CN102784639A - Coal-bed methane deoxidization catalyst and preparation method and application of coal-bed methane deoxidization catalyst - Google Patents
Coal-bed methane deoxidization catalyst and preparation method and application of coal-bed methane deoxidization catalyst Download PDFInfo
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Abstract
The invention provides a coal-bed methane deoxidization catalyst and a preparation method and application of the coal-bed methane deoxidization catalyst. The catalyst comprises platinum (Pt) oxide and a carrier, the platinum oxide is used as an active ingredient, and the carrier comprises cerium and zirconium composite oxide (Ce-Zr-O), pseudo-boehmite (Al2O3 nH2O) and aluminum hydroxide (YH). The preparation method includes preparing the carrier and soaking the active ingredient to obtain the coal-bed methane deoxidization catalyst. The activating temperature of the catalyst ranges from 300 DEG C to 360 DEG C, high-temperature stability of the catalyst is good, the content of oxygen in product gas can be reduced to be lower than 5ppm, fine reaction precision is realized, prereduction is omitted, and a start-up process is simplified.
Description
Technical field
The present invention relates to catalyst field, relate more specifically to a kind of coal bed gas deoxidation catalyst.
Background technology
Coal bed gas is as one of three major members of gas energy family, and is the same with the exploration and development of natural gas, gas hydrates, receives the attention of countries in the world day by day.China's coal bed gas resource is abundant, occupies the third place in the world.The coal bed gas of annual discharging when mining is more than 130 billion cubic meters, and coal bed gas directly is discharged in the atmosphere, and its greenhouse effects are about 21 times of carbon dioxide, and are extremely strong to environmental destruction property.If first exploiting coal bed methane before mining, the coal mine gas from explosion rate will reduce by 70% to 85%.The development and use of coal bed gas have the effect of achieving many things at one stroke: improve gas accident and take precautions against level, have safety effectiveness; Effectively GHG emissions mitigation produces good environmental protection effect; As a kind of efficient, clear energy sources; Commercialization can produce huge economic benefit; But therefore the coal bed gas of extraction must just can carry out follow-up separation after the deoxidation because the existence of oxygen makes coal bed gas in follow-up separation purification process, have bigger potential safety hazard.
" a kind of coal bed gas deoxidation catalyst, its preparation method and the application " that the open CN200910012670.4 of patent introduces; Be a kind of monolithic devices, thereby this type of catalyst carrier cost is high, preparation process complicacy is difficult to suitability for industrialized production, the filling difficulty is big in reactor, difficulty is accomplished the tightly packed channeling that very easily occurs around reactor wall and thermocouple sheath.
Patent open CN200610021760.1 provide a kind of coal bed gas coke deoxidization method, and the advantage of this method is the main and coke gasification reaction of oxygen, so the loss of methane is less.Shortcoming is to consume coke resource, and the cost of coke is about about 50% of whole service expense.The deoxidation of coke method need add Jiao slags tap, and labour intensity is big, and dust pollution is heavy, is difficult to realize automatic operation at present.
What the open CN200510047624.X of patent adopted is that transformation absorption and membrane separation technique are used in combination; Adsorb nitrogen separation through transformation; Through membrane separation technique separation of methane and oxygen, this method need be pressurizeed to coal bed gas, and the methane explosion limit can sharply enlarge along with increased pressure; Highlight this technological safety problem, and film cost issues limit industrially scalable.
Summary of the invention
The object of the invention provides and a kind ofly is easy to make, economical and practical coal bed gas deoxidation catalyst.
On the one hand, the present invention provides a kind of coal bed gas deoxidation catalyst, it is characterized in that: said catalyst comprises platinum oxide as active component, and carrier, and wherein said carrier comprises cerium zirconium compound oxide, boehmite and aluminium hydroxide.
In a preferred implementation, with respect to said coal bed gas deoxidation catalyst, the content by quality of said active component is 0.004%～1%.
In a preferred implementation, said carrier comprises the said cerium zirconium compound oxide by quality 5-30%, the said aluminium hydroxide of 40-80% and the said boehmite of 5-40%.
In a preferred implementation, said carrier comprises the said cerium zirconium compound oxide by quality 10-15%, the said aluminium hydroxide of 50-65% and the said boehmite of 25-30%.
In a preferred implementation, said carrier also comprises by the sesbania powder of quality 0-3% and/or the citric acid of 0-3%.
In a preferred implementation, said catalyst be shaped as strip, and its BET surface area is 77-186m
2/ g, pore volume 0.34-0.62ml/g, the aperture is 115-160
In a preferred implementation, be doped with lanthanum and/or yttrium in the said cerium zirconium compound oxide.
In a preferred implementation, said cerium zirconium compound oxide comprises the CeO of 30-80% in mass
2, 10-60% ZrO
2, 3-5% La
2O
3Y with 3-5%
2O
3
On the other hand, the present invention provides a kind of method for preparing above-mentioned coal bed gas deoxidation catalyst, said method comprising the steps of:
A) will mix as each component of support material, moulding and dry is then calcined, and is obtained said carrier then;
B) with the carrier impregnation that makes in the step a) in the platiniferous maceration extract, dry then, then calcine, and obtain said coal bed gas deoxidation catalyst.
In a preferred implementation, in step a), at first in aluminium hydroxide, add distilled water and optional citric acid component forming jelly shape colloid, and then said colloid is mixed with other components.
In a preferred implementation, the said moulding in the step a) is through the banded extruder extrusion.
In a preferred implementation, the baking temperature in the step a) is 80-150 ℃, and be 1-4 hour drying time; And the calcining heat in the step a) is 650-950 ℃, and the time is 2-6 hour.
In a preferred implementation, the platiniferous maceration extract that uses in the step b) is one or more the acidic aqueous solution that is selected from chloroplatinic acid, platinum nitrate, carbonic acid platinum, the platinic hydroxide.
In a preferred implementation, the platiniferous maceration extract that uses in the step b) is H
2PtCl
66H
2O solution.
In a preferred implementation, the baking temperature in the step b) is 100-180 ℃, and be 3-12 hour drying time; And the calcining heat in the step b) is 650-950 ℃, and the time is 2-6 hour.
Aspect another, the invention provides the application of above-mentioned coal bed gas deoxidation catalyst, be used for the deoxygenation of coal bed gas.
In a preferred implementation, said deoxygenation carries out in fixed bed reactors, and reaction condition is as follows: reaction pressure is 0～0.01MPa; Reaction temperature is 260-800 ℃; The volume space velocity of coal bed gas is 3,000-10,000h
-1
In a preferred implementation, behind said deoxygenation, the oxygen content of said coal bed gas is below the 5ppm.
Catalyst provided by the present invention is particularly suitable for as coal bed gas deoxidation purified treatment catalyst, but the oxygen in the effective elimination coalbed methane containing oxygen is eliminated coal bed gas and in follow-up separation purification process, had formed potential safety hazard owing to oxygen.In addition, the most of low in raw material cost of this catalyst is easy to get, and the operating procedure of production is simple, relatively is suitable for industrial processes.
Description of drawings
Fig. 1 shows the performance evaluation result's of the catalyst sample that obtains according to the embodiment of the invention 1 to 2 and comparative example curve map.
The specific embodiment
Coal bed gas catalyst of the present invention comprises active component and carrier components, and active component wherein is platinum (Pt) oxide, and with respect to this catalyst, is preferably 0.004%-1% by the active component content of quality.And carrier components mainly comprises cerium zirconium compound oxide (Ce-Zr-O), boehmite (Al
2O
3NH
2O) and aluminium hydroxide (YH).In this article, can adopt following general formula (Pt)/(Ce-Zr-O)+(Al
2O
3NH
2O)+and YH representes catalyst of the present invention, wherein n is a water molecule number.
Catalyst of the present invention can be for example obtains through following process: with aluminium hydroxide be that parent is pinched through mixing, moulding, drying, calcine technology prepare carrier, prepare high activated catalyst through dipping, dry, calcine technology again.Catalyst of the present invention improves activity of such catalysts and selectivity by interpolation rare earth metal cerium and zirconium in the catalyst carrier preparation process.
Preferably, with respect to carrier, each component consisting of in the carrier of catalyst of the present invention: cerium zirconium compound oxide 5-30% by quality; Aluminium hydroxide 40-80%; Boehmite 5-40%.
Preferably, in the present invention, the boehmite of use is with formula Al
2O
30.08～0.62H
2A kind of peptization performance that O representes is good, and caking property is strong, has the boehmite of characteristics such as specific surface height, pore volume be big.
Further preferably, with respect to carrier, each component consisting of in the carrier of catalyst of the present invention: cerium zirconium compound oxide 10-15% by quality; Aluminium hydroxide 50-65%; Boehmite 25-30%.
Preferably, the carrier of catalyst of the present invention also comprises optional member sesbania powder and/or citric acid, and its mass content with respect to carrier preferably is respectively 0-3%.
Preferably, catalyst according to the invention is shaped as strip, and its BET surface area is 77-186m
2/ g, pore volume 0.34-0.62ml/g, the aperture is 115-160
More preferably, the BET surface area is 103-186m
2/ g, pore volume 0.34-0.60ml/g, the aperture is 116-160
For example the BET specific area of this strip catalyst is 136.7443m
2/ g, pore volume 0.5773ml/g, the aperture is 116.717
In the present invention, Preparation of catalysts mainly comprises the preparation of carrier and floods two steps.For example, with aluminium hydroxide, cerium zirconium compound oxide, boehmite, sesbania powder pinch through mixing, prepared such as extrusion, drying, calcining form.
Preferably, employed aluminium hydroxide is high-ratio surface, macropore aluminium hydroxide.
Preferably, be doped with a small amount of lanthanum, yttrium in the employed cerium zirconium compound oxide, to improve its high-temperature stability and aging specific surface area; Preferably, said cerium zirconium compound oxide comprises the CeO of 30-80% in mass
2, 10-60% ZrO
2, 3-5% La
2O
3Y with 3-5%
2O
3
Preferably, in Preparation of catalysts of the present invention, at first that cerium zirconium compound oxide, aluminium hydroxide, sesbania powder premix is even; Simultaneously, in boehmite, add distilled water and be stirred to the suspension state, add a small amount of citric acid as required, and can add an amount of rare nitric acid more as required,, be stirred to and form jelly shape colloid so that the pH value is adjusted to 1.5-3.0.Afterwards, colloid that is obtained and premixed powder material are before mixed pinch, extrusion, drying, calcining.
Preferably, in above-mentioned preparation, drying condition is: baking temperature is 80-150 ℃, and be 1-4 hour drying time; And the calcining heat in the step a) is 650-950 ℃, and the time is 2-6 hour.90-130 ℃ of 110 ℃ of forced air drying 2-4h for example 3 hours for example more preferably; And calcining heat is 700-850 ℃ and for example calcined 2-6h for example 2 hours at 800 ℃.
Preferably; In above-mentioned dipping; Employing contains the Pt dipping solution, and for example chloroplatinic acid, platinum nitrate, carbonic acid platinum solution is as maceration extract, for example gets 1g chloroplatinic acid and 1g platinum nitrate and is dissolved in simultaneously and adds the hydrochloric acid of 0.5ml 12mol/L then in the 1000ml water and can obtain corresponding acidic aqueous solution.Impregnation concentration can finished catalyst in the quality percentage composition of active component for according to adjusting, the quality percentage composition that makes active component in the finished catalyst at least is that 0.004-1% gets final product.After dipping was accomplished, through dry, calcining, cooling naturally, Preparation of Catalyst was accomplished again.Preferably, the drying condition here is: baking temperature is 100-180 ℃, and be 3-12 hour drying time; And the calcining heat in the step b) is 650-950 ℃, and the time is 2-6 hour.More preferably; Baking temperature be 120-160 ℃ for example 120 ℃ dry 6-12 hour for example 3 hours; Calcination condition is for example to rise to 700-850 ℃ for example 800 ℃ in 4 hours in 3-8 hour, and under this temperature, keeps 2-6 hour for example 2 hours, and natural cooling can obtain catalyst of the present invention.
But according to the oxygen in the coal bed gas deoxidation catalyst effective elimination coalbed methane containing oxygen of the present invention, the coal bed gas oxygen content after the deoxidation can be reduced to below the 5ppm.
In the application of coal bed gas deoxidation catalyst of the present invention; The catalytic deoxidation reaction is for example carried out in fixed bed reactors; The condition of its reaction is: 1) be reflected in 0～0.01MPa pressure limit and carry out 2) be reflected in the 260-800 ℃ of temperature range and carry out 3) volume space velocity of reaction raw materials gas is 3; 000-10,000h
-
More specifically, catalyst of the present invention can prepare through following preparation method:
A, take by weighing a certain amount of aluminium hydroxide, cerium zirconium compound oxide, and optional sesbania powder joins in the kneading machine and fully mixes;
B, take by weighing a certain amount of boehmite and add 170-230mlH
2O is 200mlH for example
2O is stirred to the formation suspension; Measure a certain amount of nitric acid and be diluted to for example 40ml of 20-60ml, add an amount of citric acid, slowly join in the aforementioned boehmite slurry, between the control pH value 1.5-3, stop behind the jelly shape colloid to be formed stirring;
C, the colloid that makes among the step b is joined in the kneading machine among the step a, fully mix to reach changing the equipment that is used for moulding over to after the required condition of extrusion and carry out moulding with powder among the step a, for example through extrusion in the banded extruder;
D, bar shaped carrier that step c is made be at drying equipment for example in the baking oven, 90-130 ℃ for example 110 ℃ for example made the carrier idiosome in dry 2-4 hour in 3 hours;
E, be that idiosome changes in the Muffle furnace and calcines with dried bar shaped carrier, calcination condition is that room temperature rose to 800 ℃ through 5 hours, and 800 ℃ kept 3 hours, cooling naturally then, preparing carriers completion;
One or more mixed configuration platiniferous maceration extract solution in f, use chloroplatinic acid, platinum nitrate, carbonic acid platinum, the platinic hydroxide.As get 1g chloroplatinic acid and 1g carbonic acid platinum and put into simultaneously that hydrochloric acid that 1000ml water adds 0.5ml 12mol/L then is stirred to chloroplatinic acid and carbonic acid platinum dissolves fully, the maceration extract configuration is accomplished.With the carrier impregnation among the step e in the platiniferous maceration extract that configures; Dipping method adopts incipient impregnation; Impregnation concentration is a foundation with the quality percentage composition of active component in the finished catalyst, and the quality percentage composition of active component in the finished catalyst (platinum oxide) is 0.004-1%;
Change over to after g, dipping are accomplished drying equipment for example in the baking oven 100-180 ℃ for example 110 ℃ dry 3-12 hour for example 3 hours;
Change calciner over to after h, the dry completion and for example calcine in the Muffle furnace, calcination condition kept 2-6 hour for example 2 hours under this temperature for for example to rise to 650-900 ℃ for example 800 ℃ in 4 hours through 3-8 hour from room temperature, cooling naturally, thus Preparation of Catalyst is accomplished.
The stable performance of coal bed gas catalyst of the present invention, active high, the life-span is long, selectivity is high.In addition owing to be easy to get as the employed raw material components economy of the carrier of coal bed gas catalyst body of the present invention, though and active component to contain its loading of noble metal low, the coal bed gas catalyst of the present invention that therefore can make with low cost.Characteristics such as in addition, coal bed gas catalyst of the present invention also has the reduction of need not, light-off temperature is low, processing is large-minded.
In the present invention, used analysis test method is as follows:
1: adopt the ASAP2020M of U.S. Merck & Co., Inc to measure specific area, pore volume and the pore-size distribution of catalyst.
2 adopt the U.S. Optima2100DV of PE company inductively coupled plasma spectral emissions appearance analysis of catalyst component.
3 adopt the U.S. 6890N of Agilent company gas chromatographic analysis product to form.
Below in conjunction with the specific embodiment, the present invention is described in further detail, protection scope of the present invention is not limited by the following example.
Take by weighing cerium zirconium compound oxide 25g, aluminium hydroxide 150g, sesbania powder 3g mixes to pinch obtaining powder.Take by weighing boehmite (Al
2O
30.08～0.62H
2O) 75g puts into beaker 1, adds 200ml distilled water and continues to stir.In beaker 2, add rare nitric acid 40ml and the 3g citric acid that concentration is 3.4mol/L and be stirred to the citric acid dissolving, the liquid in the beaker 2 is poured into be stirred to suspension formation colloid in the beaker 1.Colloid moved in the kneading machine to mix with mixed powder pinch, through the banded extruder extrusion, 110 ℃ of dryings 3 hours; In Muffle furnace, calcine then, calcination condition is that room temperature rose to 800 ℃ through 5 hours, keeps 3 hours at 800 ℃; Naturally cooling then, thus preparing carriers is accomplished.
Take by weighing the carrier 23.20g of above preparation, putting into concentration is 3.86 * 10
-3Dipping is 30 minutes in the mol/L platinum acid chloride solution.The soaked carrier catalyst 110 ℃ of dryings 3 hours, is calcined in Muffle furnace, and calcination condition was protected 2 hours under this temperature for rising to 800 ℃ from room temperature through 4 hours, cooling naturally, thus the Preparation of Catalyst completion makes catalyst sample one.Adopt the U.S. Optima2100DV of PE company inductively coupled plasma spectral emissions appearance analysis of catalyst component, it consists of by oxide mass content: 0.13% PtO
2, 85.21% Al
2O
3, 14.48% Ce-Zr-O and 0.18% do not burn the sesbania powder that loses.
Process is similar to embodiment 1 basically.Take by weighing cerium zirconium compound oxide 25g, aluminium hydroxide 150g mixes to pinch obtaining powder.Take by weighing boehmite 75g and put into beaker 1, add 200ml distilled water and be stirred to formation suspension continuation stirring.In beaker 1, adding concentration is rare nitric acid 40ml of 3.4mol/L, is stirred to suspension and forms colloid.With colloid move in the kneading machine mix with mixed powder pinch, thereby extrusion, drying, roasting accomplish preparing carriers.
Take by weighing the carrier 23.20g of above preparation, putting into concentration is 3.86 * 10
-3Dipping is 30 minutes in the mol/L platinum acid chloride solution.The soaked carrier catalyst is carried out drying, roasting; Thereby make catalyst sample two; Adopt the U.S. Optima2100DV of PE company inductively coupled plasma spectral emissions appearance analysis of catalyst component, it consists of by oxide mass content: 0.15% PtO
2, 85.35% Al
2O
3, 14.50% Ce-Zr-O).In order to compare with sample one, adopt the ASAP2020M of U.S. Merck & Co., Inc to measure specific area, pore volume and the pore-size distribution of catalyst, the result is as shown in table 1 below.
Table 1
| Title | Citric acid amount/g | Sesbania powder amount/g | Specific surface | Pore volume | The aperture |
| Sample one | 3 | 3 | 112.88 | 0.57 | 144.93 |
| Sample two | 0 | 0 | 136.74 | 0.58 | 116.72 |
To prepare catalyst sample four, be to comprise La in the cerium zirconium compound oxide wherein by quality 4.9% with embodiment 1 same program
2O
3With 4.9% Y
2O
3For with sample 1 in cerium zirconium compound oxide compare, adopt the ASAP2020M of U.S. Merck & Co., Inc to measure the specific area of this cerium zirconium compound oxide, the result is as shown in table 2 below.
Table 2
Comparative example
Take by weighing aluminium hydroxide 175g, take by weighing boehmite 75g and put into beaker 1, add 200ml distilled water and be stirred to formation suspension continuation stirring.In beaker 1, adding concentration is rare nitric acid 40ml of 3.4mol/L, is stirred to suspension and forms colloid.With colloid move in the kneading machine mix with aluminium hydroxide pinch, extrusion, drying, roasting.Preparing carriers is accomplished.
Take by weighing the carrier 23.20g of above preparation, putting into concentration is 3.86 * 10
-3Dipping is 30 minutes in the mol/L platinum acid chloride solution.The soaked carrier catalyst is carried out drying, roasting, process catalyst sample three, it consists of by oxide mass content: 0.16% PtO
2, 99.84% Al
2O
3
Catalytic performance test
The coal bed gas deoxidation performance evaluation of catalyst is carried out in fixed bed; Catalyst places middle part, reactor flat-temperature zone, does supporter with stainless (steel) wire and quartz sand up and down, and wherein the feed gas volume percentage composition is a methane 51.10%; Oxygen 4.03%; Nitrogen 44.87%, reaction pressure 0.01MPa, air speed 3000h
-1Through using embodiment 1 to 2 and sample one to three that comparative example obtained to carry out deoxidation; Obtaining the long-pending percentage composition of product gas is carbon dioxide 2.38%, methane percentage composition 50.00%, nitrogen 47.62% (adopting the U.S. 6890N of Agilent company gas chromatographic analysis product to form).The evaluation result that obtains is as shown in Figure 1.
Can find out that from result shown in Figure 1 under identical immersion condition, do not contain cerium zirconium compound oxide in the carrier of the catalyst sample three that obtains in the comparative example, its temperature spot that oxygen is removed fully is 380 ℃.And in the catalyst sample one and sample two that in embodiment 1 and 2, obtain; After adding cerium zirconium compound oxide; The temperature spot that oxygen is removed fully is 300 ℃, and the adding of visible cerium zirconium compound oxide can effectively reduce removes required temperature fully with the oxygen in the coalbed methane containing oxygen.
In addition; Result according to last table 1 can know, in the preparing carriers process of the catalyst sample two of embodiment 2, do not add sesbania powder and citric acid, and the catalyst surface burr is more; These burrs can be followed the moving of catalyst, transportation, filling etc. and come off; Cause loss of active component, and owing in the preparation process, added sesbania powder and citric acid, so in the catalyst sample one that embodiment 1 obtains, then do not have this problem; In addition; There are certain difference in catalyst sample one carrier that is obtained and the specific surface and the aperture of catalyst sample two carriers; See from evaluation result; The two temperature spot that oxygen is removed fully is consistent, so the adding of sesbania powder and citric acid to the not influence of the deoxidation effect of catalyst, but can effectively improve the molding effect of catalyst.
In addition, can find out,, can improve its high-temperature stability and aging specific surface area through in employed cerium zirconium compound oxide, mix a spot of lanthanum, yttrium according to the result of last table 2.
Should be pointed out that to those skilled in the art, under the prerequisite that does not break away from know-why of the present invention, can realize multiple modification, and these modifications should be regarded as in protection scope of the present invention also these embodiment.
Claims (18)
1. coal bed gas deoxidation catalyst, it is characterized in that: said catalyst comprises platinum oxide as active component, and carrier, wherein said carrier comprises cerium zirconium compound oxide, boehmite and aluminium hydroxide.
2. coal bed gas deoxidation catalyst according to claim 1 is characterized in that, with respect to said coal bed gas deoxidation catalyst, said active component is 0.004%～1% by the content of quality.
3. coal bed gas deoxidation catalyst according to claim 1 is characterized in that, said carrier comprises the said cerium zirconium compound oxide by quality 5-30%, the said aluminium hydroxide of 40-80% and the said boehmite of 5-40%.
4. coal bed gas deoxidation catalyst according to claim 1 is characterized in that, said carrier comprises the said cerium zirconium compound oxide by quality 10-15%, the said aluminium hydroxide of 50-65% and the said boehmite of 25-30%.
5. according to each described coal bed gas deoxidation catalyst among the claim 1-4, it is characterized in that said carrier also comprises by the sesbania powder of quality 0-3% and/or the citric acid of 0-3%.
6. according to each described coal bed gas deoxidation catalyst among the claim 1-4, it is characterized in that, said catalyst be shaped as strip, and its BET surface area is 77-186m
2/ g, pore volume 0.34-0.62ml/g, the aperture is 115-160
7. according to each described coal bed gas deoxidation catalyst among the claim 1-4, it is characterized in that, be doped with lanthanum and/or yttrium in the said cerium zirconium compound oxide.
8. coal bed gas deoxidation catalyst according to claim 7 is characterized in that said cerium zirconium compound oxide comprises the CeO of 30-80% in mass
2, 10-60% ZrO
2, 3-5% La
2O
3Y with 3-5%
2O
3
9. method for preparing according to each described coal bed gas deoxidation catalyst among the claim 1-8 said method comprising the steps of:
A) will mix as each component of support material, moulding and dry is then calcined, and is obtained said carrier then;
B) with the carrier impregnation that makes in the step a) in the platiniferous maceration extract, dry then, then calcine, and obtain said coal bed gas deoxidation catalyst.
10. method according to claim 9 is characterized in that, in step a), at first in aluminium hydroxide, adds distilled water and optional citric acid component forming jelly shape colloid, and then said colloid is mixed with other components.
11., it is characterized in that the said moulding in the step a) is to carry out extrusion through banded extruder according to claim 9 or 10 described methods.
12., it is characterized in that the baking temperature in the step a) is 80-150 ℃ according to claim 9 or 10 described methods, be 1-4 hour drying time; And the calcining heat in the step a) is 650-950 ℃, and the time is 2-6 hour.
13. method according to claim 9 is characterized in that, the platiniferous maceration extract that uses in the step b) is one or more the acidic aqueous solution that is selected from chloroplatinic acid, platinum nitrate, carbonic acid platinum, the platinic hydroxide.
14. method according to claim 9 is characterized in that, the platiniferous maceration extract that uses in the step b) is H
2PtCl
66H
2O solution.
15., it is characterized in that the baking temperature in the step b) is 100-180 ℃ according to claim 9,13 or 14 described methods, be 3-12 hour drying time; And the calcining heat in the step b) is 650-950 ℃, and the time is 2-6 hour.
16., be used for the deoxygenation of coal bed gas according to the application of each described coal bed gas deoxidation catalyst among the claim 1-8.
17. application according to claim 16 is characterized in that, said deoxygenation carries out in fixed bed reactors, and reaction condition is as follows: reaction pressure is 0～0.01MPa; Reaction temperature is 260-800 ℃; The volume space velocity of coal bed gas is 3,000-10,000h
-1
18., it is characterized in that behind said deoxygenation, the oxygen content of said coal bed gas is below the 5ppm according to claim 16 or 17 described application.
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| CN111889116B (en) * | 2019-05-05 | 2022-10-11 | 中国石油化工股份有限公司 | Catalytic combustion catalyst and preparation method thereof |
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| CN111889116A (en) * | 2019-05-05 | 2020-11-06 | 中国石油化工股份有限公司 | Catalytic combustion catalyst and preparation method thereof |
| CN111889114B (en) * | 2019-05-05 | 2022-08-12 | 中国石油化工股份有限公司 | Catalyst with shell-core structure and preparation method and application thereof |
| CN112717942A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Halogen oxidation catalyst and preparation method and application thereof |
| CN112717942B (en) * | 2019-10-28 | 2022-10-11 | 中国石油化工股份有限公司 | Halogen oxidation catalyst and preparation method and application thereof |
| CN110721707B (en) * | 2019-10-30 | 2022-07-12 | 大连凯特利催化工程技术有限公司 | Low-temperature deoxidation catalyst for synthesis gas and preparation and application thereof |
| CN110721707A (en) * | 2019-10-30 | 2020-01-24 | 大连凯特利催化工程技术有限公司 | Low-temperature deoxidation catalyst for synthesis gas and preparation and application thereof |
| CN111250100A (en) * | 2020-02-25 | 2020-06-09 | 山东科技大学 | A kind of synthesis gas sulfur-tolerant shift deoxidation catalyst and preparation method thereof |
| CN111250100B (en) * | 2020-02-25 | 2023-08-25 | 山东科技大学 | Sulfur-tolerant shift deoxidation catalyst for synthesis gas and preparation method thereof |
| CN114849697A (en) * | 2022-05-23 | 2022-08-05 | 东风汽车集团股份有限公司 | Catalyst based on three-way catalyst ceramic carrier and preparation method thereof |
| CN114849697B (en) * | 2022-05-23 | 2023-10-27 | 东风汽车集团股份有限公司 | Catalyst based on three-way catalyst ceramic carrier and preparation method thereof |
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