CN1087655C - High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst - Google Patents
High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst Download PDFInfo
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- CN1087655C CN1087655C CN96115578A CN96115578A CN1087655C CN 1087655 C CN1087655 C CN 1087655C CN 96115578 A CN96115578 A CN 96115578A CN 96115578 A CN96115578 A CN 96115578A CN 1087655 C CN1087655 C CN 1087655C
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- titanium dioxide
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Abstract
The present invention relates to a catalyst which is used for hydrogenation and deoxidization in hydrogen, nitrogen and noble gas and has the advantages of high strength and good heat resistance. The catalyst is prepared from TiO2 as a main carrier, noble metal palladium and/or platinum as active ingredients. The catalyst is prepared by the method that an immersion method is used for carrying the active ingredients, and the active ingredients are strengthened in a reducing atmosphere at a high temperature of 500 to 750 DEG C. The content of the noble metal is 0.01 to 5.0%. The crystal has high activity, and depth for deodorization and purification reaches 0.02 ppm; the catalyst has a large gas processing amount in unit time, and air speed reaches 30000 hr<-1>. The crystal has the characteristics of good toxicity resistance, high strength, no pulverization below 200 DEG C, no need of activation and regeneration, etc.
Description
The invention provides a kind of high-intensity high heat-resistance and anti-middle toxicity dehydrogenation catalyst platinum, palladium/titanium oxide, aluminium oxide.It is that the quantitative deoxidization by adding hydrogen catalyst of ultra-pure hydrogen or nitrogen and inert gas is produced in thick hydrogen deoxidation, can be used for the preparation and the production of required ultra-pure hydrogen, nitrogen and inert gas of industry such as electronics industry, semi-conducting material and device production, modern chemical industry, oil chemistry, metallurgy, instrument, aerospace, building materials, food and atomic energy.
The principle of catalyst deoxygenation is to make under the effect of catalyst that impurity oxygen and hydrogen reaction generate steam (H in the impurity oxygen that is blended in the raw hydrogen or nitrogen and the inert gas
2O) remove.Catalyst with the thick hydrogen of catalytic conversion method for purifying has palladium/aluminium oxide [referring to NissanGirdle CatalystCO-LTD.Inspection ReportOn HI-P Catalyst (P.O.No738288) 1980] at present; Palladium/molecular sieve [compiling " purification for gas " 211983 National Defense Industry Press] referring to Wu Yanmin; Palladium/carbon fiber is [referring to Yang Xueren etc., catalysis journal 1 (2) 81,1980] with aluminium oxide or silica is carrier, noble metal adds catalyst such as iron, cobalt, nickel, rare earth oxide (referring to nineteen eighty-three Japan Patent J58026004, J5817239), the unit interval treating capacity of above-mentioned catalyst is calculated as 10000～20000 hours by air speed
-1, the residual oxygen content that purifies back finished product gas is at 0.5～10ppm, and generally all needs activation and regeneration.
The objective of the invention is to prepare the high catalyst of a kind of activity, improving the unit interval treating capacity of thick hydrogen deoxidation or nitrogen and the quantitative hydrogenation deoxidation of inert gas, improve the deoxidation degree of depth and in use exempt the activation and the regeneration of catalyst.
The present invention adopts titanium dioxide to add aluminium oxide and makes carrier, and the two components of noble metal platinum, palladium or platinum palladium are made the activity of such catalysts composition, handle through high-temperature hydrogen, obtain the catalytic activity of excellent performance.Bullion content is 0.01～5.0% in this catalyst; Content of titanium dioxide accounts for 50～95% in the carrier, and the most handy anatase of carrier titanium dioxide, and the most handy plan of aluminium oxide approaches the water aluminium oxide.
Preparation of catalysts step of the present invention can be by following a or b:
A: titanium dioxide is mixed in proportion with alumina powder, add salpeter solution extrusion or roller forming, handle through roasting-dipping-reduction-washing drying-hydrogen again.After being carrier moulding and roasting, dipping in the above-mentioned noble metal aqueous solution (chloride or nitrate), the hydrazine hydrate reduction, the deionized water washing, 80～120 ℃ of dryings, 500～750 ℃ of high temperature hydrogen treatment obtained catalyst in 1～4 hour in the tube furnace.
B: dipping-reduction-washing drying-moulding-roasting-hydrogen is handled.Be that support powder is suspended in the above-mentioned noble metal aqueous solution and floods, the hydrazine hydrate reduction, the deionized water washing, 80～120 ℃ of dryings, extruded moulding, in 400～700 ℃ of following roastings, 500～750 ℃ of high temperature hydrogen treatment are 1～4 hour in the tube furnace, obtain catalyst.Above-mentioned dipping process also can carry out carrier titanium dioxide and aluminium oxide respectively, after drying again with its mixed-forming, roasting and carry out hydrogen and handle.
The catalyst that makes as stated above, its specific area is about 35m
2/ g, bulk density 1.1～1.2 grams per milliliters, the moulding in the preparation process, roasting, dipping, washing and drying process all routinely technology handle.
Catalyst of the present invention is used for the reaction of the quantitative deoxidization by adding hydrogen of thick hydrogen deoxygenation, nitrogen or inert gas, in reaction temperature room temperature～200 ℃, and reaction pressure 0.1～25MPa, gas space velocity 5000～30000hr
-1Condition under, the deoxidizing purification degree of depth can reach 0.02ppm, and this catalyst to have anti-poisoning capability strong, the intensity height uses not efflorescence under 200 ℃ for a long time, need not characteristics such as activation and regeneration.
Below by embodiment technology of the present invention is further specified:
Example 1:0.25%Pd/TiO
2+ Al
2O
3Preparation of Catalyst 1
Get that (200 milliliters of 0.025 gram Pd/ milliliter palladium chloride aqueous solutions mix with 600 ml waters, the 1000 gram column carriers that will contain titanium dioxide 90% are again poured in the above-mentioned solution, flooded 4 hours, dried 1 hour for 120 ℃, get 100 milliliters of reduction of 50% hydrazine hydrate 12 hours, deionized water washs to there not being Cl
-, pH=7 placed 80～120 ℃ of baking ovens dry 1 hour, placed in the tube furnace under 600 ℃ of nitrogen atmosphere heat treatment again 4 hours, was cooled to room temperature naturally, logical nitrogen arrange take out behind the hydrogen catalyst.
Example 2:0.25%Pt+0.25%Pd/TiO
2+ Al
2O
3Preparation of Catalyst 2
A:0.25%Pt+0.25%Pd/TiO
2Preparation
Get 70 milliliters of 70 milliliters+(0.025 restrains the Pt/ milliliter) platinum chloride aqueous solution of (0.025 gram Pd/ milliliter) palladium chloride aqueous solution, pour in 600 ml waters and mix, add 700 gram anatase powder again and stirred dipping 6 hours, add 70 milliliters of (50%) hydrazine hydrate reduction 1 hour, placement is spent the night.
B:0.25%Pt+0.25%Pd/Al
2O
3Preparation:
Get 30 milliliters of 30 milliliters+(0.025 restrains the Pt/ milliliter) platinum chloride aqueous solution of (0.025 gram Pd/ milliliter) palladium chloride aqueous solution, pour in 200 ml waters and mix, add 300 grams again and intended thin water aluminium oxide stirring dipping 6 hours, add 30 milliliters of (50%) hydrazine hydrate reduction 1 hour, placement is spent the night.
C: with after b mixes half an hour, filtering and washing is to there not being 1C with a
-, pH=7 was dried 1 hour for 120 ℃.Be in harmonious proportion with 6% (weight ratio) salpeter solution, extruded moulding dries, and places in the tube furnace, logical nitrogen, 650 ℃ of roastings changed hydrogen treat 1 hour after 2 hours, were cooled to room temperature naturally, logical nitrogen arrange hydrogen take out catalyst.
Example 3: the performance 1 of catalyst
1 milliliter of the catalyst of example 1 preparation is filled on the continuous-flow reaction unit of 5mm and estimate, be equipped with hydrogen and oxygen electrolyzing, air speed 10000hr in the nitrogen
-1, follow the tracks of detection with TE-150 chromaticness spectrometer and DH-3 oxygen analyzer, it the results are shown in table 1.
The quantitative hydrogenation deoxidation performance of the general nitrogen of table 1
Oxygen content (ppm) hydrogen content (ppm) serviceability temperature (℃) remaining oxygen (ppm)
5000 ≥10000 25 0.02
*
25000 ≥50000 25 ＜0.3
* TE---150 chromaticness spectrometer is analyzed (other result analyzes with the DH-3 oxygen analyzer)
As can be seen from Table 1, during different oxygen, this catalyst has the very high effect that removes oxygen.
Example 4: the performance 2 of catalyst
The catalyst of example 2 preparation advances the experiment of poisoning of 4 kinds of different poisonous substances under example 3 appreciation conditions, table 2 has been enumerated the poisoning capability that this catalyst resists 4 kinds of different poisonous substances.
The anti-poisoning capability of table 2 catalyst
The poisonous substance component by poisonous substance cumulant reaction temperature (℃) remaining oxygen (ppm)
H
2S 14000 microlitres 25＜0.3
SO
2100 microlitres 20＜0.3
NH
3 100％ 23 ＜0.3
H
230 ℃ of saturation vapours 25＜0.3 of O vapour
As can be seen from Table 2, even 14000 milliliters of H
2S is by the catalyst of 1 ml volumes, and activity of such catalysts is not influenced by it still.
Example 5: the performance of catalyst relatively
Result with the Pd/ molecular sieve of the experimental result of the catalyst of example 2 preparation and patent documentation report, Pd/ aluminium oxide, Pd/ carbon fiber compares, and it the results are shown in table 3.
Relatively the antitoxin rerum natura of catalyst serviceability temperature activating and regenerating temperature air speed can the tail gas oxygen content for the performance of the thick hydrogen dehydrogenation catalyst of table 3
(℃) (℃) (hr
-1) (ppm) Pd/ molecular sieve normal temperature～120 350 5000～10000 be afraid of that sulfide 0.2Pd/ aluminium oxide 50～80 400～500 4000～8000 the same 0.2Pd/ carbon fiber normal temperature 250 10000 the same 0.2 examples, 2 system normal temperature are without activating and regenerating 10000～30000 anti-H
2S, 0.02 catalyst S O
2, NH
3
As can be seen from Table 3, the performance of its each side of catalyst of the present invention all is better than Pd/ molecular sieve, Pd/ aluminium oxide and Pd/ carbon fiber.
Example 6: Application of Catalyst
The catalyst that table 4 and table 5 have been enumerated example 1,2 preparations industrial result of use of deoxidization by adding hydrogen in deoxygenation and the nitrogen in electrolysis hydrogen, its catalyst amount is 100～200 kilograms.
Deoxygenation in table 4 electrolysis hydrogen (example 1 catalyst) hydrogen source working pressure reaction temperature oxygen content air speed gas flow remaining oxygen
(MPa) (℃) (ppm) (hr
-1) (M
3/ hr) (ppm) electrolysis hydrogen 25 150 2,000 5,000 500＜0.5
The quantitative deoxidization by adding hydrogen of the general nitrogen of table 5 (example 2 catalyst) nitrogen source reactant temperature oxygen content air speed gas flow remaining oxygen
(℃) (ppm) (hr
-1) (M
3/ hr) (ppm) making nitrogen by pressure swing adsorption 20 5,000 5,000 60＜0.5 nitrogen production by air separation 20＜100 8,000 1500＜0.5
From above-mentioned example as can be seen, catalyst of the present invention has active high, anti-poisoning performance is good, high pressure resistant, advantage such as high temperature resistant, and this catalyst used in industry 3～6 years, its not efflorescence of catalyst, catalytic activity does not reduce, and need not activation and regeneration, is the catalyst that a utmost point has promotional value.
Claims (6)
1. a hydrogen, nitrogen and inert gas hydrogenation deoxidation is characterized in that with platiniferous, palladium catalyst the carrier of catalyst adopts titanium dioxide and alundum (Al mixed oxide, and active constituent adopts palladium and/or platinum, and its content is 0.01～5.0%; Content of titanium dioxide is 50～95% in the carrier.
2. according to the described catalyst of claim 1, it is characterized in that the titanium dioxide anatase, aluminium oxide is with intending thin water aluminium oxide.
3. one kind according to the described Preparation of catalysts method of claim 1, it is characterized in that through the carrier moulding, flood a kind of or two kinds of precious metal chlorides or nitrate aqueous solution, add the hydrazine hydrate reduction, spend deionised water, after 80～120 ℃ of drying and other steps, under 500～750 ℃ of nitrogen atmosphere, handle being prepared into catalyst in 1～4 hour.
4. according to the described Preparation of catalysts method of claim 1, it is characterized in that carrier titanium dioxide and aluminium oxide dipping a kind of or two kinds of precious metal chlorides or nitrate aqueous solution, add the hydrazine hydrate reduction, spend deionised water, in 80～120 ℃ of dryings, extrusion or roller forming are handled under 500～750 ℃ of nitrogen atmosphere then and were prepared into catalyst in 1～4 hour.
5. according to the described Preparation of catalysts method of claim 4, it is characterized in that the carrier impregnation process is that titanium dioxide and aluminium oxide flood precious metal chloride or nitrate aqueous solution respectively, and after drying with its mixed-forming.
6. a utilization is reacted in the quantitative deoxidization by adding hydrogen of thick hydrogen deoxygenation, nitrogen and inert gas according to the described catalyst of claim 1, it is characterized in that reaction condition is: reaction temperature is room temperature～200 ℃, reaction pressure is 0.1～25MPa, and gas space velocity is 5000～30000hr
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115578A CN1087655C (en) | 1996-09-04 | 1996-09-04 | High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115578A CN1087655C (en) | 1996-09-04 | 1996-09-04 | High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1175478A CN1175478A (en) | 1998-03-11 |
| CN1087655C true CN1087655C (en) | 2002-07-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115578A Expired - Fee Related CN1087655C (en) | 1996-09-04 | 1996-09-04 | High-strength, high heat-resistance and poisoning-resistance deoxidation catalyst |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088622C (en) * | 1998-11-26 | 2002-08-07 | 北京大学 | Palladium catalyst with carrier of titanium oxide-alumina compound, and its preparing process and application |
| CN1089631C (en) * | 1999-10-26 | 2002-08-28 | 湖北省化学研究所 | Dehydrogenation catalyst for urea synthesizing CO2 gas and its preparation |
| CN1310704C (en) * | 2003-12-24 | 2007-04-18 | 中国石油化工股份有限公司 | Anti sulfur deoxidizing catalyst, its preparing process and application method |
| CN102433182A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Catalytic deoxidation method for coal bed gas in coal mine area |
| CN102433184A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Method for directly removing oxygen in coal bed gas by using hydrogen |
| CN102433183A (en) * | 2010-09-29 | 2012-05-02 | 中国石油化工股份有限公司 | Normal-temperature self-running deoxidation method for coalbed gas |
| CN102516136A (en) * | 2011-10-31 | 2012-06-27 | 天津大学 | Method for preparing 4,4 '- diaminostilbene- 2,2' - disulfonic acid by using DNS sodium salt(4,4 '- dinitrostilbene-2,2' - disulfonic acid sodium salt) |
| CN105214654A (en) * | 2015-10-07 | 2016-01-06 | 成都中科能源环保有限公司 | A kind of noble metal and the compound sulfur-tolerance deoxidation catalyst of rare earth and preparation method thereof |
| CN109012660B (en) * | 2017-06-09 | 2020-05-19 | 厦门大学 | Catalyst for removing oxygen in hydrogen and preparation method and application thereof |
| CN111215060A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Preparation of supported platinum group metal monatomic catalyst and application thereof in deoxidation reaction |
| CN115845837B (en) * | 2022-10-10 | 2024-07-12 | 河南省生物基材料产业研究院有限公司 | Furfural catalyst prepared by continuous decarbonylation of furfural in gas phase and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102710A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院大连化学物理研究所 | Platinum, Pd/TiO 2 deoxygenationcatalyst |
| CN1053843C (en) * | 1994-04-05 | 2000-06-28 | 中国科学院兰州化学物理研究所 | High effective desoxydation dehydrogenation catalyst and its preparation and application |
-
1996
- 1996-09-04 CN CN96115578A patent/CN1087655C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85102710A (en) * | 1985-04-01 | 1986-09-17 | 中国科学院大连化学物理研究所 | Platinum, Pd/TiO 2 deoxygenationcatalyst |
| CN1053843C (en) * | 1994-04-05 | 2000-06-28 | 中国科学院兰州化学物理研究所 | High effective desoxydation dehydrogenation catalyst and its preparation and application |
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| Publication number | Publication date |
|---|---|
| CN1175478A (en) | 1998-03-11 |
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