CN102309971A - Preparation method for hydro-treating catalyst - Google Patents
Preparation method for hydro-treating catalyst Download PDFInfo
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- CN102309971A CN102309971A CN2010102220332A CN201010222033A CN102309971A CN 102309971 A CN102309971 A CN 102309971A CN 2010102220332 A CN2010102220332 A CN 2010102220332A CN 201010222033 A CN201010222033 A CN 201010222033A CN 102309971 A CN102309971 A CN 102309971A
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Abstract
The invention discloses a preparation method for a hydro-treating catalyst. The final hydro-treating catalyst is prepared from a powdery hydro-treating catalyst carrier material by impregnating, drying, forming and roasting. The hydro-treating catalyst carrier material is preferably hydrothermally treated before active metals are impregnated, and the hydro-treating catalyst carrier material is preferably macroporous alumina or modified macroporous alumina. According to the method, the hydro-treating catalyst with relatively high active metal content is prepared by using the characteristic of high liquid absorption quantity of the powdery hydro-treating catalyst carrier material before forming and adopting one-time impregnation, and the catalyst has excellent service performance. The method is simple in process, can be used for preparing various hydro-treating catalysts, and is particularly suitable for preparing a heavy distillate hydro-treating catalyst.
Description
Technical field
The present invention relates to hydrodesulfurization and the preparation method of hydrodenitrogenation catalyst of the heavy distillate of a kind of preparation method of hydrotreatment catalyst, particularly high tenor.
Technical background
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 be meant that under HTHP, catalytic reactions such as hydrodesulfurization, hydrodenitrogeneration, hydrogenation deoxidation, HDM and hydrogenation of unsaturated hydrocarbons are saturated take place for feedstock oil and hydrogen on catalyst surface.
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 the 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 increasingly high requirement to the performance of hydrotreating catalyst, and the hydrotreating catalyst performance of common metal content (generally being lower than 30% 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 receives people's attention.Hydrotreating catalyst is the preparation method mainly contain; Infusion process, kneading method, coprecipitation method etc.; Wherein because infusion process characteristics such as to have a metal good at the carrier surface dispersive property, and using rate of metal is high, and metal and carrier function power are suitable; The hydrotreating catalyst of common metal content adopts immersion process for preparing mostly; Common employing modified aluminas as introducing among patent US4513097, CN94103999.4, the CN02133122.7 prepares carrier, then through infusion process carrying metal component, prepares catalyst through roasting.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, has increased the complexity of catalyst preparation process simultaneously, influences the serviceability of catalyst.Coprecipitation method is adopted in high tenor hydrotreating catalyst preparation usually, has introduced the employing coprecipitation method like patents such as patent US5086032, US4820677 and CN200410050730.9 and has prepared high tenor hydrotreating catalyst, prepares tenor up to 50%～95% hydrotreating catalyst; Catalyst has higher hydrogenation performance; But catalyst pore volume and specific area are little, can only handle below the diesel oil cut than lightweight, 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.
Through 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 receives very big restriction; 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 to existing hydrotreating catalyst technology of preparing the invention provides the method that a kind of single-steeping prepares high tenor hydrotreating catalyst.
Hydrotreating catalyst preparation method of the present invention comprises following content:
(1) chooses powdery carrier of hydrogenating catalyst material.
(2) with powdery carrier of hydrogenating catalyst material soaking in containing the solution of hydrogenation active metals, filter then, drying.
(3) final catalyst is prepared in the material forming that supports hydrogenation metal, the roasting that step (2) are obtained.
In the above-mentioned steps (1); The carrier of hydrogenating catalyst material is selected according to the needs of hydrotreating catalyst, like the precursor (aluminum oxide dry glue powder, modified aluminas dry glue powder, amorphous aluminum silicide dry glue powder etc.) of aluminium oxide, modified aluminas, amorphous aluminum silicide etc. and above-mentioned material.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, like in silicon, phosphorus, fluorine, boron, titanium, the zirconium etc. one or more.Like modified macroporous aluminium oxide of the described silicon of CN200510047483.1 etc.The carrier of hydrogenating catalyst material preferably carried out hydrothermal treatment consists before the dipping active metal component, the hydrothermal treatment consists temperature is controlled to be 400～600 ℃, and steam pressure is 0.05～0.20MPa, and the time is 30min～90min.
Hydrogenation active metals described in the step (2) is generally group vib and VIII family metallic salt, like 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 confirmed according to catalyst activity metal requirement in the dipping solution, is generally 10～150g/100mL like 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 according to the catalyst carrier material kind difference of using to some extent.For the hydrotreating catalyst that uses the macropore alumina supporter material preparation, the catalyst main character is following: specific area is 130-300m
2/ g is preferably 160～260m
2/ g; Pore volume is 0.2～0.5cm
3/ g is preferably 0.3～0.45cm
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, meleic acid amount (160 ℃ of infrared absorption spectrographic determinations of pyridine) is between 0.2～0.5mmol/g.
The process for preparing hydrotreating catalyst 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 the decentralization of metal at carrier surface.
Catalyst carrier material is through after the hydrothermal treatment consists, and pore passage structure is more stable, at follow-up dipping, roll, still can keep pore passage structure preferably in the moulding, calcination process process, has bigger pore volume and specific area.Support acidity after the hydrothermal treatment consists weakens greatly, and residue is acid to be main with weak acid, helps improving the hydrogenation performance of catalyst.In addition, behind the carrier material dipping reactive metal solution of hydrothermal treatment consists, be easy to and excessive residue dipping solution isolated by filtration.
The present invention adopts the modified macroporous aluminium oxide of extraordinary silicon as carrier, and this patented product has the pore volume and the specific area of super large, can support more metal component, and can guarantee that metal component can be good on carrier, disperseing.The inventive method can adopt single macropore alumina supporter, can not only guarantee that catalyst has the higher tenor and the uniformity that better metal component distributes, and 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.In the inventive method not the percentage of clear and definite benchmark be weight percentage.
It is following that the inventive method prepares the catalyst for hydro-processing heavy distillate process:
(1) the modified macroporous aluminium oxide of silicon being pulverized, after sieving with 180 orders, used hydrothermal treatment device, is 400～600 ℃ in temperature, and steam pressure is under 0.05～0.20MPa condition, carries out hydrothermal treatment consists, and constant temperature time is 30min～90min.
(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 20.0～50.0gWO
3/ 100mL, NiO content 2.0～15.0gNiO/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 hydrothermal treatment consists aluminium oxide that a certain amount of step (1) prepares, place stirring metal impregnation solution to 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 15%～30%, and drying is 2～6 hours under 100～150 ℃ of conditions, and containing metal powder butt is 60%～90%, pulverizes granularity control 100～200 orders then.
(4) powder that supports hydrogenation metal that step (3) is obtained rolls, and adding concentration behind 20～60min is 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 400～600 ℃, and roasting time is preferably 3～10 hours, prepares the catalyst finished product.
Instance 1 (contrast 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 71.1%), the little porous aluminum oxide of 386g (Germany produces the SB powder) preparation adhesive (butt 26.2%); 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 a 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.
Instance 2 (contrast scheme)
Just use the macroporous aluminium oxide in the instance 1 instead the modified macroporous aluminium oxide of silicon that patent CN200510047483.1 embodiment 10 provides, other is with instance 1, and the preparation bearer number is HF-2S, and catalyst is numbered HF-2A and HF-2B.
Instance 3 (contrast scheme)
Just the impregnation concentration in the instance 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 instance 2.The preparation bearer number is HF-3S, and catalyst is numbered HF-3A and HF-3B.
Instance 4 (the present invention program)
Get 578g macroporous aluminium oxide (with instance 1) and carry out hydrothermal treatment consists, the hydrothermal treatment consists temperature is 560 ℃, steam pressure 0.1MPa, time 40min.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 1.8g/100mL) and tungsten nickel solution (WO
3Content 6.3g/100mL, MoO
3Content 7.7g/100mL, NiO content 2.6g/100mL),, add respectively in the metal impregnation liquid that stirs hydrothermal treatment consists rear oxidation aluminium trisection, 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 a 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.
Instance 5 (the present invention program)
Just use the macroporous aluminium oxide in the instance 4 instead the modified macroporous aluminium oxide of silicon that patent CN200510047483.1 embodiment 10 provides, other is with instance 4, and preparation catalyst numbering is respectively HF-5A, HF-5B and HF-5C.
Instance 6 (the present invention program)
Just the impregnation concentration in the instance 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 instance 4, and preparation catalyst numbering is respectively HF-6A, HF-6B and HF-6C.
Instance 7 (the present invention program)
Just the impregnation concentration in the instance 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 instance 4, preparation catalyst numbering is respectively HF-7A, HF-7B and HF-7C.
Instance 8 (the present invention program)
Just the impregnation concentration in the instance 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 instance 4, preparation catalyst numbering is respectively HF-8A, HF-8B and HF-8C.
In the present embodiment, above each routine catalyst is carried out instrumental analysis and activity rating.Each routine catalyst physico-chemical property sees shown in the table 1 that it is benchmark that catalyst is formed with weight.Wherein instance 1～4 is a reference catalyst, and instance 5～8 prepares catalyst for this programme.
Table 1. catalyst physico-chemical property
Table 1 (continuing). the catalyst physico-chemical property
Evaluating apparatus carries out on the 200mL small hydrogenation device, before the activity rating catalyst is carried out presulfurization.Raw materials used oiliness matter of evaluation of catalyst activity and reaction process condition are seen table 2 and table 3, and catalyst denitrogenation relative activity comparing result is seen table 4.
Table 2. feedstock oil character
Table 3. evaluating catalyst process conditions
Table 4. catalyst denitrogenation relative activity comparing result
Claims (10)
1. a preparation method of hydrotreatment catalyst comprises the steps:
(1) chooses powdery carrier of hydrogenating catalyst material;
(2) with powdery carrier of hydrogenating catalyst material soaking in containing the solution of hydrogenation active metals, filter then, drying;
(3) final catalyst is prepared in the material forming that supports hydrogenation metal, the roasting that step (2) are obtained.
2. according to the described method of claim 1, it is characterized in that the described carrier of hydrogenating catalyst material of step (1) is one or more in aluminium oxide, modified aluminas, amorphous aluminum silicide, aluminum oxide dry glue powder, modified aluminas dry glue powder, the amorphous aluminum silicide dry glue powder.
3. according to the described method of claim 1, it is characterized in that the described carrier of hydrogenating catalyst material of step (1) is a macroporous aluminium oxide, the macroporous aluminium oxide pore volume is 0.6～1.3mL/g, and specific area is 200～550m
2/ g.
4. according to claim 1,2 or 3 described methods, it is characterized in that the carrier of hydrogenating catalyst material carried out hydrothermal treatment consists before the dipping active metal component.
5. according to the described method of claim 4, it is characterized in that described hydrothermal treatment consists temperature is 400～600 ℃, steam pressure is 0.05～0.20MPa, and the time is 30min～90min.
6. according to the described method of claim 1, it is characterized in that the hydrogenation active metals described in the step (2) is one or more among W, Mo, Ni and the Co.
7. according to the described method of claim 1, it is characterized in that the dipping process described in the step (2) adopts excessive impregnation method, the solid-liquid volume ratio is 1: 5～1: 20.
8. according to claim 1 or 6 described methods, it is characterized in that in the final hydrotreating catalyst that reactive metal is 35%～70% in oxide weight content.
9. according to the described method of claim 1, it is characterized in that one or more in the acid of interpolation peptization, adhesive component, expanding agent and the extrusion aid in step (3) forming process.
10. according to the described method of claim 1, it is characterized in that the described roasting condition of step (3) is 300～600 ℃ of following roastings 1～10 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285939A (en) * | 2012-03-02 | 2013-09-11 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation, preparation method and application thereof, and hydrofining method |
| CN103285940A (en) * | 2012-03-02 | 2013-09-11 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation, preparation method and application thereof, and hydrofining method |
| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
| CN112717949A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0796195A (en) * | 1993-09-29 | 1995-04-11 | Hino Motors Ltd | Exhaust gas purification catalyst |
| CN1393523A (en) * | 2001-06-29 | 2003-01-29 | 中国石油化工股份有限公司 | Process for preparing hydrocracking catalyst |
| CN1400287A (en) * | 2001-07-31 | 2003-03-05 | 中国石油化工股份有限公司 | Preparation of rare earth contained hydrocracking catalyst |
-
2010
- 2010-07-07 CN CN2010102220332A patent/CN102309971B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0796195A (en) * | 1993-09-29 | 1995-04-11 | Hino Motors Ltd | Exhaust gas purification catalyst |
| CN1393523A (en) * | 2001-06-29 | 2003-01-29 | 中国石油化工股份有限公司 | Process for preparing hydrocracking catalyst |
| CN1400287A (en) * | 2001-07-31 | 2003-03-05 | 中国石油化工股份有限公司 | Preparation of rare earth contained hydrocracking catalyst |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103285939A (en) * | 2012-03-02 | 2013-09-11 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation, preparation method and application thereof, and hydrofining method |
| CN103285940A (en) * | 2012-03-02 | 2013-09-11 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation, preparation method and application thereof, and hydrofining method |
| CN103285939B (en) * | 2012-03-02 | 2015-11-25 | 中国石油化工股份有限公司 | There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrofinishing process |
| CN107638882A (en) * | 2017-05-08 | 2018-01-30 | 中国科学院大连化学物理研究所 | A kind of catalyst for selective hydrodesulfurizationof of gasoline and its preparation and application |
| CN112717949A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
| CN112717949B (en) * | 2019-10-28 | 2022-07-12 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
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