CN102309971B - Preparation method for hydro-treating catalyst - Google Patents
Preparation method for hydro-treating catalyst Download PDFInfo
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- CN102309971B CN102309971B CN2010102220332A CN201010222033A CN102309971B CN 102309971 B CN102309971 B CN 102309971B CN 2010102220332 A CN2010102220332 A CN 2010102220332A CN 201010222033 A CN201010222033 A CN 201010222033A CN 102309971 B CN102309971 B CN 102309971B
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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 a kind of preparation method's of hydrotreating catalyst, particularly high tenor the hydrodesulfurization of heavy distillate and the preparation method of hydrodenitrogenation catalyst.
Technical background
Along with crude quality becomes heavy, variation year by year, environmental regulation is increasingly strict, and market constantly increases the demand of clear gusoline, makes the hydrogen addition technology of producing clean fuel obtain application more and more widely.Distillate hydrogenation is processed and is referred to that under HTHP, 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 the catalyst with carrier loaded active component, although carrier itself does not have direct catalytic activity in some cases, catalyst component only has the suitable carrier of the performance of support 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 larger pore volume, can improve its anti-coking or anti-Coking Behavior, and then the service life of extending catalyst, also helps simultaneously catalyst regeneration.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 increasingly, refinery has proposed more and more higher requirement to the performance of hydrotreating catalyst, and the hydrotreating catalyst performance of common metal content (in oxide hydrogenation metal total content generally lower than 30%) can not meet the current market demand fully.Improve tenor and can greatly promote the ability that hydrotreating catalyst is deviate from impurity and aromatic saturation, therefore the exploitation of high tenor hydrotreating catalyst more and more receives people's concern.Hydrotreating catalyst is the preparation method mainly contain, infusion process, kneading method, coprecipitation method etc., wherein to have a metal good at the carrier surface dispersive property due to infusion process, using rate of metal is high, the characteristics such as metal and carrier function power are suitable, the hydrotreating catalyst of common metal content adopts the infusion process preparation mostly, as the common employing modified aluminas of introducing in patent US4513097, CN94103999.4, CN02133122.7, prepare carrier, then by infusion process carrying metal component, through the roasting Kaolinite Preparation of Catalyst.But when infusion process prepares hydrotreating catalyst, generally can not obtain the hydrotreating catalyst that active metallic content is higher, although can adopt repeatedly the impregnating method to improve active metallic content, but increase rate is limited, increase simultaneously the complexity of catalyst preparation process, affected the serviceability of catalyst.coprecipitation method is adopted in high tenor hydrotreating catalyst preparation usually, as patent US5086032, the patent Introduction such as US4820677 and CN200410050730.9 the employing coprecipitation method prepare high tenor hydrotreating catalyst, prepare tenor up to 50%～95% hydrotreating catalyst, catalyst has higher Hydrogenation, but catalyst pore volume and specific area are little, can only process diesel oil following than the cut of lightweight, and because coprecipitation method Kaolinite Preparation of Catalyst using rate of metal is 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 catalyst performance prepared by kneading method is relatively poor, and the reactive metal effective rate of utilization is low, the less employing kneading method preparation of hydrotreating catalyst.
By above analysis, adopt preparation catalyst, can give full play to the performance of hydrogenation metal, 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 have large pore volume, bigger serface hydrotreating catalyst, will have very important Practical significance.
Summary of the invention
Deficiency for existing hydrotreating catalyst technology of preparing, the invention provides a kind of method that single-steeping prepares high tenor hydrotreating catalyst.
Hydrotreating catalyst preparation method of the present invention comprises following content:
(1) choose powdery carrier of hydrogenating catalyst material.
(2) by powdery carrier of hydrogenating catalyst material soaking in containing the solution of hydrogenation active metals, then filter, drying.
(3) material forming that supports hydrogenation metal, the roasting that step (2) are obtained, prepare final catalyst.
In above-mentioned steps (1), the 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, 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, be preferably 300～500m
2/ g, can contain required auxiliary agent in macroporous aluminium oxide, as one or more in silicon, phosphorus, fluorine, boron, titanium, zirconium etc.The modified macroporous aluminium oxide of silicon as described as 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 step (2) is generally group vib and VIII family metallic salt, as the saline solution of the metals such as W, Mo, Ni, Co one or more, in dipping solution, can add as required the required various auxiliary agents of catalyst.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.In dipping solution, the concentration of the slaines such as W, Mo, Ni, Co is determined according to catalyst activity metal requirement, as metal salt concentrations in dipping solution, by oxide, is generally 10～150g/100mL.Filtration after dipping and dry this area commonsense method and the condition of adopting.
In step (3), in forming process, can add as required one or more in peptization acid, adhesive component, expanding agent, extrusion aid etc., so that moulding smoothly.First dry after moulding, then roasting, obtain final catalyst prod, and in final hydrotreating catalyst, reactive metal is generally 35%～70% in oxide weight content, is preferably 40%～60%.Roasting is generally 300～600 ℃ of lower roastings 1～10 hour.Dry this area usual terms that adopts.
Hydrotreating catalyst prepared by the present invention is distinguished to some extent according to the catalyst carrier material kind difference of using.For the hydrotreating catalyst that uses the macropore alumina supporter material to prepare, the catalyst main character is as follows: specific area is 130-300m
2/ g, be preferably 160～260m
2/ g; Pore volume is 0.2～0.5cm
3/ g, be 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.
Hydrotreating catalyst preparation process of the present invention adopts carrier material powder dipping method, with carrier impregnation after the moulding of routine, compares, 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 final catalyst prod that active metallic content is higher.Due to the dipping solution that does not need high concentration, solution preparation is simple, and stable in properties is suitable for commercial scale and uses.Rarer slaine maceration extract can reduce the viscosity of solution, reduces solution surface tension, can weaken like this impact of capillary resistance phenomenon in dipping process.Can guarantee that not only in catalyst, metal component has higher content, can also further improve the decentralization of metal at carrier surface.
Catalyst carrier material is after hydrothermal treatment consists, and pore passage structure is more stable, at follow-up dipping, roll, still can keep pore passage structure preferably in moulding, calcination process process, has larger pore volume and specific area.Support acidity after hydrothermal treatment consists weakens greatly, and residue is acid take weak acid as main, is conducive to improve the Hydrogenation of catalyst.In addition, after 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 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 on 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 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 the 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
The modified macroporous aluminium oxide of silicon that below prepares take CN200510047483.1 prepares catalyst for hydro-processing heavy distillate as example as carrier material, illustrate the inventive method and technique effect, for the catalyst of other purposes, can select the carrier material that adapts.In the inventive method not the percentage of clear and definite benchmark be weight percentage.
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 being pulverized, after with 180 orders, sieving, 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) take active hydrogenation metal tungsten and nickel as example, the dipping solution preparation: get a certain amount of deionized water under stirring, add gradually nickel nitrate and ammonium metatungstate crystal, after all dissolving, static, 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 hydrothermal treatment consists aluminium oxide prepared by a certain amount of step (1), be placed in stirring metal impregnation solution and pull an oar, the solid-liquid volume ratio is 1: 5～1: 20, and beating time is 30～120min.Then carry out suction filtration, 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%, then pulverizes granularity control 100～200 orders.
(4) powder that supports hydrogenation metal that step (3) is obtained rolls, and after 20～60min, adding concentration is 2～10gHNO
3/ 100mL dilute nitric acid solution, continue 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 is controlled 3～8mm.
(5) carrier strip that step (4) is obtained, at first under 100～150 ℃ of conditions dry 2～6 hours, then carry out roasting, sintering temperature is preferably 400～600 ℃, and roasting time is preferably 3～10 hours, prepares the catalyst finished product.
Example 1 (contrast scheme)
(Tianjin Tian Jiu company 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) prepares adhesive (butt 26.2%), add 6g sesbania powder, rolled 30 minutes, add appropriate distilled water, make mixture become can squeeze the paste shape, extrusion, banded extruder orifice plate diameter is 1.5mm clover.Wet bar under 120 ℃ dry 4 hours, then carry out roasting, 550 ℃ of temperature, 3 hours time, numbering HF-1S.Get two parts of HF-1S carriers, each 120g is immersed in respectively tungsten nickel solution (WO
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, 480 ℃ of roastings 3 hours, is prepared the catalyst finished product and is numbered respectively HF-1A and HF-1B.
Example 2 (contrast scheme)
Just use the macroporous aluminium oxide in example 1 instead the modified macroporous aluminium oxide of silicon that patent CN200510047483.1 embodiment 10 provides, other is with example 1, and the preparation bearer number is HF-2S, and catalyst is numbered HF-2A and HF-2B.
Example 3 (contrast scheme)
Just the impregnation concentration in example 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 example 2.The preparation bearer number is HF-3S, and catalyst is numbered HF-3A and HF-3B.
Example 4 (the present invention program)
Get 578g macroporous aluminium oxide (with example 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), by hydrothermal treatment consists rear oxidation aluminium trisection, add respectively in the metal impregnation liquid of stirring, dip time 120min, suction filtration, under 120 ℃ dry 4 hours, then pulverize, with 180 orders, sieve.Powder is mixed with appropriate 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 under 120 ℃ dry 4 hours, then will carry out roasting, 480 ℃ of sintering temperatures, and 3 hours time, the catalyst numbering is respectively HF-4A, HF-4B, HF-4C.
Example 5 (the present invention program)
Just use the macroporous aluminium oxide in example 4 instead the modified macroporous aluminium oxide of silicon that patent CN200510047483.1 embodiment 10 provides, other is with example 4, and the Kaolinite Preparation of Catalyst numbering is respectively HF-5A, HF-5B and HF-5C.
Example 6 (the present invention program)
Just the impregnation concentration in example 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 example 4, and the Kaolinite Preparation of Catalyst numbering is respectively HF-6A, HF-6B and HF-6C.
Example 7 (the present invention program)
Just the impregnation concentration in example 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 example 4, Kaolinite Preparation of Catalyst numbering is respectively HF-7A, HF-7B and HF-7C.
Example 8 (the present invention program)
Just the impregnation concentration in example 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 example 4, Kaolinite Preparation of Catalyst numbering is respectively HF-8A, HF-8B and HF-8C.
In the present embodiment, above each routine catalyst is carried out to instrumental analysis and activity rating.Each routine catalyst physico-chemical property is shown in Table 1, and catalyst forms take weight as benchmark.Wherein example 1～4 is reference catalyst, and example 5～8 is this programme Kaolinite Preparation of Catalyst.
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 activity rating, catalyst is carried out to presulfurization.The raw materials used oil nature of evaluation of catalyst activity and reaction process condition are in Table 2 and table 3, and catalyst denitrogenation relative activity comparing result is in Table 4.
Table 2. feedstock oil character
Table 3. evaluating catalyst process conditions
Table 4. catalyst denitrogenation relative activity comparing result
Claims (10)
1. the preparation method of a hydrotreating catalyst, comprise the steps:
(1) choose powdery carrier of hydrogenating catalyst material;
(2) by powdery carrier of hydrogenating catalyst material soaking in containing the solution of hydrogenation active metals, then filter, drying;
(3) material forming that supports hydrogenation metal, the roasting that step (2) are obtained, prepare final catalyst;
In final hydrotreating catalyst, reactive metal is take oxide weight content as 40%～70%.
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, modified aluminas, amorphous aluminum silicide, aluminum oxide dry glue powder, modified aluminas dry glue powder, contained amorphous silica-alumina dry glue powder.
3. in accordance with the method for claim 1, 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.
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. in accordance with the method for 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. in accordance with the method for claim 1, it is characterized in that the hydrogenation active metals described in step (2) is one or more in W, Mo, Ni and Co.
7. in accordance with the method for claim 1, it is characterized in that the dipping process described in step (2) adopts excessive impregnation method, the solid-liquid volume ratio is 1: 5～1: 20.
8. according to the described method of claim 1 or 6, it is characterized in that in final hydrotreating catalyst, reactive metal is take oxide weight content as 40%～60%.
9. in accordance with the method for claim 1, it is characterized in that in step (3) forming process adding one or more in peptization acid, adhesive component, expanding agent and extrusion aid.
10. in accordance with the method for claim 1, it is characterized in that the described roasting condition of step (3) is 300～600 ℃ of lower roastings 1～10 hour.
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| 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 |
| CN103285940B (en) * | 2012-03-02 | 2016-03-23 | 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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