CN103191753B - Preparation method of hydrotreatment catalyst - Google Patents
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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 a kind of preparation method of hydrotreating catalyst, particularly the hydrodesulfurization of highly active heavy distillate and the preparation method of hydrodenitrogenation catalyst.
Background technology
Along with crude quality becomes heavy year by year, is deteriorated, environmental regulation is increasingly strict, and the demand of market to clear gusoline constantly increases, and the hydrogen addition technology producing clean fuel is obtained and applies more and more widely.Distillate hydrogenation process refers at high temperature under high pressure, and the catalytic reactions such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and hydrogenation of unsaturated hydrocarbons are saturated occur on catalyst surface for feedstock oil and hydrogen.
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 with the catalyst of carrier loaded active component, although carrier itself does not have direct catalytic activity in some cases, catalyst component only has the carrier of support proper properties just can play consistently its catalytic performance.Use the carrier of high-specific surface area, the loaded catalyst of high dispersive can be prepared, thus improve the reactivity worth of catalyst; Catalyst has larger pore volume, then can improve its anti-coking or coking resistivity, and then the service life of extending catalyst, also helps catalyst regeneration simultaneously.For loaded catalyst, improve pore volume and the specific area of carrier, to giving full play to active constituent catalyst activity, improving catalyst performance, having positive meaning.
Along with the demand of product quality upgrading and device capacity expansion revamping promotes increasingly, the performance of refinery to hydrotreating catalyst proposes more and more higher requirement, and the hydrotreating catalyst performance of common metal content (with oxide basis hydrogenation metal total content generally lower than 30wt%) can not meet the current market demand completely.Improve tenor and greatly can promote the ability that hydrotreating catalyst deviates from impurity and aromatic saturation, therefore the exploitation of high tenor hydrotreating catalyst more and more receives the concern of people.Hydrotreating catalyst is preparation method mainly contain, infusion process, kneading method, coprecipitation method etc., wherein due to infusion process, to have metal good at carrier surface dispersive property, using rate of metal is high, metal and the feature such as carrier function power is suitable, the hydrotreating catalyst of common metal content adopts infusion process to prepare mostly, usual employing modified aluminas as introduced in US4513097, CN94103999.4, CN02133122.7 prepares carrier, then by infusion process carrying metal component, through roasting Kaolinite Preparation of Catalyst.But when infusion process prepares hydrotreating catalyst, generally can not obtain the higher hydrotreating catalyst of active metallic content, although impregnating method can be adopted repeatedly to improve active metallic content, but increase rate is limited, add the complexity of catalyst preparation process simultaneously, affect the serviceability of catalyst.High tenor hydrotreating catalyst preparation adopts coprecipitation method usually, as US5086032, US4820677 and CN200410050730.9 etc. patent describes and adopt coprecipitation method to prepare high tenor hydrotreating catalyst, prepare tenor up to 50wt% ~ 95wt% hydrotreating catalyst, catalyst has higher Hydrogenation, but catalyst pore volume and specific area little, the cut of below diesel oil compared with lightweight can only be processed, and because coprecipitation method Kaolinite Preparation of Catalyst using rate of metal is low, metal dispersion performance is bad, and complicated process of preparation, product stability is poor, so catalyst cost performance is not high.Kneading method can prepare the catalyst of various active metallic content, but catalyst performance prepared by kneading method is relatively poor, and active metal effective rate of utilization is low, the less employing kneading method preparation of hydrotreating catalyst.
By above analysis, adopt preparation catalyst, the performance of hydrogenation metal can be given full play to, but the tenor of Kaolinite Preparation of Catalyst is very restricted; Although coprecipitation method can prepare the hydrotreating catalyst of high tenor, the utilization rate of metal is not high.Therefore, adopt infusion process to prepare high metal, and there is large pore volume, bigger serface hydrotreating catalyst, will there is very important Practical significance.
Summary of the invention
For the deficiency of existing hydrotreating catalyst technology of preparing, the invention provides a kind of method that single-steeping prepares high tenor high-activity hydrogenation catalyst.
Hydrotreating catalyst preparation method of the present invention, comprises following content:
(1) powdery carrier of hydrogenating catalyst material is chosen,
(2) carrier material is carried out carry out hydrothermal treatment consists with the water vapour containing ammonia, hydrothermal conditions is as follows: temperature is 50 ~ 200 DEG C, and pressure is 0.01 ~ 0.20MPa, and the processing time is 1 ~ 4 hour, the volume ratio wherein containing ammonia and water vapour in the water vapour of ammonia is 1:20 ~ 1:3
(3) by the powdery carrier of hydrogenating catalyst material soaking after hydrothermal treatment consists containing in the solution of hydrogenation active metals, then to filter, dry,
(4) material forming step (3) obtained, drying, roasting, obtained hydrotreating catalyst.
In above-mentioned steps (1), carrier of hydrogenating catalyst material is selected according to the needs of hydrotreating catalyst, as the precursor (aluminum oxide dry glue powder, modified aluminas dry glue powder, contained amorphous silica-alumina dry glue powder etc.) of 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, zirconium etc.For catalyst for hydro-processing heavy distillate, the preferred macroporous aluminium oxide of catalyst carrier material, macroporous aluminium oxide pore volume is 0.6 ~ 1.3mL/g, is preferably 0.8 ~ 1.2mL/g, and specific area is 200 ~ 550m
2/ g, is preferably 300 ~ 500m
2/ g, can contain required auxiliary agent, as one or more in silicon, phosphorus, fluorine, boron, titanium, zirconium etc. in macroporous aluminium oxide.Si modification macroporous aluminium oxide etc. as described in CN200510047483.1.
Hydrogenation active metals described in step (2) is generally group vib and group VIII metallic salt, as one or more of the saline solution of the metals such as W, Mo, Ni, Co, can add the various auxiliary agents needed for catalyst in dipping solution as required.Dipping process generally can adopt excessive impregnation method, and 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.In dipping solution, the concentration of the slaine such as W, Mo, Ni, Co is determined according to catalyst activity metal needs desired amount, as in dipping solution, metal salt concentrations is generally 10 ~ 150g/100mL by oxide basis.Filtration after dipping and drying adopt this area commonsense method and condition.
In step (3), one or more in peptization acid, adhesive component, expanding agent, extrusion aid etc. can be added as required in forming process, so that shaping smoothly.Shaping rear first dry, then roasting, obtains final catalyst prod, and in final hydrotreating catalyst, active metal is generally 35% ~ 70% in oxide weight content, is preferably 40% ~ 60%.Roasting generally roasting 1 ~ 10 hour at 300 ~ 600 DEG C.Dry employing this area usual terms.
Hydrotreating catalyst prepared by the present invention is distinguished to some extent according to the catalyst carrier material kind difference used.For the hydrotreating catalyst using macropore alumina supporter material to prepare, 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, hydrogenation metal total content is 35% ~ 70%, is preferably 40% ~ 60%; Average pore diameter is within the scope of 5 ~ 10nm, and usually at 6 ~ 8nm, meleic acid amount is between 0.2 ~ 0.5mmol/g.
Hydrotreating catalyst preparation process of the present invention adopts carrier material powder dipping method, and compared with the shaping rear carrier impregnation of routine, powder dipping can absorb more maceration extract, and pick up improves several times than shaping rear carrier pick up.Therefore maceration extract does not need higher metal concentration just can prepare the higher final catalyst prod of active metallic content.Owing to not needing the dipping solution of high concentration, solution preparation is simple, stable in properties, is applicable to commercial scale and uses.Rarer slaine maceration extract can reduce the viscosity of solution, reduces solution surface tension, can weaken the impact of capillary drag phenomena in dipping process like this.Not only can ensure that in catalyst, metal component has higher content, the decentralization of metal at carrier surface can also be improved further.
Catalyst carrier material of the present invention is after containing the process of ammonia vapor, the Acidity of carrier material and sour structure can be improved in ammonia atmosphere, catalyst carrier material is strengthened the ability that supports of metal, pore passage structure is more stable in addition, at follow-up dipping, roll, still can keep good pore passage structure in shaping, calcination process process, there is larger pore volume and specific area.Containing the highly acid center Preferential adsorption ammonia in the carrier after ammoniacal liquor heat treatment, retained, improve the acidity of catalyst carrier, improve the sour structure of catalyst carrier, be conducive to the saturated and open loop of large molecule aromatic hydrocarbons, improve catalyst desulfurizing and denitrification activity, be conducive to the Hydrogenation improving catalyst.
The present invention preferably adopts Si modification macroporous aluminium oxide as carrier, has pore volume and the specific area of super large, can support more metal component, and can ensure that metal component can be good at disperseing on carrier.The inventive method can adopt single macropore alumina supporter, can not only ensure that catalyst has the uniformity of higher tenor and the distribution of better metal component, can also ensure that catalyst has larger pore volume and surface area.
In the preparation process of hydrotreating catalyst of the present invention, maceration extract can recycle.Therefore the method has that preparation technology is simple, cost is low, pollute the features such as little, and applicable commercial scale is promoted the use of.
Detailed description of the invention
The Si modification macroporous aluminium oxide prepared for CN200510047483.1 below prepares catalyst for hydro-processing heavy distillate for carrier material, illustrate the inventive method and technique effect, the catalyst for other purposes can select the carrier material adapted.
It is as follows that the inventive method prepares catalyst for hydro-processing heavy distillate process:
(1) Si modification macroporous aluminium oxide is pulverized, after sieving with 180 orders, carry out the low-temperature hydrothermal process containing ammonia vapor, it is 50 ~ 200 DEG C that treatment temperature controls, steam pressure is 0.01 ~ 0.20MPa, time is 1 ~ 4 hour, and the volume ratio wherein containing ammonia in ammonia vapor and water vapour is 1:20 ~ 1:3
(2) for active hydrogenation metal tungsten and nickel, dipping solution is prepared: get a certain amount of deionized water under stirring, add nickel nitrate and ammonium metatungstate crystal gradually, after all dissolving, static, filters, obtains 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 with reference to pertinent literature,
(3) take the Si modification macroporous aluminium oxide after hydrothermal treatment consists prepared by a certain amount of step (1), be placed in and stir metal impregnation solution and pull an oar, solid-liquid volume ratio is 1:5 ~ 1:20, and beating time is 30 ~ 120min.Then carry out suction filtration, filter cake butt controls at 15wt% ~ 30wt%, drying 2 ~ 6 hours under 100 ~ 150 DEG C of conditions, and after dry, the butt of material is 60wt% ~ 90wt%, then pulverizes, granularity control 100 ~ 200 order,
(4), after the powder that step (3) obtains being carried out rolling 20 ~ 60min, adding concentration is 2 ~ 10gHNO
3/ 100mL dilute nitric acid solution, continues to roll formation and can squeeze paste shape, then extruded moulding, and catalyst shape can be column, clover, bunge bedstraw herb and other different in nature bar etc., cut to lengthen 3 ~ 8mm,
(5) by the carrier strip that step (4) obtains, first under 100 ~ 150 DEG C of conditions dry 2 ~ 6 hours, then carry out roasting, sintering temperature was preferably 300 ~ 600 DEG C, and roasting time is preferably 3 ~ 10 hours, prepares finished catalyst.
The following examples are 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 embodiments.In 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 low temperature liquid nitrogen physisorphtion.
Embodiment 1(contrasts scheme)
(Tianjin Tian Jiu company produces, pore volume 0.82mL/g, specific area 323m to get 578g macroporous aluminium oxide
2/ g, butt 71.1wt%), the little porous aluminum oxide of 386g (Germany produces SB powder) prepares adhesive (butt 26.2wt%), add 6g sesbania powder, roll 30 minutes, add appropriate distilled water, make mixture become can squeeze paste shape, extrusion, banded extruder orifice plate diameter is 1.5mm clover.Wet bar at 120 DEG C dry 4 hours, then carries out roasting, temperature 550 DEG C, 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) and molybdenum nickel solution in (MoO
3content 40.7g/100mL, NiO content 6.5g/100mL) carry out supersaturation dipping, dipping rear catalyst, 480 DEG C of roastings 3 hours, is prepared finished catalyst and is numbered HF-1A and HF-1B respectively.
Embodiment 2(contrasts scheme)
Just the macroporous aluminium oxide in embodiment 1 is used instead the Si modification macroporous aluminium oxide that patent CN200510047483.1 embodiment 10 provides, the other the same as in Example 1, preparation bearer number is HF-2S, and catalyst is numbered HF-2A and HF-2B.
Embodiment 3(contrasts scheme)
Just adjusted by the impregnation concentration in embodiment 2, 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.The other the same as in Example 2.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) to carry out containing ammonia vapor process, treatment temperature is 80 DEG C, steam pressure 0.05MPa, 1.5 hours time, and 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), by hydrothermal treatment consists rear oxidation aluminium trisection, add in the metal impregnation liquid of stirring respectively, dip time 120min, suction filtration, at 120 DEG C, drying 4 hours, then pulverizes, sieves with 180 orders.Mixed with appropriate sesbania powder by powder, adding concentration is 4gHNO
3the dust technology of/100mL carries out shaping, and extrusion orifice plate is diameter is 1.5mm clover.Wet bar at 120 DEG C dry 4 hours, then will carry out roasting, sintering temperature 480 DEG C, 3 hours time, catalyst is numbered and is respectively HF-4A, HF-4B, HF-4C.
Embodiment 5(the present invention program)
Just the macroporous aluminium oxide in embodiment 4 is used instead the Si modification macroporous aluminium oxide that patent CN200510047483.1 embodiment 10 provides, the other the same as in Example 4, Kaolinite Preparation of 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) to carry out containing ammonia vapor process, treatment temperature is 130 DEG C, steam pressure 0.1MPa, time 2 h, and the volume ratio of ammonia and water vapour is 1:5.Adjusted by impregnation concentration in embodiment 4, tungsten nickel solution is WO simultaneously
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, the other the same as in Example 4, Kaolinite Preparation of 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) to carry out containing ammonia vapor process, treatment temperature is 180 DEG C, steam pressure 0.15MPa, time 2 h, and the volume ratio of ammonia and water vapour is 1:4.Adjusted by impregnation concentration in embodiment 4, tungsten nickel solution is WO simultaneously
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 the other the same as in Example 4, Kaolinite Preparation of 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) to carry out containing ammonia vapor process, treatment temperature is 200 DEG C, steam pressure 0.2MPa, 3 hours time, and the volume ratio of ammonia and water vapour is 1:3.Adjusted by impregnation concentration in embodiment 4, tungsten nickel solution is WO simultaneously
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 the other the same as in Example 4, Kaolinite Preparation of 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), by hydrothermal treatment consists rear oxidation aluminium trisection, add in the metal impregnation liquid of stirring respectively, dip time 120min, suction filtration, at 120 DEG C, drying 4 hours, then pulverizes, sieves with 180 orders.Mixed with appropriate sesbania powder by powder, adding concentration is 4gHNO
3the dust technology of/100mL carries out shaping, and extrusion orifice plate is diameter is 1.5mm clover.Wet bar at 120 DEG C dry 4 hours, then will carry out roasting, sintering temperature 480 DEG C, 3 hours time, catalyst is numbered and is respectively HF-9A, HF-9B, HF-9C.
In the present embodiment, instrumental analysis and activity rating are carried out to above each routine catalyst.Each routine catalyst physico-chemical property is shown in Table 1, and catalyst composition is benchmark with weight.Wherein embodiment 1 ~ 4 and 9 is reference catalyst, and embodiment 5 ~ 8 is this programme Kaolinite Preparation of Catalyst.
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 |
| 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 |
| 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 | |||
| 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(continues). 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 |
| 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 |
| 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 |
| 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 on 200mL small hydrogenation device, carries out presulfurization before activity rating to catalyst.The raw materials used oil nature of evaluation of catalyst activity and reaction process condition are in table 2 and table 3, and catalyst Deitrogenatin relative activity comparing result is in table 4.
Table 2. feedstock oil character
| Density (20 DEG C), g/cm 3 | 0.9120 |
| Boiling range/DEG C | |
| IBP/10% | 327/375 |
| 30%/50% | 403/435 |
| 70%/90% | 458/500 |
| 95%/FBP | 513/543 |
| Condensation point/DEG C | 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
| 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, DEG C | 380 |
Table 4. catalyst Deitrogenatin relative activity comparing result
| Catalyst is numbered | 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. a preparation method for hydrotreating catalyst, comprising:
(1) powdery carrier of hydrogenating catalyst material is chosen,
(2) carrier material is carried out carry out hydrothermal treatment consists with the water vapour containing ammonia, hydrothermal conditions is as follows: temperature is 50 ~ 200 DEG C, and pressure is 0.01 ~ 0.20MPa, and the processing time is 1 ~ 4 hour, the volume ratio wherein containing ammonia and water vapour in the water vapour of ammonia is 1:20 ~ 1:3
(3) by the powdery carrier of hydrogenating catalyst material soaking after hydrothermal treatment consists containing hydrogenation active metals solution in,
Then filtration, drying,
(4) material forming step (3) obtained, drying, roasting, obtained hydrotreating catalyst;
Described carrier of hydrogenating catalyst material is one in aluminium oxide, amorphous aluminum silicide or its mixing.
2. in accordance with the method for claim 1, it is characterized in that described carrier of hydrogenating catalyst material is one in aluminum oxide dry glue powder, contained amorphous silica-alumina dry glue powder or its mixing.
3. in accordance with the method for claim 1, it is characterized in that in the carrier of hydrogenating catalyst material described in step (1) containing one or more in auxiliary agents of silicon, phosphorus, fluorine, boron, titanium, zirconium.
4., according to the method described in claim 1 or 3, it is characterized in that the carrier of hydrogenating catalyst material described in step (1) is macroporous aluminium oxide, macroporous aluminium oxide pore volume is 0.6 ~ 1.3mL/g, and specific area is 200 ~ 550m
2/ g.
5. in accordance with the method for claim 1, it is characterized in that the hydrogenation active metals described in step (3) is one or more in W, Mo, Ni and Co.
6. in accordance with the method for claim 1, it is characterized in that the dipping process described in step (3) adopts excessive
Impregnation method, solid-liquid volume ratio is 1:5 ~ 1:20.
7., according to the method described in claim 1 or 5, it is characterized in that in final hydrotreating catalyst, active metal in oxide weight content for 35% ~ 70%.
8. in accordance with the method for claim 1, it is characterized in that in step (4) forming process, adding one or more in peptization acid, adhesive, expanding agent and extrusion aid.
9. in accordance with the method for claim 1, it is characterized in that the drying condition described in step (3) is: drying 2 ~ 6 hours under 100 ~ 150 DEG C of conditions, after dry, the butt of material is 60wt% ~ 90wt%.
10. in accordance with the method for claim 1, it is characterized in that the drying condition described in step (4) is: under 100 ~ 150 DEG C of conditions dry 2 ~ 6 hours, roasting condition is roasting 1 ~ 10 hour at 300 ~ 600 DEG C.
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| 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 |
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| 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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