CN1024536C - Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method - Google Patents
Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method Download PDFInfo
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- CN1024536C CN1024536C CN 88105142 CN88105142A CN1024536C CN 1024536 C CN1024536 C CN 1024536C CN 88105142 CN88105142 CN 88105142 CN 88105142 A CN88105142 A CN 88105142A CN 1024536 C CN1024536 C CN 1024536C
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- catalyst
- manganese
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- lanthanum
- rare earth
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Abstract
The present invention provides an active non-uniform catalyst for water coal gas methanization at normal pressure, and a preparation method thereof. By addition of rare earth metals (lanthanum as main constituent), the catalyst has the compositions by weight percentage of 2 to 40% of nickel as main catalysis constituent, 5 to 30% of manganese, 0.5 to 10% of zirconium, 0.5 to 10% of rare earth metal (lanthanum) and Al-[2]O-[3] and TiO-[2] as the rest, wherein the concentrations of the manganese, the zirconium, the rare earth metals (lanthanum) and the nickel are radially distributed along the granules of the catalyst and have different optimum distribution functions. The present invention also provides a preparation method of the catalyst so that the present invention opens up an ideal approach for producing city domestic coal gas.
Description
The invention belongs to the chemical constitution modification that makes the industrial combustible gas that contains carbon monoxide with catalytic treatment, to produce the technical field of improved fuel, promptly provide a kind of active non-homogeneous type catalyzer and manufacture method thereof that is used for water at atmospheric pressure gas methanation production city coal gas.
Carbon monoxide content is up to more than 30% in the common water-gas, and its low heat value is at 2500 kilocalories/below the cubic meter; Through after the methanation, the carbon monoxide content in the product coal gas is reduced to below 10%, and its low heat value increases to about 3500 kilocalorie/cubic meters, becomes qualified town gas.Known water gas methanation catalyzer, knot charcoal phenomenon appears in association disproportionation when carrying out methanation reaction, causes catalyst activity to reduce until complete failure; Its reaction heat of methanation reaction is big, and known methanation catalyst speed of response rises with temperature of reaction and quickens, and thermal accumlation takes place easily, causes reaction bed " temperature runaway " and sintering of catalyst inactivation; Also, often need to take to give measures such as conversion or configuration hydrogen, will the energy consumption of system be increased because hydrogen-carbon ratio is less than 3 in the water-gas, and known methanation catalyst does not have the well-tuned function to methanation reaction and transformationreation.
The objective of the invention is to seek a kind of have methanation activity and selectivity preferably, do not tie charcoal, not " temperature runaway ", and the water gas methanation catalyzer with methanation-conversion double function characteristic and advantages of higher stability.
Water at atmospheric pressure gas methanation catalyzer provided by the present invention, with nickel is the main catalytic composition, and be added with manganese, zirconium, rare earth (mainly being lanthanum), aluminium, titanium auxiliary agent and support of the catalyst as catalyzer, it is characterized in that: (1) adds rare earth element and makes catalyst adjuvant, it is 0.5～10 that its add-on is calculated (weight percent) with lanthanoid metal, and other each components contents of catalyzer is (weight percent): nickel 2～40, manganese 5～30, zirconium 0.5～10, aluminium sesquioxide and titanium dioxide surplus are as support of the catalyst; (2) each component concentrations distribution of catalyzer is uneven, and promptly manganese, zirconium, rare earth (calculating with lanthanum) distribute along the granules of catalyst radial with nickel concentration and have different optimum distribution functions.Moreover, along with the variation of catalytic reaction kinetics parameter, transmission parameter and operating parameters etc., in the methanation catalyst particle, the optimum distribution function of each catalyst component also can change thereupon.By to the influence of the concentration distribution of nickel, manganese, zirconium and the rare earth (mainly being lanthanum) of catalyzer main component to catalyst activity, to the influence of catalyst selectivity with to the theoretical calculation and the experimental study of the influence of catalyzer disproportionation reaction (promptly tying the charcoal rate), the concentration that can draw nickel, manganese, rare earth (mainly being lanthanum) and zirconium in the non-uniform distribution type catalyzer of methanation activity provided by the present invention finds that along granules of catalyst radial optimum distribution function they respectively have its special regularity.Because their roles in catalyzer are inequality, so can be adjusted respectively and control its concentration distribution functions.
The concentration of the non-uniform distribution type catalyzer of methanation activity provided by the present invention main catalytic composition nickel along granules of catalyst radially the optimum distribution function be step type r
1～r
2(r
1, r
2≠ 0), C
Ni=constant; Or increment type C
Ni=ar
b(r changes between 0～1, b be on the occasion of); And the concentration of catalyst adjuvant manganese along granules of catalyst radially the optimum distribution function be the type that falls progressively: C
Mn=ar
b(r changes between 0～1, and b is a negative value) or mixed type C
Mn=ar
b+ C(r
1～r
2); The concentration of two kinds of composition rare earths of other in the catalyst adjuvant (mainly being lanthanum) and zirconium then is step type r along the radially-arranged optimum distribution function of granules of catalyst
1～r
2(r
1, r
2≠ 0) C
M=constant; Or increment type C
M=ar
b(r changes between 0～1, b be on the occasion of).
Methanation provided by the present invention is active by estimating in 15 milliliters of single tube fixed-bed reactor with active non-uniform type catalyzer.Reactor is got rid of reaction heat, reaction velocity 5000 hours with 360 ℃ of boiling state thermal oils
-1, the unstripped gas C of preparation
H2/ C
CO=2.1～2.7.The catalyzer of four batches of preparations, its one way CO transformation efficiency is all about 90%.CO content is less than 8%(such as table 1 in the product gas), this shows that this catalyzer has good methanation activity and preparation repeatability.(table 1 is seen the literary composition back)
Calorific value compares before and after the above-mentioned methanation reaction, with the C in the table 1
H2/ C
CO=2.1 is example, its low heat value increase by 2300 kilocalories/square metre; Outlet product calorific value yield is 82.2%, (table is seen the literary composition back) as shown in table 2
η=(Q
Layer-X)/(Q
Former); X is a shrinking percentage
Moreover, with service water coal gas (C
CO=30%) composition of the methanation after product coal gas that records for unstripped gas is listed in table 3.If (C during standard water coal gas
CO〉=35%, C
N2≤ 6%, C
H2〉=50%) product coal gas low heat value will increase to about 3500 kilocalorie/cubic meters.(table 3 is seen the literary composition back)
Methanation provided by the present invention is seen the literary composition back with its Main physical performance index of active non-uniform type catalyzer as table 4(table 4)
Methanation provided by the present invention has sufficiently high activity with active non-uniform type catalyzer, not carbon deposit, temperature runaway not in the high water-gas of carbon monoxide content, higher methanation selectivity is arranged, with catalyzer of the present invention can realize a kind of need not give conversion, not carbon deposit, only can be by the methanation new technological flow of water-gas production city coal gas through single-pass conversion.
The present invention also provides a kind of being exclusively used in to produce the novel process of above-mentioned methanation with active non-uniform type catalyzer, it comprises the preparation of carrier powder, the rolling moulding of the preparation of catalyst component powder, granules of catalyst, dipping and roasting five road master operations, its spy is:
(1) the carrier powder being put into catalyst component repeatedly floods (co-precipitation), dries, pulverizes and sieve and prepare the catalyst component powder with the aqueous solution of its esters;
(2) adopt program rolling method rolling moulding;
Adopt the surface impregnation method when (3) flooding manganese salt solution;
The water gas methanation provided by the present invention novel process of active non-uniform type catalyzer, its optimum implementation is as follows:
(1) preparation of alumina catalyst support powder
Get commercially available AL
2O
33H
2O dry powder is 300～600 ℃ of following roastings 2～6 hours, through sieve 200 powder materials.Should notice that foreign matter content needs below 1% in the carrier powder.
(2) preparation of catalyst component powder
With Ni-La-Al
2O
3Be example.With 36 gram Ni(NO
3) 6H
2O is dissolved in 30 ml waters; With La(NO
3) 6H
2The O4.7 gram is dissolved in 20 ml waters, takes by weighing 50 gram γ-Al
2O
3, divide dipping three times, placed 2～4 hours each dipping back, 100～150 ℃ of oven dry down, pulverize and sieve after it.
(3) the rolling moulding of granules of catalyst
Alumina powder and catalyst component powder are rolled onto 4～6mm bead according to 5～0.5 ratio follow procedures, and tackiness agent is 4～20% nitric acid, strengthens in rolling, and ageing in air is at last 400～500 ℃ of following roastings.
(4) dipping and roasting
Get Mn(NO
3)
250% solution, 32 grams add water to 50 milliliter, with the spherical catalysts dipping of 100 gram rolling moulding, place 4 hours, afterwards 400～600 ℃ of following roastings 4 hours, obtain active non-uniform type methanation catalyst finished product.
Total energy consumption in China, the consumption of coal accounts for more than 70%, and civilian coal consumption amount accounts for wherein 15%, because civilian coal major part is disperseed consumption with direct combustion system, thermo-efficiency is low, the coal resource waste is big, seriously polluted to urban environment.One of effective way that solves above-mentioned contradiction is the urban coal gasification, at present, China's urban coal gasification rate is very low, one of its reason is exactly: the manufacturing technology of not grasping advanced pressurized-gasification furnace on the one hand, caloric power of gas with normal pressure technology gasification gained is very low on the other hand, does not meet the standard of city domestic gas.Methanation provided by the present invention has been opened up an ideal approach with active non-uniform type catalyzer for making hydrogen and carbon monoxide synthesizing methane production city domestic gas under normal pressure, and it will produce good social benefit and economic benefit.
Table 1 water gas methanation catalyst activity
Unstripped gas tail gas forms %
Preparation lot number experiment R
C
H2/C
CoCH
4CO CO
2
85-01 single-3 2.3 90.4 50.3 6.7 15.2
85-02 single-4 2.1 89.0 47.8 7.8 17.2
85-03 single-5 2.2 92.3 50.7 5.3 17.2
85-04 single-6 2.7 92.7 49.7 4.5 12.1
Calorific value compares C before and after table 2 methanation reactionH2/C
Co＝2.1
Project actual measurement and result of calculation
Calorific value (low) Q 2703 KCal/M before the reaction
Calorific value (low) Q 5023 KCal/M after the reaction
Q
Tail/Q
Former1.86
△ Q
Increase=Q
Tail-Q
Former2311 KCal/M
Outlet caloric power of gas yield η 82.2%
The quality of table 3 methanation product coal gas (experiment of liter level industry single tube)
The main physical index of the non-homogeneous catalyzer of table 4 methanation activity
Project performance and index
Particle diameter 4.0～5.0 spheries
The color iron gray
More than the intensity 1.0kg/grain
Bulk density 0.9kg/l
Specific surface area 160～180M
3/ g
Mean pore size 90A
Claims (1)
1, a kind of water at atmospheric pressure gas methanation active non-uniform type catalyzer, it is main catalyst component with nickel, manganese and zirconium are made auxiliary agent, Al
2O
3And TiO
2Make carrier, it is characterized in that:
Add rare earth metal (is major ingredient with the lanthanum) in auxiliary agent, the composition scope of catalyzer is by weight percentage: nickel 2-10, manganese 5-30, zirconium 5-10, rare earth (calculating with lanthanum) 0.5-10, Al
2O
3And TiO
2
This Preparation of catalysts technology, it comprises the preparation of carrier powder, the preparation of catalyst component powder, granules of catalyst rolling moulding, dipping and roasting five road master operations is characterized in that:
A) preparation of catalyst component powder is to adopt the carrier powder to be put into the salts solution that contains catalyst component nickel, zirconium and rare earth metal (is major ingredient with the lanthanum) repeatedly floods or the technology of co-precipitation;
B) granules of catalyst rolling moulding is to take program rolling method, and what be about to that carrier powder and step a) obtain contains the rolling moulding in order of catalyst component powder;
C) dipping adopts the surface impregnation method during manganese, with the salt brine solution impregnation steps b of manganese) granules of catalyst that obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105142 CN1024536C (en) | 1988-10-19 | 1988-10-19 | Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105142 CN1024536C (en) | 1988-10-19 | 1988-10-19 | Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1041968A CN1041968A (en) | 1990-05-09 |
| CN1024536C true CN1024536C (en) | 1994-05-18 |
Family
ID=4833370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105142 Expired - Fee Related CN1024536C (en) | 1988-10-19 | 1988-10-19 | Active non-uniform catalyzer for ordinary pressure water-gas methanides and its making method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024536C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068036C (en) * | 1998-01-23 | 2001-07-04 | 中国科学院山西煤炭化学研究所 | Catalyst for combustion of natural gas and preparing process thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100531904C (en) * | 2007-10-23 | 2009-08-26 | 中山大学 | Catalyst used for catalytic synthesis for dimethyl carbonate directly from methanol and carbon dioxide, and preparation and using method thereof |
| CN101468311B (en) * | 2007-12-29 | 2010-12-22 | 大连普瑞特化工科技有限公司 | Catalyst for methanation of coal gas and preparation method thereof |
| CN102029162B (en) * | 2009-09-28 | 2013-01-16 | 中国科学院大连化学物理研究所 | Wide-temperature full methanation catalyst and preparation method thereof |
| KR20130035639A (en) * | 2011-09-30 | 2013-04-09 | 한국전력공사 | Spray-dried water gas shift catalyst |
| KR101328697B1 (en) * | 2012-11-15 | 2013-11-14 | 재단법인 포항산업과학연구원 | Apparatus and method for producing synthetic natural gas |
| CN103060035B (en) * | 2013-01-22 | 2014-12-10 | 新地能源工程技术有限公司 | Method for producing LNG (liquefied natural gas) by coal-based synthesis gas |
| CN105435860A (en) * | 2014-08-13 | 2016-03-30 | 中国石油化工股份有限公司 | Catalyst with non-uniformly-distributed cocatalyst and preparation method thereof |
-
1988
- 1988-10-19 CN CN 88105142 patent/CN1024536C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1068036C (en) * | 1998-01-23 | 2001-07-04 | 中国科学院山西煤炭化学研究所 | Catalyst for combustion of natural gas and preparing process thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1041968A (en) | 1990-05-09 |
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