CN102091629A - Catalyst for methanation of carbon dioxide - Google Patents
Catalyst for methanation of carbon dioxide Download PDFInfo
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- CN102091629A CN102091629A CN2009101176861A CN200910117686A CN102091629A CN 102091629 A CN102091629 A CN 102091629A CN 2009101176861 A CN2009101176861 A CN 2009101176861A CN 200910117686 A CN200910117686 A CN 200910117686A CN 102091629 A CN102091629 A CN 102091629A
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Abstract
The invention discloses a catalyst for the methanation of carbon dioxide. The carrier of the catalyst is composite oxide of rare earth and other metals, and the composition of the catalyst is represented by a general formula of AxByOz, wherein in the formula, A is a rare metal, B is one or two metals from groups IIB, IIIA, VIA, IVB, VB and VIB, x is 0 to 1, y is 0 to 2, and z is 2 to 4; and the active component of the catalyst is nickel, and the nickel loaded on the carrier accounts for 1 to 15 percent of the total weight of the catalyst. Compared with the conventional carbon dioxide methanation technique, the catalyst technique disclosed by the invention, under the similar reaction conditions, can achieve a carbon dioxide conversion rate of 100 percent, a methane selectivity of 100 percent and a methane time space yield of more than 1,000g/kg.h.
Description
Technical field
The present invention relates to the method that a kind of oxycarbide is eliminated, particularly improved carbon dioxide, carbon monoxide methanation catalyst are specially adapted to the process that hydrogenation of carbon dioxide obtains methane or remove trace amounts of oxycarbide from hydrogen.
Background technology
Hydrogen is that oil-refining chemical enterprise improves the level of crude oil processing, produces clean fuel and the indispensable important source material of synthetic ammonia, also is the raw material of many fine chemistry industry production processes simultaneously.At present, be that the steam reforming of raw material is most widely used, most effective key industry hydrogen production process with the hydro carbons.Its technical process is: hydrocarbon raw material is through purifying, allocate into steam, mix preheating, entering in 500 ℃～850 ℃ the alternating temperature reforming catalyst bed water vapour (and CO takes place
2) catalytic conversion reaction, generate and contain H
2, CO, CO
2With a small amount of CH
4Crude synthesis gas, purify through conversion and decarburization, methanation or PSA, produce high-purity industrial hydrogen and different H respectively
2The oxo-synthesis gas of/CO ratio.Thick H
2Contain a certain amount of oxycarbide (CO, CO in the product inevitably
2), must be removed and could be used for the subsequent reactions process.The general requirement through H after the purification processes
2CO and CO in the product
2Total amount be 5～10ppm, even lower.The common method of removing oxycarbide has ammonical copper solution scrubbing method, scrubbing with liquid nitrogen method, methanation method and PSA method, wherein methanation method is a kind of operation and the easiest very superior method of equipment, generally adopt at industrial quilt, depth decarburization as hydrogen in present ethylene industry and the ammonia synthesizing industry all uses this method basically, utilizes methanation reaction 0.2～1% oxycarbide can be removed to below the 5ppm.
In addition, carbon dioxide is as the main component of greenhouse gases and the global climate problem that causes has badly influenced human existence.The requirement of carbon dioxide discharge-reduction and the needs of energy sustainable development are how to realize new carbon cycle problem after all, and therefore, carbon dioxide is transformed and utilize the target that becomes scientific worker's effort for many years as carbon resource.Methane is the main composition of natural gas, and it is widely used (as combustion power generation, heat-obtaining, family expenses, as motor vehicle fuel etc.) as clean energy resource.The maximum purposes of natural gas is the huge heat energy that utilizes methyl hydride combustion to produce at present, and the carbon dioxide that generates in combustion process enters atmosphere inevitably.But carbon dioxide is obtained methane by the hydrogenation highly selective, therefore in new carbon cycle theory, methane-carbon dioxide-methane process is an aspect (George A.Olah very important, that have meaning, Alain Geoppert and G.K.Surya Prakash, Beyond oil and Gas:The MethanolEcnomy, Wiley-VCH Verlag Gmbh ﹠amp; Co.KgaA, Weinheim, 2006).
Nickel-base catalyst is industrial oxycarbide hydrogenation catalyst commonly used.The Chinese patent of application number 200710032526.8 provides with the synthetic ZrO of template agent hydro-thermal method
2, the Catalyst And Method of supported ni catalyst catalysis CO methanation again, CO can reduce to below the 100ppm, and purified gas is used for the fuel of fuel cell.Application number is in 95106946.2 the Chinese patent, to be carrier loaded Ni or Ru catalyst with sepiolite, at normal pressure, 300 ℃, air speed 3000-5000h
-1Reaction condition under, oxycarbide is reduced to below the 10ppm.Chinese patent ZL95120055.0 is with porous gel ZrO
2The rare earth of load 1-5%Ni, 0.5-3%Ru and 1-3% is a catalyst, in the time of 400 ℃, and CO
2Transform more than 90% methane selectively 100%.Chinese patent ZL95103867.2 is with ZrO
2Load Ni, Ru and rare earth catalyst, methane space-time yield 65mol/Lh in the time of 400 ℃.Chinese patent ZL93115835.4 is compound with Mo-Ni system and oxide based two class catalyst, in order to the CO methanation, to H
2S is insensitive, and the CO conversion ratio is mainly used in gas methanation and improves calorific value more than 80%.
U.S. Pat 2008139676 has been described with activated carbon loaded Ru or Rh or Ni or Co catalyst selection catalysis CO methanation, and Purge gas is used for the fuel of fuel cell.Japan Patent JP2008056539 has proposed two-stage CO methanation, the two-stage catalyst is made up of oxide carried Ni or Co catalyst and oxide carried 6A family and the 8th family's metal respectively, 120 ℃ of first order reaction temperatures, CO elimination factor 〉=98%, 180 ℃ of second level reaction temperatures, CO elimination factor 〉=98%.European patent EP 1173277 has been described with rare earth oxide and the oxide carried Ni catalyst of RE perovskite type, catalyzed carbon oxide methanation reaction, and the load capacity of catalyst nickel is higher than 20%.Russ P RU2205068 discloses a kind of Ni-Cr/Al
2O
3Catalyst CO methanation has improved catalyst activity and mechanical strength.
In above-mentioned disclosed patent, can see that the improvement of Ni methylmethane catalyst mainly is by adding second, third kind metal promoter or changing catalyst carrier to improve the mechanical strength and the anti-sulphur ability of methanation activity, stability and catalyst.Yet, can see that also these catalyst still exist some defectives, for example: (1) methanation activity is not enough to reach the optimum state that oxycarbide is transformed fully; (2) reaction velocity is not high enough, and the methane space-time yield is still lower; (3) supported nickel catalyst and carrier still leave some room for improvement or the like in structural stability.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, and a kind of carbon dioxide methanation catalyst is provided.
Purpose of the present invention can realize by following measure:
When the composite oxides that the present invention's discovery forms oxides such as rare earth oxide and IIB family, IIIB family and transition metal are used for the carrier of supported ni catalyst, Ni catalyst carbon dioxide methanation activity, selectivity are high, and the load capacity of Ni can be reduced to below 15%, be enough to make carbon dioxide to transform fully, methane selectively also reaches 100% in the gaseous product, and catalyst has good stability simultaneously.
We provide a kind of Stability Analysis of Structures, be difficult for the composite oxide carrier with Ni formation strong interaction, thereby make the Raney nickel of preparation have better carbon dioxide methanation reactivity worth.
A kind of carbon dioxide methanation catalyst is characterized in that: catalyst carrier is the composite oxides of rare earth and other metal, its composition general formula
A
xB
yO
z
Expression, A is a rare earth metal in the formula, B is one or both in IIB, IIIA, VIA, IVB, VB, the group vib metal, x=0～1, y=0～2, z=2～4; The catalyst activity component is a nickel, and the load capacity of nickel on carrier accounts for 1～15% of total catalyst weight.
The preferred rare earth metal of catalyst of the present invention is selected from lanthanum or cerium.
The preferred B of catalyst of the present invention is selected from one or both in zinc, aluminium, iron, the titanium.
The Preparation of catalysts process comprises preparing carriers, active constituent load, roasting and activation step, and wherein the preparation process of carrier is:
(1) adopt coprecipitation to prepare rare earth-metal oxide carrier: the soluble-salt that will contain rare earth metal A is mixed with the certain density aqueous solution with the soluble-salt that contains metal B, under room temperature, stirring, add certain density aqueous slkali, keep the pH value 6～9; Aging after 2-6 hour, sedimentation and filtration, wash to filtrate for neutral;
Soluble metallic salt can be selected from chloride, nitrate, sulfate, acetate, and the concentration of metal ion is 0.2mol/L～5mol/L.
Used alkali can be selected from sodium carbonate, NaOH, and the concentration of aqueous slkali is 0.1mol/L～5mol/L.
(2) be deposited in 100～180 ℃ of oven dry 5～24 hours;
(3), make metal hydroxides or metal carbonate all change corresponding oxide or solid solution, oxide into 400～800 ℃ of roastings 4～8 hours;
Precipitation-sedimentation or infusion process are used in the load of active constituent, and the solubility salt is selected in the source of nickel for use, preferred nickel nitrate.During with precipitation-sedimentation, detailed process is as follows:
(1) soluble nickel salt is mixed with the aqueous solution that nickel concentration is 0.1～1mol/L, water soluble alkali is mixed with the aqueous solution that concentration is 0.1～1.0mol/L;
(2) will be crushed to the following carrier of 100 orders and be dispersed in a certain amount of water, under room temperature, stirring, drip above-mentioned two kinds of solution simultaneously, keep pH value of solution=7～9, dropwise the back aging 2-8 hour, filter and washing;
(3) be deposited in 100～180 ℃ of oven dry after 5～24 hours, in 350～500 ℃ of roasting 2-6 hours;
(4) under hydrogen atmosphere, in 300～450 ℃ the nickel oxide on the catalyst further is reduced to metallic nickel, hydrogen gas space velocity is 500～5000h
-1, the hydrogen of use can be pure hydrogen, also can be the hydrogen through inert gas dilution, density of hydrogen＞5% (volume).Reduction process can be before reaction in-situ reducing, also can under normal pressure after the roasting, reduce.
Adopt the process of immersion process for preparing catalyst identical with normally used equi-volume impregnating.
Carbon dioxide carries out in stainless steel tubular type continuous flow reactor at the reaction evaluating on the Raney nickel, and reactor adopts fixed bed, and carbon dioxide and hydrogen obtain methane after by Raney nickel bed hydrogenation.
When carrying out methanation reaction, control reaction temperature at 250～450 ℃, reaction pressure 0.5～6.0Mpa, the total air speed 500～50000h of unstripped gas
-1Carbon dioxide was 5～20% (volumes) during unstripped gas was formed, hydrogen 94～79% (volume), and for ease of calculating, the nitrogen that adds 1% (volume) is as interior gas body.
Online gas chromatographic analysis is adopted in the analysis of reactant and product among the present invention, uses the TDX packed column of internal diameter 2mm, long 2m, and thermal conductivity detector (TCD) (TCD) is gone up and detected.
Embodiments of the invention all adopt following formula to calculate conversion ratio, the product selectivity of carbon dioxide.
Advantage that compared with the prior art the present invention is had and good effect:
A. carrier of the present invention is the composite oxides that rare earth oxide and other metal oxide sintering form, and has better rock-steady structure and heat-resistant stability.
B. the supported nickel catalyst that makes with the present invention when carrying out the carbon dioxide methanation reaction, is compared with existing process and to be had higher activity.
C. catalyst technology of the present invention is compared with existing carbon dioxide methanation technology, under close reaction condition, can obtain carbon dioxide conversion 100%, methane selectively 100%, and the methane space-time yield is higher than the result of 1000g/kgh.
The present invention is the preparation carrier A
xB
yO
zAnd supported nickel catalyst designed rational preparation technology, guarantees that this catalyst is easy to amplify to produce and in industrial steady running necessary mechanical strength.
The specific embodiment
Following listed examples only is used for illustrating carrier of the present invention and catalyst composition, preparation process and corresponding carbon dioxide methanation reaction result, but do not limit the present invention by better form, preparation method and reaction result.
1. the preparation of carrier
Embodiment 1
10.8 gram lanthanum nitrate hexahydrate and 8.8 grams, nine nitric hydrate iron are dissolved in (note is made solution I) in 100 ml distilled waters, 6.1 gram NaOH are dissolved in (note is made solution II) in the 100ml distilled water.Other gets 100ml distilled water in beaker, is warming up to 50 ℃, stirs down and drips solution I and II simultaneously, keeps pH value of solution 7～8, after dropwising, continues to stir 5 hours, and filtration, deionized water wash to there not being sodium ion.Be deposited in 110～120 oven dry after 5 hours,, obtain the kermesinus carrier and (be designated as L in 650 ℃ of roastings 4 hours
1).This carrier is a perovskite structure through XRD analysis, specific area 78 meters squared per gram.
Embodiment 2
10.8 gram lanthanum nitrate hexahydrate and 7.3 gram cabaltous nitrate hexahydrates are dissolved in (note is made solution I) in 100 ml distilled waters, 8.5 gram NaOH are dissolved in (note is made solution II) in the 100ml distilled water.Other gets 100ml distilled water in beaker, is warming up to 70 ℃, stirs down and drips solution I and II simultaneously, keeps pH value of solution at 9-10, after dropwising, continues to stir 5 hours, and filtration, deionized water wash to there not being sodium ion.Be deposited in the 110-120 oven dry after 5 hours,, obtain carrier and (be designated as L in 700 ℃ of roastings 4 hours
2).This carrier is a perovskite structure through XRD analysis, specific area 65 meters squared per gram.
Embodiment 3
22 gram Zinc diacetate dihydrates, 75 gram ANN aluminium nitrate nonahydrates are even with 36 gram urea mixed grindings, dry 12 hours for 180 ℃, and 550 ℃ of roastings 5 hours obtain pale yellow powder shape carrier and (are designated as L
3), be spinel structure through XRD analysis.
Embodiment 4
21.66 gram lanthanum nitrate hexahydrate and 7.46 gram zinc nitrate hexahydrates are dissolved in (note is made solution I) in the 100ml water, 4.5 gram NaOH are dissolved in (note is made solution II) in the 100ml water.Other gets 100ml distilled water in beaker, drips solution I and II under the stirring at room, keeps the pH value of solution value at 6-7, and all the other methods are identical with example 1.The carrier that obtains (is designated as L
4) by two kinds of thing phase compositions, i.e. lanthana and zinc oxide.
Embodiment 5
21.66 gram lanthanum nitrate hexahydrate and 18.8 grams, six nitric hydrate aluminium are dissolved in (note is made solution I) in the 100ml water, 11 gram NaOH are dissolved in (note is made solution II) in the 100ml water.Other gets 100ml distilled water in beaker, drips solution I and II under the stirring at room, keeps the pH value of solution value at 8-9, and all the other methods are identical with example 1.The carrier that obtains (is designated as L
5) perovskite structure.
Embodiment 6
42.4 the gram natrium carbonicum calcinatum is dissolved in the 400ml water, is heated to 50 ℃, drips the solution that 70.66 gram Lanthanum trichloride hexahydrates and 43.9 gram Zinc diacetate dihydrates are dissolved in 500ml water, pH=9-10, and aging 4 hours, all the other methods were identical with example 1, and the carrier that obtains (is designated as L
6) have two kinds of oxide structures, i.e. zinc oxide and an oxidation lanthanum carbonate.
Embodiment 7
100 grams, one hydration lanthanum acetate is dissolved in the methyl alcohol, is warming up to 60 ℃, adds the methanol solution of 102 gram butyl titanates, regulates pH value=2-4 with glacial acetic acid, and the colloidal sol that obtains places autoclave to place 8 hours in 150 ℃.After the cooling, filter, detergent gel, 120 ℃ of oven dry 10 hours, 600 ℃ of roastings are 4 hours in the air, the carrier that obtains containing lanthanum, titanium oxide (is designated as L
7).This carrier has perovskite structure, specific area 80 meters squared per gram.
Embodiment 8
43.3 gram lanthanum nitrate hexahydrate and 17.3 gram manganese acetates are dissolved in the 300ml water, drip the 0.5mol/L ammonia spirit under the room temperature, to pH=8-9, aging 3 hours, filter, wash, be deposited in 110 ℃ of oven dry 8 hours, 600 ℃ of roastings are 6 hours in the air, and the carrier that obtains (is designated as L
8) have a perovskite structure, specific area 110 meters squared per gram.
2. Preparation of catalysts
Embodiment 9
Take by weighing L
14 grams are heated to 80～90 ℃, add the solution that 2.21 gram Nickelous nitrate hexahydrates are dissolved in 10ml water, and the oven dry while flooding continued dry 12 hours at 120 ℃ then.400 ℃ of roastings 5 hours, so that nickel nitrate is decomposed into nickel oxide.Catalyst after the decomposition is standby for 20-40 purpose particle through compressing tablet, screening.Take by weighing 1 gram and place 14 millimeters of internal diameters, reduce in long 250 millimeters the quartz glass reaction pipe, with the nitrogen mixture that contains 10% hydrogen of flow 100 ml/min 380 ℃ of reduction after 6 hours, be cooled to room temperature, be transferred in the stainless steel reaction pipe of 18 millimeters of internal diameters, 300 millimeters of length, be warming up to 380 ℃ in hydrogen/nitrogen atmosphere, the unstripped gas that switches to hydrogen/carbon dioxide=4 carries out methanation reaction, and evaluating catalyst the results are shown in Table 1.
Embodiment 10
Use carrier L
2Adopt the method identical with example 9 to prepare catalyst, evaluation result sees Table 1.
Table 1 evaluating catalyst result
*
*Hydrogen/carbon dioxide/nitrogen=4/1/0.05, the total air speed 10000h of unstripped gas
-1
Embodiment 11
Replace Nickelous nitrate hexahydrate with Nickel dichloride hexahydrate, carrier is L
3, all the other are identical with example 9, and evaluation result is listed in table 2.
Embodiment 12
Take by weighing 5 gram L
4Be dispersed in the 200ml water, add 2.3 gram Nickelous nitrate hexahydrates, be warming up to 60 ℃, drip the 0.4mol/L aqueous sodium carbonate under the stirring, to pH=8, aging 5 hours, filter, wash, to dry 8 hours for 120 ℃, all the other processes are identical with example 9, and evaluation result sees Table 2.
Embodiment 13
With L
5Carrier replaces sodium carbonate with NaOH, and all the other processes are identical with example 12, and evaluation result sees Table 2.
Embodiment 14
With L
6Carrier is used aqueous ammonia to replace sodium carbonate, and all the other are identical with example 12, and evaluation result sees Table 2.
Embodiment 15
Replace nickel nitrate with nickel acetate, carrier is L
7, all the other are identical with example 12, and evaluation result is listed in table 2.
Embodiment 16
Get 8.1 gram Nickel dichloride hexahydrates and be dissolved in (note is made solution I) in the 400ml water, 3.8 gram natrium carbonicum calcinatums are dissolved in (note is made solution II) in the 400ml water, and other gets L
820 grams are dispersed in the 500ml water, are heated to 70 ℃, drip solution I and II simultaneously, keep pH=7-8, and are aging after 2 hours, filter, wash, and filter cake took out at 100～120 ℃ of air dryings in 12 hours.All the other steps are identical with example 12, and evaluation result sees Table 2.
Comparative example 1
Take by weighing 30-80 order gama-alumina 10.0 gram, be heated to 90 ℃, be dissolved in the solution impregnation of 20ml water with 4.68 grams, oven dry was while stirring dried 12 hours at 120 ℃ again.All the other steps are identical with example 9, and evaluation result is listed in table 2.
Comparative example 2
Replace L with 30-80 order θ-aluminium oxide
5, all the other methods are identical with example 12.
The contrast of table 2 evaluation result
*Hydrogen/carbon dioxide/nitrogen=4/1/0.05, the total air speed 10800h of unstripped gas
-1
Embodiment 17
With L
4Be carrier, the method identical with embodiment 15 prepares catalyst.At catalyst loading amount 2.0g, reaction pressure 1.5MPa, total air speed 10000h
-1, hydrogen/carbon dioxide=4 condition under, carbon dioxide conversion and methane selectively all maintain 100%, short-term stability experimental result such as table 3 are listed.
Aforesaid various embodiments of the present invention also can adopt the implementer to think that mass unit reaches relevant other unit easily, and key is that correlation and the manufacture craft process between the material meets condition of the present invention.
Table 310%Ni/La-AlO
xCatalyst short-term stability performance
Claims (3)
1. a carbon dioxide methanation catalyst is characterized in that catalyst carrier is the composite oxides of rare earth and other metal, its composition general formula
A
xB
yO
z
Expression, A is a rare earth metal in the formula, B is one or both in IIB, IIIA, VIA, IVB, VB, the group vib metal, x=0～1, y=0～2, z=2～4; The catalyst activity component is a nickel, and the load capacity of nickel on carrier accounts for 1～15% of total catalyst weight.
2. catalyst as claimed in claim 1 is characterized in that rare earth metal is selected from lanthanum or cerium.
3. catalyst as claimed in claim 1 is characterized in that B is selected from one or both in zinc, aluminium, iron, the titanium.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941098A (en) * | 2012-11-09 | 2013-02-27 | 上海应用技术学院 | Catalyst for methane synthesis through carbon dioxide hydrogenation and preparation method thereof |
| WO2013185559A1 (en) | 2012-06-15 | 2013-12-19 | 武汉凯迪工程技术研究总院有限公司 | Liquid phase co2 methanation catalyst, preparation method and use thereof |
| CN106311242A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Carbon dioxide methanation catalyst and preparation method thereof |
| WO2018141649A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| WO2018141648A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
| CN108097237B (en) * | 2017-12-06 | 2020-06-16 | 东南大学 | Modified manganese sand, transformation methanation catalyst using modified manganese sand as carrier and preparation method |
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2009
- 2009-12-09 CN CN2009101176861A patent/CN102091629A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013185559A1 (en) | 2012-06-15 | 2013-12-19 | 武汉凯迪工程技术研究总院有限公司 | Liquid phase co2 methanation catalyst, preparation method and use thereof |
| CN102941098A (en) * | 2012-11-09 | 2013-02-27 | 上海应用技术学院 | Catalyst for methane synthesis through carbon dioxide hydrogenation and preparation method thereof |
| CN102941098B (en) * | 2012-11-09 | 2014-06-11 | 上海应用技术学院 | Catalyst for methane synthesis through carbon dioxide hydrogenation and preparation method thereof |
| CN106311242A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Carbon dioxide methanation catalyst and preparation method thereof |
| CN106311242B (en) * | 2015-07-06 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of carbon dioxide methanation catalyst and preparation method thereof |
| WO2018141649A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| WO2018141646A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Nickel methanation catalysts doped with iron and manganese |
| WO2018141648A1 (en) | 2017-01-31 | 2018-08-09 | Clariant Produkte (Deutschland) Gmbh | Iron-doped nickel methanation catalysts |
| US10888846B2 (en) | 2017-01-31 | 2021-01-12 | Clariant Produkte (Deutschland) Gmbh | Manganese-doped nickel-methanation catalysts |
| CN108097237B (en) * | 2017-12-06 | 2020-06-16 | 东南大学 | Modified manganese sand, transformation methanation catalyst using modified manganese sand as carrier and preparation method |
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Application publication date: 20110615 |