CN1272102C - 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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- CN1272102C CN1272102C CN 200410012436 CN200410012436A CN1272102C CN 1272102 C CN1272102 C CN 1272102C CN 200410012436 CN200410012436 CN 200410012436 CN 200410012436 A CN200410012436 A CN 200410012436A CN 1272102 C CN1272102 C CN 1272102C
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- hydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000009738 saturating Methods 0.000 title abstract 3
- 210000003746 feather Anatomy 0.000 title 1
- 230000002194 synthesizing effect Effects 0.000 title 1
- 150000001336 alkenes Chemical class 0.000 claims abstract description 47
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 27
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 12
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 12
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 29
- 238000003786 synthesis reaction Methods 0.000 claims description 29
- 239000010936 titanium Substances 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 13
- 206010013786 Dry skin Diseases 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 229960004643 cupric oxide Drugs 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 8
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 238000006460 hydrolysis reaction Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000012805 post-processing Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 150000002603 lanthanum Chemical class 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical group [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 229910052742 iron Inorganic materials 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000000047 product Substances 0.000 description 12
- 150000002431 hydrogen Chemical class 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- 239000011324 bead Substances 0.000 description 4
- 238000006424 Flood reaction Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000008157 edible vegetable oil Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 229910020515 Co—W Inorganic materials 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a catalyst for hydrogenizing and deoxidizing a Fischer-Tropsch synthetic oil product and saturating olefin, which comprises following components: 5.0 to 18.0 wt% of nickel oxide, 0 to 11.0 wt% of cobalt oxide, 0 to 6.0 wt% of copper oxide, 0 to 12.0 wt% iron oxide, 0 to 12.0 wt% of titanium oxide, 0 to 8.0 wt% of lanthanum oxide and 46.0 to 85.0 wt% of carriers. A preparation method orderly comprises the pretreatment of the carriers and the post-treatment process of load active constituents and the catalyst. The catalyst of the present invention has higher activity for hydrogenizing and deoxidizing the oil product and for saturating the olefin and is particularly suitable for the hydrofining process of an oxygen-containing compound and the Fischer-Tropsch synthetic oil product of an iron base slurry bed with higher olefinic content.
Description
Technical field
The present invention relates to the saturated catalyst of a kind of hydrogenation deoxidation and alkene, be specially adapted to the saturated catalyst 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 fuel oil and chemicals.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 suitable method oil from Fischer-Tropsch synthesis is carried out hydrogenation deoxidation and alkene saturated.At present, industrial oil hydrogenation catalyst mainly is at oil and edible oil, mainly contains Co-Mo, Ni-Mo, Ni-W and systems such as Co-W and noble metal, and these catalyst systems mainly are hydrodesulfurization and hydrodenitrogeneration.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 catalyst has good hydrogenation activity and selectivity to aromatic hydrocarbons.Chinese patent CN1249329A discloses a kind of Mo/Ni/P/Al
2O
3Hydrobon catalyst, this catalyst 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 distillate of active component with W, Ni.Above catalyst 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.
Catalyst of the present invention is made up of nickel oxide, cobalt oxide, cupric oxide, iron oxide, titanium oxide, lanthana and catalyst carrier, it is characterized in that each component weight percent content of this catalyst is:
Nickel oxide 10.2～18.0%, cobalt oxide 0.6～2.5%, cupric oxide 2.5～5.0%, iron oxide 1.5～4.4%, titanium oxide 8.3～12.0%, lanthana 2.4～8.0%, all the other are carrier.
Catalyst 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) preliminary treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam treatment 2～8 hours, 100～120 ℃ of oven dry;
(2) load active component: according to equi-volume impregnating, by each component weight percent content of catalyst be: nickel oxide 10.2～18.0%, cobalt oxide 0.6～2.5%, cupric oxide 2.5～5.0%, iron oxide 1.5～4.4%, titanium oxide 8.3～12.0%, lanthana 2.4～8.0%, all the other are carrier; With step (1) pretreated carrier dipping 12 hours in the alcoholic solution of titanium-containing compound earlier, through the hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of nickel oxide, cobalt oxide, cupric oxide, iron oxide, lanthana, flooded 12 hours again;
(3) post processing of catalyst: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of roastings 2～6 hours obtained the saturated catalyst of hydrogenation deoxidation and alkene.
Two, step impregnation method comprises following several steps:
(1) preliminary treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam treatment 2～8 hours, 100～120 ℃ of oven dry;
(2) load active component: according to equi-volume impregnating, by each component weight percent content of catalyst be: nickel oxide 10.2～18.0%, cobalt oxide 0.6～2.5%, cupric oxide 2.5～5.0%, iron oxide 1.5～4.4%, titanium oxide 8.3～12.0%, lanthana 2.4～8.0%, all the other are carrier; With step (1) pretreated carrier dipping 12 hours in the alcoholic solution of titanium-containing compound earlier, through the hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of cobalt oxide, cupric oxide, iron oxide, lanthana, flooded 12 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 catalyst is the soluble nickel salt of 10.2～18.0wt% flooded 12 hours;
(4) post processing of catalyst: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of following roastings 2～6 hours obtained the saturated catalyst of hydrogenation deoxidation and alkene.
Aforesaid carrier is aluminium oxide, silica or active carbon.
Described carrier A l
2O
3Can be sphere or column, specific area 80～450m
2/ g.
Described carrier S iO
2Specific area be 60～220m
2/ g.
The specific area of described carrier active carbon is 300～1200m
2/ g, preferred 600～1000m
2/ g.
Aforesaid soluble nickel salt is nickelous carbonate, nickel acetate or nickel nitrate, preferred nickel nitrate; The solubility cobalt salt is cobalt nitrate or cobalt acetate, preferred cobalt nitrate; Soluble ferric iron salt is a ferric nitrate; Soluble copper salt is copper nitrate or copper sulphate, preferred copper 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 isopropyl alcohol.
Catalyst 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 condition: in the presence of hydrogen, gross pressure is 2.0～15.0MPa, hydrogen/oil volume ratio is 200～1500, preferred 500～1000; Air speed is 0.3～5.0h
-1Reaction temperature 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 catalyst 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 catalyst adopts the equi-volume impregnating preparation, can be mixed with the solution of variable concentrations according to the requirement of catalytic component content, be supported on the carrier, and oven dry, roasting can obtain catalyst prod of the presently claimed invention.
The specific embodiment:
Embodiment 1
At first, with SiO
2Carrier is in advance 120 ℃ of oven dry down.Then, according to equi-volume impregnating, with nickel nitrate (Ni (NO
3)
26H
2O, 49.5g) and cobalt nitrate (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
2Catalyst.Its percentage by weight consists of: NiO: CoO: SiO
2=12.7: 2.5: 84.8.
Take by weighing 20g Ni/Co/SiO
2Catalyst 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.Reaction temperature 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 an active carbon, needs inert gas shielding, cobalt nitrate (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 percentage by weight consists of: NiO: La
2O
3: active carbon=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 nickel nitrate (Ni (NO
3)
26H
2O, 49.5g) and copper 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
3Catalyst.Its percentage by weight ratio of components is: NiO: CuO: Al
2O
3=12.7: 5.0: 82.3.
Take by weighing 20g Ni/Cu/Al
2O
3Catalyst 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 gross 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 copper nitrate (Cu (NO
3)
23H
2O 15.2g) is ferric nitrate (Fe (NO
3)
39H
2O, 7.2g), other condition is constant, makes Ni/Fe/Al
2O
3Catalyst.Its percentage by weight 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
3Catalyst 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 gross 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 nickel nitrate (Ni (NO
3)
26H
2O, 49.5g) and copper nitrate (Cu (NO
3)
23H
2O 15.2g) is nickel 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
3Catalyst.Its percentage by weight 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
3Catalyst 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 gross 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 treatment 2 hours is dried down for 120 ℃, according to equi-volume impregnating, with TiCl
4Ethanolic solution (19.8g) joins in the alumina support, 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 nickel nitrate (Ni (NO
3)
26H
2O, aqueous solution 49.5g) joins in the above-mentioned intermediate products, floods 12 hours, and through 110 ℃ of oven dry 12 hours, 350 ℃ of roastings 5 hours made Ni/Ti/Al
2O
3Catalyst.Its percentage by weight ratio of components is: NiO: TiO
2: Al
2O
3=12.7: 8.3: 79.0.
Take by weighing 20g Ni/Ti/Al
2O
3Catalyst 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 gross 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 treatment 6 hours.According to equi-volume impregnating, with ferric 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 nickel nitrate (Ni (NO
3)
26H
2O, 59.5g) Pei Zhi the aqueous solution joins in the above-mentioned intermediate products, floods 12 hours, and through 110 ℃ of dryings 12 hours, 400 ℃ of roastings 4 hours made Ni/La/Fe/Al
2O
3Catalyst.Its percentage by weight 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
3Catalyst 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 gross 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 ferric nitrate (Fe (NO
3)
39H
2O, 10.9g) and lanthanum nitrate (La (NO
3)
36H
2O 3.1g) is cobalt nitrate (Co (NO
3)
26H
2O, 4.9g) and lanthanum nitrate (La (NO
3)
36H
2O, 4.7g), nickel nitrate (Ni (NO
3)
26H
2O 59.5g) is nickel nitrate (Ni (NO
3)
26H
2O, 39.6g), other condition is constant, makes Ni/Co/La/Al
2O
3Catalyst.Its percentage by weight ratio of components is: NiO: CoO: La
2O
3: Al
2O
3=10.2: 1.3: 3.5: 85.0.
Take by weighing 20g Ni/Co/La/Al
2O
3Catalyst 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 gross 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 treatment 4 hours.According to equi-volume impregnating, with TiCl
4Ethanolic solution (28.6g) joins in the alumina support, 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 ferric nitrate (Fe (NO
3)
39H
2O, 3.6g), lanthanum nitrate (La (NO
3)
36H
2O, 6.2g), cobalt nitrate (Co (NO
3)
26H
2O, 2.5g) and copper 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 nickel nitrate (Ni (NO
3)
26H
2O, the aqueous solution that 70.2g) is mixed with is impregnated in the above-mentioned intermediate products, floods 12 hours, and through 110 ℃ of dryings 12 hours, 350 ℃ of roastings 5 hours made Ni/La/Fe/Co/Cu/Ti/Al
2O
3Catalyst.Its percentage by weight 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
3Catalyst 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 gross 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 (10)
1, a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation and the saturated catalyst of alkene, it is characterized in that each component weight percent content of catalyst is: nickel oxide 10.2～18.0%, cobalt oxide 0.6～2.5%, cupric oxide 2.5～5.0%, iron oxide 1.5～4.4%, titanium oxide 8.3～12.0%, lanthana 2.4～8.0%, all the other are carrier;
Described carrier is aluminium oxide, silica or active carbon.
2, the preparation method 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) preliminary treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam treatment 2～8 hours, 100～120 ℃ of oven dry;
(2) load active component: according to equi-volume impregnating, by each component weight percent content of catalyst be: nickel oxide 10.2～18.0%, cobalt oxide 0.6～2.5%, cupric oxide 2.5～5.0%, iron oxide 1.5～4.4%, titanium oxide 8.3～12.0%, lanthana 2.4～8.0%, all the other are carrier, and described carrier is aluminium oxide, silica or active carbon; With step (1) pretreated carrier dipping 12 hours in the alcoholic solution of titanium-containing compound earlier, through the hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of nickel oxide, cobalt oxide, cupric oxide, iron oxide, lanthana, flooded 12 hours again;
(3) post processing of catalyst: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of roastings 2～6 hours obtained the saturated catalyst of hydrogenation deoxidation and alkene;
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
Described alcohol is ethanol, propyl alcohol or isopropyl alcohol.
3, the preparation method 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) preliminary treatment of carrier: with carrier 100～120 ℃ the oven dry or under 430～560 ℃, steam treatment 2～8 hours, 100～120 ℃ of oven dry;
(2) load active component:, contain by each weight percentages of components of catalyst according to equi-volume impregnating
Amount is: nickel oxide 10.2～18.0%, and cobalt oxide 0.6～2.5%, cupric oxide 2.5～5.0%, iron oxide 1.5～4.4%, titanium oxide 8.3～12.0%, lanthana 2.4～8.0%, all the other are carrier, described carrier is aluminium oxide, silica or active carbon; With step (1) pretreated carrier dipping 12 hours in the alcoholic solution of titanium-containing compound earlier, through the hydrolysis oven dry, 350～500 ℃ of roastings 2～6 hours; In the aqueous metal salt of cobalt oxide, cupric oxide, iron oxide, lanthana, flooded 12 hours again; Through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of following roastings 2～6 hours;
(3) flood once more: the resulting carrier of step (2) was flooded 12 hours at the aqueous solution that by each component nickel oxide content of catalyst is the soluble nickel salt of 10.2～18.0wt%;
(4) post processing of catalyst: through 100～120 ℃ of dryings 12～18 hours, 350～500 ℃ of following roastings 2～6 hours obtained the saturated catalyst of hydrogenation deoxidation and alkene;
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
Described alcohol is ethanol, propyl alcohol or isopropyl alcohol.
4, as the preparation method of claim 2 or 3 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described Al
2O
3Be sphere or column, specific area 80～450m
2/ g.
5, as the preparation method of claim 2 or 3 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described SiO
2Specific area be 60～220m
2/ g.
6, as the preparation method of claim 2 or 3 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, the specific area that it is characterized in that described active carbon is 300～1200m
2/ g.
7, the method for making of a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 6 and olefins hydrogenation, the specific area that it is characterized in that described active carbon is 600～1000m
2/ g.
8, as the preparation method of claim 2 or 3 described a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidations and olefins hydrogenation, it is characterized in that described soluble nickel salt is nickelous carbonate, nickel acetate or nickel nitrate; The solubility cobalt salt is cobalt nitrate or cobalt acetate; Soluble ferric iron salt is a ferric nitrate; Soluble copper salt is copper nitrate or copper sulphate; Solubility lanthanum salt is lanthanum nitrate.
9, the preparation method of a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 8 and olefins hydrogenation is characterized in that described soluble nickel salt is a nickel nitrate, and the solubility cobalt salt is a cobalt nitrate, and soluble copper salt is a copper nitrate.
10, a kind of oil from Fischer-Tropsch synthesis hydrogenation deoxidation as claimed in claim 1 and the saturated Application of Catalyst of alkene, it is characterized in that the saturated process conditions of hydrogenation are: gross pressure is 3.0～10.0MPa, hydrogen/oil volume ratio is 500～1000, and air speed is 0.3～5.0h
-1, reaction temperature is 240～380 ℃.
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|---|---|---|---|
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|---|---|---|---|
| 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 |
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| CN106925279A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | Fe-based selective hydrogenation catalyst, preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106925279A (en) * | 2015-12-31 | 2017-07-07 | 中国石油天然气股份有限公司 | Fe-based selective hydrogenation catalyst, preparation method and application thereof |
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