 54.3 | 51.9 | 52.1 | 40.3 | 45.7 | 48.5 |
As can be seen from table 2 data, compared with comparative catalyst, catalyst provided by the invention has higher HDM activity and hydrodesulfurization activity.
Claims (11)
1. a preparation method for residuum hydrogenating and metal-eliminating catalyst, is characterized in that comprising following content: (1) adopts polyalcohol and/or monose aqueous impregnation alumina support, carries out hydro-thermal charing process after dipping terminates in airtight container, dry; (2) alumina support after the charing of step (1) hydro-thermal being processed is through hydrogen peroxide surface modification treatment, dry, and then load active component is dry; (3) aluminium oxide of load active component step (2) obtained, first roasting under nitrogen or inert atmosphere, and then roasting under an oxygen-containing atmosphere, obtain residuum hydrogenating and metal-eliminating catalyst.
2. in accordance with the method for claim 1, it is characterized in that: the polyalcohol described in step (1) is one or more in xylitol, sorbierite, sweet mellow wine or arabite; Described monose is one or more in glucose, ribose or fructose etc.
3. in accordance with the method for claim 1, it is characterized in that: dipping described in step (1) adopts equi-volume impregnating or crosses volume impregnation method, polyalcohol and/or monose and Al in maceration extract
3+mol ratio be 0.1 ~ 1:1, dip time is 60 ~ 120 minutes.
4. in accordance with the method for claim 1, it is characterized in that: described hydro-thermal charing treatment temperature is 180-250 DEG C, and hydrothermal conditions is 6-12 hour, and hydrothermal treatment consists pressure is self-generated pressure.
5. in accordance with the method for claim 1, it is characterized in that: the alumina support after step (1) dipping terminates, before charing process, carry out sealing heat treatment, heat-treat condition is: 80 ~ 130 DEG C process 0.5 ~ 2 hour.
6. according to the method described in claim 1 or 5, it is characterized in that: hydrogen peroxide surface modification treatment process is: the alumina support taken after appropriate charing is placed in beaker, then in beaker, add hydrogen peroxide solution make the complete submergence of carrier, beaker is placed in water-bath in 40-60 DEG C of process 1-5 hour, finally by carrier filtration, drying; Wherein the mass concentration of hydrogen peroxide is 10%-30%.
7. according to the method described in claim 1 or 5, it is characterized in that: described active component is one or more in Mo, W, Co or Ni.
8. according to the method described in claim 1 or 5, it is characterized in that: the load active component described in step (2) adopted volume impregnation, incipient impregnation or spray dipping, and dip time is 1-5 hour, preferred volume impregnation excessively; Wherein in maceration extract, the concentration of active component is counted with corresponding oxide content: MoO
3and/or WO
310 ~ 80g/100ml, NiO and/or CoO 2 ~ 20g/100ml.
9. according to the method described in claim 1 or 5, it is characterized in that: described drying condition is dry 6-10 hour at 80-120 DEG C.
10. according to the method described in claim 1 or 5, it is characterized in that: the nitrogen in step (3) or the sintering temperature under inert atmosphere are 400-600 DEG C, and roasting time is 3-6 hour; Wherein inert atmosphere is one or more in helium, neon or argon gas.
11., according to the method described in claim 1 or 5, is characterized in that: the sintering temperature under the oxygen-containing atmosphere in step (3) is 350-450 DEG C, and roasting time is 1-6 hour; Wherein oxygen-containing atmosphere is the one in the mixture of purity oxygen, air, oxygen and nitrogen or the mixture of oxygen and inert gas, and oxygen volume fraction is in the gas phase 50% ~ 100%.
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