CN101347733A

CN101347733A - Nickel-based catalyst

Info

Publication number: CN101347733A
Application number: CNA2007100439432A
Authority: CN
Inventors: 王建强; 赵多; 吴征; 刘仲能
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology; China Petrochemical Corp
Priority date: 2007-07-18
Filing date: 2007-07-18
Publication date: 2009-01-21

Abstract

The invention relates to a nickel-based catalyst which is mainly used for solving the problems of low nickel content and low active specific surface area in the prior art. The nickel-based catalyst adopts the nickel-based catalyst and comprises the following components of (a) 5 to 75 percent of nickel or oxide thereof and (b) the rest of aluminium oxide carrier counted by the percent by weight of the catalyst, wherein, a precursor of the aluminium oxide carrier is aluminium sol, and the precursor of the nickel is selected from at least one of nickel acetate, nickel chloride or nickel ammonia complex; therefore, the technical proposal can better solve the problems and can be widely used in the hydrotreating industrial production of light oil fractions, heavy oil fractions, unsaturated oils and fats and pyrolysis gasoline, in particular to pyrolysis C9 and hydrocarbon thereabove.

Description

Nickel-base catalyst

Technical field

The present invention relates to a kind of nickel-base catalyst, particularly about a kind of especially nickel-base catalyst of cracking carbon nine and above hydrocarbon hydrotreatment thereof of light oil distillate, heavy oil fraction, consaturated oil, drippolene that can be used for.

Background technology

The Ni/Al of high nickel content, high activity specific surface ₂O ₃Catalyst is quite important in fields such as petrochemical industry catalytic hydrogenation, hydrodesulfurization and oil hydrogenations.United States Patent (USP) (USP 3,320,182) having provided of morning adopts coprecipitation method to prepare the Ni/Al of high nickel content ₂O ₃The method of catalyst, but well-known this method forms nickel aluminate easily.United States Patent (USP) (USP6,673,743 and USP 4,490,480), Chinese patent (ZL 00803678.0) have been set forth a kind of Raney nickel that can be used for oil hydrogenation, and nickel content can reach 5～75%.Above-mentioned catalyst adopts and the Ni ammonia solution is deposited-be deposited in the transition state of alumina suspension and gets.U.S. Pat P 6,242, and 662 have announced and a kind ofly add industrial aluminium hydroxide to method that the nickel ammonia solution decomposes again, obtain a kind of catalyst of high nickel content.These methods all need to provide alumina in Nano level or aluminium hydrate powder, just can obtain the catalyst of high degree of dispersion, high nickel content.

Utilize the catalyst of sol-gel technology preparing can control the content and the distribution of active component well, have characteristics such as high dispersive, crystalline phase are stable, Heat stability is good.Employing boehmite peptisations such as Zhang Yuhong make AlOOH colloidal sol, by disperse Ni (NO in colloidal sol ₃) ₂Solution makes the NiO/ γ-Al of high thermal stability ₂O ₃Catalyst (petroleum refining and chemical industry, 1999,30 (5): 25-29).But, Ni (NO ₃) ₂Crystallization causes the extrusion difficulty easily, and catalyst strength is not enough.

Summary of the invention

Technical problem to be solved by this invention is that the nickel content that exists in the prior art is low, the surperficial low problem of specific activity, and a kind of new nickel-base catalyst is provided.This catalyst has the high advantage of catalytic activity.

In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of nickel-base catalyst by weight percentage, comprises following component: (a) 5～75% nickel or its oxide; (b) alumina catalyst support of surplus; Wherein the presoma of alumina catalyst support is an aluminium colloidal sol, and the presoma of nickel is to be selected from least a in nickel acetate, nickel chloride or the nickel ammine.

In the technique scheme, by weight percentage, the content preferable range of metallic nickel or its oxide is 10～60%; The preferred version of alumina precursor is served as reasons and is selected from boehmite, unformed aluminium oxide or alumina hydrogel and obtains through the inorganic acid peptization; Nickel salt aqueous solution or nickel ammine that the preferred version of nickel presoma is served as reasons and is selected from least a formation in nickel acetate, the nickel chloride; The preferred version of nickel ammine serve as reasons be selected from least a in nickel nitrate, nickel oxalate, nickel acetate, the basic nickel carbonate with being selected from least a reaction in corresponding anion ammonium salt, ammoniacal liquor or the ethylenediamine complex compound that forms.

Preparation of catalysts method of the present invention comprises mixes nickel alumina gel, peptizing agent, water in the desired amount, first at 50～110 ℃ times dry 1～24 hour behind the extruded moulding, then 350～500 ℃ of following roastings 1～10 hour, obtains Ni/Al ₂O ₃Catalyst precursor.Can repeat above-mentioned steps and make required nickel content.Finished catalyst need be used hydrogen reducing before use.

The sol-gel catalyst that the present invention obtains has higher active nickel content, can be widely used in light oil distillate, heavy oil fraction, consaturated oil, drippolene especially in the industrial production of cracking carbon nine and above hydrocarbon hydrotreatment thereof.

The present invention proposes a kind of nickel-base catalyst preparation method who is different from prior art, in alumina sol, add nickel salt aqueous solution or nickel ammonia complex liquid,, can obtain Ni/Al through roasting, reduction through static aging or add the thermal decomposition complex ni-ion and obtain the nickel alumina gel ₂O ₃Catalyst.Obtain a kind of nickel content at 5～75% Ni/Al by technique scheme ₂O ₃Catalyst, preferable range are 10～60%.Nickel ion is adsorbed in the alumina sol particle of high-specific surface area, is the main cause that the present invention obtains high dispersive, high activity nickel-base catalyst.Nickel and AlOOH generate a part of nickel aluminate inevitably in roasting process, this part nickel can not provide effective active sites in hydrogenation process.Too high nickel content can cause the nickel particles reunion, forms bigger crystal grain, and higher specific activity surface area also can not be provided.It is 10～60% that nickel-base catalyst of the present invention can provide the metallic nickel of high activity specific surface or the content preferable range of nickel oxide.The Nano sol particle provides a large amount of surface area to disperse the nickel component, obtains the highly active nickel-base catalyst of high dispersive.Micropore on the catalyst of the present invention provides little crystal grain nickel particles " to inlay the space ", has fettered the migration of nickel particles, has improved the stability of catalyst.Cracking carbon nine and above hydrocarbon-fraction thereof can keep aromatic component wherein after selecting hydrogenation, hydrogenated oil can be widely used in high-knock rating gasoline, hydro-dealkylation volume increase BTX (B is a benzene, and T is a toluene, and X is a dimethylbenzene) aromatic hydrocarbons and high aromatic solvent wet goods.Adopt technical scheme of the present invention, to cracking carbon nine and above hydrocarbon thereof 40 ℃ of inlet temperatures, reaction pressure 3.0MPa, green oil air speed 1.5 hours ^-1, hydrogen to oil volume ratio H ₂Check and rate catalyst under the condition of/feedstock oil=300: 1, the reaction adiabatic temperature rise is 35～100 ℃, and outlet bromine valency mean value is reduced to 15 gram bromines/100 gram oil, and outlet diene mean value is less than 0.4 gram iodine/100 gram oil, the diolefin hydrogenation rate can reach 98.0%, has obtained better technical effect.

The invention will be further elaborated below by embodiment, but these embodiment in no case are construed as limiting scope of the present invention.

The specific embodiment

[embodiment 1]

With nitric acid at [H ⁺]/[AlOOH] mol ratio is under 0.25 the condition, with molten 24 hours of boehmite arogel, obtains the aluminium oxide solid content and be 5% alumina sol.Nickel chloride is dissolved in an amount of water, obtains the nickel salt aqueous solution of 0.10 gram nickel/milliliter.An amount of nickel salt aqueous solution is joined in the alumina sol, wore out 24 hours down at 60 ℃, drying promptly obtains corresponding catalyst precursor again.Catalyst precursor obtained oxidized form NiO/Al in 4 hours 400 ℃ of roastings ₂O ₃Catalyst.Catalyst reduced 12 hours down at 450 ℃ in 1.5 liters of/minute flow of pure hydrogen, obtained metal mold Ni/Al ₂O ₃Catalyst.

Change the amount that joins nickel salt aqueous solution in the alumina sol, obtain catalyst 1～2 successively, see Table 1.Corresponding catalyst sees Table 2 through the physical data that the nitrogen physical absorption obtains.Catalyst reduction degree, decentralization, active surface volume data see Table 3.

Table 1

Table 2

Table 3

[embodiment 2]

Preparation of catalysts and operating condition are with embodiment 1, and the presoma that just changes nickel salt aqueous solution is a nickel acetate, and the concentration of nickel salt aqueous solution is 0.04 gram nickel/milliliter.According to the amount that joins nickel salt aqueous solution in the alumina sol, obtain catalyst 3～4 successively, see Table 1.Corresponding catalyst sees Table 2 through the physical data that the nitrogen physical absorption obtains.Catalyst reduction degree, decentralization, active surface volume data see Table 3.

[embodiment 3]

With nitric acid at [H ⁺]/[AlOOH] mol ratio is under 0.25 the condition, with molten 24 hours of boehmite arogel, obtains the aluminium oxide solid content and be 5% alumina sol.With molar ratio computing, basic nickel carbonate: ammoniacal liquor: ammonium carbonate=1: 6.0: 1.5, add an amount of water, obtain the nickel ammonia complex liquid of 0.10 gram nickel/milliliter.Nickel ammonia complex liquid is joined alumina sol, under 95 ℃ complex ni-ion was added thermal decomposition 8 hours, drying or filtration promptly obtain corresponding catalyst precursor again.Catalyst precursor obtained oxidized form NiO/Al in 4 hours 400 ℃ of roastings ₂O ₃Catalyst.Catalyst reduced 12 hours down at 450 ℃ in 1.5 liters of/minute flow of pure hydrogen, obtained metal mold Ni/Al ₂O ₃Catalyst.

Change the amount that joins nickel ammonia complex liquid in the alumina sol, obtain catalyst 5～6 successively, see Table 1.Corresponding catalyst sees Table 2 through the physical data that the nitrogen physical absorption obtains.Catalyst reduction degree, decentralization, active surface volume data see Table 3.

[embodiment 4]

Preparation of catalysts and operating condition are with embodiment 3, and the part that just changes nickel salt is an ethylenediamine, prepare the nickel ammonia complex liquid of 0.10 gram nickel/milliliter equally.Amount according to joining nickel ammonia complex liquid in the alumina sol obtains catalyst 7～8 successively, sees Table 1.Corresponding catalyst sees Table 2 through the physical data that the nitrogen physical absorption obtains.Catalyst reduction degree, decentralization, active surface volume data see Table 3.

[embodiment 5]

Preparation of catalysts and operating condition are with embodiment 3, and the presoma that just changes alumina sol is an alumina hydrogel, and wherein alumina hydrogel adopts the following steps preparation: at 1307 ml concns is the Al (NO of 0.6 mol ₃) ₃9H ₂Ammonia spirit with 3 mol in the O aqueous solution dropwise adds in the above-mentioned mixed solution, and control final pH value is 8～9, and reaction temperature is 60 ℃, and gained was deposited in the mother liquor ageing 24 hours, after filtration, washing.This embodiment obtains catalyst 9, and corresponding catalyst sees Table 2 through the physical data that the nitrogen physical absorption obtains.Catalyst reduction degree, decentralization, active surface volume data see Table 3.

[comparative example 1]

At 1307 ml concns is the Al (NO of 0.6 mol ₃) ₃9H ₂171 milliliters of nickel nitrate aqueous solutions that add 0.10 gram nickel/milliliter in the O aqueous solution, ammonia spirit with 3 mol dropwise adds in the above-mentioned mixed solution, control final pH value is 8～9, reaction temperature is 40 ℃, gained was deposited in the mother liquor ageing 24 hours, after filtration, washing, drying, obtain Ni/Al ₂O ₃Catalyst precursor.Catalyst precursor obtained oxidized form NiO/Al in 4 hours 400 ℃ of roastings ₂O ₃Catalyst is designated as catalyst 10, sees Table 1.Catalyst reduced 12 hours down at 450 ℃ in 1.5 liters of/minute flow of pure hydrogen, obtained metal mold Ni/Al ₂O ₃Catalyst.Corresponding catalyst sees Table 2 through the physical data that the nitrogen physical absorption obtains.Catalyst reduction degree, decentralization, active surface volume data see Table 3.

[embodiment 6]

Aromatic hydrocarbons accounts for 65～80% in cracking carbon nine and the above hydrocarbon-fraction thereof, contains a large amount of polymerisable unsaturated components simultaneously, and concrete component sees Table 4.This test example selects for use this cracking carbon nine and above hydrocarbon thereof to carry out catalyst hydrogenation activity test of the present invention.The catalyst that embodiment 1～5 and comparative example 1 are obtained at 450 ℃ with hydrogen reducing 24 hours.Hydrogenation reaction is selected insulation fix bed reactor for use, and process conditions are: 40 ℃ of inlet temperatures, pressure 3.0MPa, green oil air speed LHSV=1.5 hour ^-1, hydrogen to oil volume ratio H ₂/ feedstock oil=300: 1.Experimental result sees Table 5.

Table 4

Table 5

Claims

1, a kind of nickel-base catalyst comprises following component by weight percentage:

A) 5～75% nickel or its oxide;

B) alumina catalyst support of surplus;

Wherein the presoma of alumina catalyst support is an aluminium colloidal sol, and the presoma of nickel is to be selected from least a in nickel acetate, nickel chloride or the nickel ammine.

2, nickel-base catalyst according to claim 1 is characterized in that the content of metallic nickel by weight percentage or its oxide is 10～60%.

3, nickel-base catalyst according to claim 1 is characterized in that alumina precursor obtains through the inorganic acid peptization by being selected from boehmite, unformed aluminium oxide or alumina hydrogel.

4, nickel-base catalyst according to claim 1 is characterized in that the nickel presoma is nickel salt aqueous solution or the nickel ammine that is selected from least a formation in nickel acetate, the nickel chloride.

5, nickel-base catalyst according to claim 1 is characterized in that nickel ammine is by at least a complex compound that forms with being selected from least a reaction in corresponding anion ammonium salt, ammoniacal liquor or the ethylenediamine that is selected from nickel nitrate, nickel oxalate, nickel acetate, the basic nickel carbonate.