CN1736591A - Natural gas partial oxidation catalyst prepared by making hydrotalcite as predecessor - Google Patents
Natural gas partial oxidation catalyst prepared by making hydrotalcite as predecessor Download PDFInfo
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- CN1736591A CN1736591A CNA2005100440727A CN200510044072A CN1736591A CN 1736591 A CN1736591 A CN 1736591A CN A2005100440727 A CNA2005100440727 A CN A2005100440727A CN 200510044072 A CN200510044072 A CN 200510044072A CN 1736591 A CN1736591 A CN 1736591A
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- catalyst
- hydrotalcite
- oxide
- predecessor
- natural gas
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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
- 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
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Abstract
The invention provides an oxidative catalyst prepared with hydrotalcite as the forerunner material, which comprises (wt %): 5- 40% NiO, 5- 15% Fe2O3, and the rest being MgO, Al2O3, and the oxides of other transient metal element, the mole ratio of divalent metallic ion to trivalent metal ion in whole oxides being among 1: 1- 10: 1. The catalyst has a perfect reaction activity and a high selectivity.
Description
(1) technical field:
The present invention relates to the synthetic and conversion of natural gas field of catalyst.
(2) background technology
With conversion of natural gas is synthesis gas (CO and H
2), again by fuel such as the cleaning vapour of synthetic not sulfur-bearing, nitrogen impurity of F-T, diesel oil, or the method for staple products such as synthesizing methanol, methyl ether is one of most important approach of conversion of natural gas.
With conversion of natural gas is that the conventional method of synthesis gas is to produce CO and H with water vapour and natural gas reaction
2, this reaction is the endothermic reaction, needs higher reaction temperature and consumes a large amount of heats.Desirable reaction path is directly to use O
2With the natural gas reaction, this reaction is little exothermic reaction, the reaction condition gentleness, and synthesis gas components is suitable, can simplify follow-up synthesis gas and form the step of regulating.The core of this technology is to use highly active catalyst, and ideal catalyst system is rhodium system and molybdenum carbide system, but rare, the unstability of material and kinetic limitation make this catalyst system fail to obtain commercial Application.Another kind of catalyst system is a nickel catalyst, and its tangible advantage is active high, and shortcoming is that carbon distribution is serious, inactivation is fast, utilizes the nickel/aluminium oxide catalyst of Prepared by Sol Gel Method, and the nickel particle is little, the decentralization height, catalyst stability is good, but activity of such catalysts is lower.With the calcium aluminate modified aluminas is the Raney nickel of preparing carriers, and catalyst activity is higher, but is subjected to preparation method's restriction, and the nickel particle is bigger, and reactivity is lower.
Hydrotalcite (Hydrotalcite, be called for short HT) be a kind of anionic clay of layer structure, complex metal hydroxide with layer structure, be to constitute by positively charged layers of metal hydroxides and interlayer balance anion, both had ion exchangeable, but have the aperture modulation again select shape absorption, catalytic performance.Hydrotalcite-based compound (Hydrotalcite-likeCompounds, abbreviation HTlc) structure of anionic clay is identical with HT, is stratiform complex hydroxide (Layered DoubleHydroxides is called for short LDH), this compounds occurring in nature exists less, mainly by artificial synthetic.This compound first Application in 1971 is in catalytic reaction, and then HTlc is used for hydrogenation reaction as base catalyst.With layered hydroxide ([Zn
0.67Al
0.33(OH)
2] (CO
3 2-)
0.170.33H
2O) Zn that makes after the roasting
0.67Al
0.33O
0.17Oxide solid solution and heteropolyacid anions α-[SiW with Keggin structure
11O
39]
8-And α-[SiV
3W
9O
4O]
7-Acid solution reaction can make compound with layer column structure.
Houghite has layer structure, its particle very thin (about 50nm), and interlamellar spacing is a nano-scale, belongs to the two-dimensional nano material.Have following characteristics: the layer structure that (1) is special causes crystalline field seriously asymmetric; (2) cation is in lattice, the interlayer of anion outside lattice.Because HTlc shows particular structure characteristic and excellent catalytic performance, in recent decades, by distinct methods synthetic anion, particularly heteropolyanion, synthetic, the sign of pillared hydrotalcite and the research of acid-base catalysis performance thereof are subjected to people's common concern.Heteropoly compound has acidity and oxidisability, and these character can be carried out system's design and regulation and control by changing component (equilibrium ion, central atom or coordination atom), are desirable acid type and oxidized form or bifunctional catalysts.There is literature research transition metal list to replace Keggin structure heteropolyanion SiW
11M (H
2O)
06-39(M=Mn
2+, Fe
2+, Co
2+, Ni
2+, Cu
2+, Zn
2+) pillared hydrotalcite shows that the heteropolyanion pillared hydrotalcite has the catalytic activity that is higher than hydrotalcite precursor and corresponding heteropolyacid salt, have soda acid two class catalytic active centers simultaneously, but the acid site is obviously stronger.
HTlc is the wide new inorganic material of a kind of range of application, can do catalyst (hydrogenation, Polymer Synthesizing and steam transforming), catalyst carrier (Ziegler one Natta), fire retardant, molecular sieve, ion-exchanger, stomach medicine, stabilization agent and adsorbent (halogen remover, PVC stabilizer and purification of waste water) or the like.HTlc has and the similar layer structure of imvite cationoid clay, and different is that skeleton is a cation, and interlayer is an anion, shows alkalescence, and interlamellar spacing can be come modulation by filling the different anion of ionic radius.In recent years, the application study of such structural compounds begins to be converted to the synthetic of the polywater talcum that contains transition metal.The hydrotalcite particular structure can make transition metal reach atom level and be evenly dispersed in the interior skeleton structure of layer, realizes that the superelevation of active component in the Preparation of Catalyst is disperseed.
Hydrotalcite as novel microporous catalyst mainly contains two big research directions at present, and the first is presoma with HTlc, will be embedded into its interlayer with many or heteropoly compound, is expected to obtain the multi-functional layer post catalysis material of large interlamellar spacing; It two is directly to utilize hydrotalcite as catalyst or obtained the application of mixed oxide catalyst by the hydrotalcite roasting.Hydrotalcite exists less at occurring in nature, utilize artificial synthesizing can get different divalent ions (Mg, Ni, Co, Zn etc.) and trivalent ion (Al, Cr, houghite material Fe).The quality of synthetic gained hydrotalcite degree of crystallinity, directly have influence on based on hydrotalcite, insert (as the heteropoly acid ion) is an object, the complete in crystal formation degree and the catalytic performance of the layer post catalyst that the carrying out of telescopiny and embedding back generate between main body one object, the hydrotalcite crystallization process is most important for this reason.Because different M
2+(divalent ion) and M
3+(trivalent ion) different in kind, synthetic corresponding HTlc condition differs greatly.
The houghite material is after its veneer structure of transition metal modulation and interlayer insert anion, and material has possessed the superelevation dispersiveness of transition metal, and with the synergy of interlayer anion.After further handling, can be used as the new catalytic material of highly active natural gas synthetic gas production process.
(3) summary of the invention:
At the deficiency that prior art exists, the invention provides a kind of have obvious high reaction activity and high and very high optionally be the natural gas partial oxidation catalyst that predecessor prepares with the hydrotalcite.
The present invention adopts following solution:
The constituent and the content of catalyst of the present invention are (by weight percentage): contain the nickel oxide NiO of 5%--40%, the di-iron trioxide Fe of 5--15%
2O
3, all the other constituents are magnesia MgO, aluminium oxide Al
2O
3And the oxide of other transition metal, the bivalent metal ion in all oxides and the mol ratio of trivalent metal ion are between 1: 1～10: 1.
Other transition metal comprises: Ca, Ba, Cr, Zn, La.
With the above-mentioned oxide and the isopolyacid or the heteropoly acid that contain Mo, W, Mn, Cr element that contains these metallic elements, the stratiform houghite predecessor that contains Mo, W, Mn, Cr element of the method preparation by ion-exchange, the catalyst that obtains preparing through 500 ℃ of high temperature roasts.
Or with the above-mentioned oxide process high temperature roast that contains these metallic elements, solution with the compound that contains Mo, W, Mn, Cr element or ion, the composite oxides that contain Mo, W, Mn, Cr element by the method preparation of dipping, through high temperature roast more than 500 ℃, the catalyst that obtains preparing.
To after 500 ℃ of roastings, be used to prepare C with the catalyst that said method makes
1～C
4Hydrocarbon compound portion oxidation synthesis gas process is as C
1～C
4The catalyst new material of hydrocarbon compound partial oxidation reaction is used for natural gas, biogas, casing-head gas, oil refinery dry gas, coke gas partial oxidation catalyst.
The present invention is that predecessor prepares catalyst with the hydrotalcite, has obvious high reaction activity and high and very high selectivity.
(4) specific embodiment:
Embodiment 1.Ni, Mg, Al-HTlc's is synthetic
Take by weighing 31.14 gram Ni (NO
3)
26H
2O, 358.3 gram Mg (NO
3)
26H
2O and 279.5 gram Al (NO
3)
39H
2O is dissolved in the 1300ml pure water; Taking by weighing 263.6 gram NaOH is dissolved in the 1500ml pure water.At N
2Protection is added drop-wise to salting liquid and NaOH solution in three mouthfuls of round-bottomed flasks of 5 liters down simultaneously, the control rate of addition, and to keep pH be particular value, adopts the synthetic NiMgAl-HTlc of constant pH method to slide the stratiform complex hydroxide.In the dropping process, follow and acutely stir the companion, dropwise about 90min greatly.Reactant liquor is kept and was stirred the companion 2 hours.Then in 80 ℃ aging 18 hours down, filter pressed powder.
Embodiment 2.Ni, Mg, Al-HTlc's is synthetic
Take by weighing 155.7 gram Ni (NO
3)
26H
2O, 315.2 gram Mg (NO
3)
26H
2O and 91.94 gram Al (NO
3)
39H
2O is dissolved in the 1200ml pure water; Taking by weighing 214.1 gram NaOH is dissolved in the 1500ml pure water.Under N2 protection, salting liquid and NaOH solution is added drop-wise to simultaneously at the bottom of three mouthfuls of gardens of 5 liters in the flask, the control rate of addition, and to keep pH be particular value, adopts the constant pH method to synthesize NiMgAl-HTlc stratiform complex hydroxide.In the dropping process, follow and acutely stir the companion, dropwise about 90min greatly.Reactant liquor is kept and was stirred the companion 2 hours.Then in 80 ℃ aging 18 hours down, filter pressed powder.
Embodiment 3.Ni, Mg, Fe, Al quaternary lamellar structure compound synthetic
Take by weighing 31.15 gram Ni (NO
3)
26H
2O, 338.4 gram Mg (NO
3)
26H
2O, 197.9 gram Al (NO
3)
39H
2O and 71.23 gram Fe (NO
3)
29H
2O is dissolved in the 1400ml pure water; Taking by weighing 249.6 gram NaOH is dissolved in the 1600ml pure water.Under N2 protection, salting liquid and NaOH solution is added drop-wise to simultaneously at the bottom of three mouthfuls of gardens of 5 liters in the flask, the control rate of addition, and to keep pH be particular value, adopts the constant pH method to synthesize NiMgFeAl-HTlc stratiform complex hydroxide.In the dropping process, follow and acutely stir the companion, dropwise about 90min greatly.Reactant liquor is kept and was stirred the companion 2 hours.Then in 80 ℃ aging 18 hours down, filter pressed powder.
Embodiment 4.Ni, Mg, Al-MoO
4Synthetic (ion-exchange)
Take by weighing NiMgAl-THLc180 gram synthetic among embodiment 1 or the embodiment 2, add and be equipped with in the there-necked flask of agitator and reflux condenser, add the 500ml pure water again, under 75 ℃, fully stirred the companion 5 hours, make its fully moistening and back filtration of expanding, filter cake adds in the there-necked flask again.Drip 315.5 gram Na
2MoO
4Dissolve in the solution of 550ml, use the HNO of 4mol/l while dripping
3The pH=4.5 of control reaction system, stablize the about l0min of this pH after, near down reaction 2 hours of fluidized state.Product is following dry 24 hours in 125 ℃ behind washing, suction filtration.
Embodiment 5.Ni, Mg, Fe, Al-MoO
4Synthetic (ion-exchange)
Take by weighing NiMgFeAl-THLc180 gram synthetic among the embodiment 3, add and be equipped with in the there-necked flask of agitator and reflux condenser, add the 500ml pure water again, fully stir under 75 ℃ and accompanied 5 hours, make its fully moistening and back filtration of expanding, filter cake adds in the there-necked flask again.Drip 315.5 gram Na
2MoO
4Dissolve in the solution of 550ml, use the HNO of 4mol/l while dripping
3The pH=4.5 of control reaction system, stablize the about 10min of this pH after, near down reaction 2 hours of fluidized state.Product is following dry 24 hours in 125 ℃ behind washing, suction filtration.
Embodiment 6.Ni, Mg, Al-MoO
4Synthetic (infusion process)
Take by weighing NiMgAl-THLc148 gram synthetic among embodiment 1 or the embodiment 2,, and behind 200～900 ℃ of roasts, add and be equipped with in the there-necked flask of agitator and reflux condenser, drip 30.0 gram Na through 100～130 ℃ of dryings
2MoO
4Dissolve in the solution impregnation of 100ml, 90 ℃ following dry 24 hours.
Embodiment 7.Ni, Mg, Fe, Al-MoO
4Synthetic (infusion process)
Take by weighing among the embodiment 3 synthetic NiMgFeAl-THLc148 gram,, and after 2 hours, add and be equipped with in the there-necked flask of agitator and reflux condenser, drip 30.0 gram Na in 200～900 ℃ of roasts through 100～130 ℃ of dryings
2MoO
4Dissolve in the solution impregnation of 100ml, 90 ℃ following dry 24 hours.
Embodiment 8. shaped catalysts
Get product synthetic in embodiment 1,2,3,4,5,6 or 7,, and behind 200～900 ℃ of roasts, be used for C through the shaping of catalyst technological forming
1～C
4The hydrocarbon compound partial oxidation catalyst.
Embodiment 9. methane gas partial oxidation catalysis
The catalyst that takes by weighing embodiment 8 preparations is used for methane drying nest oxidation catalysis, CH
4: O
2=2: 1, reach greater than 95% CO and H at the methane conversion of 750 ℃ of HTLOs composite portion oxidation catalysts
2Selectivity is near 100%.
Claims (5)
1. one kind is the natural gas partial oxidation catalyst of predecessor preparation with the hydrotalcite, it is characterized in that: the constituent of this catalyst and content are the nickel oxide NiO of (by weight percentage): 5%-40%, the di-iron trioxide Fe of 5-15%
2O
3, all the other constituents are magnesia MgO, aluminium oxide Al
2O
3And the oxide of other transition metal, the bivalent metal ion in all oxides and the mol ratio of trivalent metal ion are between 1: 1～10: 1.
2. according to claim 1 is the natural gas partial oxidation catalyst of predecessor preparation with the hydrotalcite, and it is characterized in that: described other transition metal comprises: Ca, Ba, Cr, Zn, La.
3. Preparation of catalysts method that contains the described metallic element oxide of claim 1, it is characterized in that: described metallic element oxide and the isopolyacid or the heteropoly acid that contain Mo, W, Mn, Cr element, the stratiform houghite predecessor that contains Mo, W, Mn, Cr element of the method preparation by ion-exchange makes through 500 ℃ of high temperature roasts.
4. Preparation of catalysts method that contains the described metallic element oxide of claim 1, it is characterized in that: described metallic element oxide is through the high temperature roast, solution with the compound that contains Mo, W, Mn, Cr element or ion, method by dipping prepares the composite oxides that contain Mo, W, Mn, Cr element, makes through high temperature roast more than 500 ℃.
5. an Application of Catalyst that makes as claim 3 or claim 4 is characterized in that: the catalyst that makes is used to prepare C after 500 ℃ of roastings
1～C
4Hydrocarbon compound portion oxidation synthesis gas process.
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|---|---|---|---|
| CNB2005100440727A CN100368081C (en) | 2005-07-15 | 2005-07-15 | Natural gas partial oxidation catalyst prepared by making hydrotalcite as predecessor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100440727A CN100368081C (en) | 2005-07-15 | 2005-07-15 | Natural gas partial oxidation catalyst prepared by making hydrotalcite as predecessor |
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|---|---|
| CN1736591A true CN1736591A (en) | 2006-02-22 |
| CN100368081C CN100368081C (en) | 2008-02-13 |
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ID=36079659
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|---|---|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972656A (en) * | 2010-10-20 | 2011-02-16 | 成都理工大学 | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof |
| CN102489310A (en) * | 2011-11-16 | 2012-06-13 | 成都理工大学 | Composite oxide catalyst for auto-thermal reforming of biomass-oil for preparing hydrogen |
| CN102949994A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | High-activity steam pre-conversion catalyst for hydrocarbons |
| CN107537504A (en) * | 2016-06-29 | 2018-01-05 | 华东师范大学 | A kind of self-supporting Raney nickel and its preparation and application |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399537A (en) * | 1992-12-21 | 1995-03-21 | Amoco Corporation | Method for preparing synthesis gas using nickel catalysts |
| DK0938446T3 (en) * | 1997-07-21 | 2004-04-13 | Bp Corp North America Inc | Process for Hydrocarbon Reform |
| CN1108862C (en) * | 1999-05-28 | 2003-05-21 | 中国石油化工集团公司 | Flue gas purifying catalyst |
| JP2003290657A (en) * | 2002-01-31 | 2003-10-14 | National Institute Of Advanced Industrial & Technology | Catalyst for reforming hydrocarbon, manufacture method therefor, method for manufacturing synthetic gas and catalyst precursor |
-
2005
- 2005-07-15 CN CNB2005100440727A patent/CN100368081C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101972656A (en) * | 2010-10-20 | 2011-02-16 | 成都理工大学 | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof |
| CN101972656B (en) * | 2010-10-20 | 2013-04-03 | 成都理工大学 | Nickel-base catalyst used for autothermal reforming of ethanol for producing hydrogen and preparation method thereof |
| CN102949994A (en) * | 2011-08-31 | 2013-03-06 | 中国石油化工股份有限公司 | High-activity steam pre-conversion catalyst for hydrocarbons |
| CN102489310A (en) * | 2011-11-16 | 2012-06-13 | 成都理工大学 | Composite oxide catalyst for auto-thermal reforming of biomass-oil for preparing hydrogen |
| CN102489310B (en) * | 2011-11-16 | 2015-12-02 | 成都理工大学 | A kind of composite oxide catalysts for bio-oil self-heating recapitalization hydrogen making |
| CN107537504A (en) * | 2016-06-29 | 2018-01-05 | 华东师范大学 | A kind of self-supporting Raney nickel and its preparation and application |
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| Publication number | Publication date |
|---|---|
| CN100368081C (en) | 2008-02-13 |
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