CN1597859A - Catalyst for hyrogenating deoxidating and olefine saturating of Feather synthesizing oil and its mfg. process and application - Google Patents
Catalyst for hyrogenating deoxidating and olefine saturating of Feather synthesizing oil and its mfg. process and application Download PDFInfo
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Abstract
The invention is a hydro-deoxidation and alkene-saturation catalyst of Fischer-Tropsch oil product and its components in weight percent: nickel oxide 5.0-18.0%, cobalt oxide 0-11.0%, copper oxide 0-6.0%, iron oxide 0-12.0%, titanium oxide 0-12.0%, lanthanum oxide 0-8.0% and carrier 46.0-85.0%. Its preparing method includes in turn carrier preprocessing and after-processing of supported active component and catalyst. It has higher activity to hydro-deoxidation and alkene saturation of the oil product, especially applied to the hydrofining process of the iron-base paste Fischer-Tropsch oil product with higher content of oxygen-containing compound and alkene.
Description
Technical field
The present invention relates to the saturated catalyzer of a kind of hydrogenation deoxidation and alkene, be specially adapted to the saturated catalyzer of oil from Fischer-Tropsch synthesis hydrogenation deoxidation and alkene and method for making and application.
Background technology
Oil from Fischer-Tropsch synthesis has no sulphur, do not have nitrogen and do not have the characteristics of aromatic hydrocarbons, is eco-friendly oil fuel and chemical.But contain a large amount of alkene and a certain amount of oxygenatedchemicals in the synthetic thick oil product, especially acid oxygenatedchemicals, severe corrosion equipment, be unfavorable for the further processing and the utilization of synthetic thick oil product, thus must adopt appropriate means oil from Fischer-Tropsch synthesis is carried out hydrogenation deoxidation and alkene saturated.At present, industrial oil hydrogenation catalyzer mainly is at oil and edible oil, mainly contains Co-Mo, Ni-Mo, Ni-W and systems such as Co-W and precious metal, and these catalyst systems mainly are hydrogenating desulfurization and hydrodenitrification.And oil from Fischer-Tropsch synthesis is different from oil and edible oil, and product mainly is made up of straight chain alkane, alkene and oxygenatedchemicals.
United States Patent (USP) U.S.Patent 4,498,979 openly reports a kind of hydrogenation catalyst of being made up of IIA family, group vib and VIII family metal and non-zeolitic carrier.Chinese patent CN1044816C openly reports a kind of by MgO, NiO, WO
3, MoO
3And Al
2O
3The hydrogenation catalyst of forming, this catalyzer has good hydrogenation activity and selectivity to aromatic hydrocarbons.Chinese patent CN1249329A discloses a kind of Mo/Ni/P/Al
2O
3Hydrobon catalyst, this catalyzer have very high hydrogenation and remove the organic ability of aromatic series.Chinese patent CN1458232A discloses a kind of γ of containing-Al
2O
3Precursor is an auxiliary agent with F or B, is the hydrogenation catalyst that is applicable to petroleum fractions of active ingredient with W, Ni.Above catalyzer has hydrogenation and Tuo Fang performance preferably to petroleum product, but high and to contain the hydrogenation activity of oil from Fischer-Tropsch synthesis of a certain amount of oxygenatedchemicals unsatisfactory for olefin(e) centent.
Summary of the invention:
The objective of the invention is to contain the characteristics of a large amount of alkene and oxygenatedchemicals, provide a kind of and have active high Catalysts and its preparation method and an application oil from Fischer-Tropsch synthesis hydrogenation deoxidation and alkene are saturated at oil from Fischer-Tropsch synthesis.
Catalyzer of the present invention is made up of nickel oxide, cobalt oxide, cupric oxide, ferric oxide, titanium oxide, lanthanum trioxide and support of the catalyst, it is characterized in that each component weight percent content of this catalyzer is:
Nickel oxide 5.0～18.0%, cobalt oxide 0～11.0%, cupric oxide 0～6.0%, ferric oxide 0～12.0%, titanium oxide 0～12.0%, lanthanum trioxide 0～8.0%, carrier 46.0～85.0%.
Catalyzer of the present invention adopts and soaks altogether and two kinds of method preparations of step impregnation.
One, soak method altogether, comprise following several steps:
(1) pre-treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam-treated 2～8 hours, 100～120 ℃ of oven dry, preferably water steam treatment;
(2) load active component: according to equi-volume impregnating, by each component weight percent content of catalyzer be: nickel oxide 5.0～18.0%, cobalt oxide 0～11.0%, cupric oxide 0～6.0%, ferric oxide 0～12.0%, titanium oxide 0～12.0%, lanthanum trioxide 0～8.0%, carrier 46.0～85.0%, with step (1) pretreated carrier in the alcoholic solution of titanium-containing compound, flooded 4～8 hours earlier, through hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of nickel oxide, cobalt oxide, cupric oxide, ferric oxide, lanthanum trioxide, flooded 4～8 hours again;
(3) aftertreatment of catalyzer: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of roastings 2～6 hours obtained the saturated catalyzer of hydrogenation deoxidation and alkene.
Two, step impregnation method comprises following several steps:
(1) pre-treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam-treated 2～8 hours, 100～120 ℃ of oven dry, preferably water steam treatment;
(2) load active component: according to equi-volume impregnating, by each component weight percent content of catalyzer be: cobalt oxide 0～11.0%, cupric oxide 0～6.0%, ferric oxide 0～12.0%, titanium oxide 0～12.0%, lanthanum trioxide 0～8.0%, carrier 46.0～85.0%, with step (1) pretreated carrier in the alcoholic solution of titanium-containing compound, flooded 4～8 hours earlier, through the hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of cobalt oxide, cupric oxide, ferric oxide, lanthanum trioxide, flooded 4～8 hours again; Through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of following roastings 2～6 hours;
(3) flood once more: the aqueous solution that with the resulting carrier of step (2) by each component nickel oxide content of catalyzer is the soluble nickel salt of 5.0～18.0wt% flooded 4～8 hours;
(4) aftertreatment of catalyzer: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of following roastings 2～6 hours obtained the saturated catalyzer of hydrogenation deoxidation and alkene.
Aforesaid carrier is aluminum oxide, silicon oxide or gac.
Described carrier A l
2O
3Can be sphere, column or other shape, specific surface area 80～450m
2/ g.
Described carrier S iO
2Specific surface area be 60～220m
2/ g.
The specific surface area of described carrier active carbon is 300～1200m
2/ g, preferred 600～1000m
2/ g.
Aforesaid soluble nickel salt is carbonate, acetate or nitrate, preferably nitrate; The solubility cobalt salt is Xiao Suangu or Cobaltous diacetate, preferred Xiao Suangu; Soluble ferric iron salt is an iron nitrate; Soluble copper salt is cupric nitrate or copper sulfate, preferred cupric nitrate; Solubility lanthanum salt is lanthanum nitrate.
Aforesaid titanium-containing compound is TiCl
4, Ti (NO
3)
4, Ti (OC
4H
9)
4, Ti (OC
3H
7)
4Or Ti (OC
2H
5)
4).
Aforesaid alcohol is ethanol, propyl alcohol or Virahol.
Catalyzer of the present invention is used for hydrogenation deoxidation and the saturated process of alkene, be specially adapted to the saturated process of oil from Fischer-Tropsch synthesis hydrogenation deoxidation and alkene, reaction conditions: in the presence of hydrogen, total pressure is 2.0～15.0MPa, hydrogen/oil volume ratio is 200～1500, preferred 500～1000; Air speed is 0.3～5.0h
-1Temperature of reaction is 240～380 ℃.
The present invention compared with prior art has following characteristics:
1. the present invention has added multiple metal component in catalyst preparation process, makes the prepared catalyzer of the present invention have very high hydrogenation activity to acid oxygenatedchemicals and alkene, particularly to the hydrogenation deoxidation and the saturated process of alkene of oil from Fischer-Tropsch synthesis.
2. aforesaid catalyzer adopts the equi-volume impregnating preparation, can be mixed with the solution of different concns according to the requirement of catalyst component content, be supported on the carrier, and oven dry, roasting can obtain catalyst prod of the presently claimed invention.
Embodiment:
Embodiment 1
At first, with SiO
2Carrier is in advance 120 ℃ of oven dry down.Then, according to equi-volume impregnating, with nickelous nitrate (Ni (NO
3)
26H
2O, 49.5g) and Xiao Suangu (Co (NO
3)
26H
2O 9.9g) is mixed with the aqueous solution, mixes.Above-mentioned solution is joined SiO
2In the carrier, flooded 12 hours, through 110 ℃ of oven dry 12 hours, 480 ℃ of roastings 4 hours made Ni/Co/SiO
2Catalyzer.Its weight percent consists of: NiO: CoO: SiO
2=12.7: 2.5: 84.8.
Take by weighing 20g Ni/Co/SiO
2Catalyzer places in the continuous fixed bed reactor.At first in 420 ℃ of atmosphere of hydrogen, reduced 8 hours, be cooled to 360 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 600, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 20wt%) pump into by ZB-80 type micro pump.Temperature of reaction is 360 ℃, and the reaction stagnation pressure is 4.0MPa, WHSV=0.5h
-1The product analysis result: olefin conversion is greater than 99.9wt%, and the oxygenate rate is greater than 97.0wt%.
Embodiment 2
Step by example 1 is carried out Preparation of catalysts, and the change carrier is a gac, needs protection of inert gas, Xiao Suangu (Co (NO
3)
26H
2O 9.9g) is lanthanum nitrate (La (NO
3)
36H
2O, 16.0g), other condition is constant, makes the Ni/La/ activated-carbon catalyst.Its weight percent consists of: NiO: La
2O
3: gac=12.7: 8.0: 79.3.
Take by weighing 20g Ni/La/ activated-carbon catalyst, place in the continuous fixed bed reactor.At first in 400 ℃ of atmosphere of hydrogen, reduced 8 hours, be cooled to 380 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 800, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 20wt%) pump into by ZB-80 type micro pump.The reaction stagnation pressure is 6.0MPa, WHSV=0.8h
-1The product analysis result: olefin conversion is greater than 99.9wt%, and the oxygenate rate is greater than 99.5wt%.
Embodiment 3
At first, with γ-Al
2O
3Bead is in advance 120 ℃ of oven dry down.Then, according to equi-volume impregnating, with nickelous nitrate (Ni (NO
3)
26H
2O, 49.5g) and cupric nitrate (Cu (NO
3)
23H
2O 15.2g) is mixed with the aqueous solution, mixes.Above-mentioned solution is joined Al
2O
3In the carrier, flooded 12 hours, through 110 ℃ of oven dry 12 hours, 400 ℃ of roastings 4 hours made Ni/Cu/Al
2O
3Catalyzer.Its weight percent ratio of components is: NiO: CuO: Al
2O
3=12.7: 5.0: 82.3.
Take by weighing 20g Ni/Cu/Al
2O
3Catalyzer places in the continuous fixed bed reactor.At first in 350 ℃ of atmosphere of hydrogen, reduced 6 hours, be cooled to 300 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 1000, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 15wt%) pump into by ZB-80 type micro pump.The reaction total pressure is 3.5MPa, WHSV=0.6h
-1The product analysis result: olefin conversion is greater than 99.9wt%, and the oxygenate rate is greater than 98.5wt%.
Embodiment 4
Step by example 3 is carried out Preparation of catalysts, only changes cupric nitrate (Cu (NO
3)
23H
2O 15.2g) is iron nitrate (Fe (NO
3)
39H
2O, 7.2g), other condition is constant, makes Ni/Fe/Al
2O
3Catalyzer.Its weight percent ratio of components is: NiO: Fe
2O
3: Al
2O
3=12.7: 2.9: 84.4.
Take by weighing 20g Ni/Fe/Al
2O
3Catalyzer places in the continuous fixed bed reactor.At first in 400 ℃ of atmosphere of hydrogen, reduced 4 hours, be cooled to 280 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 500, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 17wt%) pump into by ZB-80 type micro pump.The reaction total pressure is 8.0MPa, WHSV=0.3h
-1The product analysis result: olefin conversion is greater than 99.9wt%, and the oxygenate rate is greater than 99.0wt%.
Embodiment 5
Step by example 3 is carried out Preparation of catalysts, only changes nickelous nitrate (Ni (NO
3)
26H
2O, 49.5g) and cupric nitrate (Cu (NO
3)
23H
2O 15.2g) is nickelous nitrate (Ni (NO
3)
26H
2O, 59.5g) and lanthanum nitrate (La (NO
3)
36H
2O, 6.2g), other condition is constant, makes Ni/La/Al
2O
3Catalyzer.Its weight percent ratio of components is: NiO: La
2O
3: Al
2O
3=15.3: 4.7: 80.0.
Take by weighing 20g Ni/La/Al
2O
3Catalyzer places in the continuous fixed bed reactor.At first in 420 ℃ of atmosphere of hydrogen, reduced 6 hours, be cooled to 240 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 1000, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 19.3wt%) pump into by ZB-80 type micro pump.The reaction total pressure is 10.0MPa, WHSV=5.0h
-1The product analysis result: olefin conversion is greater than 99.8wt%, and the oxygenate rate is greater than 99.5wt%.
Embodiment 6
At first, with γ-Al
2O
3Bead is under 500 ℃, and steam-treated 2 hours is dried down for 120 ℃, according to equi-volume impregnating, with TiCl
4Ethanolic soln (19.8g) joins in the alumina supporter, and the room temperature hydrolysis was left standstill 8 hours, and 110 ℃ of dryings 12 hours are again 350 ℃ of following roastings 4 hours.Then, according to equi-volume impregnating, again with nickelous nitrate (Ni (NO
3)
26H
2O, aqueous solution 49.5g) joins in the above-mentioned intermediates, floods 12 hours, and through 110 ℃ of oven dry 12 hours, 350 ℃ of roastings 5 hours made Ni/Ti/Al
2O
3Catalyzer.Its weight percent ratio of components is: NiO: TiO
2: Al
2O
3=12.7: 8.3: 79.0.
Take by weighing 20g Ni/Ti/Al
2O
3Catalyzer places in the continuous fixed bed reactor.At first in 420 ℃ of atmosphere of hydrogen, reduced 6 hours, be cooled to 360 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 800, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 16.5wt%) pump into by ZB-80 type micro pump.The reaction total pressure is 8.0MPa, WHSV=1.0h
-1The product analysis result: olefin conversion is greater than 99.9.wt%, and the oxygenate rate is greater than 99.0wt%.
Embodiment 7
At first, with γ-Al
2O
3Bead in advance under 480 ℃, steam-treated 6 hours.According to equi-volume impregnating, with iron nitrate (Fe (NO
3)
39H
2O, 10.9g) and lanthanum nitrate (La (NO
3)
36H
2O 3.1g) is mixed with the aqueous solution, mixes, and above-mentioned solution is joined Al
2O
3In the carrier, flooded 12 hours 110 ℃ of dryings 12 hours, 500 ℃ of roastings 5 hours; Then, again according to equi-volume impregnating with nickelous nitrate (Ni (NO
3)
26H
2O, 59.5g) Pei Zhi the aqueous solution joins in the above-mentioned intermediates, floods 12 hours, and through 110 ℃ of dryings 12 hours, 400 ℃ of roastings 4 hours made Ni/La/Fe/Al
2O
3Catalyzer.Its weight percent ratio of components is: NiO: La
2O
3: Fe
2O
3: Al
2O
3=15.3: 2.4: 4.4: 77.9.
Take by weighing 20gNi/La/Fe/Al
2O
3Catalyzer places in the continuous fixed bed reactor.At first in 420 ℃ of atmosphere of hydrogen, reduced 8 hours, be cooled to 260 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 1000, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 16.5wt%) pump into by ZB-80 type micro pump.The reaction total pressure is 3.0MPa, WHSV=2.0h
-1The product analysis result: olefin conversion is greater than 99.9wt%, and the oxygenate rate is greater than 99.5wt%.
Embodiment 8
Step by example 7 is carried out Preparation of catalysts, only changes iron nitrate (Fe (NO
3)
39H
2O, 10.9g) and lanthanum nitrate (La (NO
3)
36H
2O 3.1g) is Xiao Suangu (Co (NO
3)
26H
2O, 4.9g) and lanthanum nitrate (La (NO
3)
36H
2O, 4.7g), nickelous nitrate (Ni (NO
3)
26H
2O 59.5g) is nickelous nitrate (Ni (NO
3)
26H
2O, 39.6g), other condition is constant, makes Ni/Co/La/Al
2O
3Catalyzer.Its weight percent ratio of components is: NiO: CoO: La
2O
3: Al
2O
3=10.2: 1 .3: 3.5: 75.0.
Take by weighing 20g Ni/Co/La/Al
2O
3Catalyzer places in the continuous fixed bed reactor.At first in 420 ℃ of atmosphere of hydrogen, reduced 8 hours, be cooled to 300 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 600, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 16.5wt%) pump into by ZB-80 type micro pump.The reaction total pressure is 4.0MPa, WHSV=2.0h
-1The product analysis result: olefin conversion is greater than 99.9wt%, and the oxygenate rate is greater than 99.5wt%.
Embodiment 9
At first, with γ-Al
2O
3Bead in advance under 480 ℃, steam-treated 4 hours.According to equi-volume impregnating, with TiCl
4Ethanolic soln (28.6g) joins in the alumina supporter, and the room temperature hydrolysis was left standstill 6 hours, and 110 ℃ of dryings 12 hours are again 350 ℃ of following roastings 4 hours.Then, according to equi-volume impregnating, with iron nitrate (Fe (NO
3)
39H
2O, 3.6g), lanthanum nitrate (La (NO
3)
36H
2O, 6.2g), Xiao Suangu (Co (NO
3)
26H
2O, 2.5g) and cupric nitrate (Cu (NO
3)
23H
2O, 7.6g) Pei Zhi the aqueous solution mixes, and above-mentioned solution is joined Al
2O
3In the carrier, flooded 12 hours 110 ℃ of dryings 12 hours, 350 ℃ of roastings 5 hours; According to equi-volume impregnating, again with nickelous nitrate (Ni (NO
3)
26H
2O, the aqueous solution that 70.2g) is mixed with is impregnated in the above-mentioned intermediates, floods 12 hours, and through 110 ℃ of dryings 12 hours, 350 ℃ of roastings 5 hours made Ni/La/Fe/Co/Cu/Ti/Al
2O
3Catalyzer.Its weight percent ratio of components is: NiO: CoO: CuO: La
2O
3: Fe
2O
3: TiO
2: Al
2O
3=18.0: 0.6: 2.5: 4.7: 1.5: 12.0: 60.7.
Take by weighing 20g Ni/La/Fe/Co/Cu/Ti/Al
2O
3Catalyzer places in the continuous fixed bed reactor.At first in 400 ℃ of atmosphere of hydrogen, reduced 5 hours, be cooled to 300 ℃ then.The reaction feed ratio is: hydrogen/oil (volume) is than being 600, and (carbon number distribution is C to oil from Fischer-Tropsch synthesis
5～C
45, alkene accounts for more than the 40wt%, and oxygenatedchemicals accounts for about 16.5wt%) pump into by ZB-80 type micro pump.The reaction total pressure is 4.0MPa, WHSV=1.0h
-1The product analysis result: olefin conversion is greater than 99.9.wt%, and the oxygenate rate is greater than 99.9wt%.
Claims (15)
1, a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation and the saturated catalyzer of alkene, it is characterized in that each component weight percent content of catalyzer is: nickel oxide 5.0～18.0%, cobalt oxide 0～11.0%, cupric oxide 0～6.0%, ferric oxide 0～12.0%, titanium oxide 0～12.0%, lanthanum trioxide 0～8.0%, carrier 46.0～85.0%.
2, a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 1 and olefins hydrogenation is characterized in that described carrier is that aforesaid carrier is aluminum oxide, silicon oxide or gac.
3, the method for making of a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 1 and olefins hydrogenation is characterized in that comprising the steps:
(1) pre-treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam-treated 2～8 hours, 100～120 ℃ of oven dry, preferably water steam treatment;
(2) load active component: according to equi-volume impregnating, by each component weight percent content of catalyzer be: nickel oxide 5.0～18.0%, cobalt oxide 0～11.0%, cupric oxide 0～6.0%, ferric oxide 0～12.0%, titanium oxide 0～12.0%, lanthanum trioxide 0～8.0%, carrier 46.0～85.0%, with step (1) pretreated carrier in the alcoholic solution of titanium-containing compound, flooded 4～8 hours earlier, through hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of nickel oxide, cobalt oxide, cupric oxide, ferric oxide, lanthanum trioxide, flooded 4～8 hours again;
(3) aftertreatment of catalyzer: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of roastings 2～6 hours obtained the saturated catalyzer of hydrogenation deoxidation and alkene.
4, the method for making of a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 1 and olefins hydrogenation is characterized in that comprising the steps:
(1) pre-treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam-treated 2～8 hours, 100～120 ℃ of oven dry, preferably water steam treatment;
(2) load active component: according to equi-volume impregnating, by each component weight percent content of catalyzer be: cobalt oxide 0～11.0%, cupric oxide 0～6.0%, ferric oxide 0～12.0%, titanium oxide 0～12.0%, lanthanum trioxide 0～8.0%, carrier 46.0～85.0%, with step (1) pretreated carrier in the alcoholic solution of titanium-containing compound, flooded 4～8 hours earlier, through the hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of cobalt oxide, cupric oxide, ferric oxide, lanthanum trioxide, flooded 4～8 hours again; Through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of following roastings 2～6 hours;
(3) flood once more: the aqueous solution that with the resulting carrier of step (2) by each component nickel oxide content of catalyzer is the soluble nickel salt of 5.0～18.0wt% flooded 4～8 hours;
(4) aftertreatment of catalyzer: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of following roastings 2～6 hours obtained the saturated catalyzer of hydrogenation deoxidation and alkene.
5, as the method for making of claim 3 or 4 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described carrier is aluminum oxide, silicon oxide or gac.
6, as the method for making of claim 3 or 4 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described Al
2O
3Be sphere, column or other shape, specific surface area 80～450m
2/ g.
7, as the method for making of claim 3 or 4 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described carrier S iO
2Specific surface area be 60～220m
2/ g.
8, as the method for making of claim 3 or 4 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, the specific surface area that it is characterized in that described carrier active carbon is 300～1200m
2/ g.
9, the method for making of a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 8 and olefins hydrogenation, the specific surface area that it is characterized in that described gac is 600～1000m
2/ g.
10, as the method for making of claim 3 or 4 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described soluble nickel salt is carbonate, acetate or nitrate; The solubility cobalt salt is Xiao Suangu or Cobaltous diacetate; Soluble ferric iron salt is an iron nitrate; Soluble copper salt is cupric nitrate or copper sulfate; Solubility lanthanum salt is lanthanum nitrate.
11, the method for making of a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 10 and olefins hydrogenation is characterized in that described soluble nickel salt is a nitrate, and the solubility cobalt salt is a Xiao Suangu, and soluble copper salt is a cupric nitrate.
12, as the method for making of claim 3 or 4 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described titanium-containing compound is TiCl
4, Ti (NO
3)
4, Ti (OC
4H
9)
4, Ti (OC
3H
7)
4Or Ti (OC
2H
5)
4).
13, as the method for making of claim 3 or 4 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described alcohol is ethanol, propyl alcohol or Virahol.
14, a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation and saturated Application of Catalyst of alkene of being used for as claimed in claim 1 or 2, it is characterized in that the saturated processing condition of hydrogenation are: total pressure is 2.0～15.0MPa, hydrogen/oil volume ratio is 200～1500, air speed is 0.3～5.0h-1, and temperature of reaction is 240～380 ℃.
15, a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation and saturated Application of Catalyst of alkene of being used for as claimed in claim 14 is characterized in that described hydrogen/oil volume ratio is 500～1000.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410012436 CN1272102C (en) | 2004-07-21 | 2004-07-21 | Catalyst for hyrogenating deoxidating and olefine saturating of Feather synthesizing oil and its mfg. process and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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