CN103191753A - Preparation method of hydrotreatment catalyst - Google Patents
Preparation method of hydrotreatment catalyst Download PDFInfo
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- CN103191753A CN103191753A CN2012104426127A CN201210442612A CN103191753A CN 103191753 A CN103191753 A CN 103191753A CN 2012104426127 A CN2012104426127 A CN 2012104426127A CN 201210442612 A CN201210442612 A CN 201210442612A CN 103191753 A CN103191753 A CN 103191753A
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Abstract
The invention discloses a preparation method of a hydrotreatment catalyst. The preparation method comprises that a powdery hydrotreatment catalyst carrier material is subjected to hydro-thermal treatment by ammonia-containing steam; and the treated hydrotreatment catalyst carrier material is dipped in a hydrogenation active metal and then is subjected to drying, molding, drying and calcination to form the hydrotreatment catalyst. The unmolded hydrotreatment catalyst carrier material is subjected to hydro-thermal treatment by ammonia-containing steam so that catalyst acidity is improved. Through a one-step dipping method, the hydrotreatment catalyst having high active metal content is obtained and has excellent use performances. The preparation method has simple processes, can be used for preparation of various hydrotreatment catalysts and is especially suitable for preparation of a heavy distillate oil hydrotreatment catalyst.
Description
Technical field
The present invention relates to the hydrodesulfurization of a kind of preparation method of hydrotreatment catalyst, particularly highly active heavy distillate and the preparation method of hydrodenitrogenation catalyst.
Background technology
Along with crude quality becomes heavy, variation year by year, environmental regulation is strict day by day, and market constantly increases the demand of cleaning oil product, makes the hydrogen addition technology of producing clean fuel obtain application more and more widely.Distillate hydrogenation is handled and is referred to that under HTHP, feedstock oil and hydrogen at catalyst surface catalytic reactions such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and hydrogenation of unsaturated hydrocarbons are saturated take place.
In catalytic field, how to prepare and have high activity, fine selectivity and long-life effective catalyst are the problems that people pay close attention to and pay attention to always.For the catalyst with carrier loaded active component, though carrier itself does not have direct catalytic activity in some cases, catalyst component has only the carrier that relies on performance to suit just can play consistently its catalytic performance.Use the carrier of high-specific surface area, can prepare the loaded catalyst of high dispersive, thereby improve the reactivity worth of catalyst; Catalyst has bigger pore volume, then can improve its anti-coking or anti-carbon deposit performance, and then prolongs the service life of catalyst, also helps catalyst regeneration simultaneously.For loaded catalyst, improve pore volume and the specific area of carrier, to giving full play to the active constituent catalyst activity, improve catalyst performance, positive meaning is arranged.
Along with the demand of product quality upgrading and device capacity expansion revamping promotes day by day, the refinery has proposed more and more higher requirement to the performance of hydrotreating catalyst, and the hydrotreating catalyst performance of common metal content (generally being lower than 30wt% in oxide hydrogenation metal total content) can not satisfy current market demand fully.The raising tenor can greatly promote hydrotreating catalyst and deviate from impurity and the saturated ability of aromatic hydrocarbons, and therefore the exploitation of high tenor hydrotreating catalyst more and more is subjected to people's attention.Hydrotreating catalyst is the preparation method mainly contain, infusion process, kneading method, coprecipitation method etc., wherein since infusion process to have a metal good at the carrier surface dispersive property, the using rate of metal height, characteristics such as metal and carrier function power are suitable, the hydrotreating catalyst of common metal content adopts immersion process for preparing mostly, prepare carrier as the common employing modified aluminas of introducing among US4513097, CN94103999.4, the CN02133122.7, by infusion process carrying metal component, prepare catalyst through roasting then.But during the immersion process for preparing hydrotreating catalyst, generally can not obtain the higher hydrotreating catalyst of active metallic content, though can adopt repeatedly the impregnating method to improve active metallic content, but increase rate is limited, increase the complexity of catalyst preparation process simultaneously, influenced the serviceability of catalyst.Coprecipitation method is adopted in high tenor hydrotreating catalyst preparation usually, as US5086032, patent such as US4820677 and CN200410050730.9 has been introduced the employing coprecipitation method and has been prepared high tenor hydrotreating catalyst, prepare tenor up to 50wt% ~ 95wt% hydrotreating catalyst, catalyst has higher hydrogenation performance, but catalyst pore volume and specific area are little, can only handle the following cut than lightweight of diesel oil, and since coprecipitation method to prepare the catalyst metals utilization rate low, metal dispersion can be bad, and complicated process of preparation, product stability is poor, so the catalyst cost performance is not high.Kneading method can prepare the catalyst of various active metallic contents, but the catalyst performance of kneading method preparation is relatively poor relatively, and the reactive metal effective rate of utilization is low, the less employing kneading method preparation of hydrotreating catalyst.
By above analysis, adopt the immersion process for preparing catalyst, can give full play to the performance of hydrogenation metal, but the tenor of preparation catalyst is very restricted; Though coprecipitation method can prepare the hydrotreating catalyst of high tenor, the utilization rate of metal is not high.Therefore, adopt the high metal of immersion process for preparing, and have large pore volume, bigger serface hydrotreating catalyst, will have very important Practical significance.
Summary of the invention
Deficiency at existing hydrotreating catalyst technology of preparing the invention provides the method that a kind of single-steeping prepares high tenor high-activity hydrogenation catalyst.
Hydrotreating catalyst preparation method of the present invention comprises following content:
(1) choose powdery carrier of hydrogenating catalyst material,
(2) carrier material is used the water vapour that contains ammonia carry out hydrothermal treatment consists, the hydrothermal treatment consists condition is as follows: temperature is 50 ~ 200 ℃, and pressure is 0.01 ~ 0.20MPa, and the processing time is 1 ~ 4 hour, contain wherein that the volume ratio of ammonia and water vapour is 1:20 ~ 1:3 in the water vapour of ammonia
(3) with the powdery carrier of hydrogenating catalyst material soaking after the hydrothermal treatment consists in containing the solution of hydrogenation active metals, filter then, drying,
(4) material forming, drying, the roasting that step (3) is obtained makes hydrotreating catalyst.
In the above-mentioned steps (1), the carrier of hydrogenating catalyst material is selected according to the needs of hydrotreating catalyst, precursor (aluminum oxide dry glue powder, modified aluminas dry glue powder, amorphous aluminum silicide dry glue powder etc.) as aluminium oxide, amorphous aluminum silicide etc. and above-mentioned material, described carrier material can adopt conventional auxiliary agent to carry out modification, and auxiliary agent generally comprises one or more in silicon, phosphorus, fluorine, boron, titanium, the zirconium etc.For catalyst for hydro-processing heavy distillate, the preferred macroporous aluminium oxide of catalyst carrier material, the macroporous aluminium oxide pore volume is 0.6 ~ 1.3mL/g, is preferably 0.8 ~ 1.2mL/g, specific area is 200 ~ 550m
2/ g is preferably 300 ~ 500m
2/ g can contain required auxiliary agent in the macroporous aluminium oxide, as in silicon, phosphorus, fluorine, boron, titanium, the zirconium etc. one or more.As modified macroporous aluminium oxide of the described silicon of CN200510047483.1 etc.
Hydrogenation active metals described in the step (2) is generally group vib and group VIII metallic salt, as the saline solution of metals such as W, Mo, Ni, Co one or more, can add the required various auxiliary agents of catalyst in the dipping solution as required.Dipping process generally can adopt excessive impregnation method, and the dipping solution amount is more than the saturated pick up of carrier material, and general solid-liquid volume ratio is 1:5 ~ 1:20, is beneficial to abundant dipping.The concentration of slaines such as W, Mo, Ni, Co is determined according to catalyst activity metal requirement in the dipping solution, is generally 10 ~ 150g/100mL as metal salt concentrations in the dipping solution by oxide.Filtration behind the dipping and dry this area commonsense method and the condition of adopting.
In the step (3), in forming process, can add in peptization acid, adhesive component, expanding agent, the extrusion aid etc. one or more as required, so that moulding smoothly.Dry earlier after the moulding, roasting then obtains final catalyst prod, and in the final hydrotreating catalyst, reactive metal is generally 35% ~ 70% in oxide weight content, is preferably 40% ~ 60%.Roasting is generally 300 ~ 600 ℃ of following roastings 1 ~ 10 hour.Dry this area usual terms that adopts.
The hydrotreating catalyst of the present invention's preparation is distinguished to some extent according to the catalyst carrier material kind difference of using.For the hydrotreating catalyst that uses the preparation of macropore alumina supporter material, the catalyst main character is as follows: specific area is 150 ~ 350m
2/ g is preferably 160 ~ 300m
2/ g; Pore volume is 0.3 ~ 0.6cm
3/ g is preferably 0.3 ~ 0.5cm
3/ g, the hydrogenation metal total content is 35% ~ 70%, is preferably 40% ~ 60%; Average pore diameter is in 5 ~ 10nm scope, and usually at 6 ~ 8nm, the meleic acid amount is between 0.2 ~ 0.5mmol/g.
Hydrotreating catalyst preparation process of the present invention adopts carrier material powder dipping method, compares with carrier impregnation after the moulding of routine, and the powder dipping can absorb more maceration extract, pick up than moulding after the carrier pick up improve several times.Therefore maceration extract does not need higher metal concentration just can prepare the higher final catalyst prod of active metallic content.Owing to do not need the dipping solution of high concentration, the solution preparation is simple, and stable in properties is fit to commercial scale and uses.Rarer slaine maceration extract can reduce the viscosity of solution, reduces solution surface tension, can weaken the influence of capillary resistance phenomenon in the dipping process like this.Can guarantee that not only metal component has higher content in the catalyst, can also further improve metal at the decentralization of carrier surface.
Catalyst carrier material of the present invention is through after containing the processing of ammonia vapor, in ammonia atmosphere, can improve acid matter and the sour structure of carrier material, make catalyst carrier material strengthen the ability that supports of metal, pore passage structure is more stable in addition, at follow-up dipping, roll, still can keep pore passage structure preferably in the moulding, calcination process process, have bigger pore volume and specific area.Contain the highly acid center preferential adsorption ammonia in the carrier after the ammoniacal liquor heat treatment, kept, improved the acidity of catalyst carrier, improved the sour structure of catalyst carrier, be conducive to the saturated and open loop of big molecule aromatic hydrocarbons, improve catalyst desulfurizing and denitrification activity, be conducive to improve the hydrogenation performance of catalyst.
The present invention preferably adopts the modified macroporous aluminium oxide of silicon as carrier, has pore volume and the specific area of super large, can support more metal component, and can guarantee that metal component can be good at disperseing at carrier.The inventive method can adopt single macropore alumina supporter, can not only guarantee that catalyst has the uniformity of higher tenor and better metal component distribution, can also guarantee that catalyst has bigger pore volume and surface area.
In the preparation process of hydrotreating catalyst of the present invention, maceration extract can recycle.Therefore this method has characteristics such as preparation technology is simple, cost is low, pollution is little, and suitable commercial scale is promoted the use of.
The specific embodiment
Be that to prepare catalyst for hydro-processing heavy distillate be example to carrier material with the modified macroporous aluminium oxide of silicon of CN200510047483.1 preparation below, specify the inventive method and technique effect, can select the carrier material that adapts for the catalyst of other purposes.
It is as follows that the inventive method prepares the catalyst for hydro-processing heavy distillate process:
(1) the modified macroporous aluminium oxide of silicon is pulverized, after sieving with 180 orders, the low-temperature hydrothermal that contains ammonia vapor is handled, treatment temperature is controlled to be 50 ~ 200 ℃, steam pressure is 0.01 ~ 0.20MPa, time is 1 ~ 4 hour, contains wherein that the volume ratio of ammonia and water vapour is 1:20 ~ 1:3 in the ammonia vapor
(2) be example with active hydrogenation metal tungsten and nickel, the dipping solution preparation: get a certain amount of deionized water under stirring, add nickel nitrate and ammonium metatungstate crystal gradually, static after treating all to dissolve, filter, obtain metal impregnation solution, wherein WO
3Content 20.0 ~ 50.0 gWO
3/ 100mL, NiO content 2.0 ~ 15.0 gNiO/100mL.The preparation of various metal impregnation solution belongs to this area mature technology, can be with reference to pertinent literature,
(3) take by weighing the modified macroporous aluminium oxide of silicon after the hydrothermal treatment consists of a certain amount of step (1) preparation, place and stir metal impregnation solution and pull an oar, the solid-liquid volume ratio is 1:5 ~ 1:20, and beating time is 30 ~ 120min.Carry out suction filtration then, the filter cake butt is controlled at 15wt% ~ 30wt%, and drying is 2 ~ 6 hours under 100 ~ 150 ℃ of conditions, and the butt of dry back material is 60wt% ~ 90wt%, pulverize then, and granularity control 100 ~ 200 orders,
(4) after the powder that step (3) is obtained rolled 20 ~ 60min, adding concentration was 2 ~ 10gHNO
3/ 100mL dilute nitric acid solution continues to roll formation and can squeeze the paste shape, extruded moulding then, and catalyst shape can be column, clover, bunge bedstraw herb and other different in nature bar etc., length control 3 ~ 8mm,
(5) carrier strip that step (4) is obtained, at first under 100 ~ 150 ℃ of conditions dry 2 ~ 6 hours, carry out roasting then, sintering temperature is preferably 300 ~ 600 ℃, and roasting time is preferably 3 ~ 10 hours, prepares the catalyst finished product.
The following examples are used for illustrating in greater detail the preparation method of carrier of the present invention, but scope of the present invention is not only limited to the scope of these embodiment.Among the present invention, wt% is mass fraction, and v% is volume fraction.
The analytical method that the present invention adopts: specific area and pore volume adopt the low temperature liquid nitrogen physisorphtion.
Embodiment 1(contrasts scheme)
(sky, Tianjin company of a specified duration produces pore volume 0.82mL/g, specific area 323m to get the 578g macroporous aluminium oxide
2/ g, butt 71.1wt%), the little porous aluminum oxide of 386g (Germany produces the SB powder) preparation adhesive (butt 26.2wt%), add 6g sesbania powder, rolled 30 minutes, add an amount of distilled water, make mixture become can squeeze the paste shape, extrusion, banded extruder orifice plate diameter is 1.5mm clover.Wet bar descended dry 4 hours at 120 ℃, carried out roasting then, 550 ℃ of temperature, 3 hours time, numbering HF-1S.Get two parts of HF-1S carriers, each 120g is immersed in tungsten nickel solution (WO respectively
3Content 43.1g/100mL, NiO content 7.2g/100mL) (MoO and in the molybdenum nickel solution
3Content 40.7g/100mL, NiO content 6.5g/100mL) carry out the supersaturation dipping, the dipping rear catalyst is prepared the catalyst finished product and is numbered HF-1A and HF-1B respectively 480 ℃ of roastings 3 hours.
Embodiment 2(contrasts scheme)
Just use the macroporous aluminium oxide among the embodiment 1 instead the modified macroporous aluminium oxide of silicon that patent CN200510047483.1 embodiment 10 provides, other is with embodiment 1, and the preparation bearer number is HF-2S, and catalyst is numbered HF-2A and HF-2B.
Embodiment 3(contrasts scheme)
Just the impregnation concentration among the embodiment 2 is adjusted, the tungsten nickel solution is WO
3Content 51.5g/100mL, NiO content 11.4g/100mL, molybdenum nickel solution MoO
3Content 50.3g/100mL, NiO content 12.4g/100mL.Other is with embodiment 2.The preparation bearer number is HF-3S, and catalyst is numbered HF-3A and HF-3B.
Embodiment 4(the present invention program)
Get 578g macroporous aluminium oxide (with embodiment 1) and contain the ammonia vapor processing, treatment temperature is 80 ℃, steam pressure 0.05MPa, and 1.5 hours time, the volume ratio of ammonia and water vapour is 1:10.Get three kinds of slaine maceration extract 800mL, be respectively tungsten nickel solution (WO
3Content 12.1g/100mL, NiO content 2.1g/100mL), molybdenum nickel solution (MoO
3Content 11.7g/100mL, NiO content 1.8 g/100mL) and tungsten nickel solution (WO
3Content 6.3g/100mL, MoO
3Content 7.7g/100mL, NiO content 2.6g/100mL), with hydrothermal treatment consists rear oxidation aluminium trisection, add respectively in the metal impregnation liquid that stirs, dip time 120min, suction filtration, 120 ℃ dry 4 hours down, pulverize then, sieve with 180 orders.Powder is mixed with an amount of sesbania powder, and adding concentration is 4gHNO
3Rare nitric acid of/100mL carries out moulding, and the extrusion orifice plate is that diameter is 1.5mm clover.Wet bar descended dry 4 hours at 120 ℃, will carry out roasting then, 480 ℃ of sintering temperatures, and 3 hours time, the catalyst numbering is respectively HF-4A, HF-4B, HF-4C.
Embodiment 5(the present invention program)
Just use the macroporous aluminium oxide among the embodiment 4 instead the modified macroporous aluminium oxide of silicon that patent CN200510047483.1 embodiment 10 provides, other is with embodiment 4, and preparation catalyst numbering is respectively HF-5A, HF-5B and HF-5C.
Embodiment 6(the present invention program)
Get 578g macroporous aluminium oxide (with embodiment 1) and contain the ammonia vapor processing, treatment temperature is 130 ℃, steam pressure 0.1MPa, and 2 hours time, the volume ratio of ammonia and water vapour is 1:5.Simultaneously the impregnation concentration among the embodiment 4 is adjusted, the tungsten nickel solution is WO
3Content 18.0g/100mL, NiO content 2.8g/100mL; Molybdenum nickel solution MoO
3Content 17.8g/100mL, NiO content 2.9g/100mL; Tungsten nickel solution WO
3Content 8.7g/100mL, MoO
3Content 9.9g/100mL, NiO content 3.5g/100mL, other is with embodiment 4, and preparation catalyst numbering is respectively HF-6A, HF-6B and HF-6C.
Embodiment 7(the present invention program)
Get 578g macroporous aluminium oxide (with embodiment 1) and contain the ammonia vapor processing, treatment temperature is 180 ℃, steam pressure 0.15MPa, and 2 hours time, the volume ratio of ammonia and water vapour is 1:4.Simultaneously the impregnation concentration among the embodiment 4 is adjusted, the tungsten nickel solution is WO
3Content 20.8g/100mL, NiO content 3.4g/100mL; Molybdenum nickel solution MoO
3Content 21.3g/100mL, NiO content 4.1g/100mL; Tungsten nickel solution WO
3Content 8.4g/100mL, MoO
3Content 12.1g/100mL, NiO content 4.3g/100mL other with embodiment 4, preparation catalyst numbering is respectively HF-7A, HF-7B and HF-7C.
Embodiment 8(the present invention program)
Get 578g macroporous aluminium oxide (with embodiment 1) and contain the ammonia vapor processing, treatment temperature is 200 ℃, steam pressure 0.2MPa, and 3 hours time, the volume ratio of ammonia and water vapour is 1:3.Simultaneously the impregnation concentration among the embodiment 4 is adjusted, the tungsten nickel solution is WO
3Content 24.3g/100mL, NiO content 4.0g/100mL; Molybdenum nickel solution MoO
3Content 25.3g/100mL, NiO content 5.4g/100mL; Tungsten nickel solution WO
3Content 8.9g/100mL, MoO
3Content 15.4g/100mL, NiO content 4.9g/100mL other with embodiment 4, preparation catalyst numbering is respectively HF-8A, HF-8B and HF-8C.
Embodiment 9(contrasts scheme)
Get 578g macroporous aluminium oxide (with embodiment 1) and get three kinds of slaine maceration extract 800mL, be respectively tungsten nickel solution (WO
3Content 14.1g/100mL, NiO content 2.5g/100mL), molybdenum nickel solution (MoO
3Content 12.1g/100mL, NiO content 2.0 g/100mL) and tungsten nickel solution (WO
3Content 6.5g/100mL, MoO
3Content 7.7g/100mL, NiO content 2.7g/100mL), with hydrothermal treatment consists rear oxidation aluminium trisection, add respectively in the metal impregnation liquid that stirs, dip time 120min, suction filtration, 120 ℃ dry 4 hours down, pulverize then, sieve with 180 orders.Powder is mixed with an amount of sesbania powder, and adding concentration is 4gHNO
3Rare nitric acid of/100mL carries out moulding, and the extrusion orifice plate is that diameter is 1.5mm clover.Wet bar descended dry 4 hours at 120 ℃, will carry out roasting then, 480 ℃ of sintering temperatures, and 3 hours time, the catalyst numbering is respectively HF-9A, HF-9B, HF-9C.
In the present embodiment, above each routine catalyst is carried out instrumental analysis and activity rating.Each routine catalyst physico-chemical property is shown in Table 1, and it is benchmark that catalyst is formed with weight.Wherein embodiment 1 ~ 4 and 9 is reference catalyst, and embodiment 5～8 prepares catalyst for this programme.
?
Table 1. catalyst physico-chemical property
| Numbering | HF-1A | HF-2A | HF-3A | HF-4A |
| WO 3，wt% | 23.1 | 27.7 | 34.2 | 26.5 |
| NiO，wt% | 5.6 | 6.3 | 10.3 | 6.4 |
| Total metal contents in soil, wt% | 28.7 | 34.0 | 44.5 | 32.9 |
| The heap ratio, g/mL | 0.92 | 0.88 | 0.96 | 0.90 |
| Specific area, m 2/g | 188 | 266 | 201 | 213 |
| Pore volume, mL/g | 0.34 | 0.41 | 0.35 | 0.36 |
| Average pore diameter, nm | 7.5 | 9.0 | 8.2 | 8.3 |
| Numbering | HF-1B | HF-2B | HF-3B | HF-4B |
| MoO 3，wt% | 22.3 | 29.5 | 36.1 | 35.9 |
| NiO，wt% | 5.3 | 6.5 | 10.3 | 6.3 |
| Total metal contents in soil, wt% | 27.6 | 36.0 | 46.4 | 42.2 |
| The heap ratio, g/mL | 0.90 | 0.87 | 0.99 | 1.02 |
| Specific area, m 2/g | 197 | 277 | 187 | 168 |
| Pore volume, mL/g | 0.36 | 0.40 | 0.33 | 0.35 |
| Average pore diameter, nm | 8.0 | 9.3 | 7.1 | 9.7 |
| Numbering | ? | ? | ? | HF-4C |
| WO 3，wt% | ? | ? | ? | 13.5 |
| MoO 3，wt% | ? | ? | ? | 14.4 |
| NiO，wt% | ? | ? | ? | 5.6 |
| Total metal contents in soil, wt% | ? | ? | ? | 33.5 |
| The heap ratio, g/mL | ? | ? | ? | 0.89 |
| Specific area, m 2/g | ? | ? | ? | 210 |
| Pore volume, mL/g | ? | ? | ? | 0.37 |
| Average pore diameter, nm | ? | ? | ? | 8.2 |
Table 1(is continuous). the catalyst physico-chemical property
| Numbering | HF-5A | HF-6A | HF-7A | HF-8A | HF-9A |
| WO 3，wt% | 27.3 | 41.5 | 48.6 | 56.3 | 28.6 |
| NiO，wt% | 7.2 | 9.8 | 12.6 | 14.1 | 7.1 |
| Total metal contents in soil, wt% | 34.5 | 51.3 | 61.2 | 70.4 | 35.7 |
| The heap ratio, g/mL | 0.86 | 0.98 | 1.09 | 1.20 | 0.88 |
| Specific area, m 2/g | 321 | 261 | 180 | 153 | 318 |
| Pore volume, mL/g | 0.454 | 0.421 | 0.340 | 0.291 | 0.41 |
| Average pore diameter, nm | 11.3 | 9.7 | 7.9 | 7.3 | 10.6 |
| Numbering | HF-5B | HF-6B | HF-7B | HF-8B | HF-9B |
| MoO 3，wt% | 28.4 | 42.6 | 46.9 | 54.6 | 29.4 |
| NiO，wt% | 7.7 | 11.1 | 10.1 | 16.4 | 8.4 |
| Total metal contents in soil, wt% | 36.1 | 53.7 | 57.0 | 71.0 | 37.8 |
| The heap ratio, g/mL | 0.85 | 0.98 | 1.12 | 1.26 | 0.88 |
| Specific area, m 2/g | 350 | 278 | 213 | 164 | 342 |
| Pore volume, mL/g | 0.471 | 0.415 | 0.364 | 0.312 | 0.456 |
| Average pore diameter, nm | 12.1 | 10.6 | 8.4 | 8.0 | 11.8 |
| Numbering | HF-5C | HF-6C | HF-7C | HF-8C | HF-9C |
| WO 3，wt% | 14.6 | 18.5 | 16.7 | 20.6 | 15.0 |
| MoO 3，wt% | 16.4 | 22.4 | 26.1 | 30.1 | 15.9 |
| NiO，wt% | 6.9 | 10.9 | 9.7 | 13.4 | 7.2 |
| Total metal contents in soil, wt% | 37.9 | 51.8 | 52.5 | 64.1 | 38.1 |
| The heap ratio, g/mL | 0.85 | 1.0 | 1.12 | 1.26 | 0.86 |
| Specific area, m 2/g | 341 | 286 | 231 | 200 | 336 |
| Pore volume, mL/g | 0.424 | 0.397 | 0.350 | 0.332 | 0.419 |
| Average pore diameter, nm | 11.0 | 10.1 | 9.0 | 7.9 | 10.5 |
Evaluating apparatus carries out at the 200mL small hydrogenation device, before the activity rating catalyst is carried out presulfurization.The raw materials used oil nature of evaluation of catalyst activity and reaction process condition see Table 2 and table 3, and catalyst denitrogenation relative activity comparing result sees Table 4.
Table 2. feedstock oil character
| Density (20 ℃), g/cm 3 | 0.9120 |
| Boiling range/℃ | ? |
| ? IBP/10% | 327/375 |
| ? 30%/50% | 403/435 |
| ? 70%/90% | 458/500 |
| ? 95%/FBP | 513/543 |
| Condensation point/℃ | 32 |
| Refractive power/n D 70 | 1.4899 |
| Carbon residue, wt% | 0.28 |
| S，wt% | 1.60 |
| N，wt% | 0.1575 |
Table 3. evaluating catalyst process conditions
| The reactive hydrogen dividing potential drop, MPa | 14.7 |
| Volume space velocity during liquid, h -1 | 1.0 |
| Hydrogen to oil volume ratio | 900：1 |
| Reaction temperature, ℃ | 380 |
Table 4. catalyst denitrogenation relative activity comparing result
| The catalyst numbering | Relative denitrification activity, wt% |
| HF-1A | 100 |
| HF-1B | 105 |
| HF-2A | 96 |
| HF-2B | 98 |
| HF-4A | 107 |
| HF-6A | 119 |
| HF-6B | 136 |
| HF-6C | 138 |
| HF-8A | 124 |
| HF-9A | 99 |
Claims (10)
1. preparation method of hydrotreatment catalyst comprises:
(1) choose powdery carrier of hydrogenating catalyst material,
(2) carrier material is used the water vapour that contains ammonia carry out hydrothermal treatment consists, the hydrothermal treatment consists condition is as follows: temperature is 50 ~ 200 ℃, and pressure is 0.01 ~ 0.20MPa, and the processing time is 1 ~ 4 hour, contain wherein that the volume ratio of ammonia and water vapour is 1:20 ~ 1:3 in the water vapour of ammonia
(3) with the powdery carrier of hydrogenating catalyst material soaking after the hydrothermal treatment consists in containing the solution of hydrogenation active metals, filter then, drying,
(4) material forming, drying, the roasting that step (3) is obtained makes hydrotreating catalyst.
2. in accordance with the method for claim 1, it is characterized in that the described carrier of hydrogenating catalyst material of step (1) is one or more in aluminium oxide, amorphous aluminum silicide, aluminum oxide dry glue powder, the amorphous aluminum silicide dry glue powder.
3. in accordance with the method for claim 1, it is characterized in that containing in the described carrier of hydrogenating catalyst material of step (1) in auxiliary agents of silicon, phosphorus, fluorine, boron, titanium, the zirconium one or more.
4. according to claim 1,2 or 3 described methods, it is characterized in that the described carrier of hydrogenating catalyst material of step (1) is macroporous aluminium oxide, the macroporous aluminium oxide pore volume is 0.6 ~ 1.3mL/g, and specific area is 200 ~ 550m
2/ g.
5. according to claim 1 or 4 described methods, it is characterized in that the hydrogenation active metals described in the step (3) is one or more among W, Mo, Ni and the Co.
6. according to claim 1 or 4 described methods, it is characterized in that the dipping process described in the step (3) adopts excessive impregnation method, the solid-liquid volume ratio is 1:5 ~ 1:20.
7. according to claim 1 or 5 described methods, it is characterized in that in the final hydrotreating catalyst that reactive metal is 35% ~ 70% in oxide weight content.
8. in accordance with the method for claim 1, it is characterized in that one or more in the acid of interpolation peptization, adhesive, expanding agent and the extrusion aid in step (4) forming process.
9. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (3) is: drying is 2 ~ 6 hours under 100 ~ 150 ℃ of conditions, and the butt of dry back material is 60wt% ~ 90wt%.
10. in accordance with the method for claim 1, it is characterized in that the described drying condition of step (4) is: drying is 2 ~ 6 hours under 100 ~ 150 ℃ of conditions, and roasting condition is 300 ~ 600 ℃ of following roastings 1 ~ 10 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210442612.7A CN103191753B (en) | 2012-01-06 | 2012-11-08 | Preparation method of hydrotreatment catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210002953 | 2012-01-06 | ||
| CN201210002953.2 | 2012-01-06 | ||
| CN2012100029532 | 2012-01-06 | ||
| CN201210442612.7A CN103191753B (en) | 2012-01-06 | 2012-11-08 | Preparation method of hydrotreatment catalyst |
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| CN103191753B CN103191753B (en) | 2015-06-17 |
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| CN103274482A (en) * | 2013-06-17 | 2013-09-04 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4 material with high specific surface area and crystallization hole wall, as well as preparation method and application thereof |
| CN105709808A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Hydro-cracking catalyst and preparation method thereof |
| CN105749933A (en) * | 2014-12-16 | 2016-07-13 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN110785856A (en) * | 2017-06-23 | 2020-02-11 | 信越化学工业株式会社 | Method for manufacturing high-efficiency solar cell |
| CN111375396A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst and preparation method thereof |
| CN111375438A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof |
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| CN115518645A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method and recycling thereof |
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| CN107297215B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | Hydrotreating catalyst and preparation method thereof |
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| US11986813B2 (en) * | 2009-04-21 | 2024-05-21 | Ketjen Netherlands B.V. | Hydrotreating catalyst containing phosphorus and boron |
| US20220219157A1 (en) * | 2009-04-21 | 2022-07-14 | Albemarle Catalysts Company B. V. | Hydrotreating catalyst containing phosphorus and boron |
| CN103274482A (en) * | 2013-06-17 | 2013-09-04 | 中国科学院上海硅酸盐研究所 | Mesoporous Co3O4 material with high specific surface area and crystallization hole wall, as well as preparation method and application thereof |
| CN105709808B (en) * | 2014-12-04 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and preparation method thereof |
| CN105709808A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Hydro-cracking catalyst and preparation method thereof |
| CN105749933B (en) * | 2014-12-16 | 2018-09-28 | 中国石油化工股份有限公司 | A kind of preparation method of hydrogenation catalyst |
| CN105749933A (en) * | 2014-12-16 | 2016-07-13 | 中国石油化工股份有限公司 | Preparation method of hydrogenation catalyst |
| CN110785856A (en) * | 2017-06-23 | 2020-02-11 | 信越化学工业株式会社 | Method for manufacturing high-efficiency solar cell |
| CN110785856B (en) * | 2017-06-23 | 2022-09-27 | 信越化学工业株式会社 | Method for manufacturing high-efficiency solar cell |
| CN111375396A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst and preparation method thereof |
| CN111375438A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Heavy oil hydrotreating catalyst carrier, catalyst and preparation method thereof |
| CN111375396B (en) * | 2018-12-29 | 2022-06-07 | 中国石油化工股份有限公司 | Hydrotreating catalyst carrier, catalyst and preparation method thereof |
| CN115518645A (en) * | 2021-06-25 | 2022-12-27 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method and recycling thereof |
| CN115518645B (en) * | 2021-06-25 | 2024-01-09 | 中国石油化工股份有限公司 | Hydrodemetallization catalyst and preparation method and recycling thereof |
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