CN1095401C - Hydrogenolysis catalyst for low-temp synthesis of methanol with methyl formate and its preparing process - Google Patents
Hydrogenolysis catalyst for low-temp synthesis of methanol with methyl formate and its preparing process Download PDFInfo
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- CN1095401C CN1095401C CN98108654A CN98108654A CN1095401C CN 1095401 C CN1095401 C CN 1095401C CN 98108654 A CN98108654 A CN 98108654A CN 98108654 A CN98108654 A CN 98108654A CN 1095401 C CN1095401 C CN 1095401C
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- methyl formate
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Abstract
The present invention relates to a hydrogenolysis catalyst used for synthesizing methanol with methyl formate at a low temperature and a preparation method thereof, methyl formate is used as a raw material, methanol is synthesized by hydrogenolysis under the conditions that the reaction temperature range is from 100 to 200 DEGC, the pressure is from 1.0 to 3.0MPa, and the air speed is 3600(ml/h. g. catal); catalyst predecessor metals of Cu, Al and La, or C, or Nd are proportionally refined into alloy at a high temperature, strong alkali is used for extracting the alkaline solubility element Al after the alloy is powdered, and the catalyst is prepared. The catalyst of the present invention has characteristics of higher hydrogenolysis activity, catalyst hydrogen performance improvement, considerable increase of the hydrogen quantity, catalyst CO adsorbability improvement, high CO inhibiting capacity, etc.
Description
The invention belongs to a kind of hydrogenolysis catalyst, relate in particular to a kind of hydrogenolysis catalyst that is used for low-temp synthesis of methanol with methyl formate and preparation method thereof.
In a large amount of hydrogenation catalysts,, thereby it is studied the very active of performance because the skeleton catalyst of Raney system has all obtained application very widely in prepared in laboratory work or commercial Application.The Raney Preparation of catalysts mainly is divided into two steps, at first adopts direct high temperature refining presoma alloy, uses the alkali solubility element in the strong base solution extracting Raney catalyst precursor alloy then, obtains the Raney catalyst of respective metal.The thing phase composition of alloy, the degree of lattice structure and dealuminzation all directly affects catalytic performance, surface property and the pore passage structure of target product catalyst.People have studied many one pack system Raney catalyst such as Fe, Co, Ni, Cu, Ag, Pd, Re, and respective metal and aluminium make alloy earlier, fully react with strong base solution after crushed and slough aluminium element, obtain the Raney catalyst.Trimm makes Raney Cu catalyst hydrogenolysis of methyl formate is reacted, and exists the performance of catalyst absorption hydrogen low, the shortcoming of the inhibition ability of anti-CO.
Goal of the invention of the present invention provides a kind of performance height of absorption hydrogen, and the inhibition ability of anti-CO good be used for hydrogenolysis catalyst of low-temp synthesis of methanol with methyl formate and preparation method thereof.
Goal of the invention of the present invention is achieved in that with complex catalyst precursor thing metal Cu, Al, La or Ce or Nd refines into alloy through high temperature by a certain percentage, and alloy with strong base solution extracting alkali solubility element al, makes catalyst after crushed.
The consisting of of catalyst of the present invention (percentage by weight)
Cu:70-99% Al0.1-10% Nd or Ce or La 0.8-29%
Preparation of catalysts method of the present invention is:
(1) preparation of alloy
Get metal Cu, La or Ce or the Nd and the Al of purity 〉=99.95%, in the copper sample cell of the electric arc furnaces of packing into by a certain percentage, under argon shield, the electric arc melting that ignites refining.Because sample cell is in the water-cooled state all the time, arc flame one goes out, and liquid metal solidifies at once, and is even for guaranteeing alloy component, " melts-cold " 2-3 time repeatedly in melting the refining process;
(2) alkali extracting dealuminzation
It is 40-60 purpose particle that the bulk alloyed powder is broken to granularity; under the high pure nitrogen protection; add 40%KOH solution; its addition is alloy: KOH=1g:20-50ml; fully reaction is not till have hydrogen and separate out; discharge unnecessary liquid, wash repeatedly with deionized water rapidly and carefully, till the pH of equilibrium liquid value≤7.0.The high pure nitrogen protection is transferred to the porous alloy that makes in the reaction tube down, after the drying, moves into rapidly in the seal box in the hydrogen stream, and the high pure nitrogen sealing is preserved stand-by, makes catalyst;
The ratio (percentage by weight) that it is characterized in that described Cu, Al, La or Ce or Nd metal is: Cu 30-60% Al 40-60% Nd or Ce or La 0.5-15%.
Catalyst of the present invention be with the methyl formate be raw material in 100-200 ℃ range of reaction temperature, the pressure of 1.0-3.0MPa, air speed is to carry out the hydrogenolysis synthesizing methanol under the condition of 3600 (ml/h.g.catal).
The present invention compares with existing Raney Cu catalyst has following advantage:
1. under identical reaction condition, has higher hydrogenolysis activity.
2. obviously improved catalyst hydrogen absorption property, hydrogen adsorptive capacity has increase by a relatively large margin.
3. obviously improve the Catalyst for CO absorption property, and demonstrated the inhibition ability of very strong anti-CO.
Embodiment 1
(1) refining of alloy: take by weighing simple metal Cu 5.4g, Nd 0.5g and Al 5.0g, in the copper sample cell of the electric arc furnaces of packing into, under argon shield, the electric arc melting that ignites refining.Because sample cell is in the water-cooled state all the time, arc flame one goes out, and liquid metal solidifies at once, and is even for guaranteeing alloy component, in melting the refining process 3 times repeatedly, must consist of Cu 46.7%, and Nd 4.7%, the Cu-Nd-Al alloy of Al 48.9%;
(2) alkali extracting dealuminzation prepares catalyst: it is 40-60 purpose particle that bulk Cu-Nd-Al alloyed powder is broken to granularity; take by weighing the 2.0g alloying pellet; under the high pure nitrogen protection; separate out to there not being hydrogen with 40%KOH solution 80ml abundant reaction under 50-80 ℃; outwell supernatant liquid; wash repeatedly with deionized water rapidly and carefully, till the pH of equilibrium liquid value≤7.0.The high pure nitrogen protection is transferred to the porous alloy that makes in the reaction tube the dry Cu 89.4% that must consist of in the hydrogen stream down; Nd7.62%, the Raney Cu-Nd catalyst of Al 0.42% moves in the seal box rapidly; the high pure nitrogen sealing is preserved stand-by, is designated as RN1.
Embodiment 2
(1) refining of alloy: take by weighing simple metal Cu 4.0g, Nd 1.0g and Al 5.0g, must consist of Cu 41.1%, Nd 7.5%, the Cu-Nd-Al alloy of Al 51.5%;
(2) alkali extracting dealuminzation prepares catalyst: take by weighing 5.0g alloying pellet (40-60 order) and 40%KOH solution 200ml reaction, all the other steps are with embodiment 1.Must consist of Cu 83.4%, Nd 13.8%, and the Raney Cu-Nd catalyst of Al0.94% is designated as RN2.
Embodiment 3
(1) refining of alloy: take by weighing simple metal Cu 3.5g, Nd 1.5g and Al 5.0g, must consist of Cu 32.2%, Nd 11.9%, the Cu-Nd-Al alloy of Al 54.9%;
(2) alkali extracting dealuminzation prepares catalyst: take by weighing 5.0g alloy granule (40-60 order); under high pure nitrogen protection, fully react till do not have hydrogen and separate out with 40%KOH200ml solution, discharge unnecessary liquid; wash repeatedly with deionized water, till the pH of equilibrium liquid value≤7.0 rapidlyly and for a short time.The high pure nitrogen protection claims the porous alloy commentaries on classics that makes to reaction tube down, the dry Cu 78.1% that must consist of in the hydrogen stream, and Nd 20.1%, and the Raney Cu-Nd catalyst of Al 0.51% moves into rapidly in the seal box, and the high pure nitrogen sealing is preserved stand-by.
Embodiment 4
(1) refining of alloy: take by weighing simple metal Cu 4.5g, Ce 0.5g and Al 5.0g, must consist of Cu 46.7%, Ce 3.9%, the Cu-Nd-Al alloy of Al 49.31;
(2) alkali extracting dealuminzation prepares catalyst: take by weighing 5.0g alloying pellet (40-60 order) and 40%KOH solution 200ml reaction, all the other steps are with embodiment 1.Must consist of Cu 91.4%, Ce 7.5%, and the Raney Cu-Ce catalyst of Al0.44% is designated as RCl.
Embodiment 5
(1) refining of alloy: take by weighing simple metal Cu 4.0g, Ce 1.0g and Al 5.0g, must consist of Cu 42.3%, Ce 7.4%, the Cu-Nd-Al alloy of Al 50.21;
(2) alkali extracting dealuminzation prepares catalyst: take by weighing 5.0g alloying pellet (40-60 order) and 40%KOH solution 200ml reaction, all the other steps are with embodiment 1.Must consist of Cu 84.4%, Ce 14.7%, and the Raney Cu-Ce catalyst of Al0.69% is designated as RC2.
Embodiment 6
(1) refining of alloy: take by weighing simple metal Cu 4.0g, La 1.0g and Al 5.0g, must consist of Cu 46.6%, La 2.8%, the Cu-Nd-Al alloy of Al 50.5%;
(2) alkali extracting dealuminzation prepares catalyst: take by weighing 5.0g alloying pellet (40-60 order) and 40%KOH solution 200ml reaction, all the other steps are with embodiment 1.Must consist of Cu 88.56, La 9.9%, and the Raney Cu-La catalyst of Al0.81% is designated as RL1.
The comparative example
(1) refining of alloy: take by weighing simple metal Cu 5.0g and Al 5.0g, must consist of Cu 49.5%, the Cu-Al alloy of Al 50.51;
(2) alkali extracting dealuminzation prepares catalyst: take by weighing 5.0g alloying pellet (40-60 order) and 40%KOH solution 200ml reaction, all the other steps are with embodiment 1.Must consist of Cu 99.2%, the Raney Cu catalyst of Al 0.65% is designated as RCu.
Reaction result
Raney Cu-Nd (Ce or La) catalyst is 140 ℃ in reaction temperature, H in the unstripped gas
2/ methyl formate mol ratio 3.8 or H
2/ CO/ methyl formate=2: 1: 1, catalyst amount 1.0g, pressure 1.0Mpa, weight space velocity are that unstripped gas is that pure hydrogenolysis the results are shown in following table under the condition of 3600 (ml/h.g.cat).RaneyCu-La, Ce, Nd catalyst hydrogenolysis of methyl formate reaction result
| Catalyst | Catalyst is formed (wt%) | Reaction atmosphere | Methyl formate conversion ratio (wt%) | Methyl alcohol is selected (wt%) |
| Cu Ma Al | ||||
| RN1 | 89.42 7.62 0.42 | H 2 CO(33％)+H 2 | 78.14 80.41 | 97.91 89.18 |
| RN2 | 83.40 13.85 0.94 | H 2 CO(33％)+H 2 | 58.98 59.97 | 92.92 90.82 |
| RC1 | 91.41 7.54 0.44 | H 2 CO(33％)+H 2 | 58.93 66.21 | 93.69 88.47 |
| RC2 | 84.44 14.76 0.69 | H 2 CO(33％)+H 2 | 58.85 61.21 | 94.50 90.59 |
| RL1 | 88.56 9.91 0.81 | H 2 CO(33％)+H 2 | 58.26 59.79 | 96.84 88.67 |
| RCu | 98.72 ---- 0.95 | H 2 CO(33％)+H 2 | 57.82 55.62 | 96.49 95.57 |
Claims (2)
1. hydrogenolysis catalyst that is used for low-temp synthesis of methanol with methyl formate is characterized in that the percentage by weight of described catalyst consists of:
Cu:70-99% Al 0.1-10% Nd or Ce or La 0.8-29%.
2. the preparation method who is used for the hydrogenolysis catalyst of low-temp synthesis of methanol with methyl formate according to claim 1 is characterized in that:
(1) preparation of alloy
Get metal Cu, La or Ce or the Nd and the Al of purity 〉=99.95%, in the copper sample cell of the electric arc furnaces of packing into by a certain percentage, under argon shield, the electric arc melting that ignites refining " is melted-cold " 2-3 time in melting the refining process repeatedly; The percentage by weight of described Cu, Al and La or Ce or Nd metal is: Cu30-60%Al40-60% Nd or Ce or La 0.5-15%;
(2) alkali extracting dealuminzation
It is 40-60 purpose particle that the bulk alloyed powder is broken to granularity; under the high pure nitrogen protection; add 40%KOH solution; its addition is alloy: KOH=1g:20-50ml; 50-80 ℃ of abundant reaction till do not have hydrogen and separate out; discharge unnecessary liquid; wash repeatedly with deionized water rapidly and carefully; till the pH of balance value≤7.0, the high pure nitrogen protection is transferred to the porous alloy that makes in the reaction tube down; in the hydrogen stream after the drying; move into rapidly in the seal box, the high pure nitrogen sealing is preserved stand-by, makes catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108654A CN1095401C (en) | 1998-05-22 | 1998-05-22 | Hydrogenolysis catalyst for low-temp synthesis of methanol with methyl formate and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98108654A CN1095401C (en) | 1998-05-22 | 1998-05-22 | Hydrogenolysis catalyst for low-temp synthesis of methanol with methyl formate and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1236669A CN1236669A (en) | 1999-12-01 |
| CN1095401C true CN1095401C (en) | 2002-12-04 |
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| CN98108654A Expired - Fee Related CN1095401C (en) | 1998-05-22 | 1998-05-22 | Hydrogenolysis catalyst for low-temp synthesis of methanol with methyl formate and its preparing process |
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| CN101239313B (en) * | 2008-01-29 | 2011-05-11 | 清华大学 | Copper cerium aluminium catalyst capable of simultaneously removing carbon smoke granule and nitrogen oxide and preparation |
| WO2019013272A1 (en) * | 2017-07-12 | 2019-01-17 | 国立研究開発法人科学技術振興機構 | Intermetallic compound, hydrogen storage/release material, catalyst and method for producing ammonia |
| CN115475618B (en) * | 2022-10-17 | 2023-09-22 | 南京工程学院 | Preparation method of polygonal prismatic quaternary photocatalyst based on combustible amorphous strips |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037283A (en) * | 1988-04-14 | 1989-11-22 | 格雷斯公司 | The catalyst of moulding and preparation method |
| US5015766A (en) * | 1987-12-16 | 1991-05-14 | Mitsui Toatsu Chemicals, Incorporated | Preparation process of acrylamide |
| JPH05155831A (en) * | 1991-12-05 | 1993-06-22 | Asahi Chem Ind Co Ltd | Production of amide by hydration of nitrile |
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1998
- 1998-05-22 CN CN98108654A patent/CN1095401C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5015766A (en) * | 1987-12-16 | 1991-05-14 | Mitsui Toatsu Chemicals, Incorporated | Preparation process of acrylamide |
| CN1037283A (en) * | 1988-04-14 | 1989-11-22 | 格雷斯公司 | The catalyst of moulding and preparation method |
| JPH05155831A (en) * | 1991-12-05 | 1993-06-22 | Asahi Chem Ind Co Ltd | Production of amide by hydration of nitrile |
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