CN103962165A - Transition metal phosphide hydrogenation catalyst and preparation method thereof - Google Patents
Transition metal phosphide hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN103962165A CN103962165A CN201310035314.0A CN201310035314A CN103962165A CN 103962165 A CN103962165 A CN 103962165A CN 201310035314 A CN201310035314 A CN 201310035314A CN 103962165 A CN103962165 A CN 103962165A
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Abstract
The invention relates to a transition metal phosphide hydrogenation catalyst and a preparation method thereof. An inorganic porous material is used as a carrier for loading active components and a metal cocatalyst; the active components comprise tungsten, nickel and phosphorus, the total weight of tungsten and nickel oxides is 1-60% of that of the catalyst, the molar ratio of the tungsten and nickel material is 1:10-10:1, and total molar ratio of the total amount of tungsten and nickel to phosphorus is 1:4-6:1; the metal catalyst is selected from the group consisting of cerium and / or titanium element; the content of the amorphous silicon aluminum material in the inorganic porous material is 3-75 wt.% of the carrier; the content of macroporous alumina is 10-80 wt.% of the carrier; the content of a mesoporous molecular sieve is 0-50 wt.% of the carrier; the content of a binder is 1-15 wt.% of the carrier; and the content of metal cocatalyst is 0.1-30 wt.% of the catalyst. The catalyst can effectively remove the sulfur-containing compounds and nitrogen-containing compounds in petroleum fractions, so as to reach the purpose of depth desulfurization and denitrification.
Description
Technical field
The present invention relates to a kind of fraction oil hydrodesulfurizing, denitrification catalyst, particularly a kind of transition metal phosphide hydrogenation catalyst and preparation method thereof.
Background technology
In oil refining industry, hydrofinishing has become the preferred means that oil product cleans, and its main purpose is to remove sulphur in oil product, nitrogen impurity.In unifining process, traditional industrial catalyst is mainly Co-Mo, Ni-Mo, Ni-W, Ni-Mo-W, Co-Mo-Ni catalyst, this class thing catalyst is to exist with sulphided state form, sometimes in catalyst, also can add as Phosphorus co-catalyst, though this type of catalyst has certain hydrodesulfurization, denitrification activity, but along with current environmental regulation increasingly stringent, and crude oil heaviness is day by day serious, the hydrogenation catalyst of this quasi-tradition can not meet the demands, and more efficient hydrogenation catalyst is developed in an urgent demand.
Phosphide catalyst, as a kind of novel hydrogenation catalyst, owing to having the characteristic of class noble metal and excellent Hydrogenation, therefore receives the domestic very big concern for many research institutions.In the time of document and patent retrieval, find, mainly concentrate on and adopt the whole bag of tricks to prepare transition monometallic phosphide catalyst for the research of transition metal phosphide hydrogenation catalyst, as nickel phosphide, tungsten phosphide, phosphatization molybdenum, its hydrofinishing activity is not very desirable, in the present invention, adopt many preparation of metals transition metal phosphide hydrogenation catalyst, in catalyst, introduce the metal promoters high active of hydrogenation catalysis that improved it simultaneously.
Summary of the invention
The object of this invention is to provide a kind of transition metal phosphide hydrogenation catalyst and preparation method thereof efficiently, this catalyst can effectively be removed sulfur-containing compound and the nitrogen-containing compound in petroleum distillate, reaches the object of deep desulfuration, denitrogenation.
In the present invention, transition metal phosphide hydrogenation catalyst, is characterized in that by inorganic porous material load active component and metal promoters.Described active component is tungsten and nickel, phosphorus, and the oxide gross weight of tungsten and nickel is total catalyst weight 1% ~ 60%, preferably 5% ~ 45%, tungsten is 1:10 ~ 10:1 with the amount of substance ratio of nickel, preferably 1:2 ~ 5:1, tungsten is 1:4 ~ 6:1 with total amount of substance of nickel and the amount of substance of phosphorus ratio, preferably 1:3 ~ 3:1.
Carrier is inorganic porous material, is selected from one or more in amorphous aluminum silicide, macroporous aluminium oxide, zeolite molecular sieve, mesopore molecular sieve, adds adhesive kneading extrusion to form.Wherein amorphous aluminum silicide content is vehicle weight 3% ~ 75%, and macroporous aluminium oxide content is vehicle weight 10% ~ 80%, and mesopore molecular sieve is vehicle weight 0 ~ 50%, and binder content is total weight of carrier 1% ~ 15%, and described extrusion aid is sesbania powder.
Metal promoters selected from cerium element and/or titanium elements, its content is 0.1 ~ 30% of catalyst total amount, preferably 0.5% ~ 15%.Wherein Ce elements is selected from cerous nitrate and/or ceria, and titanium elements is selected from titanium dioxide and/or titanium trichloride.
In the present invention, tungsten source is selected from ammonium tungstate, metatungstic acid by one or more in, wolframic acid nickel, potassium tungstate; Nickel source is selected from basic nickel carbonate and/or nickel nitrate; Phosphorus source is selected from one or more in phosphoric acid, diammonium hydrogen phosphate, ammonium hydrogen phosphate.
Transition metal phosphide hydrogenation catalyst of the present invention adopts equal-volume dipping method preparation altogether, and its preparation method is as follows: the compound of tungsten, nickel and P elements is mixed with to solution A, containing cerium and/compound of titanium is mixed with solution B.The first dipping solution A taking inorganic porous material as carrier, then dipping solution B, or dipping solution A separately, then in 90 ~ 120 DEG C of oven dry, within 4 ~ 8 hours, obtain transition metal phosphide hydrogenation catalyst precursor through 500 ~ 550 DEG C of roastings, this precursor with 10 ~ 30 DEG C/h at N
2under atmosphere, temperature programming to 210 DEG C ~ 290 DEG C, constant temperature 4 ~ 6 hours, and under hydrogen atmosphere, 10 ~ 30 DEG C/h is warming up to 400 ~ 600 DEG C of constant temperature, reduces and after 4 ~ 8 hours, obtains highly active transition metal phosphide hydrogenation catalyst.
Phosphide catalyst is as a kind of novel hydrogenation catalyst, owing to thering is the characteristic of class noble metal and excellent Hydrogenation, in the present invention, adopt many preparation of metals to go out highly active transition metal phosphide hydrogenation catalyst, active component is selected from tungsten and nickel element combination, in catalyst, introduce metal promoters Ce elements and/or titanium elements, improved the high active of hydrogenation catalysis of catalyst simultaneously.Can effectively remove sulfur-containing compound and nitrogen-containing compound in petroleum distillate, reach the object of deep desulfuration, denitrogenation.
Detailed description of the invention
In the embodiment of the present invention, prepared transition metal phosphide hydrogenation catalyst process is as follows:
Inorganic porous material preparation: 53% amorphous silicon aluminium, 39% macroporous aluminium oxide and 8% sesbania make inorganic porous material through kneading, extrusion, dry, roasting.
With wolframic acid amine (NH
4)
10w
12o
414H
2o is tungsten source, nickel nitrate (Ni (NO
3)
26H
2o) be nickel source, phosphoric acid dihydro amine (NH
4h
2pO
4) be phosphorus source, they are respectively with WO, NiO and P
2o
5content meter (quality), total load amount is catalyst weight 30%.Adopt equal-volume to be total to dipping method and prepare transition metal phosphide hydrogenation catalyst.
Embodiment 1
By 10.9g wolframic acid amine (in WO 8.4g), 47.1g nickel nitrate (in NiO 12.5g) and 14.6g phosphoric acid dihydro amine (with P
2o
5meter 9.1g) be dissolved in 54.3g deionized water, be mixed with solution A 1.At room temperature, solution A 1 incipient impregnation is to 70g inorganic porous material, and drying at room temperature in 110 DEG C of oven dry 8 hours, obtained transition metal phosphide hydrogenation catalyst precursor for 6 hours in 530 DEG C of roastings after 12 hours.This precursor at room temperature with 30 DEG C/h at N
2under atmosphere, rise to 250 DEG C, constant temperature 5 hours, switches under hydrogen atmosphere, be warming up to 550 DEG C with 30 DEG C/h after constant temperature reduction 6 hours, obtain transition metal phosphide hydrogenation catalyst, called after Cat-A.
Embodiment 2
By 12.9g wolframic acid amine (in WO 9.9g), 41.9g nickel nitrate (in NiO 11.1g) and 14.4 phosphoric acid dihydro amines (with P
2o
5meter 9.0g) be dissolved in 54.3g deionized water, be mixed with solution A 2, following steps are identical with example 1, obtain Cat-B.
Embodiment 3
By 20.4g wolframic acid amine (in WO 15.7g), 21.9g nickel nitrate (in NiO 5.8g) and 13.7g phosphoric acid dihydro amine (with P
2o
5meter 8.5g) be dissolved in 54.3g deionized water, be mixed with solution A 3, following steps are identical with example 1, obtain Cat-C.
Embodiment 4
By 12.9g wolframic acid amine (in WO 9.9g), 41.9g nickel nitrate (in NiO 11.1g) and 14.4g phosphoric acid dihydro amine (with P
2o
5meter 9.0g) be dissolved in 30.1g deionized water, be mixed with solution A 4.With cerous nitrate (Ce (NO
3)
36H
2o) be cerium source, 12.7g cerous nitrate is (with CeO
2meter 5.0g) be dissolved in 24.2g deionized water, be mixed with solution B.At room temperature, solution A 4 and solution B are successively impregnated on 70g inorganic porous material, and following steps are identical with example 1, obtain Cat-D.
Comparative example 1
By 25.9g wolframic acid amine (in WO 19.9g) and 17.8g phosphoric acid dihydro amine (with P
2o
5meter 11.1g) be dissolved in 50.3g deionized water, be mixed with solution A 5.At room temperature, solution A 1 incipient impregnation is to 70g γ-Al
2o
3(traditional industrial carrier) is upper, and following steps are identical with example 1, obtain Cat-E.
Comparative example 2
By 75.8g nickel nitrate (in NiO 20.1g) and 15.9g phosphoric acid dihydro amine (with P
2o
5meter 9.9g) be dissolved in 50.3g deionized water, be mixed with solution A 6.At room temperature, solution A 1 incipient impregnation is to 70g γ-Al
2o
3(traditional industrial carrier) is upper, and following steps are identical with example 1, obtain Cat-F.
Adopting the miscella of AGO (atmospheric gas oil) AGO and catalytic diesel oil LCO is raw material, and catalyst is carried out to hydrofinishing evaluation, and feedstock oil character lists in table 1 and evaluation result is listed in table 2.
Table 1 feedstock oil character and appreciation condition
Table 2 appreciation condition
Table 2 catalyst hydrogenation evaluation result
Table 3 result can be found out, transition metal phosphide hydrogenation catalyst of the present invention
Hydrofinishing activity, want high compared with the monometallic phosphide activity of hydrocatalyst of identical load amount, add the phosphide activity of hydrocatalyst of metal promoters higher simultaneously, show that transition metal phosphide hydrogenation catalyst of the present invention is a kind of comparatively desirable Hydrobon catalyst.
Claims (4)
1. a transition metal phosphide hydrogenation catalyst, it is characterized in that: use inorganic porous material as carrier, load active component and metal promoters, described active component is tungsten, nickel and phosphorus, the oxide gross weight of tungsten and nickel is total catalyst weight 1 ~ 60%, tungsten is with the amount of substance of nickel than being 1:10 ~ 10:1, and tungsten is 1:4 ~ 6:1 with total amount of substance of nickel and the amount of substance of phosphorus ratio, described metal promoters selected from cerium element and/or titanium elements; Its content is 0.1 ~ 30% of catalyst total amount.
Described inorganic porous material is selected from one or more in amorphous aluminum silicide, macroporous aluminium oxide, mesopore molecular sieve, adds extrusion aid kneading extrusion to form; Amorphous aluminum silicide content is 3 ~ 75% of vehicle weight, and macroporous aluminium oxide content is vehicle weight 10 ~ 80%, and mesopore molecular sieve is vehicle weight 0 ~ 50%, and binder content is total weight of carrier 1 ~ 15%;
Described metal promoters, its content is total catalyst weight 0.1 ~ 30%.
2. transition metal phosphide hydrogenation catalyst according to claim 1, it is characterized in that: the oxide gross weight of active component tungsten and nickel is selected 5 ~ 45% of total catalyst weight, tungsten selects 1:2 ~ 5:1 with the amount of substance ratio of nickel, and tungsten is elected 1:3 ~ 3:1 as with total amount of substance of nickel and the amount of substance ratio of phosphorus.
3. transition metal phosphide hydrogenation catalyst according to claim 1, is characterized in that: its content is 0.5% ~ 15% of catalyst total amount.
4. a transition metal phosphide hydrogenation catalyst preparation method claimed in claim 1, is characterized in that: adopt equal-volume dipping method preparation altogether, the compound of tungsten, nickel and P elements is mixed with to solution A, be mixed with solution B containing the compound of cerium and/or titanium; The first dipping solution A taking inorganic porous material as carrier, then dipping solution B, or independent dipping solution A, then in 90 ~ 120 DEG C of oven dry, obtain transition metal phosphide hydrogenation catalyst precursor for 4 ~ 8 hours through 500 ~ 550 DEG C of roastings, and this precursor is at N
2under atmosphere, with 10 ~ 30 DEG C/h temperature programming to 210 DEG C ~ 290 DEG C, constant temperature 4 ~ 6 hours, and under hydrogen atmosphere, be warming up to 400 ~ 600 DEG C of constant temperature with 10 ~ 30 DEG C/h, reduce and after 4 ~ 8 hours, obtain highly active transition metal phosphide hydrogenation catalyst.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105582952A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of rare-earth-containing hydrodemetallization catalyst |
| CN105642324A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Non-noble metal selective hydrogenation catalyst, preparation method and application thereof |
| CN111635736A (en) * | 2020-06-03 | 2020-09-08 | 长安大学 | Porous alumina-based composite wave-absorbing material and preparation method thereof |
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| US20090188834A1 (en) * | 2004-09-22 | 2009-07-30 | Patrick Euzen | Doped alumino-silicate catalyst and improved process for treatment of hydrocarbon feeds |
| WO2009139053A1 (en) * | 2008-05-14 | 2009-11-19 | 千代田化工建設株式会社 | Process for producing metal-bearing catalyst |
| CN101992109A (en) * | 2010-09-06 | 2011-03-30 | 常州介孔催化材料有限公司 | Transition metal phosphide hydrofined catalyst and preparation method thereof |
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2013
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Patent Citations (4)
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| CN1274002A (en) * | 1999-05-18 | 2000-11-22 | 中国石油化工集团公司 | Process for preparing hydrorefining catalyst |
| US20090188834A1 (en) * | 2004-09-22 | 2009-07-30 | Patrick Euzen | Doped alumino-silicate catalyst and improved process for treatment of hydrocarbon feeds |
| WO2009139053A1 (en) * | 2008-05-14 | 2009-11-19 | 千代田化工建設株式会社 | Process for producing metal-bearing catalyst |
| CN101992109A (en) * | 2010-09-06 | 2011-03-30 | 常州介孔催化材料有限公司 | Transition metal phosphide hydrofined catalyst and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105582952A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method of rare-earth-containing hydrodemetallization catalyst |
| CN105582952B (en) * | 2014-10-22 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth |
| CN105642324A (en) * | 2014-12-04 | 2016-06-08 | 中国石油化工股份有限公司 | Non-noble metal selective hydrogenation catalyst, preparation method and application thereof |
| CN105642324B (en) * | 2014-12-04 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of base metal selective hydrocatalyst and its preparation method and application |
| CN111635736A (en) * | 2020-06-03 | 2020-09-08 | 长安大学 | Porous alumina-based composite wave-absorbing material and preparation method thereof |
| CN111635736B (en) * | 2020-06-03 | 2023-08-08 | 怀化恒安石化有限公司 | Porous alumina-based composite wave-absorbing material and preparation method thereof |
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