CN1385241A - Catalyst for synthesizing methyl isobutyl ketone and preparation process thereof - Google Patents
Catalyst for synthesizing methyl isobutyl ketone and preparation process thereof Download PDFInfo
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- CN1385241A CN1385241A CN 01119169 CN01119169A CN1385241A CN 1385241 A CN1385241 A CN 1385241A CN 01119169 CN01119169 CN 01119169 CN 01119169 A CN01119169 A CN 01119169A CN 1385241 A CN1385241 A CN 1385241A
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- molecular sieve
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- isobutyl ketone
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 title claims abstract description 22
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 239000002808 molecular sieve Substances 0.000 claims abstract description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 20
- 101150003085 Pdcl gene Proteins 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000009833 condensation Methods 0.000 abstract description 6
- 230000005494 condensation Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000018044 dehydration Effects 0.000 abstract description 5
- 238000006297 dehydration reaction Methods 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- -1 dipropyl alcohol ketone Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- LZFZLDBWYPXYCF-UHFFFAOYSA-N CC(=O)C.[F] Chemical compound CC(=O)C.[F] LZFZLDBWYPXYCF-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
一种合成甲基异丁基酮的催化剂及其制备方法,催化剂的重量百分比组成为:Pd:0.051～0.750%,ZSM－5分子筛:99.250～99.949%。本发明集丙酮缩合、脱水、加氢三种催化功能于一体,大大简化现有的反应工艺流程,即降低生产成本,又增加可操作性;催化剂选择性高,简化了产物分离步骤。A catalyst for synthesizing methyl isobutyl ketone and a preparation method thereof. The weight percent composition of the catalyst is: Pd: 0.051-0.750%, ZSM-5 molecular sieve: 99.250-99.949%. The invention integrates three catalytic functions of acetone condensation, dehydration and hydrogenation, greatly simplifies the existing reaction process flow, not only reduces production costs, but also increases operability; the catalyst has high selectivity and simplifies the product separation steps.
Description
The invention belongs to a kind of Catalysts and its preparation method of synthesize methyl-isobutyl ketone, relate in particular to a kind of ZSM-5 Catalysts and its preparation method of synthesize methyl-isobutyl ketone.
Methyl iso-butyl ketone (MIBK) (MIBK) is the broad-spectrum meticulous organic chemical industry's product of a kind of excellent property, and it not only is used for organic solvents such as manufacture of ink, paint, Resins, epoxy, and is also a large amount of as organic synthesis intermediates such as oxidation inhibitor and different fluorine acetone.Along with the continuous expansion of Application Areas, demand constantly increases both at home and abroad in recent years, therefore researchs and develops new synthesis route tool and has very important significance.
Present industrial production MIBK still adopts traditional three-step approach, be that acetone condensation under base catalysis obtains the dipropyl alcohol ketone, dipropyl alcohol ketone dehydration generates mesityl oxide under the acid catalysis effect then, again nickel or the effect of copper system and in depress hydrogenation and obtain MIBK at last.This technical process complexity, the production cycle is long, and cost height and energy consumption are lacked competitiveness greatly.
The research of carrying out the synthetic MIBK of acetone single stage method in recent years more and more comes into one's own.This method collects condensation of acetone, dehydration and hydrogenation three-step reaction to be finished in a reactor, has advantages such as technical process weak point, less investment and production cost are low, has represented the developing direction of MIBK production technique, has broad application prospects.
But also there is its weak point in the technology of the synthetic MIBK of single stage method, shows that mainly acetone per pass conversion and MIBK selectivity hang down two aspects, and the emerging grade of Ru Wuhui has been delivered the method that a kind of single stage method is synthesized MIBK in " molecular sieve communication " (1993 (2) 5).This method adopts and carries Ni basic zeolite, year Pd Y zeolite transition or Pd ZSM-5 is catalyzer, under T=180～260 ℃, P=2.0～4.0Mpa condition, acetone is through condensation, dehydration, hydrogenation one-step synthesis MIBK, and its acetone per pass conversion is 41.8%, and the MIBK selectivity is 82.4%.
The purpose of this invention is to provide a kind of highly selective and high conversion synthesize methyl-isobutyl ketone catalyst and preparation method thereof.
Catalyst weight per-cent of the present invention consists of:
Pd 0.051～0.750％
ZSM-5 molecular sieve 99.250～99.949%
Aforesaid ZSM-5 molecular sieve is that the Si/Al mol ratio is the Hydrogen ZSM-5 molecular sieve of 28-70.
Preparation of catalysts method of the present invention comprises the steps:
(1) at first be with Si/Al (mol) 28～70 Hydrogen ZSM-5 molecular sieve at 520～540 ℃ of following roasting 3-5 hours to remove the impurity of its physical adsorption;
(2) molecular sieve after (1) step is handled and auxiliary agent are 72～63: 28～37 mixed by weight, evenly grinding;
(3) nitric acid is mixed with 2～4% drips of solution and adds in the ground material of (2) step, mix and pinch suitable back extrusion molding, 100～120 ℃ of oven dry down;
(4) material after the oven dry of (3) step is crushed to 10～40 orders, then 500～520 ℃ of roastings 3～5 hours, to take off nitric acid and moisture;
(5) PdCl
2Adopt deionized water to be made into the solution of 0.01～0.08 volumetric molar concentration, and need add solvent, stir, make steeping fluid, consist of Pd:0.051～0.750% by catalyst weight per-cent with the amount that every mol sieve is not less than 1.5ml; The ZSM-5 molecular sieve: 99.250～99.949%, (4) the ZSM-5 molecular sieve that makes of step is immersed in the steeping fluid 3-6 hour, and stirred once every 1-2 hour;
(6) the ZSM-5 molecular sieve after will flooding at 200～250 ℃ of roasting 3-4 hours, makes catalyzer then 100～120 ℃ of oven dry 10-12 hour.
Aforesaid auxiliary agent is to intend thin water aluminum oxide or γ-Al
2O
3
Aforesaid solvent is an acetone or alcohol.
Advantage of the present invention is:
(1) integrates condensation of acetone, dehydration, three kinds of catalysiss of hydrogenation, simplify existing reaction process flow process greatly, promptly reduce production costs, increase operability again.
(2) catalyst selectivity height can improve more than 15% than the result of document, therefore can simplify the product separating step.
Embodiments of the invention are as follows:
Embodiment 1
(1) at first be 28 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 13 mol sieve is restrained γ-Al with 7
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be pressed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 5 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) with PdCl
2Adopt deionized water to be mixed with 0.01mol PdCl
2Solution shakes up stand-by;
(6) the Pd content that makes is 0.08% o'clock, with 1.58ml PdCl
2Solution is put into beaker and is stirred adding 18.43ml acetone, stirs once again with 10 mol sieve dipping wherein 5 hours, and every 1 hour;
(7) again it is inserted keep 10～12 hours in 120 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 200 ℃ of roastings.
Embodiment 2
(1) at first be 35.3 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 14 mol sieve is restrained γ-Al with 6
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be pressed into the bar column type of Φ 2, insert in the baking oven and dry down in 105 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 510 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) with PdCl
2Adopt deionized water to be mixed with 0.05mol PdCl
2Solution shakes up stand-by;
(6) the Pd content that makes is 0.25% o'clock, with 0.98ml PdCl
2Solution is put into beaker and is stirred adding 19.02ml acetone, stirs once again with 10 mol sieve dipping wherein 3 hours, and every 1 hour;
(7) again it is inserted keep 10 hours in 120 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 200 ℃ of roastings.
Embodiment 3
(1) at first be 35.3 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 14.4 mol sieve is put into mortar simultaneously with the thin water aluminum oxide of 5.6 gram plans and mix, evenly grind;
(3) 2% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be pressed into the bar column type of Φ 2, insert in the baking oven and dry down in 115 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) with PdCl
2Adopt deionized water to be mixed with 0.10mol PdCl
2Solution shakes up stand-by;
(6) the Pd content that makes is 0.45% o'clock, with 0.90ml PdCl
2Solution is put into beaker and is stirred adding 19.11ml acetone, stirs once again with 10 mol sieve dipping wherein 8 hours, and every 2 hours;
(7) again it is inserted keep 10 hours in 120 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 230 ℃ of roastings.
Embodiment 4
(1) at first be 67.8 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 12.8 mol sieve is restrained γ-Al with 7.2
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be pressed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) with PdCl
2Adopt deionized water to be mixed with 0.10mol PdCl
2Solution shakes up stand-by;
(6) the Pd content that makes is 0.65% o'clock, with 1.29ml PdCl
2Solution is put into beaker and is stirred adding 18.72ml ethanol, stirs once again with 10 mol sieve dipping wherein 4 hours, and every 1 hour;
(7) again it is inserted keep 10～12 hours in 120 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 200 ℃ of roastings.
Embodiment 5
(1) at first be 52.5 Hydrogen ZSM-5 molecular sieve 540 ℃ of following roastings 3 hours to remove the impurity of its absorption with 20 gram Si/Al (mol);
(2) 12.8 mol sieve is restrained γ-Al with 7.2
2O
3Put into mortar simultaneously and mix, evenly grind;
(3) 3% salpeter solution is dripped in the good material of mill, mix and pinch suitably, be pressed into the bar column type of Φ 2, insert in the baking oven and dry down in 120 ℃ with manual spiral banded extruder;
(4) again the strip molecular sieve is crushed to the 10-40 order and puts into retort furnace and be warming up to 520 ℃ of roastings 3 hours,, treat that temperature is reduced to below 60 ℃ can take out to take off nitric acid and moisture;
(5) with PdCl
2Adopt deionized water to be mixed with 0.05mol PdCl
2Solution shakes up stand-by;
(6) the Pd content that makes is 0.65% o'clock, with 2.96ml PdCl
2Solution adds 17.05ml acetone again to be put into beaker and stirs, and stirs once again with 10 mol sieve dipping wherein 6 hours, and every 1 hour;
(7) again it is inserted keep 8 hours in 110 ℃ the baking oven after, put into retort furnace and made catalyzer in 3 hours in 240 ℃ of roastings.
Catalyst performance characterizes with reactive behavior and measures: adopt NH3-TPD to measure the strong faintly acid Changing Pattern of differing molecular sieve, see Table 1.Table 1
The evaluation of catalyzer: on 2ml pressurization fixation reaction device different content PdZSM-5 is reacted, its condition is as follows: T=220 ℃, and P=2.5Mpa, LHSV=1.5hr
-1, product collection is taken out by sampling jug after the condensation in ice condenser, by day island proper Tianjin GC-7A hydrogen flame identifier analyze, chromatographic column is the capillary column of 30 meters of polyoxyethylene glycol.Its reaction result sees Table 2.Table 2
Claims (4)
1. the catalyzer of a synthesize methyl-isobutyl ketone is characterized in that the weight percent of catalyzer consists of: Pd:0.051～0.750%
ZSM-5 molecular sieve: 99.250～99.949%;
Described ZSM-5 molecular sieve is that the Si/Al mol ratio is the Hydrogen ZSM-5 molecular sieve of 28-70.
2. the preparation method of a synthesize methyl-isobutyl ketone catalyst is characterized in that the Preparation of catalysts method comprises the steps:
(1) at first be with Si/Al (mol) 28～70 Hydrogen ZSM-5 molecular sieve at 520～540 ℃ of following roasting 3-5 hours to remove the impurity of its physical adsorption;
(2) molecular sieve after (1) step is handled and auxiliary agent are 72～63: 28～37 mixed by weight, evenly grinding;
(3) nitric acid is mixed with 2～4% drips of solution and adds in the ground material of (2) step, mix and pinch suitable back extrusion molding, 100～120 ℃ of oven dry down;
(4) material after the oven dry of (3) step is crushed to 10～40 orders, then 500～520 ℃ of roastings 3～5 hours, to take off nitric acid and moisture;
(5) PdCl
2Adopt deionized water to be made into the solution of 0.01～0.08 volumetric molar concentration, and need add solvent, stir, make steeping fluid, consist of Pd:0.051～0.750% by catalyst weight per-cent with the amount that every mol sieve is not less than 1.5ml; The ZSM-5 molecular sieve: 99.250～99.949%, (4) the ZSM-5 molecular sieve that makes of step is immersed in the steeping fluid 3-6 hour, and stirred once every 1-2 hour;
(6) the ZSM-5 molecular sieve after will flooding at 200～250 ℃ of roasting 3-4 hours, makes catalyzer then 100～120 ℃ of oven dry 10-12 hour.
3. the preparation method of a kind of synthesize methyl-isobutyl ketone catalyst as claimed in claim 2 is characterized in that described auxiliary agent is to intend thin water aluminum oxide or γ-Al
2O
3
4. the preparation method of a kind of synthesize methyl-isobutyl ketone catalyst as claimed in claim 2 is characterized in that described solvent is an acetone or alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01119169 CN1120750C (en) | 2001-05-14 | 2001-05-14 | Catalyst for synthesizing methyl isobutyl ketone and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01119169 CN1120750C (en) | 2001-05-14 | 2001-05-14 | Catalyst for synthesizing methyl isobutyl ketone and preparation process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1385241A true CN1385241A (en) | 2002-12-18 |
| CN1120750C CN1120750C (en) | 2003-09-10 |
Family
ID=4663581
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01119169 Expired - Fee Related CN1120750C (en) | 2001-05-14 | 2001-05-14 | Catalyst for synthesizing methyl isobutyl ketone and preparation process thereof |
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|---|---|
| CN (1) | CN1120750C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745050A (en) * | 2016-11-17 | 2017-05-31 | 中国科学院生态环境研究中心 | A kind of molecular sieves of noble metal support type ZSM 5 and its preparation method and application |
| CN113019435A (en) * | 2021-03-26 | 2021-06-25 | 福州大学 | Monoatomic palladium/molecular sieve catalyst, preparation thereof and application thereof in preparation of ketone by selective hydrogenation of biomass molecules |
-
2001
- 2001-05-14 CN CN 01119169 patent/CN1120750C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106745050A (en) * | 2016-11-17 | 2017-05-31 | 中国科学院生态环境研究中心 | A kind of molecular sieves of noble metal support type ZSM 5 and its preparation method and application |
| CN113019435A (en) * | 2021-03-26 | 2021-06-25 | 福州大学 | Monoatomic palladium/molecular sieve catalyst, preparation thereof and application thereof in preparation of ketone by selective hydrogenation of biomass molecules |
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| Publication number | Publication date |
|---|---|
| CN1120750C (en) | 2003-09-10 |
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