CN104492279A - Method for preparing sulfur resistant palladium composite membrane by separating hydrogen from synthesis gas from coal - Google Patents
Method for preparing sulfur resistant palladium composite membrane by separating hydrogen from synthesis gas from coal Download PDFInfo
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- CN104492279A CN104492279A CN201410808377.XA CN201410808377A CN104492279A CN 104492279 A CN104492279 A CN 104492279A CN 201410808377 A CN201410808377 A CN 201410808377A CN 104492279 A CN104492279 A CN 104492279A
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- hydrogen
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Abstract
The invention relates to a method for preparing a sulfur resistant palladium composite membrane by separating hydrogen from synthesis gas from coal. The method comprises the following steps: depositing a Ta film on a ceramic carrier by adopting a magnetron sputtering technology or vapor deposition method to obtain a Ta film deposited base body with a certain thickness; forming a metal palladium composite membrane with sulfur resistance on the surface of the base body by adopting an electroless plating method. The formed composite membrane can be Pd-Cu-Ce, Pd-Cu-La, and Pd-Ag-Ce. The composite membrane has good sulfur resistance in the process of purifying the hydrogen from the synthesis gas from the coal, and has the advantages of high hydrogen permeability and high mechanical properties. In an atmosphere of the synthesis gas, the membrane prepared by adopting the method can be used for extracting the hydrogen with the high purity, can permeate more hydrogen than a pure palladium membrane, is durable, and can also be used at high temperatures.
Description
Technical field
The present invention relates to a kind of method preparing the sulfur resistive composite membrane of separating hydrogen gas from producing synthesis gas from coal, first at the certain thickness Ta metal of porous carrier surface deposition, then with chemical plating method, the metals such as palladium are plated to metal carrier surface; Due to inserting of Ta metal, thus can strengthen palladium film strength, hydrogen permeability improves, and has higher mechanical strength, can at high temperature carry out pure hydrogen separation.The composite metal membrane prepared by the present invention can be separated pure hydrogen under the producing synthesis gas from coal condition of sulfur-bearing, thus has comparatively wide application prospect.
Background technology
Along with the chemical industry develop rapidly centered by semiconductor, petroleum industry and three large synthetic materials, and use hydrogen as the utilization of aerospace fuel, the demand of hydrogen is increased sharply, simultaneously many electronics industries, metallurgical industry are also in the urgent need to a large amount of hydrogen, therefore hydrogen energy source and widely being paid attention to by people.How to expand hydrogen source and be day by day subject to people's common concern, wherein an important approach is separating hydrogen gas from coal/biomass synthesis gas; Be separated H traditionally
2the method of admixture of gas mainly contains chemical absorbing, cryogenic separation, pressure-variable adsorption and membrane separation process; Chemical absorption process application is divided into narrow, is only only applicable to CO
2and H
2separation; Deep cooling process for separating investment is higher, only when unit scale is larger, just has preferably economy; Pressure swing adsorption method is widely used in Hydrogen Separation in the gases such as synthetic ammonia, semiwater gas, town gas, coke-stove gas, but the method needs multiple adsorption plant just can complete, and energy consumption is high, and equipment investment is large, and operating cost is high; Also have a kind of hydrate separation method at present, but also at laboratory stage; Gas membrane Seperation Technology is a kind of new and high technology, and Membrane Gas Separation Processes produces without phase transformation, and energy consumption is low, and small investment is easy to use, and operating flexibility is large.Since the eighties in 20th century, America and Japan Korea Spro and European Countries adopt gas membrane Seperation Technology recover hydrogen from refinery gas one after another; The development of more than 30 year of China's film industry experience, is also widely used in the industries such as oil, chemical industry, electric power, the energy, medicine and environmental protection at present.
Producing synthesis gas from coal purifying hydrogen of hydrogen is the technical method proposed external recent years, due to gas composition more complicated, and the especially existence of sulfide, relevant report is few, especially adopts the less of membrane separating method application; Hydrogen permeation membrane is main both at home and abroad belongs to platinum family element and alloy film thereof with Pd, and this film has good machinery and heat endurance and catalytic activity, causes the increasing interest of people in catalytic membrane reaction and hydrogen isolation and purification application aspect and studies widely; Also some are not had report containing other compact metal hydrogen permeation membrane of palladium, as platinum film, vanadium film, vanadium nickel alloy film, niobium film, tantalum film etc., but existing problems mainly low, the poor stability of saturating hydrogen rate; The difficult point of synthesis gas hydrogen manufacturing is gas cleaning, and membrane separating property can be caused to decline; Due to H a small amount of in synthesis gas
2the existence of S and COS, can make the inoranic membrane permanent " poisoning " of picture palladium and palldium alloy class, cause membrane separating property to be lost; Correlative study shows, several refractory metal is as high with the hydrogen permeability of vanadium (V) relative palladium in niobium (Nb), tantalum (Ta), zirconium (Zr), but also has acceptable mechanical strength; Copper (Cu), silver (Ag), aluminium (Al) and rare earth have certain effect to anti-H 2 S.
In addition, current internal membrane partition method is applied more in ammonia synthesizing industry, water-gas, natural gas etc., and in coal gasification preparing synthetic gas purifying hydrogen of hydrogen, research report is less; In synthesis gas, hydrogen content reaches as high as 70% nearly, is a kind of fine raw material of purifying hydrogen of hydrogen.USDOE announces at present, subsidizes 5,900,000 dollars to 4 advanced Coal Gasification projects, and exploitation membrane separation technique is used for coal or gasification of biomass produces synthesis gas.Such as from integrated stalk gasification combined circulation power generation system, utilize membrane technology to be separated hydrogen and carbon dioxide, these projects will make modularization amplify further, make Design and manufacture reach commercial scale, and combination is used for advanced power plant; The unit of these exploitations of current participation mainly comprises, and Praxair company develops palldium alloy cooperatively in Colorado School of Mines, is carried on ceramic monolith, for the synthesis gas separating hydrogen gas that coal is derivative.Having of other exploitations, US National Technical Research Center adopts the composite metal film of 3 kinds of forms, western research institute cooperates with Chart energy chemistry company, exploitation plane palladium base pottery-anodic alumina films, Nie Si secret service institute cooperates with energy u s company of Siemens, verify that palldium alloy load is on porous ceramics, separating hydrogen gas from synthesis gas.
Therefore, using membrane separating technology adopts hydrogen purification, selective high metal composite film, and from producing synthesis gas from coal, extract highly purified hydrogen is necessary; It is the developing direction that composite membrane is separated hydrogen that porous metals group compound film synthesis gas extracts hydrogen, further exploitation sulfur resistance is good, mechanical strength and the higher film support of heat resistance, establish the preparation method that palladium-based composite membrane is more cheap, under studying different film condition and operating condition, palladium-based composite membrane is to synthesis gas separative efficiency and Hydrogen Separation purity, furtheing investigate the Novel composite membrane of high service life, high permeability, is the direction of palladium film development from now on.
Summary of the invention
The present invention is intended to provide a kind of method adopting membrane separation technique to extract high-purity hydrogen from producing synthesis gas from coal; By to support modification, choose the composition metal of applicable sulfur resistive effect, take the coating process be applicable to, produce palladium group compound film, make from producing synthesis gas from coal, extract hydrogen and utilized efficiently.
To achieve these goals, first with homemade desulfurizing agent, the total sulfur in synthesis gas is removed to 1000mg/m
3below; Then on pottery or stainless steel supporter, one deck small-bore Ta film is prepared, adopt magnetron sputtering technique or vapour deposition process deposit Ta film on ceramic monolith, obtain the carrier of certain thickness Ta film deposition, then, chemical plating is adopted to form the metal palladium-based composite membrane with sulfur resistance at carrier surface; Final formation supporter, Ta film and palladium-based composite membrane multilayer system; Formed composite membrane can be Pd-Cu-Ce, Pd-Cu-La, Pd-Ag-Ce.Composite membrane of the present invention has good sulfur resistive characteristic in producing synthesis gas from coal purifying hydrogen of hydrogen process, and the advantage of this film is high to the permeability of hydrogen, also has very high mechanical performance.Film prepared by the method, under synthesis gas atmosphere, has the purity of higher extracting hydrogen, can permeate more hydrogen than pure palladium film, and durable, can also at high temperature use.
This technique can be carried out according to the following steps.
1. use NaOH and HCl to clean carrier, then clean by deionized water, dry to constant weight.
2. sputter certain thickness Ta film with magnetic control sputtering device at carrier surface under vacuum, the through hydrogen capacity of palladium film is not the strongest in metal, and Ta film has higher saturating hydrogen rate than palladium film, and mechanical strength is better, but be easy to oxidation, can oxidation be eliminated at the outer alloy plating film of Ta film; Form sandwich type or sandwich type composite membrane.
3. carrier sensitization and activation in the solution, solution adopts PdCl respectively
2, AgNO
3, CuSO
4, Ce (NO
3)
3, La (NO
3)
2.
4. porous carrier is immersed in chemical plating fluid, wherein chemical plating fluid consist of Na
2eDTA2H
2o, NH
4oH, NaOH, N
2h
5oH, CH
2o and HCl; Chemical plating fluid concentration is along with adding different metal and addition change.
5. pair porous material processes, and by composite membrane under 120 DEG C of conditions dry 3 hours, then roasting 12 hours at 550-800 DEG C, obtained composite membrane.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described.
Detailed description of the invention
Embodiment 1.
Vehicle element: choose tubular ceramic pipe carrier, pipe external diameter 10mm, internal diameter 7mm, average pore size 0.3 μm, voidage 23%; By earthenware at 5%NaOH, after removing surface impurity and oxide in concentrated hydrochloric acid and phosphoric acid, by dried for standby after washed with de-ionized water.
Ta film preparation: sputter Ta with magnetic control sputtering device on earthenware carrier, thickness is 50nm.Temperature is room temperature, system vacuum 10
-4pa, sputter gas is high-purity argon gas.
Prepared by palladium alloy membrane: carry out plated film by traditional chemical electroplating method to carrier; PH value 9-11, solution composition is: PdCl
2(5g/l), AgNO
3(5g/l), CuSO
4(6g/l), Na
2eDTA2H
2o(50g/l), NH
4oH(300g/l), N
2h
5oH(2g/l), CH
2o(10g/l).First at earthenware deposited on supports palladium film, then deposit silverskin and copper film successively, by composite membrane under 120 DEG C of conditions dry 3 hours, then roasting 12 hours at 550 DEG C, obtained Pa-Ta-Ag-Cu composite membrane.
Hydrogen permeability can be tested and be carried out under analog synthesis gas atmosphere, and synthesis gas proportioning is 95% H
2, H
2s 100 mg/m
3, COS 20 mg/m
3, Balance Air Ar; At 500 DEG C, under 0.1MPa condition, composite membrane permeated hydrogen amount is 0.89 molm
-2s
-1bar
-1.
Embodiment 2.
Vehicle element: choose tubular ceramic pipe carrier, pipe external diameter 10mm, internal diameter 7mm, average pore size 0.3 μm, voidage 23%; By earthenware at 5%NaOH, after removing surface impurity and oxide in concentrated hydrochloric acid and phosphoric acid, by dried for standby after washed with de-ionized water.
Ta film preparation: sputter Ta with magnetic control sputtering device on earthenware carrier, thickness is 60nm; Temperature is room temperature, system vacuum 10
-4pa, sputter gas is high-purity argon gas.
Prepared by palladium alloy membrane: carry out plated film by traditional chemical electroplating method to carrier; PH value 10, solution composition is: PdCl
2(5g/l), AgNO
3(5g/l), Ce (NO
3)
3(5g/l), Na
2eDTA2H
2o(30g/l), NH
4oH(500g/l), N
2h
5oH(2g/l), CH
2o(10g/l); First at earthenware deposited on supports palladium film, then deposit silverskin and cerium film successively, by composite membrane under 120 DEG C of conditions dry 3 hours, then roasting 12 hours at 600 DEG C, obtained Pd-Ta-Ag-Ce composite membrane.
Hydrogen permeability can be tested and be carried out under analog synthesis gas atmosphere, and synthesis gas proportioning is 70% H
2, 10%CO
2, 2%CO, H
2s 100 mg/m
3, COS 20 mg/m
3, Balance Air Ar; At 500 DEG C, under 0.1MPa condition, composite membrane permeated hydrogen amount is 0.95 molm
-2s
-1bar
-1.
Embodiment 3.
Vehicle element: choose tubular ceramic pipe carrier, pipe external diameter 10mm, internal diameter 7mm, average pore size 0.3 μm, voidage 23%.By earthenware at 5%NaOH, after removing surface impurity and oxide in concentrated hydrochloric acid and phosphoric acid, by dried for standby after washed with de-ionized water.
Ta film preparation: sputter Ta with magnetic control sputtering device on earthenware carrier, thickness is 60nm.Temperature is room temperature, system vacuum 10
-4pa, sputter gas is high-purity argon gas.
Prepared by palladium alloy membrane: carry out plated film by traditional chemical electroplating method to carrier.PH value 10, solution composition is: PdCl
2(5g/l), CuSO
4(6g/l), Ce (NO
3)
3(5g/l), Na
2eDTA2H
2o(30g/l), N
2h
5oH(2g/l).First at earthenware deposited on supports palladium film, then deposited copper and cerium film successively, by composite membrane under 120 DEG C of conditions dry 3 hours, then roasting 12 hours at 600 DEG C, obtains Pd-Ta-Cu-Ce composite membrane.
Hydrogen permeability can be tested and be carried out under analog synthesis gas atmosphere, and synthesis gas proportioning is 60% H
2, 20%CO
2, 2%CO, H
2s 100 mg/m
3, COS 20 mg/m
3, Balance Air Ar.At 500 DEG C, under 0.1MPa condition, composite membrane permeated hydrogen amount is 1.05 molm
-2s
-1bar
-1.
Embodiment 4.
Vehicle element: choose porous stainless steel carrier, average pore size 0.1-0.2 μm, thickness 0.1mm.First by stainless steel carrier sand papering, then at 5%NaOH, after removing surface impurity and oxide in concentrated hydrochloric acid and 40% phosphoric acid, by dried for standby after washed with de-ionized water.
Ta film preparation: sputter Ta with magnetic control sputtering device on stainless steel carrier, thickness is 50 nm.Temperature is room temperature, system vacuum 10
-4pa, sputter gas is high-purity argon gas.
Prepared by palladium alloy membrane: carry out plated film by traditional chemical electroplating method to carrier.Solution composition is: PdCl
2(5g/l), CuSO
4(6g/l), Ce (NO
3)
3(5g/l), Na
2eDTA2H
2o(30g/l), N
2h
5oH(2g/l).First depositing Pd film on stainless steel carrier, then deposited copper and cerium film successively, by composite membrane under 120 DEG C of conditions dry 3 hours, then roasting 12 hours at 600 DEG C, obtained Pd-Ta-Cu-Ce composite membrane.
Hydrogen permeability can be tested and be carried out under analog synthesis gas atmosphere, and synthesis gas proportioning is 60% H
2, 20%CO
2, 2%CO, H
2s 100 mg/m
3, COS 20 mg/m
3, Balance Air Ar.At 500 DEG C, under 0.1MPa condition, composite membrane permeated hydrogen amount is 1.17 molm
-2s
-1bar
-1.
Embodiment 5.
Vehicle element: choose porous stainless steel carrier, average pore size 0.1-0.2 μm, thickness 0.1mm.First by stainless steel carrier sand papering, then at 5%NaOH, after removing surface impurity and oxide in concentrated hydrochloric acid and 40% phosphoric acid, by dried for standby after washed with de-ionized water.
Ta film preparation: sputter Ta with magnetic control sputtering device on stainless steel carrier, thickness is 50 nm.Temperature is room temperature, system vacuum 10
-4pa, sputter gas is high-purity argon gas.
Prepared by palladium alloy membrane: carry out plated film by traditional chemical electroplating method to carrier.Solution composition is: PdCl
2(5g/l), CuSO
4(6g/l), La (NO
3)
2(5g/l), Na
2eDTA2H
2o(30g/l), N
2h
5oH(2g/l).First depositing Pd film on stainless steel carrier, then deposited copper and cerium film successively, by composite membrane under 120 DEG C of conditions dry 3 hours, then roasting 12 hours at 600 DEG C, obtained Pd-Ta-Cu-La composite membrane.
Hydrogen permeability can be tested and be carried out under analog synthesis gas atmosphere, and synthesis gas proportioning is 60% H
2, 20%CO
2, 2%CO, H
2s 100 mg/m
3, COS 20 mg/m
3, Balance Air Ar.At 500 DEG C, under 0.1MPa condition, composite membrane permeated hydrogen amount is 1.02 molm
-2s
-1bar
-1.
Claims (6)
1. one kind is separated the preparation method of the sulfur resistive palladium-based composite membrane of pure hydrogen from producing synthesis gas from coal, be characterised in that at ceramic or stainless steel-based surface employing magnetron sputtering technique or vapour deposition process deposit Ta film, adopt chemical plating to form the metal palladium-based composite membrane with sulfur resistance at matrix surface; Formed composite membrane have good sulfur resistive characteristic, high to the permeability of hydrogen, there is very high mechanical performance, can also at high temperature use.
2. according to the method that right 1 requires, be characterised in that under vacuum, magnetron sputtering Ta metal film on ceramic matrix, Ta film Direct precipitation on a ceramic substrate, adopts chemical plating to form the metal palladium-based composite membrane with sulfur resistance at matrix surface subsequently.
3., according to the method that claim 2 requires, be characterised in that sensitization and the activation in the solution of modified matrix, solution adopts PdCl respectively
2, AgNO
3, CuSO
4, Ce (NO
3)
3, La (NO
3)
2.
4. according to the method for claim 2 and 3, wherein chemical plating fluid consist of Na
2eDTA2H
2o, NH
4oH, NaOH, N
2h
5oH, CH
2o and HCl.
5. any one method in requiring according to right 2-4, is characterised in that and uses porous ceramics or porous stainless steel to be substrate, before Pd composite metal film deposition, at the Ta layer that deposited on substrates 50-100 nm is thick; Ta film adopts magnetically controlled sputter method preparation, and the Ta film that 50-100 nm is thick is directly deposited on substrate.
6. obtain many metal levels palladium-based composite membrane according to the method for any one in claim 2-5; Composite metal membrane can containing H
2in the producing synthesis gas from coal atmosphere of S and COS, effective separating hydrogen gas, can carry out pure hydrogen separation under 500 DEG C of conditions.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984665A (en) * | 2015-05-27 | 2015-10-21 | 天津工业大学 | Preparation method of composite separation membrane |
| CN108097065A (en) * | 2018-01-02 | 2018-06-01 | 兰州理工大学 | A kind of preparation method of low cost sulfur resistive palladium alloy composite membrane |
| CN114797496A (en) * | 2022-05-20 | 2022-07-29 | 西北有色金属研究院 | Palladium-tantalum composite membrane and preparation method thereof |
| CN115029677A (en) * | 2022-06-27 | 2022-09-09 | 商丘市鸿大光电有限公司 | Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx gradient barrier layer |
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| WO2014157876A1 (en) * | 2013-03-26 | 2014-10-02 | 한국에너지기술연구원 | Hydrogen separation membrane and preparation method therefor |
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| CN104178754A (en) * | 2013-05-23 | 2014-12-03 | 中国科学院大连化学物理研究所 | A cyclic chemical plating method for a multi-channel metal palladium composite film |
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2014
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104984665A (en) * | 2015-05-27 | 2015-10-21 | 天津工业大学 | Preparation method of composite separation membrane |
| CN104984665B (en) * | 2015-05-27 | 2017-06-30 | 天津工业大学 | The preparation method of composite separating film |
| CN108097065A (en) * | 2018-01-02 | 2018-06-01 | 兰州理工大学 | A kind of preparation method of low cost sulfur resistive palladium alloy composite membrane |
| CN114797496A (en) * | 2022-05-20 | 2022-07-29 | 西北有色金属研究院 | Palladium-tantalum composite membrane and preparation method thereof |
| CN115029677A (en) * | 2022-06-27 | 2022-09-09 | 商丘市鸿大光电有限公司 | Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx gradient barrier layer |
| CN115029677B (en) * | 2022-06-27 | 2023-10-31 | 商丘市鸿大光电有限公司 | Preparation process of high-hydrogen-permeability isotope and high-temperature-resistant TaVNbZr/(TaVNbZrM) Nx composite gradient barrier layer |
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Application publication date: 20150408 |