CN101099932A - High-efficient iron-series catalyst and its preparation method - Google Patents
High-efficient iron-series catalyst and its preparation method Download PDFInfo
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- CN101099932A CN101099932A CNA2007100228198A CN200710022819A CN101099932A CN 101099932 A CN101099932 A CN 101099932A CN A2007100228198 A CNA2007100228198 A CN A2007100228198A CN 200710022819 A CN200710022819 A CN 200710022819A CN 101099932 A CN101099932 A CN 101099932A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910052742 iron Inorganic materials 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 18
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 239000011949 solid catalyst Substances 0.000 claims description 13
- 238000009413 insulation Methods 0.000 claims description 12
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000571 coke Substances 0.000 claims description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010457 zeolite Substances 0.000 claims description 4
- 239000002817 coal dust Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000003077 lignite Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000010117 shenhua Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000011882 ultra-fine particle Substances 0.000 description 3
- 229910006299 γ-FeOOH Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001570 bauxite Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910021506 iron(II) hydroxide Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- -1 wherein Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention discloses one kind of nanometer iron catalyst and its preparation process and apparatus. The nanometer iron catalyst is prepared through the following steps: adding liquid iron pentacarbonyl; heating iron pentacarbonyl in a reactor for the iron pentacarbonyl to infiltrate into the pores of catalyst carrier; further heating or introducing high temperature pressurized high purity nitrogen or other inert gas to decompose iron pentacarbonyl to obtain nanometer level iron particle; cooling, filling the prepared nanometer iron catalyst into package filled with high purity nitrogen and sealing for preserving. The present invention utilizes solid carrier to block the aggregation of iron particle for obtain nanometer iron particle. The nanometer iron catalyst has high activity, high dispersivity, high stability and simple preparation process, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of Fe-series catalyst and preparation method thereof, be specifically related to a kind of iron pentacarbonyl decomposition in situ on the solid catalyst carrier of utilizing and produce homodisperse Fe-series catalyst and preparation method thereof efficiently.
Background technology
Transition element iron is because of having special d electron orbit, to H
2, N
2, NH
3, C
2H
2, C
2H
4Deng producing chemisorbed, generate the surface intermediate kind, make to be adsorbed molecule activation and to be dissociated into atom, offering reactant carries out various chemical reactions, thereby is a kind of good chemical catalyst.Fe-series catalyst is used widely at Coal Chemical Industry, petroleum refining, ammonia synthesis and decomposition catalytic field.
Fe-series catalyst commonly used at present mainly contains natural pyrite, troilite and various melting waste slag.Its particle generally several microns to tens of micron, difficulties in dispersion, catalytic effect is restricted.Studies show that catalyst particle is thin more, its dispersion in coal slurry or oil product is good more, and catalytic effect is also good more.Use the high dispersive Ultra-fine Particle Catalysts, can improve hydrogenation conversion, reduce catalyst amount, reduce cost, reduce environmental pollution.From existing report, adopt the mechanical lapping means to reduce catalyst particle size, reaching micron order has been the limit.
For reducing iron series hydrocatalyst particle diameter, the various countries researcher develops the kinds of artificial synthetic method.
In the west, particularly the scientist of European and American countries is devoted to the exploitation of dispersed catalysts always.Current research at most, the most popular be that the Fe series catalysts is made particle diameter at the ultrafine particle below 1 micron, particularly (1～100nm) particle, the preparation method who has proposed has nanoscale: the Rapid Thermal solution of laser cracking process, solution, the coprecipitation of metal salt solution and reversed phase micelle microemulsion method etc.The U.S. mainly adopts trivalent iron salt as the catalyst raw material, is prepared into nano particle, but trivalent iron salt price height, cost is big; Germany adopts aluminium making residue, and this technology does not need independent grinding, has reduced cost, but does not meet the low national conditions of China's bauxite resource iron content.
Japan's New Energy Development Organization (NEDO) with ferric sulfate and sulphur as raw material, 480-500 ℃ of synthetic iron sulfide (SIS) in the continuous fluid bed bioreactor.The primary particle of catalyst is 50-200nm, owing to reunite, the particle mean size of catalyst offspring is 108um, needs to be dispersed into submicron-scale by ultrasonic vibrations.Japan brown coal liquefaction company is a raw material with ferrous sulfate and ammoniacal liquor, add ammonium hydrogen phosphate after making ferrous hydroxide, 40 ℃ of air oxidations 20 hours, make γ-FeOOH ultrafine particle, γ-FeOOH powder is dry down at 100 ℃, γ-FeOOH reunites easily, needs to be crushed to the submicron order particle diameter by ultra-fine mill in process solvent.
The nearest achievement in research of China's 863 Program shows, divalent iron salt as base stock synthesis of nano grade particles, can be played good catalytic effect, but the nanocatalyst precursor that generates in the preparation process is a kind of metastable solids thing, as untimely dispersion, secondary agglomeration can take place; When the precursor oxidation generates catalyst prod, also the phenomenon that particle is grown up can take place, the specific area that reduces Fe-series catalyst is with active.
Summary of the invention
The objective of the invention is to: a kind of high-efficient iron-series catalyst and preparation method thereof is provided, the Fe-series catalyst catalytic activity height that adopts this preparation method to produce, preparation technology is simple, is easy to amplify carry out industrialization production.
Fe-series catalyst of the present invention is dispersed in the solid catalyst carrier micropore less than the iron particle of 100nm by particle diameter to be formed.
The preparation method of high-efficient iron-series catalyst of the present invention is made up of following steps:
1. in autoclave, add the solid catalyst carrier, vacuumize or with air in high purity nitrogen or the inert gas replacement still, adding iron pentacarbonyl liquid;
2. start heater, be incubated after being heated to temperature, make iron pentacarbonyl in reactor, be evaporated to steam and fully expand, infiltrate in the catalyst carrier micropore;
3. continue to heat up or press high pure nitrogen or other inert gas, make the iron pentacarbonyl decomposition in situ that is adsorbed in the carrier micropore, obtain the nano-level iron particle to reactor Nei Tonggao temperate zone;
4. cooling is discharged gas to exhaust treatment system, and the nanometer iron-series catalyst finished product that makes is put into the packing that is full of high pure nitrogen or other inert gas, and sealing is preserved.
Among the preparation method of high-efficient iron-series catalyst of the present invention, the 1. middle solid catalyst carrier of step is zeolite, active carbon, γ-Al
2O
3, at least a in diatomite, coke, coal dust or other porous material, iron pentacarbonyl liquid accounts for the 0.1-0.8 of reactor volume.
Among the preparation method of high-efficient iron-series catalyst of the present invention, the 2. middle heating-up temperature of step is 60-285 ℃, preferably at 103-180 ℃, and insulation 0.5-2h.
Among the preparation method of high-efficient iron-series catalyst of the present invention, step 3. described in high temperature be 200-400 ℃, the insulation 0.1-1h, high purity inert gas pressure is 5-10MPa.
The present invention has the following advantages: 1. by Fe (CO)
5Evaporation, steam fully expands and penetrates in the carrier micropore, and the high-purity gas medium through heating or feeding heat makes Fe (CO) again
5Decomposition in situ goes out iron particle, because the obstruct of carrier, iron atom can't be assembled grows up, thereby form stabilized nano iron-carrier system, this nascent state iron is compared with the nanometer molysite and is had more activity, and dispersed, good stability, particle is difficult to secondary agglomeration, therefore can remedy the deficiency of various catalyst; 2. preparation technology is simple, is easy to amplify carry out industrialization production.
The specific embodiment
High-efficient iron-series catalyst of the present invention is dispersed in the solid catalyst carrier micropore less than the iron particle of 100nm by particle diameter to be formed.
The preparation method of high-efficient iron-series catalyst of the present invention is made up of following steps:
1. in autoclave, add the solid catalyst carrier, vacuumize or with air in high purity nitrogen or the inert gas replacement still, adding iron pentacarbonyl liquid;
2. start heater, be incubated after being heated to temperature, make iron pentacarbonyl in reactor, be evaporated to steam and fully expand, infiltrate in the catalyst carrier micropore;
3. continue to heat up or press high pure nitrogen or other inert gas, make the iron pentacarbonyl decomposition in situ that is adsorbed in the carrier micropore, obtain the nano-level iron particle to reactor Nei Tonggao temperate zone;
4. cooling is discharged gas to exhaust treatment system, and the nanometer iron-series catalyst finished product that makes is put into the packing that is full of high pure nitrogen or other inert gas, and sealing is preserved.
Among the preparation method of high-efficient iron-series catalyst of the present invention, the 1. middle solid catalyst carrier of step is zeolite, active carbon, γ-Al
2O
3, at least a in diatomite, coke, coal dust or other porous material, iron pentacarbonyl liquid accounts for the 0.1-0.8 of reactor volume.
Among the preparation method of high-efficient iron-series catalyst of the present invention, the 2. middle heating-up temperature of step is 60-285 ℃, preferably 80 ℃ of 103-1, and insulation 0.5-2h.
Among the preparation method of high-efficient iron-series catalyst of the present invention, step 3. described in high temperature be 200-400 ℃, the insulation 0.1-1h, high purity inert gas pressure is 5-10MPa.
Embodiment 1
Zeolite is added in the autoclave of 2L, logical nitrogen replacement goes out residual air in still and the pipeline, add 200ml iron pentacarbonyl liquid, be heated to 60 ℃ of insulation 2h, continue to be heated to 200 ℃, insulation 1h, cooling, open drain tap and discharge gas reactor, obtain nanometer iron-series catalyst, nanometer iron-series catalyst takes out puts into the airtight preservation of the packaging bag that is full of high purity nitrogen.
Above-mentioned nanometer iron-series catalyst is applied to the DCL/Direct coal liquefaction experiment: use Huo Lin river brown coal, with the hydrogenated residue is solvent, 350 ℃ of reaction temperatures, initial hydrogen pressure 6MPa, catalyst addition 3%, press Fe: the S mass ratio adds Cosan, reaction time 1.5 hour at 2: 3, coal conversion ratio 84.3%, oil-collecting ratio 56.2%.
Embodiment 2
Adopt the preparation method identical with embodiment 1 to produce nanometer iron-series catalyst, wherein, solid catalyst is an active carbon, iron pentacarbonyl liquid 800ml, and 1 03 ℃ of heating-up temperatures, insulation 1.2h continues to be heated to 250 ℃ and is incubated half an hour.Coal is changed to Shenhua east victory brown coal carries out coal liquefaction experiment, coal conversion ratio 83.2%, oil-collecting ratio 58.7%.
Embodiment 3
Coke is added in the autoclave, logical nitrogen replacement goes out residual air in still and the pipeline, add 1600ml iron pentacarbonyl liquid, be heated to 180 ℃ of insulation 2h, feed temperature then and be 400 ℃, pressure and be the high pure nitrogen insulation 0.1 hour of 5MPa, cooling, open drain tap and discharge gas reactor, obtain nanometer iron-series catalyst, take out nanometer iron-series catalyst and put into the packaging bag that is full of high purity nitrogen, airtight preservation.
Above-mentioned nanometer iron-series catalyst is applied to the DCL/Direct coal liquefaction experiment: use Huo Lin river brown coal, with the naphthane is solvent, 350 ℃ of reaction temperatures, initial hydrogen pressure 6MPa, catalyst addition 4%, press Fe: the S mass ratio adds Cosan, reaction time 0.5 hour at 2: 3, coal conversion ratio 93.8%, oil-collecting ratio 59%.
Embodiment 4
Adopt the preparation method identical with embodiment 3 to produce nanometer iron-series catalyst, wherein the solid catalyst carrier is γ-Al
2O
3, iron pentacarbonyl liquid 400ml, 285 ℃ of insulations of heating-up temperature 0.5h, the high pure nitrogen that feeds 300 ℃ of pressure 8MPa of temperature then is incubated half an hour.Coal is changed to Shenhua east victory brown coal carries out coal liquefaction experiment, coal conversion ratio 92.1%, oil-collecting ratio 60.5%.
Embodiment 5
Adopt the preparation method identical with embodiment 3 to prepare nanometer iron-series catalyst, wherein solid catalyst is a diatomite, 280 ℃ of pressure 10MPa of feeding temperature high pure nitrogen.Coal is changed to Shenhua east victory brown coal carries out coal liquefaction experiment, coal conversion ratio 86.6%, oil-collecting ratio 59.4%.
Claims (6)
1. high-efficient iron-series catalyst is characterised in that: it is dispersed in the solid catalyst carrier micropore less than the iron particle of 100nm by particle diameter forms.
2. the preparation method of the described high-efficient iron-series catalyst of claim 1 is characterized in that this method is made up of following steps:
1. in autoclave, add the solid catalyst carrier, vacuumize or with air in high purity nitrogen or the inert gas replacement still, adding iron pentacarbonyl liquid;
2. start heater, be incubated after being heated to temperature, make iron pentacarbonyl in reactor, be evaporated to steam and fully expand, infiltrate in the catalyst carrier micropore;
3. continue to heat up or press high pure nitrogen or other inert gas, make the iron pentacarbonyl decomposition in situ that is adsorbed in the carrier micropore, obtain the nano-level iron particle to reactor Nei Tonggao temperate zone;
4. cooling is discharged gas to exhaust treatment system, and the nanometer iron-series catalyst finished product that makes is put into the packing that is full of high pure nitrogen or other inert gas, and sealing is preserved.
3. the preparation method of high-efficient iron-series catalyst according to claim 2 is characterized in that: step 1. in the solid catalyst carrier be zeolite, active carbon, γ-Al
2O
3, at least a in diatomite, coke, coal dust or other porous material.
4. the preparation method of high-efficient iron-series catalyst according to claim 2, it is characterized in that: iron pentacarbonyl liquid accounts for the 0.1-0.8 of reactor volume.
5. the preparation method of high-efficient iron-series catalyst according to claim 2 is characterized in that: step 2. in heating-up temperature be 60-285 ℃, preferably at 103-180 ℃, insulation 0.5-2h.
6. the preparation method of high-efficient iron-series catalyst according to claim 2 is characterized in that: step 3. described in high temperature be 200-400 ℃, insulation 0.1-1h, high purity inert gas pressure is 5-10MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100228198A CN101099932B (en) | 2007-05-23 | 2007-05-23 | High-efficient iron-series catalyst and its preparation method |
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|---|---|---|---|
| CN2007100228198A CN101099932B (en) | 2007-05-23 | 2007-05-23 | High-efficient iron-series catalyst and its preparation method |
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| CN101099932A true CN101099932A (en) | 2008-01-09 |
| CN101099932B CN101099932B (en) | 2010-04-21 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009106567A1 (en) * | 2008-02-27 | 2009-09-03 | Basf Se | Method for the production of iron-doped carbons |
| WO2010051619A1 (en) * | 2008-11-10 | 2010-05-14 | Institut National De La Recherche Scientifique | Catalyst precursors, catalysts and methods of producing same |
| WO2011073123A2 (en) | 2009-12-18 | 2011-06-23 | Basf Se | Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides |
| CN104001532A (en) * | 2014-05-12 | 2014-08-27 | 昆明理工大学 | Preparation method for supported metal cluster catalyst |
| CN105967242A (en) * | 2016-05-11 | 2016-09-28 | 江油核宝纳米材料有限公司 | Preparation method of nano carbonyl iron powder |
| CN111484158A (en) * | 2020-04-03 | 2020-08-04 | 镇江江南化工有限公司 | Pretreatment method of glyphosate production wastewater |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3428121A1 (en) * | 1984-07-31 | 1986-02-13 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING IRON POWDER |
| CN1159259C (en) * | 2002-04-05 | 2004-07-28 | 北京化工大学 | A kind of preparation method of nanometer metal particle/carbon composite material |
| CN100364549C (en) * | 2006-04-12 | 2008-01-30 | 浙江大学 | Iron supplement for loaded superfine iron powder, preparation method and application |
| CN1857775A (en) * | 2006-06-05 | 2006-11-08 | 浙江大学 | Carbonyl nickel powder and carbonyl iron powder on palygorskite carrier and their preparing method |
-
2007
- 2007-05-23 CN CN2007100228198A patent/CN101099932B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009106567A1 (en) * | 2008-02-27 | 2009-09-03 | Basf Se | Method for the production of iron-doped carbons |
| WO2010051619A1 (en) * | 2008-11-10 | 2010-05-14 | Institut National De La Recherche Scientifique | Catalyst precursors, catalysts and methods of producing same |
| WO2011073123A2 (en) | 2009-12-18 | 2011-06-23 | Basf Se | Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides |
| US9517461B2 (en) | 2009-12-18 | 2016-12-13 | Basf Se | Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides |
| CN104001532A (en) * | 2014-05-12 | 2014-08-27 | 昆明理工大学 | Preparation method for supported metal cluster catalyst |
| CN104001532B (en) * | 2014-05-12 | 2017-04-12 | 昆明理工大学 | Preparation method for supported metal cluster catalyst |
| CN105967242A (en) * | 2016-05-11 | 2016-09-28 | 江油核宝纳米材料有限公司 | Preparation method of nano carbonyl iron powder |
| CN105967242B (en) * | 2016-05-11 | 2018-02-06 | 江油核宝纳米材料有限公司 | The preparation method of nanometer carbonyl iron dust |
| CN111484158A (en) * | 2020-04-03 | 2020-08-04 | 镇江江南化工有限公司 | Pretreatment method of glyphosate production wastewater |
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| CN101099932B (en) | 2010-04-21 |
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