CN1301591A - Non-crystalline alloy catalyst for olefine selective hydrogenation - Google Patents
Non-crystalline alloy catalyst for olefine selective hydrogenation Download PDFInfo
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- CN1301591A CN1301591A CN 99120660 CN99120660A CN1301591A CN 1301591 A CN1301591 A CN 1301591A CN 99120660 CN99120660 CN 99120660 CN 99120660 A CN99120660 A CN 99120660A CN 1301591 A CN1301591 A CN 1301591A
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Abstract
A catalyst is especially suitable for selective hydrogenation of non-conjugated diene to produce monoene. The catalyst is a carried catalyst comprising Ni-Cu-B non-crystalline alloy in 0.1-30.0 wt% and porous carrier material in 70-99.9 wt% with the weight ratio of Ni to Cu to B being 0.1-30 to 0-10 to 0.001-3.5 and the specific surface area being 10-1000 sq.m/g. During its preparation, a porous carrier material connecting Ni and/or Cu is made to contact with 0.5-10.0 mol/L molarity BH4 solution in the B to Ni and/or Cu atom of 0.1-10.0 at the temperature of solution freezing point to 100 deg.C. The catalyst results in selective hydrogenation under mild condition.
Description
The present invention relates to a kind of catalyzer that is used for conversion of olefines technology.The present invention directly relates to a kind of solid catalyst that is used for diolefine is converted to monoolefine.This catalyzer can be used for reducing the concentration of the diolefine that material generates owing to dehydrogenation reaction.The present invention be more particularly directed to selective hydrogenation catalyst, this catalyzer is made carrier by aluminum oxide, silicon oxide, alumina/silica composition or gac, component or their compositions such as nickel-loaded, copper, iron, manganese, magnesium and boron.
In refining of petroleum and petrochemical complex industry, wish sometimes optionally to convert alkynes or diolefine to monoolefine.This conversion advantage has economically been impelled the Study of Catalyst that is used for this purpose in a large number.Many these type of catalyzer load on the reactive metal of traditional hydrogenation catalyst such as nickel, platinum and palladium on solid-state carrier such as the aluminum oxide.US3 for example, 234,298 (Cosynset al) have narrated a kind of selective hydrogenation catalyst, and the load on alumina supporter of this catalyzer has 1～20% nickel, and it exists as the form of nickel oxide.The document points out that before being used for selective hydrogenation, the most handy sulfide carries out pre-treatment to this catalyzer.US4,440,956 (Couvillion) proposed a kind of can be with the acetylene class material that removes in the liquid hydrocarbonaceous streams that contains diolefine, and do not reduce the content of diolefine in this raw material basically.CN87106441 (mark J Jia Tusuo etc.) has proposed a kind of catalyzer that the non-conjugated diene hydrocarbon-selective is hydrogenated into monoolefine that is specifically designed to, this catalyzer comprises being deposited on and contains lip-deep nickel of macropore alumina supporter and sulphur, the feature of catalyzer is, most pore volume is that the big well format of 500 to 1500 dusts exists with the aperture.The catalyzer that the present invention relates to a kind of uniqueness is very suitable for the selective hydrogenation effect from the diolefine to the monoolefine.This catalyzer has the function of selective hydrogenation in containing unsaturated functional group compound hydrogenation reaction.Catalyzer provided by the present invention is a kind of carried non-crystal alloy catalyst, specifically a kind of M1-M2-R/Z type amorphous alloy catalyst, wherein M1 is the Primary Catalysts active ingredient, comprise activity of hydrocatalyst component Ni commonly used, Co, Mo, W etc., M2 is the promotor active ingredient, comprise Cu, Fe, Mn, Zn, transition metal such as Ag, R is for playing the reductive action component in catalyst preparation process, comprise B, P etc., Z is the porous material that is used for supported amorphous alloy, described porous material refers to not have the porous carrier materials of oxidisability, comprises porous inorganic oxide, gac, in the molecular sieve one or more.For example, according to one of catalyzer provided by the present invention, its porous material that contains the Ni-Cu-B amorphous alloy can be by loading on γ-Al with Ni-Cu-B
2O
3On the carrier and obtain.
Amorphous alloy can be made the sample of various compositions in very wide scope, thus can be in a big way its electronic property of modulation, prepare suitable catalytic active center with this; Its catalytic active center can be uniformly distributed in the uniform environment of chemistry with single form; Its surface has the height nonsaturation, has higher surface energy.These characteristics make the catalytic activity of amorphous alloy catalyst and selectivity generally be better than corresponding crystal alloy catalyzer.Journalof Catalysis 150,434～438, (1994) have been reported and will have been contained 100 grams per liter nickel acetate [Ni (CH
3COO)
2], 100 grams per liter sodium-acetate [(CH
3COONa] and 100 grams per liter ortho phosphorous acid sodium dihydrogen [NaH
2PO
2] mixing solutions under agitation be heated to 90 ℃, prepare a kind of non-crystalline state Ni-P Ultra-fine Particle Catalysts, the hydrogen adsorption specific surface of this catalyzer can reach 2.78 meters
2/ gram.At Applied Catalysis 37,339～343, reported in (1988) with the method for electroless plating (Chemical Planting), the Ni-P amorphous alloy is deposited on the silicon oxide, prepare a kind of carried non-crystal alloy catalyst, this catalyst specific surface can reach 85 meters
2/ gram, and its thermostability increases than ultrafine particle.Proposed a kind of Ni-B amorphous alloy catalyst in CN 96120054, this catalyzer has higher thermostability when possessing than large specific surface.
The catalyzer that the present invention relates to a kind of uniqueness is very suitable for the selective hydrogenation effect from the diolefine to the monoolefine.This catalyzer is transforming C
8Have good especially selectivity during above diolefine, thereby increase the productive rate of monoolefine in the intermediate product.Catalyzer provided by the present invention is a kind of carried non-crystal alloy catalyst, and its concrete compositing range is the heavy % in Ni0.1～30.0, the heavy % in Cu0.01～10.0, the heavy % in B0.001～3.5, porous carrier materials 56.5～99.899 heavy %.
Monoene is produced or is consumed in many refining of petroleum technical process.In a lot of these class technical process, diolefine is regarded as impurity.For example, in the joint process that linear alkylbenzene is produced (US3,484,498), monoolefine produces in dehydrogenation workshop section, enters alkylation workshop section then.Wherein, alkene and benzene reaction generate the linear alkyl aromatic hydrocarbons product.It is that inevitably these diolefine are present in the alkene that enters alkylation workshop section usually to a certain extent that dehydrogenation workshop section produces diolefine.The existence of straight chain diolefine causes the generation of undesirable by product such as various biphenol compounds.These impurity will influence the quality of linear alkylbenzene.The existence of diolefine causes high boiling production of by-products, also will increase the consumption of acid.If diolefine is regarded as the inapt component in monoolefine and paraffins mixture or the pure basically olefin stream, then the resulting selective hydrogenation catalyst of the present invention is applied to just can improve above-mentioned situation in the corresponding flow process.The resulting catalyzer of the present invention also can be used for the purifying step of effluent liquid in the alkene separation process, and this separation process refers to such as by the application choice absorption techniques, the flow process of separating alkene from alkene and paraffins mixture.
One of purpose of the present invention provides a kind ofly has high thermal stability and simultaneously than the Ni-Cu-B amorphous alloy catalyst of large specific surface; Two of purpose of the present invention provides this Preparation of catalysts method; Three of purpose of the present invention provides the operational condition that this catalyzer is optimized in the diolefine selective hydrogenation process.
Catalyzer provided by the present invention has three phase transformation peaks in crystallization process, its peak value is respectively 178,284,360～449 ℃, and prior art (J.catal.150,434～438,1994) Zhi Bei three phase transformation peaks of Ni-B amorphous superfine particle have only 144.1,25 3.4 and 341.1 ℃ respectively, this illustrates that catalyzer provided by the invention has than the higher thermostability of Ni-B amorphous superfine particle, the character of easier its amorphous alloy of maintenance in catalytic process is so there is long catalytic life.
According to catalyzer provided by the present invention, its specific surface changes with carrier specific surface size, and its specific surface can be 10～1000 meters
2/ gram is preferably 100～1000 meters
2/ gram.And Ni-B amorphous superfine particle specific surface can only reach 29.7 meters
2About/gram, the specific surface of the Ni-RE-P amorphous alloy catalyst (RE represents rare earth element) of large specific surface also can only reach 130 meters
2/ gram.
Catalyzer provided by the present invention consists of Ni-Cu-B amorphous alloy 0.1～30.0 heavy %, porous carrier materials 70.0～99.9 heavy %.It preferably consists of the heavy % in Ni:0.5～15.0, the heavy % in Cu:0.03～5.0, the heavy % in B:0.01～2.00, porous carrier materials 78.0～99.19 heavy %.
Preparation of catalysts method provided by the present invention is included in and is higher than in freezing point of solution to the 100 ℃ temperature range, with the BH that contains of a kind of porous carrier materials of nickeliferous and/or copper and volumetric molar concentration 0.5～10.0
4 -Solution is by 0.1～10.0 boron nickel and/or the copper atom ratio contact that feeds intake.Adopted ammoniacal liquor to make lysate when adding cocatalyst component, owing to increased cocatalyst component, made this catalyzer have the unique selectivity hydrogenating function, this is not appear in the newspapers in the preparation method of so far amorphous alloy catalyst.
According to catalyzer provided by the present invention, described porous carrier materials refers to not have the porous carrier materials of oxidisability, comprises in porous inorganic oxide, gac, the molecular sieve one or more; Described porous inorganic oxide refers to the oxide compound of II A family, IV B, VI B family, III A, IV A family element, one or more in wherein preferred silicon oxide, aluminum oxide, zirconium white, magnesium oxide, the calcium oxide; Described molecular sieve refers to various types of Si-Al molecular sieves, hetero-atom molecular-sieve etc.; Preferred porous carrier materials is silicon oxide, aluminum oxide or gac.
The catalyzer that provides of the present invention, active ingredient all exists with non-crystalline state, with the x-ray diffraction spectra such as the accompanying drawing 1 of CuK α target mensuration.This catalyzer is used for C
6～C
15The mixture of hydrocarbon in diene selective hydrogenation, in the diene transformation efficiency that obtains more than 70%, can obtain monoene selectivity greater than 50%, processing condition are pressure 0.5Mpa, 50 ℃ of temperature, volume space velocity 10h during liquid
-1The diene selective hydrogenation process using that prior art is carried out the dehydrogenation of long-chain alkane product be the crystalline state nickel catalyzator, the data that industrial application obtains show, diene transformation efficiency about 65%, the monoene selectivity is about 30%, and processing condition are: pressure 1.1Mpa, 200 ℃ of temperature, volume space velocity 6h-1 during liquid.
The raw material that is fit to this catalyzer of use includes the mixture of the saturated and unsaturated hydrocarbons of suitable scope carbonatoms.For example, using the logistics of this catalyzer can be to contain C basically
3～C
5Hydro carbons.In addition, feed stream can comprise C
6～C
15The mixture of hydrocarbon, in the mixture of this class hydrocarbon, comprise alkane, monoolefine and diolefine.The conclusion that generally draws is that this catalyzer is being handled C
8～C
20The mixture of hydrocarbon the time very effective.Selective hydrogenation process is being operated under the demulcent condition usually relatively.The normally processed hydrocarbon mixture of these conditions is in liquid state.Generally speaking, reactant is maintained under the emergent pressure that is near or below itself.Use catalyzer provided by the present invention, its suitable operating restraint is about: pressure 0.1～2Mpa, 25～200 ℃ of temperature, volume space velocity 1～30h during liquid
-1In addition, be selectively hydrogenated into monoolefine for keeping diolefine, the amount of used hydrogen should have a suitable ratio with the amount of diene in the raw material, and generally speaking, the molar ratio of hydrogen and diolefine is between 0.75: 1 and 5: 1.
According to catalyzer provided by the present invention, when the selective hydrogenation that is used for diolefine, its preferred operating restraint is about: pressure 0.1～1Mpa, 25～100 ℃ of temperature, liquid hourly space velocity 5～30h
-1, the suitable relatively hydrogen and the molar ratio of diene are between 1: 1 and 2.5: 1.Under concrete situation, optimal operation conditions will depend on such as the composition of raw material and the desired factors such as diolefine degree of saturation that reach, and for example, handle C
8～C
20The mixture of hydrocarbon the time, the molar ratio of best hydrogen and diene is between 1: 1 and 1.5: 1.
According to catalyzer provided by the present invention, be preferably in the tubular fixed-bed reactor and use, reactant moves with vertical direction in this beds.This catalyzer can exist with forms such as ball shape, spherical, cylindrical extrusion, cloverleaf pattern extrusion or anomocytic type particles in reactor.
The following examples will the present invention will be further described, but not thereby limiting the invention.
Example 1～15
The preparation method and the catalytic performance thereof of example 1～15 and Comparative Examples 1～4 explanation carried non-crystal alloy catalyst provided by the invention.
Used carrier 1 (numbering Z1) is γ-Al
2O
3(Chang Ling refinery catalyst plant), carrier 2 (numbering Z2) is α-Al
2O
3(Z1 is through 1000 ℃ of roasts), carrier 3 (numbering Z3) is γ-Al
2O
3(daily chemical industry institute, Taiyuan), carrier 5 (numbering Z5) is γ-Al
2O
3(Tianjin chemical research institute), carrier 7 (numbering Z7) is amorphous Al
2O
3-SiO
2(Wenzhou catalyst plant), carrier 9 (numbering Z9) is gac (a Nanjing chemistry of forest product industrial research institute).Described carrier character is listed in table 1.Wherein crystalline phase is measured with x-ray diffraction method; Specific surface, pore volume determination of adsorption method.
Table 1 carrier character
| Bearer number | Bearer type | Crystalline phase | Specific surface m 2/g | Pore volume ml/g | Outward appearance |
| ????Z1 | ???Al 2O 3 | ????γ | ????220.1 | ????0.51 | The cloverleaf pattern strip |
| ????Z 2 | ???Al 2O 3 | ????α | ????184.6 | ????0.42 | Z1 is through 1000 ℃ of roasts |
| ????Z3 | ???Al 2O 3 | ????γ | ????237.9 | ????0.55 | Bead |
| ????Z5 | ???Al 2O 3 | ????γ | ????160.3 | ????0.37 | Cylindrical strip |
| ????Z7 | ??Al 2O 3-SiO 2 | Amorphous | ????313.2 | ????0.72 | Bead |
| ????Z9 | Gac | Amorphous | ????911.7 | ????2.10 | 20～50 orders |
Take by weighing quantitatively different above-mentioned carrier respectively, in 100～150 ℃ of oven dry down; Take by weighing quantitative M1 salt respectively and be configured to solution and flood different carriers, dry under 120 ℃ to such an extent that contain the carrier of M1; Take by weighing quantitative M2 salt respectively and be configured to solution and impregnated in the different carriers of the above-mentioned M1 of containing, dry under 120 ℃ to such an extent that contain the carrier of M1 and M2; Take by weighing quantitative POTASSIUM BOROHYDRIDE respectively and be configured to solution, solution of potassium borohydride at room temperature is added drop-wise in the carrier that contains M1 and M2, reaction is carried out and releasing hydrogen gas immediately, drip off treat that no hydrogen is emitted after, show that reaction finishes.The solid product that obtains with distilled water wash is not to there being acid group, and the oven dry back is standby.
Adopt U.S. Waters590 constant flow pump, 810 type RZ detectors, the U6K sampler, valve is taken off in the Rheodyne7040 of Autech company backwash, and the 810BASELINE workstation carries out quantitative analysis.This method can be carried out accurate quantitative analysis with the alkane in the logistics, monoolefine, diolefine (comprising conjugation and non-conjugated diene hydrocarbon) and aromatic hydrocarbons on abundant isolating basis.Compare through analyze chemical analysis such as bromine valency and maleic anhydride method analysis conjugated diene with protopetroleum portion ministerial standard (SY2123-77), the result shows that liquid phase chromatography is more accurate to the quantitative analysis of each component concentration in the sample, can satisfy needed precision.
Below in each table and the text listed diolefine transformation efficiency and monoolefine selective data all calculate by formula (1) and formula (2).
Table 2, catalyzer are selected the hydrogenation performance
| Example number | The catalyzer numbering | Transformation efficiency % | Selectivity % | Reaction conditions |
| ????1 | ????FT-809 | ????81.0 | ????32.2 | ????0.5Mpa,60℃,10h -1 |
| ????2 | ????FT-810 | ????90.5 | ????-23.5 | ????0.5Mpa,60℃,10h -1 |
| ????3 | ????FT-811 | ????70.1 | ????56.5 | ????0.5Mpa,50℃,10h -1 |
| ????4 | ????FT-815 | ????75.5 | ????58.2 | ????0.5Mpa,50℃,10h -1 |
| ????5 | ????FT-816 | ????40.4 | ????51.1 | ????0.5Mpa,50℃,10h -1 |
| ????6 | ????FT-817 | ????3.5 | ????1.5 | ????0.5Mpa,50℃,10h -1 |
| ????7 | ????FT-818 | ????78.0 | ????15.4 | ????0.5Mpa,50℃,10h -1 |
| ????8 | ????FT-820 | ????54.0 | ????-l0.5 | ????0.5Mpa,50℃,30h -1 |
| ????9 | ????FT-821 | ????57.3 | ????11.4 | ????0.5Mpa,50℃,30h -1 |
| ????10 | ????FT-822 | ????56.5 | ????12.5 | ????0.5Mpa,50℃,10h -1 |
| ????11 | ????FT-827 | ????73.6 | ????42.9 | ????0.5Mpa,50℃,10h -1 |
| ????12 | ????FT-838 | ????34.2 | ????51.2 | ????0.5Mpa,50℃,30h -1 |
| ????13 | ????FT-840 | ????29.2 | ????56.9 | ????0.5Mpa,50℃,30h -1 |
| ????14 | ????FT-842 | ????50.5 | ????11.0 | ????0.5Mpa,50℃,10h -1 |
| ????15 | ????FT-843 | ????80.5 | ????0 | ????0.5Mpa,50℃,10h -1 |
Table 3 method for preparing catalyst
| Example number | The catalyzer numbering | Carrier | Reactive metal heavy (g) | Lysate (ml) | Reductive agent heavy (g) | Reactive metal and reductive agent mol ratio |
| ????1 | ??FT-809 | ????Z1 | ??Ni=2.4894 | Ammoniacal liquor 11+0.5 * 2 | ??B=1.5015 | ????1∶2.8 |
| ????2 | ??FT-810 | ????Z1 | ?Ni=1.9877 | Ammoniacal liquor 9+0.5 * 2 | ?B=0.612?7 | ????1∶2.8 |
| ?Mo=0.4909 | ||||||
| ????3 | ??FT-811 | ????Z1 | ?Ni=1.6488 | Water 11+0.5 * 2 | ??B=1.5188 | ????1∶2.8 |
| ??Cu=0.6531 | ||||||
| ????4 | ??FT-815 | ????Z1 | ?Ni=1.6475 | Ammoniacal liquor 9+0.5 * 2 | ?B=1.5115 | ????1∶2.8 |
| ??Cu=0.6519 | ||||||
| ????5 | ??FT-816 | ????Z1 | ??Ni=0.8485 | Ammoniacal liquor 11+0.5 * 2 | ??B=1.4982 | ????1∶2.8 |
| ??Cu=1.6736 | ||||||
| ????6 | ??FT-817 | ????Z1 | ????Ni=0 | Ammoniacal liquor 11+0.5 * 2 | ?B=1.5006 | ????1∶2.8 |
| ??Cu=2.4880 | ||||||
| ????7 | ??FT-818 | ????Z1 | ?Ni=2.8948 | Water 11+1 * 2 | ??B=1.5052 | ????1∶2.8 |
| ??P=3.0063 | ||||||
| ????8 | ??FT-820 | ????Z5 | ??Ni=2.4729 | Ammoniacal liquor 12+1+0.5 | ??B=1.5154 | ????1∶2.8 |
| ????9 | ??FT-821 | ????Z7 | ??Ni=2.4810 | Ammoniacal liquor 11+0.5 * 2 | ??B=1.4950 | ????1∶2.8 |
| ????10 | ??FT-822 | ????Z3 | ?Ni=2.4792 | | ??B=1.5054 | ????1∶2.8 |
| ????11 | ??FT-827 | ????Z1 | ??Ni=3.6924 | Water 11+0.5 * 2 | ??B=2.2591 | ????1∶2．8 |
| ????12 | ??FT-838 | ????Z5 | ??Ni=2.1113 | Water 11+0.5 * 2 | ??B=1.7786 | ????1∶2．9 |
| ????13 | ??FT-840 | ????Z7 | ??Ni=2.3232 | Water 11+0.5 * 2 | ??B=1.4728 | ????1∶4．1 |
| ????14 | ??FT-842 | ????Z3 | ??Ni=2.0261 | Water 11+1+0.6 | ??B=1.3234 | ????1∶3.0 |
| ????15 | ??FT-843 | ????Z9 | ?Ni=1.9987 | Water 12+1+0.6 | ??B=1.3084 | ????1∶3．0 |
Comparative Examples 1～4
Select two kinds of commercial catalyst Rf-1 and Rf-2 for use, a kind of noble metal catalyst Rf-3 of preparation voluntarily and a kind of non-precious metal catalyst Rf-4 that is provided by the Dalian Chemistry and Physics Institute compare the selective hydrogenation performance of diolefin in the dehydrogenation of long-chain alkane product as reference.(wherein reference catalyst Rf-1 is a kind of non-noble metal supported commercial catalyst, and reference catalyst Rf-2 is a kind of noble metal support type commercial catalyst.)
Several catalyzer of table 4 are selected the hydrogenation performance comparison
| Reference catalyst | Active ingredient | Transformation efficiency % | Selectivity % | Reaction conditions |
| ????Rf-1 | ????Ni | ????69.0 | ????31.2 | ????1.1Mpa,200℃,6.4h -1 |
| ????Rf-2 | ????Pd | ????70.5 | ????29.0 | ????0.5Mpa,50℃,10h -1 |
| ????Rf-3 | ????Pd | ????78.4 | ????13.7 | ????0.5Mpa,50℃,10h -1 |
| ????Rf-4 | ????Ni,S | ????58.5 | ????33.2 | ????1.1Mpa,200℃,6.4h -1 |
Accompanying drawing 1 is the x-ray diffraction spectra of the Ni-Cu-B amorphous alloy catalyst of different carriers provided by the invention.
Accompanying drawing 2 is the x-ray diffraction spectra of commercial catalyst Raney Ni.
Claims (11)
1. catalyzer that is used for diolefine is selectively hydrogenated into monoolefine.Comprise that the Ni-Cu-B amorphous alloy and 70.0～99.9 that contains 0.1～30.0 heavy % weighs the porous carrier materials of %, the weight ratio of its Ni, Cu, B is 0.1～30: 0～10: 0.001～3.5, and specific surface is 10～1000 meters
2/ gram.
2. catalyzer according to claim 1 is characterized in that, catalyzer consists of the Ni-Cu-B amorphous alloy and accounts for 1.0～12.0 heavy %, and porous carrier materials accounts for 88.0～99.0 heavy %.
3. catalyzer according to claim 1 and 2 is characterized in that, specific surface is 10～1000 meters
2/ gram.
4. according to claim l or 2 described catalyzer, it is characterized in that the atomic ratio of described Ni, Cu, B is 0.5: 0.1: 10.
5. according to the described catalyzer of claim 4, it is characterized in that described porous material is selected from one or more in inorganic oxide, gac, the molecular sieve.
6. the described Preparation of catalysts method of claim 1 is included in and is higher than in freezing point of solution to the 100 ℃ temperature range, with the BH that contains of a kind of porous carrier materials of nickeliferous and/or copper and volumetric molar concentration 0.5～10.0
4 -Solution is by 0.1～10.0 boron nickel and/or the copper atom ratio contact that feeds intake.
7. according to the described catalyzer of claim 6, it is characterized in that the described BH that contains
4 -Ion solution refers to contain BH
4 -The ionic aqueous solution or alcoholic solution, BH
4 -Ion is from KBH
4Or NaBH
4Or their mixture.
8. according to claim 6 or 7 described methods, it is characterized in that described contact is in the scope of room temperature to 50 ℃, will contain BH
4 -Ion solution slowly is added drop-wise in the porous carrier materials of nickeliferous and/or copper.
9. one kind is selectively hydrogenated into the method for monoolefine with diolefine, and the hydrocarbon material flow that following of the hydroconversion condition that is included in certain limit contains diolefine contacts with the described arbitrary catalyzer of claim 1 to 8 under hydrogen atmosphere.
10. according to the described method of claim 9, it is characterized in that this hydroconversion condition comprises that pressure is 0.1 to 2Mpa, temperature is 25～200 ℃, liquid hourly space velocity 1～30h
-1
11., it is characterized in that the molar ratio of hydrogen and diolefine is between 0.75: 1 and 5: 1 according to the described method of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991206606A CN1141181C (en) | 1999-12-24 | 1999-12-24 | Non-crystalline alloy catalyst for olefine selective hydrogenation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991206606A CN1141181C (en) | 1999-12-24 | 1999-12-24 | Non-crystalline alloy catalyst for olefine selective hydrogenation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1301591A true CN1301591A (en) | 2001-07-04 |
| CN1141181C CN1141181C (en) | 2004-03-10 |
Family
ID=5281625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991206606A Expired - Fee Related CN1141181C (en) | 1999-12-24 | 1999-12-24 | Non-crystalline alloy catalyst for olefine selective hydrogenation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794178A (en) * | 2011-05-24 | 2012-11-28 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation thereof |
| CN103447060A (en) * | 2013-08-07 | 2013-12-18 | 中国科学院过程工程研究所 | Catalyst and treatment method for upgrading tar by using catalyst |
| US9669392B2 (en) | 2012-08-30 | 2017-06-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for selective hydrogenation of dienes, preparation method and application thereof |
-
1999
- 1999-12-24 CN CNB991206606A patent/CN1141181C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102794178A (en) * | 2011-05-24 | 2012-11-28 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst and preparation thereof |
| CN102794178B (en) * | 2011-05-24 | 2015-09-16 | 中国石油化工股份有限公司 | A kind of selective hydrogenation catalyst and preparation thereof |
| US9669392B2 (en) | 2012-08-30 | 2017-06-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalyst for selective hydrogenation of dienes, preparation method and application thereof |
| CN103447060A (en) * | 2013-08-07 | 2013-12-18 | 中国科学院过程工程研究所 | Catalyst and treatment method for upgrading tar by using catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1141181C (en) | 2004-03-10 |
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