CN1428192A - Catalyst for synthesis of low-carbon alcohol - Google Patents
Catalyst for synthesis of low-carbon alcohol Download PDFInfo
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- CN1428192A CN1428192A CN 01131681 CN01131681A CN1428192A CN 1428192 A CN1428192 A CN 1428192A CN 01131681 CN01131681 CN 01131681 CN 01131681 A CN01131681 A CN 01131681A CN 1428192 A CN1428192 A CN 1428192A
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Abstract
The present invention relates to a catalyst for synthesizing low-carbon alcohol. The composition of said catalyst includes 40-60% of Zr, 20-40% of Cu, 1%-10% of Ma, 1-30% of Ni and 1-10% of Mn, in which Ma is one of alkali metal, alkaline earth metal and transition elements or combination of several elements. Its preparation method adopts coprecipitation method, including the following steps: Zr which adopts the form of zirconium oxychloride and other elements which adopt the form of nitrate are dissolved in distilled water to form mixed solution, then said mixed solution and sodium carbonate solution are coprecipitated, stirred, its pH is reduced in 5-12, and its precipitate is washed with distilled water until the chlorine ion is not detected, the Ma adjuvants which adopts the form of oxalate, citrate, carbonate or nitrate are added by utilizing impregnating mode.
Description
Technical field:
The invention belongs to a kind of catalyst of synthesis of low-carbon alcohol, relate in particular to a kind of copper Zirconium oxide catalyst of additive modification.
Background technology:
MAS is to improve the desirable additive of leadless gasoline octane rating, has vast market prospect, so this reaction has a generic catalyst for methanol modification in the Catalytic processes process of maturation at present, modification Cu-Zn-Al catalyst system and catalyzing (E.Supp, Paper presented atthe 78 as German Lurgi company
ThSpring National AIChE Meeting, New Orleans, April, 1986) and the Zn-Cr-K catalyst system and catalyzing (C.Hoftadz of Italian Snam company, Eur.Patent 0034338-A2 (1982)) etc., employed modified additive is alkali metal or alkaline-earth metal, and the characteristics of this class catalyst are the space-time yields (being generally about 0.3g/ml h) with higher generation alcohol, the one-tenth alcohol selectivity of unstripped gas is higher, but C
2 +The selectivity of alcohol in total alcohol only is 30wt%, therefore is necessary above-mentioned catalyst system and catalyzing is done further improvement, to improve C
2 +The selectivity of alcohol in total alcohol descends the technology cost of entire reaction course.
Summary of the invention:
The catalyst that the purpose of this invention is to provide a kind of synthesis of low-carbon alcohol of high selectivity.
Catalyst molar percentage of the present invention consists of: Zr:40～60%; Cu:20～40%; M
A: 1%～10%; Ni 1～30%; Mn 1-10%;
M wherein
ABe the combination of one or more elements in alkali metal, alkaline-earth metal and the transition elements, comprise Li, Na, K, Cs, Al, Mg, Ca, Ba, Cr, Mn, Fe, Co, Mo, Ru, Rh, Pd, Zn etc.
Preparation of catalysts method of the present invention comprises the steps:
Catalyst adopts the coprecipitation preparation, removes the form of Zr with zirconium oxychloride, and all the other elements all are dissolved in the distilled water with the form of nitrate, form the mixed solution of 5-30%.20-90 ℃ down with the sodium carbonate liquor co-precipitation, precipitation process needs fully to stir, and keeps pH=5-12, precipitation is washed till do not have chlorion and detect through distilled water, M
AAuxiliary agent is with oxalates, citrate, and the form of carbonate or nitrate adds with dipping method, dip time 1-10h.Dry under 60-160 ℃ then, 200-750 ℃ of roasting.
Condition when catalyst of the present invention is used for the synthesis gas low-carbon alcohols is: pressure=5.0-20.0MPa, temperature=300-500 ℃, air speed=1000-100000h
-1, H
2/ CO=0.5-3.
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 CO2 gas in reduction and course of reaction, greatly reduces operating cost.
The specific embodiment:
Embodiment 1:
With following metallic atom molar percentage preparation mixed solution: Cu30Zr40Mn20Ni10, (remove the form of Zr with zirconium oxychloride, all the other elements form certain density mixed solution in the middle of all being dissolved in distilled water with the form of nitrate).70 ℃ down with 30% sodium carbonate liquor co-precipitation, precipitation process needs fully to stir, and keeps pH=9, precipitation till do not have chlorion and detect, 120 ℃ of dry down and 350 ℃ of roastings, is crushed to the 20-40 order through the distilled water washing.CO+H
2Be reflected in the stainless steel reactor of 6mm internal diameter and carry out, before the reaction with pure hydrogen at 300 ℃ of reductase 12s-10 hour, switch to synthesis gas and react, service condition is as follows: P=12.0MPa, T=350 ℃, GHSV=5000h
-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 alcohol selectivity
*Space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 50.44 74.95 0.30 79.34 4.58 2.16 8.24
*CO
2Do not count
Embodiment 2. catalysis consist of: Cu20Zr60Al4Ni15, all the other are with embodiment 1.
P=12.0MPa, T=380 ℃, GHSV=8000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 65.48 66.85 0.21 46.21 24.83 11.10 12.39
Embodiment 3: catalyst consists of: all the other are with embodiment 1.Cu30Zr60Mg7Ni3
P=12.0MPa, T=350 ℃, GHSV=8000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 24.17 73.22 0.37 62.68 16.66 9.46 7.48
Embodiment 4: catalyst is composed as follows: all the other are with embodiment 1.Cu35Zr60Co4Nil
P=12.0MPa, T=380 ℃, GHSV=8000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 38.39 63.94 0.39 42.99 21.55 14.01 12.88
Embodiment 5: catalyst is composed as follows: all the other are with embodiment 1.Cu30Zr50Ru5Ni14Csl
P=12.0MPa, T=360 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 51.27 69.24 0.26 54.46 20.68 9.11 11.45
Embodiment 6: catalyst is composed as follows: all the other are with embodiment 1.Cu35Zr50Mo14Nil
P=12.0MPa, T=360 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 48.43 73.25 0.34 67.22 15.34 6.69 7.55
Embodiment 7: catalyst is composed as follows: all the other are with embodiment 1.Cu20Zr55Fe5Ni20
P=14.0MPa, T=370 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 38.52 73.94 0.41 55.72 21.29 9.69 6.35
Embodiment 8: catalyst consists of: all the other are with embodiment 1.Cu40Zr40Zn10Ni10
P=12.0MPa, T=360 ℃, GHSV=5000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 40.30 69.59 0.54 62.70 19.40 8.10 5.21
Embodiment 9: catalyst consists of: all the other are with embodiment 1.Cu20Zr40Mn15Ni5Zn20
P=12.0MPa, T=370 ℃, GHSV=10000h
-1, H
2/ CO=2, the gained result is: CO conversion ratio alcohol selectivity space-time yield alcohol distribution wt% % % g/ml h methanol propyl alcohol isobutanol 27.13 68.05 0.49 60.43 20.21 8.74 5.52
Claims (2)
1. the catalyst of a synthesis of low-carbon alcohol is characterized in that the catalyst molar percentage consists of: Zr:40～60%; Cu:20～40%; M
A: 1%～10%; Ni 1～30%; Mn 1-10%; M wherein
AIt is the combination of one or more elements in alkali metal, alkaline-earth metal and the transition elements.
2. the catalyst of a kind of synthesis of low-carbon alcohol as claimed in claim 1 is characterized in that described M
ABe Li, Na, K, Cs, Al, Mg, Ca, Ba, Cr, Mn, Fe, Co, Mo, Ru, Rh, Pd or Zn.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131681 CN1428192A (en) | 2001-12-27 | 2001-12-27 | Catalyst for synthesis of low-carbon alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01131681 CN1428192A (en) | 2001-12-27 | 2001-12-27 | Catalyst for synthesis of low-carbon alcohol |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614936A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102614937A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof and catalyst and preparation method thereof |
| CN105727982A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Catalyst for synthesizing lower alcohols and preparation method for catalyst |
| CN106311272A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst used for production of isobutanol from synthetic gas, and preparation method of catalyst |
| CN106311267A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for synthesizing isobutanol from synthetic gas as well as preparation method and application thereof |
| CN106831328A (en) * | 2017-01-18 | 2017-06-13 | 武汉大学 | The technique that a kind of biomass synthesis gas produce MAS |
| CN107213905A (en) * | 2016-03-21 | 2017-09-29 | 中国石油化工股份有限公司 | Catalyst of isobutanol and its preparation method and application is synthesized by synthesis gas |
-
2001
- 2001-12-27 CN CN 01131681 patent/CN1428192A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102614936A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof as well as catalyst and preparation method thereof |
| CN102614937A (en) * | 2012-03-09 | 2012-08-01 | 烟台大学 | Mesoporous material and preparation method thereof and catalyst and preparation method thereof |
| CN105727982A (en) * | 2014-12-11 | 2016-07-06 | 中国石油化工股份有限公司 | Catalyst for synthesizing lower alcohols and preparation method for catalyst |
| CN105727982B (en) * | 2014-12-11 | 2019-03-29 | 中国石油化工股份有限公司 | A kind of catalyst of synthesis of low-carbon alcohol and preparation method thereof |
| CN106311272A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst used for production of isobutanol from synthetic gas, and preparation method of catalyst |
| CN106311267A (en) * | 2015-07-06 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for synthesizing isobutanol from synthetic gas as well as preparation method and application thereof |
| CN107213905A (en) * | 2016-03-21 | 2017-09-29 | 中国石油化工股份有限公司 | Catalyst of isobutanol and its preparation method and application is synthesized by synthesis gas |
| CN106831328A (en) * | 2017-01-18 | 2017-06-13 | 武汉大学 | The technique that a kind of biomass synthesis gas produce MAS |
| CN106831328B (en) * | 2017-01-18 | 2021-02-09 | 武汉大学 | Process for preparing low-carbon mixed alcohol from biomass synthesis gas |
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