CN1421269A - Methanol synthesizing catalyst - Google Patents
Methanol synthesizing catalyst Download PDFInfo
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- CN1421269A CN1421269A CN 01130542 CN01130542A CN1421269A CN 1421269 A CN1421269 A CN 1421269A CN 01130542 CN01130542 CN 01130542 CN 01130542 A CN01130542 A CN 01130542A CN 1421269 A CN1421269 A CN 1421269A
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Abstract
The methanol synthesizing catalyst has the molar composition of: Zr 40-60%, Cu 20-40%, MA 10-20% and Ni 1-30%, where MA is alkali metal, alkali earth metal or transition element(s). During the preparation, zirconium hydroxide and the nitrates of the other elements are dissolved in distilled water to form mixed solution of 5-30 % concentration; coprecipitation with sodium carbonate at 60-90 deg.c while stirring and maintaining pH 9-12; washing the precipitate with distilled water until no chlorine oil; soaking with the citrate, carbonate, oxalate or nitrate of MA to add MA as assistant; drying at 80-160 deg.c, roasting at 200-750 deg.c and crushing to 20-40 mesh. The catalyst has high mechanical strength and low cost.
Description
Technical field:
The invention belongs to a kind of methanol synthesis catalyst, relate in particular to a kind of copper Zirconium oxide catalyst of additive modification.
Background technology:
Methyl alcohol is a kind of important basic chemical industry raw material.The industrial methanol synthetic catalyst mainly is the Cu-Zn-Al catalyst system and catalyzing at present.Although obtained large-scale commercial Application, this catalyst system and catalyzing still exists some weakness, and is relatively poor as hear resistance, needs 3～12%CO in reduction and course of reaction
2Keep its catalytic activity, and operating cost is bigger.
In order to overcome the shortcoming of industrial methanol synthetic catalyst.In recent years, corresponding reported some novel carbinol catalyst system and catalyzings (Owen Geoffyey, Hawkes C.M.Lloyd Deborach, Appl.Catal.1987,33:405), thorium-copper intermetallic compound catalyst copper/rare earth oxide (Cu/CeO
2Or Cu/La
2O
3) catalyst, the CO hydrogenation is all showed higher activity and selectivity, but these catalyst are all easily by CO
2Poison and inactivation.Discovering in recent years, Cu/ZrO
2Catalyst based is the catalst for synthesis of methanol of function admirable.The Cu/ZrO that reports on the present document
2Catalyst adopts immersion process for preparing mostly, adopts ultra-fine ZrO as Liu Yuan (Liu Yuan Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences doctorate paper)
2Cu/ZrO as preparing carriers
2Catalyst is at P=4.0MPa, T=250 ℃ and GHSV=5000h
-1Reaction condition under, its liquid yield can reach 0.6g/ml/h
[4]Yet its stability is poor.Chen Xiaoping and Andriamasinoro once reported the Cu/MnO of coprecipitation preparation respectively
2/ ZrO
2And Cu/La
2Zr
4O
7The synthesizing methanol catalyst system and catalyzing (Chen Xiaoping, Wu Guisheng, Sun Yuhan, clock is bright, the gas chemical industry, 1998,23 (5) 1, Andriasinoro.D., Kiffer R., KiennemannA, Appl.Catal., 1993,106:201), it is at P=6.0MPa, GHSV=3000-5000h
-1Under T=280 ℃ condition, its liquid yield can reach 0.3g/ml/h and 0.4g/g/h respectively.But catalyst is overall active also on the low side.
Summary of the invention:
The purpose of this invention is to provide the high methanol synthesis catalyst of a kind of low temperature active.
Catalyst molar percentage of the present invention consists of: Zr:40～60%; Cu:20～40%; M
A: 10%～20%; Ni 1～30%;
M wherein
ABe the combination of one or more elements in alkali metal, alkaline-earth metal and the transition elements, comprise K, Li, Na, Cs, Ca, Ba, Al, Mg, Zn, Mo, Co, Rh, Ru, Pd etc.
Preparation method of the present invention is:
Ratio in above-mentioned catalyst composition, remove the form of Zr with zirconium oxychloride, all the other elements all are dissolved in the distilled water with the form of nitrate, form 5～30% mixed solution, 60～90 ℃ down with the sodium carbonate liquor co-precipitation, precipitation process needs fully to stir, maintenance pH=9～12, precipitation through distilled water washing till do not have chlorion and detect, M
AAuxiliary agent adds with the form dipping method of citrate, carbonate, oxalates or nitrate, and dip time 1 hour 80～160 ℃ of dry and 200～750 ℃ of roastings down, is crushed to 20～40 orders then, makes catalyst.
Condition when catalyst of the present invention is used for the synthesis gas synthesizing methanol is: pressure 1.0～20.0Mpa, and temperature is 200～400 ℃, air speed is 500～100000h
-1
The present invention compared with prior art has following advantage:
(1) this method for preparing catalyst is simple, easy operating, and catalyst performance repeatability is relatively good, realizes the industry amplification easily.
(2) each component distribution is more even, and has strong interaction between each component, and anti-agglutinatting property is relatively good.
(3) but catalyst straight forming before dry does not need adding additives.And catalyst is after roasting, and mechanical strength is relatively good.
(4) catalyst does not need to add CO in reduction and course of reaction
2Gas greatly reduces operating cost.
(5) activity of such catalysts height, in the liquid product of reaction, accessory substance is fewer, and the total content of its senior alcohol and water all is lower than 0.5%.
The specific embodiment:
Embodiment 1:
With following metallic atom mol ratio preparation mixed solution: Cu25Zr50Mn12Ni13, (remove the form of Zr with zirconium oxychloride, all the other elements all are dissolved in the mixed solution of formation 15% in the distilled water with the form of nitrate).Down carry out co-precipitation with the sodium carbonate liquor of 30 (Wt) % at 70 ℃, precipitation process needs fully to stir, and keeps pH=9, and till do not have chlorion and detect, 120 ℃ of dryings and through 350 ℃ of roastings down, it is stand-by to be crushed to 20～40 orders through the distilled water washing for precipitation.CO+H
2Be reflected in the stainless steel reactor of 10mm internal diameter and carry out, the reaction procatalyst, switches to synthesis gas and reacts 280 ℃ of reduction 10 hours with pure hydrogen, and service condition is as follows: P=12.0MPa, T=280 ℃, GHSV=10000h
-1, H
2/ CO=2 collects liquid product with ice-water bath, and the gas chromatographic analysis product is formed.The gained result is as follows: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr62.37 1.79 4.31 94.10 2.31
Embodiment 2 catalysis are composed as follows: Cu24Zr49Mn13Ni13K1, method for preparing catalyst is with embodiment 1.P=12.0MPa, T=280 ℃, GHSV=8000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr61.85 1.36 3.10 95.53 2.20
Embodiment 3 catalyst are composed as follows: (preparation method is with embodiment 1) Cu20Zr60Mn10Ni10P=12.0MPa, T=300 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr31.05 1.68 0.68 97.64 1.15
Embodiment 4 catalyst are composed as follows: (preparation method is equal to example 1) Cu27Zr54Mn14Ni5P=8.0MPa, T=300 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr24.25 3.62 4.98 91.41 0.82
Embodiment 5 catalyst are composed as follows: (preparation method is equal to example 1) Cu40Zr40Mn10Ni5Zn5P=12.0MPa, T=300 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr32.5 3.67 5.09 91.24 1.20
Embodiment 6: catalyst is composed as follows: (preparation method is equal to example 1) Cu30Zr50Mg15Ni5P=12.0MPa, T=300 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr37.6 4.53 5.36 90.11 1.46
Embodiment 7: catalyst is composed as follows: (preparation method is equal to example 1) Cu27Zr50Ni5Ca18P=12.0MPa, T=300 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr40.05 5.01 4.25 90.74 1.58
Embodiment 8: catalyst consists of: (preparation method is equal to example 1) Cu30Zr50Co14Ni5Cs1P=12.0MPa, T=300 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr40.29 2.96 3.05 93.99 1.68
Embodiment 9: catalyst consists of: (preparation method is equal to example 1) Cu30Zr40Mo10Ni10Fe10P=12.0MPa, T=300 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio hydrocarbon-selective (%) CO
2The pure selectivity of selectivity (%) (%) space-time yield g/ml cat hr42.06 4.59 4.27 91.14 0.82
Claims (2)
1. a methanol synthesis catalyst is characterized in that the mol ratio of catalyst consists of: Zr:40～60%; Cu:20～40%; M
A: 10%～20%; Ni 1～30%; M wherein
AIt is the combination of one or more elements in alkali metal, alkaline-earth metal and the transition elements.
2. a kind of methanol synthesis catalyst as claimed in claim 1 is characterized in that M
ABe K, Li, Na, Cs, Ca, Ba, Al, Mg, Zn, Mo, Co, Rh, Ru or Pd.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011305428A CN1151874C (en) | 2001-11-27 | 2001-11-27 | Methanol synthesizing catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011305428A CN1151874C (en) | 2001-11-27 | 2001-11-27 | Methanol synthesizing catalyst |
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|---|---|
| CN1421269A true CN1421269A (en) | 2003-06-04 |
| CN1151874C CN1151874C (en) | 2004-06-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011305428A Expired - Fee Related CN1151874C (en) | 2001-11-27 | 2001-11-27 | Methanol synthesizing catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191747A (en) * | 2013-04-07 | 2013-07-10 | 昆明理工大学 | Method for synthesizing low-carbon alcohol catalyst through carbon dioxide hydrogenation |
| CN106423171A (en) * | 2016-08-01 | 2017-02-22 | 中南民族大学 | Ni/Cu/M catalyst for catalytic methanol synthesis reaction and preparation method thereof |
| CN104722305B (en) * | 2013-12-23 | 2017-11-14 | 中国科学院上海高等研究院 | One kind is applied to multi component mixed gas catalst for synthesis of methanol and its preparation method and application |
-
2001
- 2001-11-27 CN CNB011305428A patent/CN1151874C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191747A (en) * | 2013-04-07 | 2013-07-10 | 昆明理工大学 | Method for synthesizing low-carbon alcohol catalyst through carbon dioxide hydrogenation |
| CN103191747B (en) * | 2013-04-07 | 2015-08-26 | 昆明理工大学 | A kind of method of hydrogenation of carbon dioxide formate low-carbon alcohol catalyst |
| CN104722305B (en) * | 2013-12-23 | 2017-11-14 | 中国科学院上海高等研究院 | One kind is applied to multi component mixed gas catalst for synthesis of methanol and its preparation method and application |
| CN106423171A (en) * | 2016-08-01 | 2017-02-22 | 中南民族大学 | Ni/Cu/M catalyst for catalytic methanol synthesis reaction and preparation method thereof |
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| CN1151874C (en) | 2004-06-02 |
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