CN102029173A - Rhodium-based catalyst used in process of preparing low carbon mixed alcohols from synthesis gas - Google Patents
Rhodium-based catalyst used in process of preparing low carbon mixed alcohols from synthesis gas Download PDFInfo
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Abstract
The invention discloses a rhodium-based catalyst used in a process of preparing low carbon mixed alcohols from synthesis gas. The catalysts consists of an active ingredient and a carrier, wherein the active ingredient is Rh; the Rh accounts for 1 to 10 percent based on the weight of the catalyst; the carrier is a molecular sieve with a regular hexagonal hole structure; and the hole size of the molecular sieve is 1 to 30nm, the hole volume is 1 to 5 cm<3>/g, and the specific surface area is 100 to 1,000 m<2>/g. The rhodium-based catalyst can improve the conversion rate of CO, and selectivity of ethanol to ensure that the main product is ethanol.
Description
Technical field
The present invention relates to a kind of catalyst, specifically relate to a kind of rhodium base catalyst that is used for by the synthesis gas preparation MAS.
Background technology
Containing the low-carbon (LC) alcohols of 2 or 2 above carbon atoms such as ethanol, propyl alcohol, butanols etc. is important chemical material, also is a kind of high-octane rating, oligosaprobic vehicle fuel additive.The traditional preparation process method of these products is many to be raw material with grain and oil, if can be synthetic from one step of synthesis gas, can save a large amount of grains, and make full use of abundant and cheap coal and the natural gas resource of price of storage, has a extensive future.
After the twentieth century world at the end of the seventies stands the secondary oil crisis, once coming into one's own and obtained certain progress by the research of synthesis gas preparation low-carbon alcohols, but the material synthesis gas conversion per pass and
The selectivity of alcohol is all lower.In recent years owing to the reason of environmental protection aspect, methyl tertiary butyl ether(MTBE) is as the oil dope use that is under an embargo in some countries and regions, make low-carbon alcohols double as the use value of oil dope, the industrialization of low-carbon alcohols synthesis technique causes the interest of fuel chemical circles again, and how to improve activity of such catalysts and selectivity to improve the efficient of production process, become restriction low-carbon alcohols synthesis technique practicability and industrialized technical bottleneck.
Be in the reaction of feedstock production low-carbon alcohols with the synthesis gas, Rh is a necessary active metal component in the high activated catalyst, as: american documentation literature US4014913 discloses with Rh-Mn/SiO
2Be oxygenatedchemicals such as catalyst synthesizing alcohol; Disclose with Rh-V-M/SiO among the Chinese patent literature CN 117549A
2Be the synthetic C of catalyst
2Oxygenatedchemicals etc.In document before, mostly adopt SiO
2Be carrier, and also fewer with molecular sieve as the research of preparing carriers catalyst with regular hex hole structure.Be used for C with the Rh/NaY catalyst
2Synthetic (Xu Baiqing, W.M.H.Sachtler, SCI, 1999 of oxygenatedchemicals; 12 (5): 794-796), its primary product is an acetate, rather than low-carbon alcohols, though the selectivity of acetate is higher; about 50%, but the CO conversion ratio is low, has only about 1%.It is that the catalyst of carrier is used for C that Chinese patent literature CN1354043A discloses with MCM-41 and MCM-22
2Synthesizing of oxygenatedchemicals, its primary product is ethanol, acetate and acetaldehyde, though the CO conversion ratio increases, remains lower.
Summary of the invention
The object of the present invention is to provide a kind of rhodium base catalyst that is used for by the synthesis gas preparation MAS, improve the conversion ratio of CO and the selectivity of ethanol, make that primary product is an ethanol.
The present invention adopts following technical scheme to realize: a kind of rhodium base catalyst that is used for by the synthesis gas preparation MAS, to form by active component and carrier, and described active component is Rh, the weight percentage of described Rh is 1%-10%; Described carrier is the molecular sieve with regular hexagonal pore structure, and the pore size of described molecular sieve is that 1nm～30nm, pore volume are 1cm
3/ g～5cm
3/ g, specific area are 100m
2/ g～1000m
2/ g.
Above-mentioned rhodium base catalyst, the pore size of described molecular sieve are 5nm～10nm.
Above-mentioned rhodium base catalyst, the weight percentage of described Rh are 5%-7%; The pore size of described molecular sieve is that 7.2nm～8.6nm, pore volume are 0.93cm
3/ g～1.23cm
3/ g, specific area are 495m
2/ g～505m
2/ g.
Above-mentioned rhodium base catalyst, described active component also comprises Fe, the weight percentage of described Fe is 1%～10%.
Above-mentioned rhodium base catalyst, the weight percentage of described Rh is 2: 1 with the ratio of the weight percentage of described Fe.
Above-mentioned rhodium base catalyst, described active component also comprises Mn, the weight percentage of described Mn is 1%～10%.
Above-mentioned rhodium base catalyst, the ratio of the weight percentage of described Rh and the weight percentage of described Mn is 0.5～10.
Above-mentioned rhodium base catalyst, described molecular sieve are SBA-15.
Above-mentioned rhodium base catalyst, described molecular sieve is to adopt following method preparation: (1) is dissolved in 4.37mol water with 3g triblock polymer polyvinyl alcohol, add 0.00021mol heteropoly acid and 0.0065mol hydrochloric acid, stirring at normal temperature adds the 0.031mol ethyl orthosilicate, stir 24h, transfer in the polymeric kettle, put into baking oven, oven temperature is set to 100 ℃, after 48 hours, be cooled to room temperature filtration, washing, drying; (2) with gained solid in above-mentioned (1) in the Muffle furnace roasting, 1 ℃/min of programming rate, 550 ℃ of constant temperature 6h.
Above-mentioned rhodium base catalyst, described rhodium base catalyst prepares with dipping method, and reduces in 300 ℃～500 ℃ in hydrogen.
Rhodium base catalyst of the present invention has following beneficial technical effects: adopt rhodium base catalyst of the present invention, the conversion ratio of CO and the selectivity of ethanol are improved, make that primary product is an ethanol.
The specific embodiment
Embodiment 1
The preparation of carrier
(1) with 3g triblock polymer polyvinyl alcohol (P123, M=5800) be dissolved in 4.37mol water, add 0.00021mol phosphomolybdic acid and 0.0065mol hydrochloric acid, stirring at normal temperature, add 0.031mol ethyl orthosilicate (TEOS), stir 24h, transfer in the polymeric kettle, put into baking oven, oven temperature is provided with 100 ℃, after 48 hours, be cooled to room temperature filtration washing drying, obtain molecular screen primary powder.(2) with molecular screen primary powder in the Muffle furnace roasting, 1 ℃/min of programming rate, 550 ℃ of constant temperature 6h, the carrier of present embodiment, i.e. SBA-15 molecular sieve.With N
2It is 7.8nm that absorption and HRTEM measure pore size.
The preparation of rhodium base catalyst
Adopt infusion process with active constituent loading to carrier, concrete steps are: will be equipped with the good mixed solution that contains 0.25g Rh and 0.125g Fe and put into the dipping bottle, take by weighing carrier 5g (about 1: 2 of the volume ratio of carrier and solution) and immerse fast in the solution, stir to make and flood evenly.Need guarantee in the dipping process that solution is little excessive after the carrier saturated absorption.The impregnated sample room temperature is placed, after the air dry, in 120 ℃ of following 24h oven dry.
The activity rating of rhodium base catalyst
In the present embodiment catalyst A, the Rh percentage composition is 5%, and the weight percentage of Rh is 2: 1 with the ratio of the weight percentage of Fe.Get catalyst A 0.5g and pack in the solid-bed reactor, reduce 7h with pure hydrogen at 400 ℃, be cooled to reaction temperature after, switch to synthesis gas and react: pressure is 1Mpa, temperature is 300 ℃, synthesis gas air speed 2500h
-1, H
2/ CO is 2: 1.Product liquid adopts ice-cooled, and gas-phase product is directly used the gas-chromatography on-line analysis, and the selectivity of ethanol is up to 17.56%, and the CO conversion ratio of this moment is 17.50%.
Embodiment 2
The preparation of carrier
With 3g triblock polymer polyvinyl alcohol (P123, M=5800) be dissolved in 4.37mol water, add 0.0086mol hydrochloric acid, stirring at normal temperature, add 0.031mol ethyl orthosilicate (TEOS), stir 24h, transfer in the polymeric kettle, put into baking oven, oven temperature is provided with 100 ℃, after 48 hours, be cooled to room temperature filtration washing drying, obtain molecular screen primary powder.
The activity rating of the preparation of rhodium base catalyst and rhodium base catalyst is all identical with embodiment 1 in the present embodiment, and its difference only is the preparation difference of carrier.
Embodiment 3
The preparation of carrier
With 3g triblock polymer polyvinyl alcohol (P123, M=5800) be dissolved in 4.37mol water, add 0.00021mol phosphotungstic acid and 0.0065mol hydrochloric acid, stirring at normal temperature, add 0.031mol ethyl orthosilicate (TEOS), stir 24h, transfer in the polymeric kettle, put into baking oven, oven temperature is provided with 100 ℃, after 48 hours, be cooled to room temperature filtration washing drying, obtain molecular screen primary powder.
The activity rating of the preparation of rhodium base catalyst and rhodium base catalyst is all identical with embodiment 1 in the present embodiment, and its difference only is the preparation difference of carrier.
Embodiment 4
With 3g triblock polymer polyvinyl alcohol (P123, M=5800) be dissolved in 4.37mol water, add 0.00021mol silico-tungstic acid and 0.0065mol hydrochloric acid, stirring at normal temperature, add 0.031mol ethyl orthosilicate (TEOS), stir 24h, transfer in the polymeric kettle, put into baking oven, oven temperature is provided with 100 ℃, after 48 hours, be cooled to room temperature filtration washing drying, obtain molecular screen primary powder.
The activity rating of the preparation of rhodium base catalyst and rhodium base catalyst is all identical with embodiment 1 in the present embodiment, and its difference only is the preparation difference of carrier.
The fundamental property of carrier sees Table 1 among embodiment 1, embodiment 2, embodiment 3, the embodiment 4, and the low-carbon alcohols synthetic reaction performance of rhodium base catalyst sees Table 2 among embodiment 1, embodiment 2, embodiment 3, the embodiment 4.
The fundamental property of carrier among table 1 embodiment 1, embodiment 2, embodiment 3, the embodiment 4
Annotate: S
BET: specific area, PV: pore volume=micro pore volume+mesopore volume, APD: the aperture, crystal structure is through XRD and N
2Adsorption test confirms.
The low-carbon alcohols synthetic reaction performance of rhodium base catalyst among table 2 embodiment 1, embodiment 2, embodiment 3, the embodiment 4
At embodiment 1 to embodiment 4, the weight percentage of Rh is 5% in the used rhodium base catalyst, and the weight percentage of Rh is 2: 1 with the ratio of the weight percentage of Fe, and 300 ℃ of reaction temperatures, reaction pressure are 1MPa, H
2/ CO is 2: 1, and air speed is 2500h
-1Four kinds of prepared among the embodiment 1-embodiment 4 molecular sieves have similar structure, but aperture and pore volume vary in size (seeing Table 1).As can be seen from Table 2: have larger aperture (8.55nm) and pore volume (1.23cm among the embodiment 1
3/ g) molecular sieve is made carrier, and resulting rhodium base catalyst is used for by the synthesis gas preparation MAS, and the conversion ratio of CO and the selectivity of ethanol are all than higher.
Embodiment 5
In the present embodiment, the preparation of carrier, the preparation of rhodium base catalyst and the activity rating of rhodium base catalyst are all with embodiment 1; Its difference only is that variation has taken place the weight percentage consumption of Rh, and variation has taken place the ratio of the weight percentage of Fe and the weight percentage of Rh, specifically sees Table 3.
The influence of the comparison reactivity worth of the weight percentage of the weight percentage of table 3Rh and the weight percentage of Fe and Rh
In the present embodiment, 300 ℃ of reaction temperatures, reaction pressure are 1MPa, H
2/ CO is 2: 1, and air speed is 2500h
-1As can be seen from Table 3: the weight percentage of (1) Rh is 5%, and the weight percentage of Fe is 0.5 o'clock with the ratio of the weight percentage of Rh, and the selectivity ratios of ethanol is higher; (2) weight percentage of Rh is 5%, and the weight percentage of Fe is 0.1 o'clock with the ratio of the weight percentage of Rh, and the conversion ratio of CO is than higher.
Embodiment 6
In the present embodiment, as the preparation method of the molecular sieve of carrier, the active testing step of the load of active component and rhodium base catalyst is all with embodiment 1.In the present embodiment, the Rh weight percentage is 5%, and active component also comprises Mn, and wherein the weight percentage of Mn is 1: 1 with the ratio of the weight percentage of Rh.At pressure (1MPa), temperature is 300 ℃, synthesis gas air speed 2500h
-1Condition under, the selectivity of ethanol is 12.87%, this moment the CO conversion ratio be 21.9%.
Embodiment 7
The activity rating method of the preparation method of the preparation of carrier, rhodium base catalyst and rhodium base catalyst is all identical with embodiment 3 in the present embodiment, in the rhodium base catalyst that present embodiment obtains, the Rh percentage composition is 5%, and the percentage by weight of Rh and Mn element is: Rh: Mn=1: 1.
Embodiment 8
The activity rating method of the preparation method of the preparation of carrier, rhodium base catalyst and rhodium base catalyst is all identical with embodiment 4 in the present embodiment, in the rhodium base catalyst that present embodiment obtains, the Rh percentage composition is 5%, and the percentage by weight of Rh and Mn element is: Rh: Mn=1: 1.
Embodiment 9
The activity rating method of the preparation method of the preparation of carrier, rhodium base catalyst and rhodium base catalyst is all identical with embodiment 5 in the present embodiment, in the rhodium base catalyst that present embodiment obtains, the Rh percentage composition is 5%, and the percentage by weight of Rh and Mn element is: Rh: Mn=1: 1.
The low-carbon alcohols synthetic reaction performance of rhodium base catalyst sees Table 4 among embodiment 6, embodiment 7, embodiment 8, the embodiment 9.
The low-carbon alcohols synthetic reaction performance of rhodium base catalyst among table 4 embodiment 6, embodiment 7, embodiment 8, the embodiment 9
Embodiment 6 to embodiment 9, and having investigated with the molecular sieve of distinct methods preparation conversion ratio and the ethanol to CO optionally influences, and the percentage composition of Rh is 5% in the rhodium base catalyst, the percentage composition of Mn is 2: 1 with the ratio of the percentage composition of Rh, 300 ℃ of reaction temperatures, reaction pressure are 1MPa, H
2/ CO=2, air speed is 2500h
-1These four kinds of molecular sieves have similar structure, but aperture and pore volume vary in size, and (seeing Table 2) as can be seen from Table 4, has larger aperture (8.55nm) and pore volume (1.23cm
3/ g) molecular sieve is made carrier, the ethanol selectivity of resulting rhodium base catalyst the highest (embodiment 6).
Embodiment 10
In this example, the preparation method of carrier, the preparation method of rhodium base catalyst and evaluation method are all with embodiment 1, and the ratio of the weight percentage of Mn and the weight percentage of Rh sees Table 5 to the influence of reactivity worth.
The influence of the comparison reactivity worth of the weight percentage of table 5Mn and the weight percentage of Rh
In the present embodiment, 300 ℃ of reaction temperatures, pressure 1MPa, air speed 2500h
-1As can be seen from Table 5, when the ratio of the weight percentage of Mn and the weight percentage of Rh was 2: 1, the selectivity ratios of ethanol was higher, is 22.2%; But the conversion ratio of CO is lower, is 9.29%.And when the ratio of the weight percentage of Mn and the weight percentage of Rh was 1: 1, the conversion ratio of CO was 21.90% than higher; This moment, the selectivity of ethanol was 12.87%.
Embodiment 11
In this example, the preparation method of carrier, the preparation method of rhodium base catalyst and evaluation method are all with embodiment 1, and the weight percentage of Rh is shown in Table 6 the influence of reactivity worth.
The weight percentage of table 6Rh is to the influence of reactivity worth
The weight percentage of Mn is 1: 1 with the ratio of the weight percentage of Rh in the present embodiment, 300 ℃ of reaction temperatures, pressure 1MPa, air speed 2500h
-1As can be seen from Table 6, along with the increase of Rh consumption, the conversion ratio of CO increases, and the selectivity of ethanol is 5% to reach maximum at the Rh percentage composition then.
In sum:
Rhodium base catalyst of the present invention, for the Rh-Fe/SBA-15 catalyst system and catalyzing, The optimum reaction conditions is: the ratio of the weight percentage of Fe and the weight percentage of Rh 1: 2,300 ℃ of reaction temperatures, pressure 1MPa, air speed 2500h
-1With this understanding, the selectivity of ethanol is up to 12.87%, and the CO conversion ratio of this moment is up to 21.9%.
For the Rh-Mn/SBA-15 catalyst system and catalyzing, The optimum reaction conditions is: the ratio of the weight percentage of Mn and the weight percentage of Rh 1: 1,300 ℃ of reaction temperatures, pressure 1MPa, air speed 2500h
-1The conversion ratio of CO is 21.90% under this condition, and the selectivity of ethanol is 12.87%.
Claims (10)
1. a rhodium base catalyst that is used for by the synthesis gas preparation MAS is made up of active component and carrier, it is characterized in that, described active component is Rh, and the weight percentage of described Rh is 1%-10%; Described carrier is the molecular sieve with regular hexagonal pore structure, and the pore size of described molecular sieve is that 1nm～30nm, pore volume are 1cm
3/ g～5cm
3/ g, specific area are 100m
2/ g～1000m
2/ g.
2. rhodium base catalyst according to claim 1 is characterized in that, the pore size of described molecular sieve is 5nm～10nm.
3. rhodium base catalyst according to claim 1 is characterized in that, the weight percentage of described Rh is 5%-7%; The pore size of described molecular sieve is that 7.2nm～8.6nm, pore volume are 0.93cm
3/ g～1.23cm
3/ g, specific area are 495m
2/ g～505m
2/ g.
4. rhodium base catalyst according to claim 1 is characterized in that described active component also comprises Fe, and the weight percentage of described Fe is 1%～10%.
5. rhodium base catalyst according to claim 4 is characterized in that, the weight percentage of described Rh is 2: 1 with the ratio of the weight percentage of described Fe.
6. rhodium base catalyst according to claim 1 is characterized in that described active component also comprises Mn, and the weight percentage of described Mn is 1%～10%.
7. rhodium base catalyst according to claim 6 is characterized in that, the ratio of the weight percentage of described Rh and the weight percentage of described Mn is 0.5～10.
8. according to the arbitrary described rhodium base catalyst of claim 1 to 7, it is characterized in that described molecular sieve is SBA-15.
9. according to the arbitrary described rhodium base catalyst of claim 1 to 7, it is characterized in that described molecular sieve is to adopt following method preparation: (1) is dissolved in 4.37mol water with 3g triblock polymer polyvinyl alcohol, adds 0.00021mol heteropoly acid and 0.0065mol hydrochloric acid, stirring at normal temperature, add the 0.031mol ethyl orthosilicate, stir 24h, transfer in the polymeric kettle, put into baking oven, oven temperature is set to 100 ℃, after 48 hours, is cooled to room temperature filtration, washing, drying; (2) with gained solid in above-mentioned (1) in the Muffle furnace roasting, 1 ℃/min of programming rate, 550 ℃ of constant temperature 6h.
10. according to the arbitrary described rhodium base catalyst of claim 1 to 7, it is characterized in that: described rhodium base catalyst prepares with dipping method, and reduces in 300 ℃～500 ℃ in hydrogen.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351641A (en) * | 2011-08-18 | 2012-02-15 | 内蒙古大学 | Preparation method and application of molybdenum sulfide catalyst using SBA-15 as carrier for producing low-carbon alcohols from synthetic gas |
| CN102407112A (en) * | 2011-09-26 | 2012-04-11 | 上海应用技术学院 | Catalyst for preparing C2-oxygenates through hydrogenation of carbon monoxide as well as preparation method and application thereof |
| CN102417437A (en) * | 2011-08-18 | 2012-04-18 | 内蒙古大学 | Catalyst for low-carbon mixed alcohol synthesis from syngas, and preparation method and application thereof |
| CN102500392A (en) * | 2011-09-26 | 2012-06-20 | 上海应用技术学院 | Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst |
| CN103537282A (en) * | 2013-10-11 | 2014-01-29 | 浙江大学 | Rhodium-based catalyst for synthesis of ethanol and co-product methane from synthetic gas and preparation method thereof |
| CN103752341A (en) * | 2014-01-24 | 2014-04-30 | 郑州大学 | Keggin type heteropoly acid-silicon oxide catalyst of mesopore structure and preparation method thereof |
| CN105536853A (en) * | 2016-02-01 | 2016-05-04 | 李璐 | Molecular sieve catalyst used for preparing low-carbon mixed alcohol from synthesis gas |
| CN110354852A (en) * | 2018-03-26 | 2019-10-22 | 中国科学院大连化学物理研究所 | A kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound |
| CN110773216A (en) * | 2019-08-27 | 2020-02-11 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in preparation of low-carbon alcohol from synthesis gas |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102351641A (en) * | 2011-08-18 | 2012-02-15 | 内蒙古大学 | Preparation method and application of molybdenum sulfide catalyst using SBA-15 as carrier for producing low-carbon alcohols from synthetic gas |
| CN102417437A (en) * | 2011-08-18 | 2012-04-18 | 内蒙古大学 | Catalyst for low-carbon mixed alcohol synthesis from syngas, and preparation method and application thereof |
| CN102407112A (en) * | 2011-09-26 | 2012-04-11 | 上海应用技术学院 | Catalyst for preparing C2-oxygenates through hydrogenation of carbon monoxide as well as preparation method and application thereof |
| CN102500392A (en) * | 2011-09-26 | 2012-06-20 | 上海应用技术学院 | Catalyst for preparing oxygenated dicarbide by synthesis gas and preparation method of catalyst |
| CN103537282A (en) * | 2013-10-11 | 2014-01-29 | 浙江大学 | Rhodium-based catalyst for synthesis of ethanol and co-product methane from synthetic gas and preparation method thereof |
| CN103752341A (en) * | 2014-01-24 | 2014-04-30 | 郑州大学 | Keggin type heteropoly acid-silicon oxide catalyst of mesopore structure and preparation method thereof |
| CN103752341B (en) * | 2014-01-24 | 2016-01-20 | 郑州大学 | Keggin-type heteropoly acid-silicon oxide catalyst of a kind of central hole structure and preparation method thereof |
| CN105536853A (en) * | 2016-02-01 | 2016-05-04 | 李璐 | Molecular sieve catalyst used for preparing low-carbon mixed alcohol from synthesis gas |
| CN105536853B (en) * | 2016-02-01 | 2020-06-26 | 辽宁恒顺达新材料有限公司 | Molecular sieve catalyst for preparing low-carbon mixed alcohol from synthesis gas |
| CN110354852A (en) * | 2018-03-26 | 2019-10-22 | 中国科学院大连化学物理研究所 | A kind of support type rhodium base catalyst, preparation method and in synthesis gas C2Application in oxycompound |
| CN110354852B (en) * | 2018-03-26 | 2021-05-25 | 中国科学院大连化学物理研究所 | Supported rhodium-based catalyst, preparation method thereof and method for preparing C from synthesis gas2Use in oxygenates |
| CN110773216A (en) * | 2019-08-27 | 2020-02-11 | 浙江工业大学 | Application of carbon nano tube embedded metal particle catalyst in preparation of low-carbon alcohol from synthesis gas |
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Application publication date: 20110427 |