CN101327433A - Nano metallic carbide catalyst and preparation and use - Google Patents
Nano metallic carbide catalyst and preparation and use Download PDFInfo
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- CN101327433A CN101327433A CNA2008100555300A CN200810055530A CN101327433A CN 101327433 A CN101327433 A CN 101327433A CN A2008100555300 A CNA2008100555300 A CN A2008100555300A CN 200810055530 A CN200810055530 A CN 200810055530A CN 101327433 A CN101327433 A CN 101327433A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a nanometer-sized metallic carbide catalyst which is characterized in that the nanometer-sized metallic carbide catalyst consists of M1MC/SiO2, wherein, a second metal M1 is one kind or multiple kinds of Fe, Co, Ni, Cu, Zn or Mn; a main metal is one kind of multiple kinds of Mo, Fe, Cr, W, V, Ti, Zr or Hf. The catalyst of the present invention is prepared by a sol-gel method. The catalyst has the advantages of high specific surface area, nanometer scale, low cost and the high selectivity of low-carbon alcohol.
Description
Technical field
The present invention relates to a kind of Preparation of catalysts methods and applications, is a kind of preparation method and application that is used for the metal carbides nanocatalyst of synthesis gas preparation low-carbon alcohols and hydrocarbon specifically.
Background technology
Along with the increase day by day of the energy and environmental pressure, non-petroleum path obtains liquid fuel and bulk chemical has caused worldwide extensive attention at present.MAS (C
1-C
5Mixed alcohol) have performances such as high-octane rating, explosion-proof, antidetonation, it is used and is positioned eco-friendly fuel additive and for oil product always, and to produce MAS with coal and natural gas via synthesis gas be that an optimization utilizes the energy and resources effective approach.
Existing at present a large amount of reports by the CO hydrogenation synthesizing low carbon mixed alcohol, patent EP-0034338-A2 and US Patent-4513100 disclose the methanol synthesis catalyst (Cu-Zn/Al that utilizes modification, Zn-Cr) catalyst as the CO hydrogenation reacts, though this catalyst is active higher, isobutanol content height in the product, but (pressure is 14～20Mpa to severe reaction conditions, temperature is 350～450 ℃), higher alcohol selectivity low (being generally less than 35%), water content height in the product (being generally 30～50%).France Petroleum Institute (IFP) has at first developed Cu-Co co-precipitation low-carbon alcohol catalyst, only is mainly C with regard to having obtained four catalyst patents (USPatent 4122110 and 4291126 and GB Patent 2118061 and 2158730) synthetic product of this catalyst before 1985
1-C
6The straight chain n-alkanol, accessory substance is mainly C
1-C
6Aliphatic hydrocarbon, reaction condition gentleness (similar) to the low pressure methanol synthetic catalyst.The shortcoming of this catalyst is a less stable.It is catalyst based that US Patent-4014913he and 4096164 discloses Rh again, behind one to two kind of transition metal of adding or the metal oxide auxiliary agent, to low-carbon alcohols is synthetic higher activity and selectivity arranged, particularly to C in support type Rh catalyst
2 +The selectivity of alcohol is higher, and product is based on ethanol.But the Rh compound costs an arm and a leg, and catalyst is easily by CO
2Poison, its activity and selectivity generally do not reach industrial requirement.The molybdenum of U.S. DOW company exploitation is that sulfide catalyst (main patent is seen people's such as Stevens US patent4882360) not only has anti-sulphur, and product is moisture few, and higher alcohol content is higher, reaches 30-70%, wherein mainly is ethanol and normal propyl alcohol.The subject matter that this catalyst exists be wherein auxiliary element very easily and form carbonyls between the carbon monoxide, cause the loss of auxiliary element, influence activity of such catalysts and selectivity, cause catalyst stability and life-span to be restricted; Contain more sulfur-containing compound in the product simultaneously, have relatively high expectations for later separation is refining.
At present in the multiple low-carbon alcohol catalyst system of exploitation, metal carbide catalyst, the performance with the anti-sulphur of its excellence and good synthesis of low-carbon alcohol is considered to the quite promising catalyst system of a class.Metal carbides are subjected to common concern as a class new catalytic material with its precious metal catalyst characteristic, and activation CO ability and hydrogenation performance that it is high make first appearance at the synthesis gas chemical field, are expected to become the novel Fischer-Tropsch synthesis catalytic of class system.Primary Study in the synthetic field of C1 shows that metal carbides can generate oxygenatedchemicals such as light paraffins, alkene and alcohol ether, and catalyst has the active and certain sulfur resistance of higher water gas shift reaction.The modification of interpolation alkaline assistant can make the selectivity of product of carbide CO hydrogenation reaction change, and obviously improves and the decline of alkane selectivity as low-carbon alkene and pure selectivity.In addition, after modifications such as VIII group 4 transition metal Co, Ru, the CO hydrogenation activity of carbide catalyst can further strengthen, and can reduce alcohol product as adding metal Ru, and metal Co has then strengthened C
5 +The formation ability of hydrocarbon.This shows that the product of carbide catalyst CO hydrogenation reaction can be regulated and control by adding different auxiliary agents, modified carbonize thing catalyst is the potential novel F-T synthetic catalyst of a class.
The preparation of carbide and many metal carbides at present mainly is divided into two steps: the preparation of (1) metal or many metal carbides presoma, the carbonization of (2) presoma.Wherein the first step is the committed step of decision carbide or many metal carbides catalytic performance, and the preparation of conventional metals or many metal precursor mainly is the mixing that metal or many metal precursor is realized main metal and promoter metal by mechanical mixture or incipient impregnation.Because these methods all are to mix by the physics method, main metal and promoter metal can not realize the mixing on atom or the molecule meaning, and each metal component of the presoma that obtains mixes inhomogeneous; The metal that the method for while physical mixed prepares or many metal precursor particle diameter be micron order more normally.Therefore carbide or the many metal carbides of presoma through obtaining after the carbonization that obtain by these methods, promoter metal and main metal disperse inhomogeneous, and carbide particle diameter (micron order) greatly, the less (100m of specific area
2.g
-1Below), these factors have all restricted the reactivity worth of catalyst greatly.In addition, traditional metal or many metal precursor carbonisation all are to carry out in carbonaceous gas such as methane, ethane, propane or butane, and the Preparation of catalysts cost is all than higher.Therefore, the nano-carbide catalyst of low-cost preparation with high degree of dispersion, high-specific surface area is catalyst based and improve its catalytic perfomance and have great importance for the carbide of development of new.
Summary of the invention
The present invention is primarily aimed at the shortcoming of conventional method preparation, and a kind of high-specific surface area, nano metal carbide catalyst and preparation method and application are provided.
Nano metal carbide catalyst provided by the invention consists of: M
1MC/SiO
2Second metal M wherein
1For Fe, Co, Ni, Cu, Zn or Mn one or more, main metal M be Mo, Fe, Cr, W, V, Ti, Zr or Hf one or more.
Institute of the present invention Preparation of catalysts method may further comprise the steps:
(1) under 0～60 ℃, with the presoma and second metal M of main metal M
1In the solvent that presoma is distributed to, through adding the Si support precursor after 1-24 hour the stirring, and the base catalyst and the distilled water that add, continue 1-24 hour stirring, the product that obtains 60～150 ℃ of dryings 1～24 hour, can be obtained M-M
1/ SiO
2Oxygenatedchemicals;
(2) with M-M
1/ SiO
2Oxygenatedchemicals grind to form Powdered less than 0.5mm, inert gas or carbonaceous gas are fed Powdered M-M
1/ SiO
2Oxygenatedchemicals with 1～10 ℃ heating rate, rises to 400 ℃ from room temperature, and then rises to 500 ~ 800 ℃ with 0.2～3 ℃ heating rate from 400, and constant temperature 1～8 hour;
(3) after temperature reaction finishes, step (2) material is cooled to room temperature in inert atmosphere.
(4) in room temperature, be that 0.5～2% passivation gas was carried out passivation 1～8 hour to (3) material with oxygen concentration, promptly obtain nano metal carbide catalyst.
As above the presoma of (1) described main metal M can be: the presoma (molybdenum carbonyl of molybdenum, ammonium molybdate and molybdenum chloride), the presoma (ferric nitrate, carbonyl iron, iron chloride etc.) of iron, the presoma (chromic nitrate, potassium chromate etc.) of chromium, the presoma (nitric acid tungsten, ammonium tungstate, tungsten fluoride, sodium tungstate etc.) of tungsten, the presoma (ammonium vanadate etc.) of vanadium, the presoma (titanium tetrachloride, butyl titanate etc.) of titanium, the presoma (zirconium chloride of zirconium, propyl alcohol zirconium, zirconium iso-propoxide etc.) and the presoma (hafnium tetrachloride etc.) of hafnium etc.
As above (1) described second metal M
1Presoma can be: the presoma of iron (ferric nitrate, carbonyl iron, iron chloride etc.), the presoma of cobalt (cobalt nitrate, cobalt chloride etc.), the presoma of nickel (nickel nitrate etc.), the presoma of copper (copper nitrate, basic copper carbonate etc.), the presoma (manganese nitrate, manganese chloride etc.) of presoma of zinc (zinc nitrate, zinc chloride etc.) and manganese etc.
As above second metal M in (1) described course of reaction
1(M
1=Fe, Co, Ni, Cu, Zn or Mn one or more) with the molar ratio of main metal M (M=Mo, Fe, Cr, W, V, Ti, Zr or Hf one or more) be: 1: 1～10.
As above (1) described solvent can be: methyl alcohol and ethanol or acetone etc., the consumption of solvent is specially main metal M: solvent=0.01mol: 50～200ml by the decision of the amount of main metal.
As above (1) described the Si support precursor can be: polymethyl hydrogen siloxane, dimethyl silicone polymer or poly-ethylene methacrylic radical siloxane etc., the molar ratio of Si: M (M=Mo, Fe, Cr, W, V, Ti, Zr or Hf) is: 1: 1～10.
As above (1) described base catalyst can be: ammoniacal liquor, ethylenediamine or triethylamine etc., the amount of base catalyst and distilled water is specially main metal M: base catalyst: distilled water=0.01mol: 0.5-2mL: 0.5-2mL by the amount decision of main metal.
As above (3) and (4) described inert gas can be: one or more of nitrogen, argon gas, helium, wherein oxygen content requires to be lower than 0.1%.
As above (3) described carbonaceous gas can be: CO, CO
2, methane, ethane, ethene, butane one or more.
As above (4) described passivation gas can be the mixture of air and nitrogen, argon gas or helium, or the mixture of oxygen and nitrogen, argon gas or helium.
Application of Catalyst condition of the present invention is: reaction temperature is 260～360 ℃, and pressure is 1.0～10.0MPa, and air speed is 1000～8000h
-1, H
2/ CO=1～3.
The present invention compared with prior art has following characteristics:
(1) the present invention prepares many metal carbides presoma by sol-gel process, each metal component is realized the abundant mixing of atom or molecular level, reduce the presoma particle diameter greatly, further suppressed metal or the increase of many metal precursor particle diameter in carbonisation and the decline of specific surface by adding the Si support precursor simultaneously.
(2) catalyst particle size that utilizes the present invention to prepare is nanoscale, and scope is 5～100nm, and specific area is 100～500m
2.g
-1
(3) because the Si support precursor that the present invention selects for use has high carbon content, in the temperature programming carbonisation, do not need additionally to add again carbonaceous gas, realize the original position carbonization, can reduce preparation cost greatly.
(4) catalyst provided by the invention has higher low-carbon alcohols selectivity when keeping high reaction activity and high.
The analysis that the present invention adopts and being calculated as follows:
Gas and product liquid adopt the analysis of Tianjin, island GC-8A gas chromatograph.Thermal conductivity detector (TCD) (TCD) detects CO, the CO in the gas
2, H
2, CH
4Volume content and the H in the product liquid
2O, CH
3The percentage by weight of OH, its chromatographic column use carbon molecular sieve and the TDX401 packed column of 2m respectively, and column temperature is 100 ℃.Hydrocarbon in the gas and the mixed alcohol in the liquid are then detected by hydrogen flame ionization detector, and its chromatographic column is the Porapak Q packed column of 2m.
Gas-phase product is that intermediate carries out related normalizing calculating by methane gas, and liquid product is that the related normalizing of intermediate calculates by methyl alcohol.
Be the feature of this catalyst of detailed presentations, now specify as follows in conjunction with the embodiments:
Embodiment 1
Under 30 ℃, with Fe (CO)
5(NH
4)
6Mo
7O
244H
2O is distributed in the 80ml ethanol with the Fe/Mo mol ratio and stirred 12 hours at 1: 4, and then adding 1.5g polymethyl hydrogen siloxane, add 0.6mL ethylenediamine and 0.2mL distilled water subsequently, continue to stir 12 hours, the product that obtains is handled obtaining Fe-Mo/SiO in 24 hours at 60 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed helium, flow velocity is 120mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 10 ℃/min, and then constant temperature 4 hours after continuing to rise to 700 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 1% O
2/ N
2Mist purges passivation and promptly obtained FeMoC/SiO in 4 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 320 ℃, and pressure is 8.0MPa, and air speed is 3000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 2
Under 40 ℃, with Fe (NO
3)
39H
2The presoma [(NH of O and main metal M (M=Mo and Cr)
4)
6Mo
7O
244H
2O and Cr (NO
3)
39H
2The mixture of O] with Fe: Mo: the Cr mol ratio is distributed in the 140ml ethanol and stirred 12 hours at 1: 2: 1, and then adding 1.0g dimethyl silicone polymer, add 1.0mL ethylenediamine and 0.6mL distilled water subsequently, continue to stir 14 hours, the product that obtains is handled obtaining Fe-MoCr/SiO in 24 hours at 80 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed nitrogen, flow velocity is 80mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 4 ℃/min, and then constant temperature 4 hours after continuing to rise to 700 ℃ with 2 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 2% O
2/ N
2Mist purges passivation and promptly obtained FeMoCrC/SiO in 8 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 8.0MPa, and air speed is 2000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 3
Under 50 ℃, with Fe (CO)
5Presoma [(NH with main metal M (M=Mo, V and Fe)
4)
6Mo
7O
244H
2O, NH
4VO
3And Fe (NO
3)
39H
2The mixture of O] with Fe: Mo: V: Fe mol ratio 1: 5: 1.5: 0.5 is distributed in the 180ml ethanol and stirred 12 hours, and then adding 1.0g polymethyl hydrogen siloxane, add 1.6mL ethylenediamine and 0.8mL distilled water subsequently, continue to stir 24 hours, the product that obtains is handled obtaining Fe-MoVFe/SiO in 24 hours at 120 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed methane gas, flow velocity is 100mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 6 ℃/min, and then constant temperature 6 hours after continuing to rise to 600 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 2% O
2/ Ar mist purges passivation and promptly obtained FeMoVFeC/SiO in 3 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 8.0MPa, and air speed is 2000h
-1, H
2/ CO=2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 4
Under 40 ℃, with Fe (NO
3)
39H
2The presoma [(NH of O and main metal M (M=Mo, Cr, V and Ti)
4)
6Mo
7O
244H
2O, Cr (NO
3)
39H
2O, NH
4VO
3And Ti (OC
4H
9)
4] mixture] with Fe: Mo: Cr: V: Ti mol ratio 1: 5: 1: be distributed in 180ml ethanol at 1: 1 and stirred 12 hours, and then adding 1.5g polymethyl hydrogen siloxane, add 1.8mL ethylenediamine and 0.9mL distilled water subsequently, continue to stir 12 hours, the product that obtains is handled obtaining Fe-MoCrVTi/SiO in 24 hours at 100 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed ethane gas, flow velocity is 120mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 2 ℃/min, and then with constant temperature after continuing 2 ℃/min heating rate and rising to 700 ℃ 6 hours, reducing to after the room temperature with oxygen concentration was air/N of 0.5%
2Mist purges passivation and promptly obtained FeMoCrVTiC/SiO in 4 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 310 ℃, and pressure is 6.0MPa, and air speed is 1000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 5
Under 35 ℃, with Co (NO
3)
36H
2O and (NH
4)
6Mo
7O
244H
2O is distributed in the 50ml ethanol with the Co/Mo mol ratio and stirred 12 hours at 1: 2, and then adding 2.0g polymethyl hydrogen siloxane, add 0.8mL ethylenediamine and 0.2mL distilled water subsequently, continue to stir 12 hours, the product that obtains is handled obtaining Co-Mo/SiO in 24 hours at 60 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed argon gas, flow velocity is 100mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 1 ℃/min, and then constant temperature 6 hours after continuing to rise to 700 ℃ with 0.2 ℃/min heating rate, reduce to after the room temperature with 2% (v/v) O
2/ N
2Mist purges passivation and promptly obtained CoMoC/SiO in 4 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 360 ℃, and pressure is 8.0MPa, and air speed is 2000h
-1, H
2/ CO=2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 6
Under 50 ℃, with Co (NO
3)
36H
2The presoma [(NH of O and main metal M (M=Mo and Cr)
4)
6Mo
7O
244H
2O and Cr (NO
3)
39H
2The mixture of O] with Co: the M mol ratio is distributed in the 140ml ethanol and stirred 12 hours at 1: 6, and then adding 1.5g dimethyl silicone polymer, add 1.4mL ethylenediamine and 0.9mL distilled water subsequently, continue to stir 16 hours, the product that obtains is handled obtaining Co-MoCr/SiO in 24 hours at 130 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed helium, flow velocity is 100mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 3 ℃/min, and then constant temperature 6 hours after continuing to rise to 700 ℃ with 2 ℃/min heating rate, reduce to after the room temperature with 1% (v/v) O
2/ N
2Mist purges passivation and promptly obtained CoMoCrC/SiO in 6 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 8.0MPa, and air speed is 1000h
-1, H
2/ CO=2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 7
At room temperature, with second metal M
1Presoma [Fe (NO
3)
39H
2O and Cu (NO
3)
33H
2The O mixture] and (NH
4)
6Mo
7O
244H
2O is with Fe: Cu: the Mo mol ratio is distributed in the 80ml ethanol and stirred 12 hours at 0.8: 0.2: 5, and then adding 1.0g polymethyl hydrogen siloxane, add 0.6mL ethylenediamine and 0.2mL distilled water subsequently, continue to stir 12 hours, the product that obtains is handled obtaining FeCu-Mo/SiO in 24 hours at 80 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed helium, flow velocity is 100mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 4 ℃/min, and then constant temperature 4 hours after continuing to rise to 600 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 1% O
2/ Ar mist purges passivation and promptly obtained FeCuMoC/SiO in 8 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 320 ℃, and pressure is 8.0MPa, and air speed is 3000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 8
Under 20 ℃, with second metal M
1Presoma [Fe (NO
3)
39H
2O and Cu (NO
3)
33H
2The mixture of O] with the presoma [(NH of main metal M (M=Mo and Cr)
4)
6Mo
7O
244H
2O and Cr (NO
3)
39H
2The mixture of O] with Fe: Cu: Mo: Cr mol ratio 0.5: 0.5: 3: 1 is distributed in the 160ml ethanol and stirred 12 hours, and then adding 1.5g polymethyl hydrogen siloxane, add 1.2mL ethylenediamine and 0.6mL distilled water subsequently, continue to stir 14 hours, the product that obtains is handled obtaining FeCu-MoCr/SiO in 24 hours at 80 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed nitrogen, flow velocity is 80mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 1 ℃/min, and then constant temperature 4 hours after continuing to rise to 600 ℃ with 0.5 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 1.5% O
2/ N
2Mist purges passivation and promptly obtained FeCuMoCrC/SiO in 5 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 6.0MPa, and air speed is 1000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 9
Under 55 ℃, with second metal M
1Presoma [Fe (CO)
5And Cu (NO
3)
33H
2The mixture of O] with the presoma [(NH of main metal M (M=Mo, V and Fe)
4)
6Mo
7O
244H
2O, NH
4VO
3And Fe (NO
3)
39H
2The mixture of O] with Fe: Cu: Mo: V: Fe mol ratio 0.2: 0.8: 5: be distributed in 200ml ethanol at 2: 1 and stirred 12 hours, and then adding 2.0g dimethione, add 1.8mL ethylenediamine and 0.8mL distilled water subsequently, continue to stir 16 hours, the product that obtains is handled obtaining FeCu-MoVFe/SiO in 24 hours at 160 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed helium, flow velocity is 100mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 2 ℃/min, and then constant temperature 6 hours after continuing to rise to 800 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 2% O
2/ He mist purges passivation and promptly obtained FeCuMoVFeC/SiO in 3 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 8.0MPa, and air speed is 2000h
-1, H
2/ CO=2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 10
Under 45 ℃, with second metal M
1Presoma [Fe (NO
3)
39H
2O and Cu (NO
3)
33H
2The mixture of O] with the presoma [(NH of main metal M (M=Mo, Cr, V and Ti)
4)
6Mo
7O
244H
2O, Cr (NO
3)
39H
2O, NH
4VO
3And Ti (OC
4H
9)
4] mixture] with Fe: Cu: Mo: Cr: V: Ti mol ratio 0.5: 0.5: 6: be distributed in 180ml ethanol at 0.6: 0.4: 1 and stirred 12 hours, and then adding 1.5g polymethyl hydrogen siloxane, add 1.8mL ethylenediamine and 0.9mL distilled water subsequently, continue to stir 12 hours, the product that obtains is handled obtaining FeCu-MoCrVTi/SiO in 24 hours at 100 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed methane gas, flow velocity is 120mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 10 ℃/min, and then constant temperature 6 hours after continuing to rise to 800 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is air/N of 2%
2Mist purges passivation and promptly obtained FeCuMoCrVTiC/SiO in 4 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 310 ℃, and pressure is 6.0MPa, and air speed is 1000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 11
Under 35 ℃, with second metal M
1Presoma [Fe (NO
3)
39H
2O, Cu (NO
3)
33H
2O and Co (NO
3)
36H
2The mixture of O] and (NH
4)
6Mo
7O
244H
2O is with Fe: Cu: Co: Mo mol ratio 0.2: 0.5: 0.3: 6 are distributed in the 120ml ethanol and stirred 12 hours, and then adding 1.0g polymethyl hydrogen siloxane, add 1.6mL ethylenediamine and 0.8mL distilled water subsequently, continue to stir 12 hours, the product that obtains is handled obtaining FeCuCo-Mo/SiO in 24 hours at 120 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed helium, flow velocity is 100mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 5 ℃/min, and then constant temperature 4 hours after continuing to rise to 500 ℃ with 2 ℃/min heating rate, reduce to after the room temperature O with oxygen concentration to be 1%
2/ Ar mist purges passivation and promptly obtained FeCuCoMoC/SiO in 4 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 8.0MPa, and air speed is 3000h
-1, H
2/ CO=2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 12
Under 60 ℃, with second metal M
1Presoma [Fe (NO
3)
39H
2O, Cu (NO
3)
33H
2O and Co (NO
3)
36H
2The mixture of O] with the presoma [(NH of main metal M (M=Mo and Cr)
4)
6Mo
7O
244H
2O and Cr (NO
3)
39H
2The mixture of O] with Fe: Cu: Co: Mo: Cr mol ratio 0.1: 0.4: 0.5: be distributed in 160ml ethanol at 3: 1 and stirred 12 hours, and then adding 1.5g polymethyl hydrogen siloxane, add 1.2mL ethylenediamine and 0.6mL distilled water subsequently, continue to stir 14 hours, the product that obtains is handled obtaining FeCuCo-MoCr/SiO in 24 hours at 80 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed ethylene gas, flow velocity is 80mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 4 ℃/min, and then constant temperature 4 hours after continuing to rise to 600 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 0.5% O
2/ N
2Mist purges passivation and promptly obtained FeCuCoMoCrC/SiO in 8 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 340 ℃, and pressure is 6.0MPa, and air speed is 1000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 13
Under 55 ℃, with the presoma [Fe (NO of second metal M 1
3)
39H
2O, Cu (NO
3)
33H
2O and Co (NO
3)
36H
2The mixture of O] with the presoma of main metal M (M=Mo, V and Fe) [(NH4)
6Mo
7O
244H
2O, NH
4VO
3And Fe (NO
3)
39H
2The mixture of O] with Fe: Cu: Co: Mo: V: Fe mol ratio 0.1: 0.3: 0.6: be distributed in 200ml ethanol at 5: 1: 2 and stirred 12 hours, and then adding 2.0g polymethyl hydrogen siloxane, add 1.8mL ethylenediamine and 0.8mL distilled water subsequently, continue to stir 16 hours, the product that obtains is handled obtaining FeCuCo-MoVFe/SiO in 24 hours at 160 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed helium, flow velocity is 100mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 2 ℃/min, and then constant temperature 8 hours after continuing to rise to 500 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 1.5% O
2/ N
2Mist purges passivation and promptly obtained FeCuCoMoVFeC/SiO in 3 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 360 ℃, and pressure is 8.0MPa, and air speed is 2000h
-1, H
2/ CO=2.0, the catalytic perfomance evaluation is listed in the table 1.
Embodiment 14
Under 45 ℃, with second metal M
1Presoma [Fe (NO
3)
39H
2O, Cu (NO
3)
33H
2O and Co (NO
3)
36H
2The mixture of O] with the presoma [(NH of main metal M (M=Mo, Cr, V and Ti)
4)
6Mo
7O
244H
2O, Cr (NO
3)
39H
2O, NH
4VO
3And Ti (OC
4H
9)
4] mixture] with Fe: Cu: Co: Mo: Cr: V: Ti mol ratio 0.1: 0.4: 0.5: 6: 1: 0.8: 0.2 is distributed in the 200ml ethanol and stirred 12 hours, and then adding 1.5g polymethyl hydrogen siloxane, add 1.8mL ethylenediamine and 0.8mL distilled water subsequently, continue to stir 12 hours, the product that obtains is handled obtaining FeCuCo-MoCrVTi/SiO in 24 hours at 140 ℃
2Oxygenatedchemicals.The oxygenatedchemicals that obtains is ground to particle diameter to be placed in the crystal reaction tube less than 0.5mm, feed argon gas, flow velocity is 120mL/min, adopt two sections temperature programming controls to rise to 400 ℃ from room temperature with the heating rate of 5 ℃/min, and then constant temperature 6 hours after continuing to rise to 700 ℃ with 1 ℃/min heating rate, reducing to after the room temperature with oxygen concentration is 2% O
2/ N
2Mist purges passivation and promptly obtained FeCuCoMoCrVTiC/SiO in 4 hours
2Catalyst.Be ground to 40～60 orders with pulverizing behind the catalyst compressing tablet that makes, carry out evaluating catalyst, the evaluating catalyst condition: reaction temperature is 310 ℃, and pressure is 8.0MPa, and air speed is 1000h
-1, H
2/ CO=1.0, the catalytic perfomance evaluation is listed in the table 1.
Claims (14)
1, a kind of nano metal carbide catalyst is characterized in that nano metal carbide catalyst consists of: M
1MC/SiO
2
Second metal M wherein
1For Fe, Co, Ni, Cu, Zn or Mn one or more,
Main metal M be Mo, Fe, Cr, W, V, Ti, Zr or Hf one or more.
2, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 1 is characterized in that comprising the steps:
(1) under 0～60 ℃, with the presoma and second metal M of main metal M
1In the solvent that presoma is distributed to, through adding the Si support precursor after 1-24 hour the stirring, and the base catalyst and the distilled water that add, continue 1-24 hour stirring, the product that obtains 60～150 ℃ of dryings 1～24 hour, can be obtained M-M
1/ SiO
2Oxygenatedchemicals;
(2) with M-M
1/ SiO
2Oxygenatedchemicals grind to form Powdered less than 0.5mm, inert gas or carbonaceous gas are fed Powdered M-M
1/ SiO
2Oxygenatedchemicals with 1～10 ℃ heating rate, rises to 400 ℃ from room temperature, and then rises to 500～800 ℃ with 0.2～3 ℃ heating rate from 400, and constant temperature 1～8 hour;
(3) after temperature reaction finishes, step (2) material is cooled to room temperature in inert atmosphere.
(4) in room temperature, be that 0.5～2% passivation gas was carried out passivation 1～8 hour to (3) material with oxygen concentration, promptly obtain nano metal carbide catalyst.
3, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2 is characterized in that the presoma of the described main metal M of step (1) is: the presoma of the presoma of the presoma of molybdenum, the presoma of iron, chromium, the presoma of tungsten, vanadium, the presoma of titanium, the presoma of zirconium or the presoma of hafnium.
4, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 3, the presoma that it is characterized in that described molybdenum is molybdenum carbonyl, ammonium molybdate or molybdenum chloride, the presoma of iron is ferric nitrate, carbonyl iron or iron chloride, the presoma of chromium is chromic nitrate or potassium chromate, the presoma of tungsten is nitric acid tungsten, ammonium tungstate, tungsten fluoride or sodium tungstate, the presoma of vanadium is an ammonium vanadate, the presoma of titanium is titanium tetrachloride or butyl titanate, the presoma of zirconium is zirconium chloride, propyl alcohol zirconium or zirconium iso-propoxide, and the presoma of hafnium is a hafnium tetrachloride.
5, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2 is characterized in that described second metal M of step (1)
1Presoma can be: the presoma of the presoma of iron, the presoma of cobalt, nickel, the presoma of copper, the presoma of zinc or the presoma of manganese.
6, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 5, the presoma that it is characterized in that described iron is ferric nitrate, carbonyl iron or iron chloride, the presoma of cobalt is cobalt nitrate or cobalt chloride, the presoma of nickel is a nickel nitrate, the presoma of copper is copper nitrate or basic copper carbonate, the presoma of zinc is zinc nitrate or zinc chloride, and the presoma of manganese is manganese nitrate or manganese chloride.
7, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2 is characterized in that described second metal M of step (1)
1With the molar ratio of main metal M be: 1: 1～10.
8, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2, it is characterized in that the described solvent of step (1) is: methyl alcohol, ethanol or acetone, the consumption of solvent are main metal M: solvent=0.01mol: 50～200ml.
9, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2, it is characterized in that the described Si support precursor of step (1) is: polymethyl hydrogen siloxane, dimethyl silicone polymer or poly-ethylene methacrylic radical siloxane, the molar ratio of Si: M is: 1: 1～10.
10, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2, it is characterized in that the described base catalyst of step (1) is: ammoniacal liquor, ethylenediamine or triethylamine, 11, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2, the amount that it is characterized in that described base catalyst, distilled water and main metal is main metal M: base catalyst: distilled water=0.01mol: 0.5-2mL: 0.5-2mL.
12, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2 is characterized in that step (3) or (4) described inert gas are: one or more of nitrogen, argon gas, helium, wherein oxygen content requires to be lower than 0.1%.
13, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2 is characterized in that the described carbonaceous gas of step (3) is: CO, CO
2, methane, ethane, ethene, butane one or more.
14, the preparation method of a kind of nano metal carbide catalyst as claimed in claim 2 is characterized in that the described passivation gas of step (4) is the mixture of air and nitrogen, argon gas or helium, or the mixture of oxygen and nitrogen, argon gas or helium.
15, the application of a kind of nano metal carbide catalyst as claimed in claim 1 is characterized in that reaction temperature is 260～360 ℃, and pressure is 1.0～10.0MPa, and air speed is 1000～8000h
-1, H
2/ CO=1～3.
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|---|---|---|---|
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| CN102247852A (en) * | 2011-05-18 | 2011-11-23 | 中国科学院广州能源研究所 | Cu-Fe-Co base catalyst used for synthesizing low carbon alcohol by utilizing synthesis gas as well as preparation method and application thereof in low carbon alcohol synthesizing process by virtue of synthesis gas |
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