WO2011083833A1 - 水素燃焼触媒及びその製造方法並びに水素燃焼方法 - Google Patents
水素燃焼触媒及びその製造方法並びに水素燃焼方法 Download PDFInfo
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- WO2011083833A1 WO2011083833A1 PCT/JP2011/050150 JP2011050150W WO2011083833A1 WO 2011083833 A1 WO2011083833 A1 WO 2011083833A1 JP 2011050150 W JP2011050150 W JP 2011050150W WO 2011083833 A1 WO2011083833 A1 WO 2011083833A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J33/00—Protection of catalysts, e.g. by coating
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21B—FUSION REACTORS
- G21B1/00—Thermonuclear fusion reactors
- G21B1/11—Details
- G21B1/115—Tritium recovery
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B5/00—Water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/10—Nuclear fusion reactors
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Definitions
- the present invention relates to a catalyst for burning hydrogen (including isotopes) in an air-containing gas.
- the present invention provides a hydrogen combustion catalyst which is resistant to the influence of water mist or steam in the atmosphere and water generated by hydrogen combustion, and can maintain its activity even at a relatively low temperature.
- tritium removal equipment In nuclear fusion plants that use deuterium (D) and tritium deuterium (tritium, T) as fuel, tritium removal equipment is required to treat exhaust from building facilities where nuclear fusion reactors and the like are installed. This is because tritium contained in the exhaust is a radioactive substance, which can not be released outside the facility even by a small amount.
- the tritium removal equipment passes the exhaust from the building facility through the catalyst layer to burn hydrogen containing tritium into water, removes and recovers the water component, and discharges the clean exhaust.
- a conventionally known hydrogen combustion catalyst has been used because tritium is an isotope of hydrogen and can be combusted in the same manner as hydrogen.
- a hydrogen combustion catalyst one in which a catalyst metal such as platinum is supported on a pellet-like carrier made of a metal oxide such as silica or alumina is generally used.
- the active platinum is covered with a water film, hydrogen diffusion to platinum is inhibited, and there is a problem that the catalyst is deactivated.
- the process object gas is heated to about 200 degreeC, and it is made to pass through a catalyst layer.
- This is based on the general knowledge that the activity of the catalyst is higher when the reaction temperature is higher, and at the same time, the diffusion of hydrogen by the steam generated by the hydrogen combustion and the steam originally contained in the processing gas To inhibit the inhibition of That is, these moistures are adsorbed to the metal oxide which is the carrier, but such adsorbed water causes the activity of the catalyst to be reduced. Therefore, it is necessary to make the reaction temperature high in order to evaporate generated water simultaneously with production and release it out of the catalyst.
- heating of the exhaust gas for hydrogen combustion as described above is essential to maintain the progress of the reaction, it is positioned as an important facility to ensure safety from the viewpoint of safety of the fusion plant The fact is that it is desirable to avoid raising the temperature of the catalytic oxidation reactor.
- reaction continuation at low temperature may be required.
- the reaction at low temperature leads to a decrease in activity due to the adsorption of generated water. Therefore, the present invention provides a hydrogen combustion catalyst that does not need to consider the influence of moisture in the atmosphere or water produced by the combustion reaction, and can maintain the reaction at low temperature.
- the present invention for solving the above problems is a hydrogen combustion catalyst comprising a catalyst metal supported on a carrier comprising an inorganic oxide, wherein the hydroxyl group on the surface of the carrier has at least one alkyl group having 3 or less carbon atoms at its terminal.
- a hydrogen combustion catalyst characterized in that a functional group is substituted and bonded.
- the present inventors examined the hydrophobization by the surface treatment, making a support
- the hydrogen moiety of the hydroxyl group (OH group) on the metal oxide surface is substituted with a functional group having an alkyl group.
- the functional group modifying the hydroxyl group has at least one alkyl group at the end.
- the terminal of the hydroxyl group on the surface of the carrier is an alkyl group because it is excellent in the effect of reducing the polarity of the surface of the carrier, and water molecules can be quickly discharged without being adsorbed to the carrier.
- the carbon number of the alkyl group is required to be 3 or less (methyl group, ethyl group, propyl group). According to the present inventors, the carbon number of the alkyl group affects the heat resistance to the hydrophobization effect of the catalyst.
- a support modified with an alkyl group (such as a butyl group) having a carbon number of 3 or more tends to lose hydrophobicity at high temperature, which causes water adsorption and catalyst deactivation.
- an alkyl group such as a butyl group
- this heat resistance does not pose a direct problem to the present invention on the premise of a low temperature reaction, it causes reaction nonuniformity when a local temperature rise due to the heat of reaction occurs in the catalyst layer. It should be avoided.
- the number of the alkyl groups which the functional group has may be at least one, but may have a plurality of alkyl groups.
- the organic silane which has an alkyl group is preferable. It is because it has various forms as a functional group which has an alkyl group, and the reactivity with respect to a hydroxyl group is also favorable. As a specific example, the following manufacturing method will be described.
- the support of the catalyst according to the present invention is a metal oxide, preferably alumina, silica, silica-alumina, zeolite or zirconia. These metal oxides are conventionally used as catalyst carriers, and are excellent in porosity and heat resistance.
- the shape of the carrier is not particularly limited. In general, those formed into cylindrical and spherical pellets are coated with these metal oxides on an appropriate support such as a honeycomb, mesh or the like, and the coating layer is subjected to a hydrophobization treatment. It can also be a carrier.
- the catalytic metal is formed by adsorbing a metal salt solution to a carrier and reducing it according to the loading method to be described later, and forming an atomic metal formed by reducing the metal salt solution or a colloid prepared by adsorbing a metal colloid solution prepared in advance to the carrier. It is in the form of metallic (cluster-like) metal, but may be in any state.
- the particle diameter of the catalyst metal is 1 to 100 nm according to these conditions.
- the loading amount (loading ratio) of the catalyst metal is not particularly limited, but generally 0.1 to 10% by weight based on the weight of the carrier.
- the catalyst according to the present invention one having a specific surface area of 100 to 300 m 2 / g, an average pore diameter of 100 to 300 nm, and a pore volume of 0.3 to 1.0 mL / g is preferable.
- the hydroxyl group on the surface of the support is immersed by immersing the inorganic oxide as the support in a solution of a functional group compound having an alkyl group having 3 or less carbon atoms at its terminal. And the step of supporting the catalyst metal on the carrier.
- the hydrophobization treatment of the carrier is to adsorb a solution of a compound containing a functional group that modifies the hydroxyl group on the surface of the inorganic oxide.
- a silane inorganic surface modifier is preferable, and as a silane inorganic surface modifier having an alkyl group at the end, trimethylmethoxysilane, trimethylethoxysilane, trimethylchlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane , Dimethyldichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, triethylmethoxysilane, triethylethoxysilane, triethylchlorosilane, triethylchlorosilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldichlor
- the carrier is immersed in a solution in which the above-mentioned compound is dissolved in a solvent. At this time, the hydrogen of the hydroxyl group on the surface of the carrier is replaced by the hydrophobic functional group. Thereafter, the carrier is taken out of the solution, and appropriately washed and dried.
- the catalyst according to the present invention is preferably completely substituted by hydroxyl groups on the surface of the carrier.
- the amount of compound to be mixed into the solution can be calculated from the coated area (m 2 / g) specified for each compound, the weight (g) of the carrier and the specific surface area (m 2 / g) ( (Carrier weight ⁇ carrier specific surface area) / compound coating area), approximately 1.0 to 100 g of the compound is used based on 100 g of the carrier.
- the amount of the solution (solvent) be such that the carrier is completely soaked.
- the support of the catalyst metal on the hydrophobized support is similar to that of the conventional catalyst.
- a method of supporting a catalytic metal there has conventionally been a method of immersing a carrier in a solution of a metal salt, and thereafter supporting an atomic metal by addition of a reducing agent or heat treatment.
- the metal salt in this case is a platinum salt such as dinitrodiammine platinum or chloroplatinic acid for platinum, and a palladium salt such as palladium nitrodiammine or palladium chloride for palladium.
- Another method of supporting catalytic metals is a method of supporting metal colloids.
- the metal colloid is produced by adding a metal salt and, if necessary, an organic compound as a protective agent to a solvent, and adding a reducing agent thereto.
- the carrier is brought into contact with a solution after colloid production or a solution in which a metal colloid obtained by filtering once is dispersed again in a solvent to adsorb metal colloid particles, and appropriately washing and heat treatment
- the catalyst can be adjusted by application.
- the hydrogen combustion catalyst according to the present invention described above does not require heating for suppressing adsorption of water produced by hydrogen combustion reaction and water in the atmosphere, and can continue the hydrogen combustion reaction at a relatively low temperature.
- the hydrogen-containing gas to be treated is also effective for those containing water of the amount of saturated steam at the reaction temperature,
- the reaction temperature can be room temperature, specifically 0 to 40 ° C.
- the hydrogen combustion catalyst according to the present invention can suppress the adsorption of the moisture in the water produced by hydrogen combustion or the processing gas on the carrier by providing the carrier with hydrophobicity. Thereby, the catalyst activity can be maintained without raising the temperature of the catalyst layer. At the same time, since it repels water also to liquid water such as sprinkler in an emergency fire etc., resistance to water wet deterioration is given.
- the hydrogen combustion catalyst according to the present invention is applicable to various devices for hydrogen combustion, a catalytic oxidation reactor which oxidizes tritium in exhaust gas from a tritium utilization facility and converts it into water from the above merit It is useful.
- the carrier was washed with pure water, and the carrier was immersed in an ethanol solution (concentration 15% by weight) of various silane inorganic surface modifiers for 24 hours. Thereafter, the carrier was taken out, washed with pure water and dried at 200 ° C. In this case, the weight increase due to the silane treatment was about 13%.
- the hydrophobizing treatment for this silica support is carried out using dimethyldimethoxysilane, n-propyltrimethoxysilane, n-butyltrimethoxysilane, n-hexylmethoxysilane, which are silane inorganic surface modifiers other than the above methyltrimethoxysilane. The same process was performed using.
- each silane mineral surface modifier is recognized from Table 1, when the carbon number of the alkyl group to couple
- a catalyst was produced using a silica support treated with methyltrimethoxysilane which was particularly excellent in the hydrophobicity effect in the above test, and its performance was evaluated.
- the alumina support was also subjected to hydrophobization treatment with methyltrimethoxysilane to produce a catalyst.
- Table 2 shows the physical properties of each carrier before and after the hydrophobization treatment.
- a solution obtained by diluting 25 g of a 5% solution of chloroplatinic acid in ethanol in 100 g of ethanol is added to each support (100 g) and impregnated. Subsequently, ethanol was evaporated by a rotary evaporator, and then put into a column, and 3% hydrogen gas (N 2 balance) was circulated at 300 ° C. for 2 hours to be reduced to obtain a catalyst.
- the catalyst produced above has a platinum concentration of 1.0% by weight.
- platinum colloid particles were supported on each carrier as a catalyst metal.
- the supported platinum colloid was prepared by mixing 44.5 g (2.0 g as platinum) of a dinitrodiammine platinum nitrate solution (4.5% platinum), 4.0 g of tetramethylammonium and 500 mL of ethanol in 2000 mL of water, It was made to react for 11 hours, making it reduce, stirring, heating and reducing in a bath.
- the colloidal solution after reaction was filtered through a 0.2 ⁇ m membrane filter, and then concentrated by a rotary evaporator to a 2% platinum colloidal solution.
- the support of platinum colloid was prepared by taking 100 g of the support in a beaker containing 200 mL of ethanol, and adding 25 g of the platinum colloid solution thereto to adsorb platinum colloid on the support. Then, the solution was put into a rotary evaporator to evaporate water and ethanol, and then the carrier was put into a column, and 3% hydrogen gas (nitrogen balance) was allowed to flow at 300 ° C. for 2 hours to make a catalyst.
- the catalyst produced above has a platinum concentration of 1.0% by weight.
- the hydrogen concentration in the mixed gas at the catalyst layer inlet and at the catalyst layer outlet was measured using a gas chromatograph. From the performance of the gas chromatograph used, the effective measurement upper limit of decomposition efficiency was 1000.
- the details of the test conditions are as follows. ⁇ Hydrogen concentration in mixed gas before passing through catalyst bed 10,300 ppm ⁇ Humidity concentration 95% relative humidity ⁇ Catalyst bed inlet temperature 20 ° C ⁇ The amount of catalyst in the catalyst bed 100 cm 3 ⁇ Mixed gas flow rate 500, 2000, 5000 cm 3 (STP) / min
- the hydrophobized catalyst according to each example exhibits excellent decomposition efficiency even for a reaction gas saturated with water vapor. This is due to the suppression of the adsorption of moisture in the gas as well as the water produced by the hydrogen combustion reaction. It can be said that the hydrophobization effect in each of the examples is comparable to that of the resin carrier of the reference example, but the catalyst of the example is excellent in handleability in that there is no risk of damage at high temperatures like resin carriers. It can be said.
- FIG. 2 shows a test apparatus of the tritium combustion test.
- a test gas from a test gas source was passed through the catalyst tower of two towers, the first catalyst tower was filled with the catalyst of each example (50 cc), and the two towers.
- the eye catalyst was loaded with a commercial platinum catalyst (100 cc). Then, the water vapor generated in each catalyst tower was collected by HTO (tritium water) trap and sampled, and the tritium combustion amount was quantified by a liquid scintillation counter.
- HTO tritium water
- the performance evaluation of each example is tritium burnup (H1) in the first catalyst tower, tritium burnup (H2) in the second catalyst tower, (H1 / (H1 + H2)) ⁇ 100 (% Was evaluated as the reaction rate.
- the details of the test conditions are as follows. ⁇ Tritium concentration in test gas 1000 Bq / cc (Equivalent to 0.02 ppm hydrogen) ⁇ Moisture saturated water vapor entrainment ⁇ Catalytic bed temperature 15 ° C (first column), 250 ° C (second column) ⁇ Test gas flow rate 500, 1000, 2500 cm 3 (STP) / min
- the catalysts subjected to the hydrophobization treatment of Examples 1 and 2 show a significant improvement in the reaction rate as compared to the catalyst without the hydrophobization treatment. Further, the catalysts of Examples 1 and 2 have performance equal to or higher than that of the resin-supported catalysts of Reference Examples 1 and 2, and can be said to be extremely advantageous in combination with the point that there is no risk of damage at high temperatures.
- the reaction rate of this test is in the range of a few percent and appears to be low at first glance, but this is due to the fact that the tritium concentration of the test gas is considerably low, and the reaction heat is small due to it. It is presumed that this is due to the fact that there is no improvement in catalyst activity. However, it is considered that the counterefficiency can be coped with by optimizing the operating conditions.
- the hydrogen combustion catalyst according to the present invention As described above, in the hydrogen combustion catalyst according to the present invention, the reduction of the catalytic activity due to the moisture in the atmosphere and the water generated by the combustion reaction is suppressed. Therefore, it is effective when the reaction continuation at low temperature is required, etc., and it can be expected to be applied to a high purity hydrogen purification plant as well as a nuclear fusion plant.
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Abstract
Description
まず、担体としてシリカ担体(被表面積230m2/g)100gを用意し、これを疎水化処理した。疎水化処理は、シリカ担体に、メチルトリメトキシシラン40gと純水50gとエタノール50gとを均一に溶解した混合液を加え振とうし、攪拌することにより行った。1日経過後取り出し、純水にて洗浄した後、200℃にて乾燥する。処理前に担体を純水洗浄し、各種シラン無機質表面改質剤のエタノール溶液(濃度15重量%)に担体を24時間浸漬した。その後、担体を取り出し、純水にて洗浄後、200℃で乾燥した。尚、この場合のシラン処理による重量増加は約13%であった。
上記試験で特に疎水化効果に優れたメチルトリメトキシシランで処理したシリカ担体を用いて触媒を製造し、その性能を評価した。また、ここでは、アルミナ担体についてもメチルトリメトキシシランで疎水化処理し、触媒を製造した。表2に各担体の疎水化処理前後の物性を示す。
以上で製造した各触媒について、その疎水化効果を確認するため、各触媒を粉砕し、水の入ったデシケータへ入れ、常温で平衡水分吸着となるまで十分な時間静置し、水の吸着量を測定した。吸着量の測定は、触媒粉末について熱質量分析(TG-DTA)により行った。この吸着量の測定は、疎水化処理を行わない担体から製造された触媒についても行った。その結果を表3に示す。
次に、上記で製造した各触媒及び製造条件を変更して製造した触媒を用いて水素混合ガスの燃焼性能を評価した。この試験で追加した触媒は、上記触媒の白金担持量を変えたものと、白金原料として白金コロイドを用いたものである。白金担持量については、塩化白金酸エタノール溶液の使用量により調整した。
・触媒層通過前の混合ガス中の水素濃度 10300ppm
・湿分濃度 95% 相対湿度
・触媒層入口温度 20℃
・ 触媒層内触媒量 100cm3
・
混合ガス流量 500、2000、5000cm3(STP)/min
次に、トリチウムの燃焼試験を行った。この試験は、上記水素燃焼試験の結果が良好であった実施例1、2、その対比のため比較例1、2、参考例1、2について行った。図2は、トリチウム燃焼試験の試験装置を示す。トリチウム燃焼試験は、試験ガス供給源からの試験ガスを、二塔の触媒塔を通過させるものであり、一塔目の触媒塔に各実施例の触媒を充填した(50cc)、また、二塔目の触媒には市販の白金触媒を充填した(100cc)。そして、各触媒塔で生じた水蒸気をHTO(トリチウム水)トラップで捕集してサンプリングし液体シンチレーションカウンターでトリチウム燃焼量を定量した。各実施例の性能評価は、一塔目の触媒塔でのトリチウム燃焼量(H1)、二塔目の触媒塔でのトリチウム燃焼量(H2)とし、(H1/(H1+H2))×100(%)を反応率として評価した。試験条件の詳細は以下の通りである。
・試験ガス中のトリチウム濃度 1000Bq/cc
(0.02ppm水素相当)
・湿分 飽和水蒸気同伴
・触媒層温度 15℃(一塔目)、250℃(二塔目)
・試験ガス流量 500、1000、2500cm3(STP)/min
Claims (9)
- 無機酸化物からなる担体に触媒金属が担持されてなる水素燃焼触媒において、
前記担体表面の水酸基に、その末端に炭素数3以下のアルキル基を少なくとも一つ有する官能基を置換結合させたものであることを特徴とする水素燃焼触媒。 - 担体表面の水酸基に結合する官能基は有機シランである請求項1記載の水素燃焼触媒。
- 担体を構成する無機酸化物は、アルミナ、シリカ、シリカ-アルミナ、ゼオライト、ジルコニアのいずれかである請求項1又は請求項2のいずれかに記載の水素燃焼触媒。
- 触媒金属は、白金、パラジウム、又はこれらの合金よりなる請求項1~請求項3のいずれかに記載の水素燃焼触媒。
- 請求項1~請求項4のいずれかに記載の水素燃焼触媒の製造方法であって、
末端に炭素数3以下のアルキル基を有する官能基の化合物の溶液に担体となる無機酸化物を浸漬することにより、前記担体表面の水酸基に前記官能基を置換結合させる疎水化処理をし、
その後、担体に触媒金属を担持する工程を含む方法。 - 官能基を含む化合物は、シラン無機質表面改質剤である請求項5記載の水素燃焼触媒の製造方法。
- シラン無機質表面改質剤は、トリメチルメトキシシラン、トリメチルエトキシシラン、トリメチルクロロシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジクロロシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリクロロシラン、トリエチルメトキシシラン、トリエチルエトキシシラン、トリエチルクロロシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジクロロシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリクロロシラン、トリプロピルメトキシシラン、トリプロピルエトキシシラン、トリプロピルクロロシラン、ジプロピルジメトキシシラン、ジプロピルジエトキシシラン、ジプロピルジクロロシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、プロピルトリクロロシランのいずれかである請求項6記載の水素燃焼触媒の製造方法。
- 請求項1~請求項4のいずれかに記載の水素燃焼触媒に水素含有ガスを通過させ、前記水素含有ガス中の水素を燃焼させる方法であって、
前記水素含有ガスはその反応温度における飽和水蒸気量以下の水分を含むものであり、
前記反応温度を0~40℃として水素を燃焼させる水素燃焼方法。 - トリチウム利用施設に設置され、施設からの排気中のトリチウムを酸化させトリチウム水に変換する触媒酸化反応器であって、請求項1~請求項4のいずれかに記載の水素燃焼触媒を備える触媒酸化反応器。
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