CN1321740C - Catalyst of preparaing ethylene and synthetic gas using methane and carbon dioxide coactivation method - Google Patents
Catalyst of preparaing ethylene and synthetic gas using methane and carbon dioxide coactivation method Download PDFInfo
- Publication number
- CN1321740C CN1321740C CNB2004100219551A CN200410021955A CN1321740C CN 1321740 C CN1321740 C CN 1321740C CN B2004100219551 A CNB2004100219551 A CN B2004100219551A CN 200410021955 A CN200410021955 A CN 200410021955A CN 1321740 C CN1321740 C CN 1321740C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tio
- hours
- ceo
- methane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a preparation process of a coactivating catalyst of methane and carbon dioxide, and an application of the catalyst. The catalyst adopts TiO2, CeO2 and r-Al2O3 as carriers, and one to three kinds of the nitrate of Ca, Mg, Ni, Co, Fe, etc. as active constituents, and the granular catalyst is prepared by an impregnating method; then, the monolithic catalyst is prepared by using cordierite as a second carrier; the granular catalyst and the monolithic catalyst are applied to the preparation of ethene and synthetic gas by the coactivation of the methane and the carbon dioxide. The present invention has simple method, cheap raw materials and easy obtainment of the raw materials, and the present invention has important theoretical significance and actual significance.
Description
The present invention relates to a kind of methane and carbon dioxide co-activating Preparation of catalysts method.
Methane and carbon dioxide are contained abundant but reactivity is lower at occurring in nature, thus the activation utilization of the two be in the chemistry one have challenging problem, and a large amount of relevant reports is arranged.
Methane vapor transforms last synthetic ammonia, methyl alcohol and Related product, and this technology is comparative maturity, is in the batch process stage, but the increment of natural gas is little.
Last century, the eighties, the later stage began with O
2For oxidant carries out the partial oxidation utilization research of methane, as methane oxidation coupling system ethene and methyl hydride catalyzed portion oxidation synthesis gas etc.
Reaction for methane oxidation coupling system ethene: 2CH
4+ O
2=C
2H
4+ 2H
2O/ Δ rH
0 298K=-282KJ/mol Δ rG
0 298K=-287KJ/mol once was considered to utilize the most direct effective method of natural gas.In recent years, the research of methane oxidation coupling had obtained gratifying progress, and wherein Yoon etc. [Appl.Catal.A:1997,161:L5-L10] is with the Na of precipitation method preparation
4P
2O
4-ZrOCl
2Catalyst and Na
+-ZrO
2-Cl
-/ SiO
2Catalyst, the catalytic performance that in reaction, shows, the former C
2Selectivity reaches 79%, CH
4Conversion ratio reaches 28%.The problem that exists in the research of methane oxidation coupling system ethene is: poor catalyst stability, because this reaction is the high temperature strong exothermal reaction, easily cause the beds temperature runaway, and make catalyst efflorescence inactivation; Deep oxidation easily takes place in methane and ethene simultaneously, generates CO
x(x=0,1,2).
Since the above problem that oxidative coupling of methane exists, so the reaction of methyl hydride catalyzed portion oxidation synthesis gas has caused people's attention in recent years, CH
4+ 1/2O
2=CO+2H
2Δ rH
0 298K=-36KJ/mol/ Δ rG
0 298K=-86KJ/mol.This reaction is gentle exothermic reaction, and mainly carrying out from hot mode, energy consumption is low; The selectivity height of methane conversion and synthesis gas, H in the synthesis gas that reaction simultaneously generates
2With the CO mol ratio be 2, need not adjust processes such as just being suitable for synthetic gasoline (F-T synthetic), synthesizing methanol.But because this process adopts air oxidant, subsequent technique does not allow nitrogen to exist again, therefore need carry out the sky branch before reaction, empty at present method of dividing general employing cryogenic freezing or transformation absorption, and these method investments are very big; This type of reaction system exists the danger of blasting simultaneously, and reaction condition is comparatively harsh.
Carbon dioxide be to methane carry out another important oxidant of activation utilization, this type of reaction also claims methane and carbon dioxide co-activating.Mainly contain preparing synthetic gas by reforming methane with carbon dioxide and synthetic C of one step of carbon dioxide oxidizing of methylene
2Hydrocarbon.
The reaction equation of preparing synthetic gas by reforming methane with carbon dioxide is: CH
4+ CO
2=2CO+2H
2Δ rH
0 298K=247KJ/mol Δ rG
0 298K=172KJ/mol.H in the synthesis gas that this reaction produces
2/ CO value approaches 1, is suitable for the preparation of the synthetic and oxygen-containing organic compound of carbonyl.Loaded noble metal catalyst is the reforming catalyst of effective methane and carbon dioxide, and it is Ru＞Pd＞Rh＞Pt＞Ir in proper order that Solymosi etc. [Catal.Lett., 1991.11.149] provide its catalytic activity.Use noble metal to make catalyst, production cost is higher, exists carbon distribution problem catalyst short service life simultaneously.
Synthetic C of one step of carbon dioxide oxidizing of methylene
2The hydrocarbon reaction formula is:
2CH
4+2CO
2＝C
2H
4+2CO+H
2O/ΔrH
0 298K＝196.28KJ/mol/ΔrG
0 298K＝209.54KJ/mol2CH
4+CO
2＝C
2H
6+CO+H
2O/ΔrH
0 298K＝62.18KJ/mol/ΔrG
0 298K＝88.61KJ/mol
The existing research method that report adopted about this route mainly contains two kinds at present: catalytic activation method and plasma method.Most of metal oxides all have certain C2 hydrocarbon-selective, and wherein rare earth oxide catalyst has C preferably
2Hydrocarbon-selective [Kenji Asami et al.Appl.Catal., 1995,126:245-255].But generally speaking, reaction-ure conversion-age and C
2The hydrocarbon yield is all not as people's will.The CO of this route generation yet needs to seek to utilize method simultaneously.
The methane and carbon dioxide co-activating be badly in need of to be sought new response path to reduce reaction temperature, reduces carbon distribution, improves the conversion ratio of reactant, thereby and enhancing and being connected of subsequent technique the added value that promotes natural gas etc.
Integral catalyzer is used more in the research of the catalyst combustion reaction of methane as [Ryuji Kikuchj, etal.Appl.Catal., A:239 (2003) 169-179] etc.But be applied to methane and the carbon dioxide co-activating yet there are no report.
The present invention aims to provide a kind of co-activating methane and carbon dioxide producing the effective catalyst of ethene and synthesis gas, changing the limitation of prior art, and a kind of new purposes of exploitation methane.
Technical scheme of the present invention: with TiO
2, CeO
2And r-Al
2O
3Being carrier, is that the catalyst activity component prepares powder catalyst with Ca, Mg, Ni, Co, Fe, La, W etc. wherein a kind or 2-3, and wherein active component is 1-25% with respect to the weight content Ca and the Mg of carrier, and Ni, Co and Fe are 0.1-15%.The gross weight content of various active component is 0.1-30%, and the powder catalyst of being formed is Ca-Ni/TiO
2, Mg-Ni/TiO
2, Co/r-Al
2O
3, Fe/r-Al
2O
3, Ca-Ni/CeO
2, Ca/CeO
2, Mg-Ni/CeO
2, Mg-Ni-La/TiO
2
Above-mentioned carrier is ground, screening 20-60 purpose particle, 400-700 ℃ aging 2-3 hour down, use the solution impregnating carrier of active component again, leave standstill, ageing.The supernatant liquor that inclines, vacuum drying.400-650 ℃ keeps carrying out in 2-6 hour thermal decomposition down in the air stream that air blast forms.Make pellet type catalyst.(seeing accompanying drawing)
Above-mentioned preparation technology's optimum condition is: carrier granular 20-40 order, 500-600 ℃ of carrier aging temperature, heat decomposition temperature 500-550 ℃, thermal decomposition time 3-4 hour.
Grinding carrier is selected the particle between the 80-150 order, takes the preparation method identical with pellet type catalyst to make powder catalyst, and again with cordierite cut growth 18-22mm, diameter was the cylinder of 12mm, at 400-700 ℃ of aging 3-6 hour.Then the powder catalyst that makes is added water for ball milling slurrying, and the cordierite cylinder is immersed into carries out coating in the gained slurries.With the cordierite after the coating in 120 ℃ of oven dry, 400-700 ℃ roasting 2-5 hour.Make integral catalyzer.(seeing accompanying drawing)
Above-mentioned preparation technology's optimum condition is: carrier granular 80-100 order, 450-550 ℃ of cordierite aging temperature, ageing time 3-4 hour, sintering temperature 450-600 ℃, roasting time 3-4 hour.
Preparation is during catalyst, and each active component can be with oxide, salt and the alkali etc. of this element.For example Ca can use CaO, Ca (OH)
2, CaCl
26H
2O or Ca (NO
3)
24H
2O etc.; Mg can use MgO, MgCl
2Or Mg (NO
3)
26H
2O etc.; Ni can use NiCl
26H
2O and Ni (NO
3)
26H
2O etc.; Co can use Co (OAc)
2, Co (NO
3)
26H
2O, CoCl
2Deng; Fe can use FeCl
3, Fe
2O
3, Fe
3O
4, Fe (NO
3)
39H
2O, Fe (OAc)
2, FeC
2O
42H
2O, Fe
2(C
2O
4)
36H
2O etc.; W Na
2WO
4Deng; La can use La
2O
3, La (NO
3)
36H
2O etc.
Compared with the prior art the present invention has following characteristics: the preparation method is simple, and raw material is cheap and easy to get.Be used for the co-activating reaction of methane and carbon dioxide, the ethene of generation and synthesis gas can be used for the synthetic reaction of propionic aldehyde, and this is mature technology.The present invention is for alleviating energy crisis, reduces methane and emission of carbon-dioxide, and what alleviate that " greenhouse effects " cause has far reaching significance to environment damage.
Embodiment 1,
Grind TiO
2, screening 40-60 purpose particle wore out 3 hours in 500 ℃.Take by weighing 6.195 gram Ca (NO
3)
24 H
2O and 0.039 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 500 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Ca-Ni/TiO
2, the activity of such catalysts constituent content is Ca-21Wt%, Ni-0.15Wt%.
Embodiment 2,
Grind TiO
2, screening 40-60 purpose particle wore out 3 hours in 500 ℃.Take by weighing 2.065 gram Ca (NO
3)
24 H
2O and 0.257 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 500 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Ca-Ni/TiO
2, the activity of such catalysts constituent content is Ca-7Wt%, Ni-1Wt%.
Embodiment 3,
Grind TiO
2, screening 20-40 purpose particle wore out 3 hours in 500 ℃.Take by weighing 2.065 gram Ca (NO
3)
24 H
2O and 1.285 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Ca-Ni/TiO
2, the activity of such catalysts constituent content is Ca-7Wt%, Ni-5Wt%.
Embodiment 4,
Grind TiO
2, screening 20-40 purpose particle wore out 3 hours in 700 ℃.Take by weighing 7.467 gram Mg (NO
3)
26H
2O and 0.039 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Mg-Ni/TiO
2, the activity of such catalysts constituent content is Mg-14Wt%, Ni-0.15Wt%.
Embodiment 5,
Grind TiO
2, screening 20-40 purpose particle wore out 3 hours in 700 ℃.Take by weighing 5.334 gram Mg (NO
3)
26H
2O and 1.285 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Mg-Ni/TiO
2, the activity of such catalysts constituent content is Mg-10Wt%, Ni-5Wt%.
Embodiment 6,
Grind r-Al
2O
3, screening 20-40 purpose particle wore out 3 hours in 500 ℃.Take by weighing 0.794 gram Co (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 3 gram r-Al
2O
3In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 500 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Co/r-Al
2O
3, the activity of such catalysts constituent content is Co-5Wt%.
Embodiment 7,
Grind r-Al
2O
3, screening 20-40 purpose particle wore out 3 hours in 700 ℃.Take by weighing 1.429 gram Co (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 3 gram r-Al
2O
3In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Co/r-Al
2O
3, the activity of such catalysts constituent content is Co-9Wt%.
Embodiment 8,
Grind r-Al
2O
3, screening 20-40 purpose particle wore out 3 hours in 500 ℃.Take by weighing 1.154 gram Fe (NO
3)
29H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 3 gram r-Al
2O
3In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Fe/r-Al
2O
3, the activity of such catalysts constituent content is Fe-5Wt%.
Embodiment 9,
Grind r-Al
2O
3, screening 20-40 purpose particle wore out 3 hours in 500 ℃.Take by weighing 2.077 gram Fe (NO
3)
29H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 3 gram r-Al
2O
3In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Fe/r-Al
2O
3, the activity of such catalysts constituent content is Fe-9Wt%.
Embodiment 10,
Grind CeO
2, screening 40-60 purpose particle wore out 3 hours in 600 ℃.Take by weighing 4.720 gram Ca (NO
3)
24 H
2O and 0.041 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 8 gram CeO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Ca-Ni/CeO
2, the activity of such catalysts constituent content is Ca-10Wt%, Ni-0.1Wt%.
Embodiment 11,
Grind CeO
2, screening 40-60 purpose particle wore out 3 hours in 600 ℃.Take by weighing 4.720 gram Ca (NO
3)
24H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 8 gram CeO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Ca/CeO
2, the activity of such catalysts constituent content is Ca-10Wt%.
Embodiment 12,
Grind CeO
2, screening 40-60 purpose particle wore out 3 hours in 600 ℃.Take by weighing 5.973 gram Mg (NO
3)
26H
2O and 0.041 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 8 gram CeO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Mg-Ni/CeO
2, the activity of such catalysts constituent content is Mg-7Wt%, Ni-0.1Wt%.
Embodiment 13,
Grind TiO
2, screening 20-40 purpose particle wore out 3 hours in 600 ℃.Take by weighing 3.734 gram Mg (NO
3)
26H
2O, 1.285 gram Ni (NO
3)
26H
2O and 0.358 gram La (NO
3)
36H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours, the cooling back is stand-by naturally.Catalyst consist of Mg-Ni-La/TiO
2, the activity of such catalysts constituent content is Mg-7Wt%, Ni-5Wt%, La-2Wt%.
Embodiment 14,
Grind TiO
2, screening 80-100 purpose particle wore out 3 hours in 500 ℃.Take by weighing 6.195 gram Ca (NO
3)
24 H
2O and 0.039 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 500 ℃ of thermal decompositions 3 hours.The Ca-Ni/TiO that makes
2(then long 20mm, the cordierite cylinder of diameter 12mm immerses in the slurries catalyst, leaves standstill 2 hours for Ca-21Wt%, Ni-0.15Wt%) ball milling slurrying.Take out cordierite, 120 ℃ of oven dry, and in 500 ℃ of roastings 3 hours, the cooling back was stand-by naturally.Make integral catalyzer Ca-Ni/TiO
2, the activity of such catalysts constituent content is Ca-21Wt%, Ni-0.15Wt%.
Embodiment 15,
Grind TiO
2, screening 80-100 purpose particle wore out 3 hours in 500 ℃.Take by weighing 2.065 gram Ca (NO
3)
24H
2O and 0.257 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 500 ℃ of thermal decompositions 3 hours.The Ca-Ni/TiO that makes
2(then long 20mm, the cordierite cylinder of diameter 12mm immerses in the slurries catalyst, leaves standstill 2 hours for Ca-7Wt%, Ni-0.15Wt%) ball milling slurrying.Take out cordierite, 120 ℃ of oven dry, and in 500 ℃ of roastings 3 hours, the cooling back was stand-by naturally.Make integral catalyzer Ca-Ni/TiO
2, the activity of such catalysts constituent content is Ca-7Wt%, Ni-1Wt%.
Embodiment 16,
Grind CeO
2, screening 80-100 purpose particle wore out 3 hours in 600 ℃.Take by weighing 4.720 gram Ca (NO
3)
24H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 8 gram CeO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, and in 550 ℃ of thermal decompositions 3 hours.The Ca/CeO that makes
2The slurrying of catalyst (Ca-10Wt%) ball milling, then long 20mm, the cordierite cylinder of diameter 12mm immerses in the slurries, leaves standstill 2 hours.Take out cordierite, 120 ℃ of oven dry, and in 500 ℃ of roastings 3 hours, the cooling back was stand-by naturally.Make integral catalyzer Ca/CeO
2, the activity of such catalysts constituent content is Ca-10Wt%.
Embodiment 17,
Grind CeO
2, screening 80-100 purpose particle wore out 3 hours in 600 ℃.Take by weighing 0.041 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 8 gram CeO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, and in 550 ℃ of thermal decompositions 3 hours.The Ni/CeO that makes
2The slurrying of catalyst (Ni-0.1Wt%) ball milling, then long 20mm, the cordierite cylinder of diameter 12mm immerses in the slurries, leaves standstill 2 hours.Take out cordierite, 120 ℃ of oven dry, and in 500 ℃ of roastings 3 hours, the cooling back was stand-by naturally.Make integral catalyzer Ni/CeO
2, the activity of such catalysts constituent content is Ni-0.1Wt%.
Embodiment 18,
Grind TiO
2, screening 80-100 purpose particle wore out 3 hours in 500 ℃.Take by weighing 2.065 gram Ca (NO
3)
24H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 500 ℃ of thermal decompositions 3 hours.The Ca/TiO that makes
2The slurrying of catalyst (Ca-7Wt%) ball milling, then long 20mm, the cordierite cylinder of diameter 12mm immerses in the slurries, leaves standstill 2 hours.Take out cordierite, 120 ℃ of oven dry, and in 500 ℃ of roastings 3 hours, the cooling back was stand-by naturally.Make integral catalyzer Ca/TiO
2, the activity of such catalysts constituent content is Ca-7Wt%.
Embodiment 19,
Grind TiO
2, screening 100-140 purpose particle wore out 3 hours in 700 ℃.Take by weighing 5.334 gram Mg (NO
3)
26H
2O and 1.285 gram Ni (NO
3)
26H
2O is dissolved in 10 ml distilled waters, then gained solution is poured into 5 gram TiO
2In.After still aging 24 hours, supernatant liquor inclines.Vacuum drying, 550 ℃ of thermal decompositions 3 hours.The catalyst Mg-Ni/TiO that makes
2(then long 20mm, the cordierite cylinder of diameter 12mm immerses in the slurries, leaves standstill 2 hours for Mg-10Wt%, Ni-5Wt%) ball milling slurrying.Take out cordierite, 120 ℃ of oven dry, and in 500 ℃ of roastings 3 hours, the cooling back was stand-by naturally.Make integral catalyzer Mg-Ni/TiO, the activity of such catalysts constituent content is Mg-10Wt%, Ni-5Wt%.
Embodiment 20,
The present invention is used for the situation that methane and carbon dioxide co-activating are produced ethene and synthesis gas.
| Catalyst | Temperature (℃) | Methane conversion (%) | Hydrogen selective (%) | Carbon monoxide selective (%) | Ethylene selectivity (%) |
| Ca/CeO 2(10Wt%) graininess | 700 | 56.62 | 12.87 | ?82.58 | ?4.55 |
| Ca-Ni/TiO 2(21,0.15Wt%) graininess | 700 | 37.69 | 20.16 | ?71.43 | ?8.41 |
| Co/r-Al 2O 3(5Wt%) graininess | 780 | 12.17 | 23.80 | ?63.57 | ?1.54 |
| Fe/r-Al 2O 3(5Wt%) graininess | 800 | 12.95 | 20.12 | ?78.85 | ?1.42 |
| Ca-Ni/TiO 2(21,0.15Wt%) monoblock type | 750 | 5.25 | 12.59 | ?76.35 | ?11.05 |
| 770 | 11.21 | 11.91 | ?73.77 | ?14.32 | |
| Ca-Ni/TiO 2(7,0.15Wt%) monoblock type | 750 | ?5.53 | ?16.91 | ?67.09 | ?16.00 |
| 780 | ?12.90 | ?8.79 | ?78.92 | ?12.29 |
Claims (3)
1, methane and carbon dioxide co-activating are produced the preparation method of the integral catalyzer of ethene and synthesis gas, it is characterized in that:
1., with TiO
2, CeO
2Or γ-Al
2O
3Be carrier, among Ca, Mg, Ni, Co, Fe, the La a kind or 2-3 kind prepare powder catalyst for the catalyst activity component, wherein active component is 1-25% with respect to the weight content Ca and the Mg of carrier, Ni, Co and Fe are 0.1-15%, the gross weight of various active component is 0.1-30%, and the powder catalyst of being formed is Ca-Ni/TiO
2, Mg-Ni/TiO
2, Co/ γ-Al
2O
3, Fe/ γ-Al
2O
3, Ca-Ni/CeO
2, Mg-Ni/CeO
2, Mg-Ni-La/TiO
2
2., with carrier TiO
2, CeO
2Or γ-Al
2O
3Grind, screening 80-150 purpose particle wore out 2-3 hour down at 400-700 ℃;
3., will be 1. described in the nitrate of catalyst activity component be dissolved in the water, impregnated carrier 20-30 hour, the supernatant liquor that inclines, vacuum drying then;
4., 400-650 ℃ of following roasting decomposed 2-6 hour in air stream, made powder catalyst;
5., with cordierite cut growth 18-22mm, the cylinder of diameter 12mm, 400-700 ℃ aging 3-6 hour down;
6., powder catalyst adding distil water ball milling slurrying that step is made in 4., step 5. in the good cordierite cylinder of preliminary treatment be immersed into and carry out coating in the gained slurries;
7., with the cordierite after the coating in 120 ℃ of oven dry, 400-700 ℃ roasting 2-5 hour, make integral catalyzer.
2, by the described method of claim 1, it is characterized in that said nitrate is Ni (NO
3)
26H
2O, Ca (NO
3)
24H
2O, Mg (NO
3)
26H
2O, Co (NO
3)
26H
2O, Fe (NO
3)
39H
2O, La (NO
3)
36H
2O.
3, by the described method of claim 1, it is characterized in that said carrier TiO
2, CeO
2Or γ-Al
2O
3Particle is the 80-100 order.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100219551A CN1321740C (en) | 2004-03-03 | 2004-03-03 | Catalyst of preparaing ethylene and synthetic gas using methane and carbon dioxide coactivation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100219551A CN1321740C (en) | 2004-03-03 | 2004-03-03 | Catalyst of preparaing ethylene and synthetic gas using methane and carbon dioxide coactivation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1559674A CN1559674A (en) | 2005-01-05 |
| CN1321740C true CN1321740C (en) | 2007-06-20 |
Family
ID=34440940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100219551A Expired - Fee Related CN1321740C (en) | 2004-03-03 | 2004-03-03 | Catalyst of preparaing ethylene and synthetic gas using methane and carbon dioxide coactivation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1321740C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744080A (en) * | 2012-06-19 | 2012-10-24 | 东南大学 | Composite Fe3O4 type structured catalyst used for hydrogen production from methane, and preparation method thereof |
| CN107108401A (en) * | 2014-12-09 | 2017-08-29 | 沙特基础工业全球技术公司 | By the way that methane oxidation coupling is reacted into the method for combining and producing ethene and synthesis gas with methane dry reforming |
| CN109289833B (en) * | 2018-10-30 | 2021-08-03 | 中国科学院兰州化学物理研究所 | Preparation method of catalyst for preparing ethylene solid acid by oxidative coupling of methane |
| CN112403470B (en) * | 2020-11-25 | 2023-07-14 | 陕西榆大科技发展有限公司 | Catalyst for preparing synthetic gas by reforming methane and carbon dioxide and application thereof |
-
2004
- 2004-03-03 CN CNB2004100219551A patent/CN1321740C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| FE2O3/YSZ－γ－AL2O3催化剂在甲烷催化剂燃烧中的催化性能研究 李丽娜等，高等学校化学学报，第24卷第12期 2003 * |
| FE2O3/YSZ－γ－AL2O3催化剂在甲烷催化剂燃烧中的催化性能研究 李丽娜等，高等学校化学学报，第24卷第12期 2003;ZRO2、Y2O3、对CH4燃烧催化剂FE2O3/γ－AL2O3的改性作用 李丽娜等，化学研究与应用，第15卷第1期 2003;过渡金属氧化物催化剂上甲烷催化燃烧的研究 张鑫等，化学研究与应用，第14卷第3期 2003;金属与CEO2、TIO2相互作用的研究 谭晓燕等，天然气化工，第26卷第3期 2001;整体式甲烷燃烧催化剂的活性研究 唐晓兰等，天然气化工，第25卷第6期 2000 * |
| ZRO2、Y2O3、对CH4燃烧催化剂FE2O3/γ－AL2O3的改性作用 李丽娜等，化学研究与应用，第15卷第1期 2003 * |
| 整体式甲烷燃烧催化剂的活性研究 唐晓兰等，天然气化工，第25卷第6期 2000 * |
| 过渡金属氧化物催化剂上甲烷催化燃烧的研究 张鑫等，化学研究与应用，第14卷第3期 2003 * |
| 金属与CEO2、TIO2相互作用的研究 谭晓燕等，天然气化工，第26卷第3期 2001 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1559674A (en) | 2005-01-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100903439B1 (en) | Preparation method of direct synthesis of light hydrocarbons from natural gas | |
| KR20150058219A (en) | Hydrogen generation catalyst and method for producing hydrogen | |
| CN110975938A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN111389404A (en) | Preparation method and application of cerium oxide supported nickel catalyst | |
| CN108043406B (en) | A kind of derivative cobalt-base catalyst of auxiliary agent promotion hydrotalcite of acetic acid self-heating reforming hydrogen manufacturing | |
| CN109796428A (en) | A kind of copper-based catalysts add the application in hydrogen in 5 hydroxymethyl furfural | |
| CN114768859B (en) | Nickel-silicon catalyst suitable for methane dry reforming and preparation method thereof | |
| CN109999878A (en) | For photo catalytic reduction CO2Nonmetal doping Co3O4-CeO2Composite catalyst and preparation method thereof | |
| CN101890361B (en) | Preparation method of catalyst for use in highly selective preparation of gasoline fractions from synthesis gas | |
| CN111389405B (en) | Method for preactivating methane vapor hydrogen production catalyst | |
| CN111151245B (en) | Gold nanoflower catalyst with biomass activated carbon as carrier and preparation method and application thereof | |
| CN114887625B (en) | Fe-based metal organic framework material derivative catalyst and preparation method and application thereof | |
| CN110508315A (en) | A kind of catalyst for preparing hydrogen by reforming methanol and water vapour and preparation method thereof | |
| CN101972656A (en) | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof | |
| CN100478071C (en) | Catalyst for making synthetic gas from methane by catalyzing partly oxidation and its preparation method | |
| CN101249434A (en) | Methane transform preparing ethylene and preparation of dual-function catalyst of synthesis gas | |
| CN104447248A (en) | Preparation method for anhydrous formaldehyde | |
| CN1321740C (en) | Catalyst of preparaing ethylene and synthetic gas using methane and carbon dioxide coactivation method | |
| CN111450834B (en) | Ceria-supported cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen | |
| CN104549342A (en) | Iron catalyst for preparing light olefins by use of synthesis gas and preparation method of iron catalyst | |
| CN111359644B (en) | Non-noble metal-based molybdenum carbide catalyst for dimethyl ether steam reforming hydrogen production and preparation method and application thereof | |
| CN109851473B (en) | Method for preparing 1,3-propylene glycol by hydrogenolysis of glycerol solution | |
| CN1176746C (en) | Fischer-Tropsch catalyst and its preparing process | |
| CN115155571A (en) | Reduced metal catalyst and preparation method and application thereof | |
| CN104275189A (en) | High-temperature sintering type catalyst for preparing light olefins from synthetic gas and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070620 Termination date: 20120303 |