CN101992099A - Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof - Google Patents
Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof Download PDFInfo
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- CN101992099A CN101992099A CN2009100578237A CN200910057823A CN101992099A CN 101992099 A CN101992099 A CN 101992099A CN 2009100578237 A CN2009100578237 A CN 2009100578237A CN 200910057823 A CN200910057823 A CN 200910057823A CN 101992099 A CN101992099 A CN 101992099A
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Abstract
The invention relates to a catalyst for preparing low-carbon alcohol from synthesis gas and a preparation method thereof, mainly aiming at solving the problems of more alkane byproducts of a catalyst for preparing low-carbon alcohol from synthesis gas, or high cost and rigorous and complicated treatment conditions in the prior art. In the technical scheme of invention, the problems are favorably solved by preparing the catalyst from the following components in percentage by weight: (a) 0.1-15 percent of Rh; (b) 0-5 percent of Mn; (c) 0-5 percent of M, (d) 0-5 percent of Fe; and (e) 70.0-99.9 percent of silicon oxide, wherein the M is selected from at least one of Li, Na or K, the silicon oxide is in a composite pore structure and simultaneously has micron-scale macropores and nanoscale mesopores, the volume of macropores is 0.4-3.0cm<3>/g and the volume of mesopores is 0.4-1.5cm<3>/g. The catalyst can be used in industrial production for preparing the low-carbon alcohol from the synthesis gas.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method that is used for low carbon alcohol by synthetic gas.
Background technology
Petroleum resources in short supply makes to be developed rapidly based on the C1 chemistry that utilizes coal and gas production liquid fuel and organic chemical industry's product that producing MAS by synthesis gas is the problem that has important research meaning and wide application prospect in the C1 chemical field.Be suitable as very much gasoline additive and use because of having superior functions such as octane number height, explosion-proof, antidetonation by the low-carbon alcohols of coal, natural gas via synthesis gas preparation, simultaneously, low-carbon alcohols still is important chemical material and the desirable free of contamination vehicle fuel of high-octane rating.If can directly make low-carbon alcohols from natural gas, then both can save food, also can make full use of the coal and the natural gas resource of China's abundant, thereby alleviate the industrial consumption of China's grain and alleviate petroleum resources contradiction in short supply, have the important strategic meaning aspect the national economy uplifting the people's living standard and develop.
Catalyst is the core content of catalytic reaction, and in decades, the countries in the world scientific research personnel produces at synthesis gas and done a large amount of work aspect the research of low-carbon alcohol catalyst, develops multiple catalyst system, wherein Rh/SiO
2System is the research focus of nearly section time.Metal Rh is owing to have the moderate CO absorption and the ability of dissociating, and especially after adding transition metal or rare earth metal auxiliary agent, this system is synthesized low-carbon alcohols and had very high activity and selectivity.From the angle of actual industrialization, at present the maximum deficiency that exists of Rh series catalysts be in the product except oxygenatedchemicals such as methyl alcohol, ethanol and acetate, also be accompanied by the generation of a large amount of alkane (mainly being methane).It is generally acknowledged that methane is that the CO hydrogenation that is adsorbed on by force on the activated centre generates.Rh/SiO in bibliographical information at present
2Generally up to more than 40%, and the added value of alkane is low to the selectivity of alkane for catalyst series, and follow-up conversion difficulty, this be in the actual production do not wish to see.
Document CN1179993A discloses a kind of rhodium base catalyst of low carbon alcohol by synthetic gas, obtains better oxygenate selectivity by the method that increases auxiliary agent content, claims that the overall selectivity of oxygenates such as its methyl alcohol, ethanol can reach more than 90%.But its adjuvant used Na (or Li) content improves more than ten times than common rhodium-based catalyst systems, and this catalyst need adopt the preparation method of step impregnation and substep hydrogen high temperature reduction to obtain, caused the increase greatly of catalyst cost and the loss of energy on the one hand, Fu Za preparation process also makes this catalyst be difficult to realize real industry popularization on the other hand.Simultaneously, according to its disclosed content, be difficult to repeat out its result.The bag letter and the research group of Dalian Chemical Physics Research Institute have reported that in the recent period with CNT be carrier loaded Rh-Mn-Li-Fe active component, found that preliminary treatment makes the CNT opening, active component is introduced in the hole of CNT, the catalyst of acquisition is keeping higher C
2In the time of the oxygenatedchemicals space-time yield to the selectivity of methane only less than 20%.Chinese patent (CN1390638) also proposes the rhodium base catalyst (Rh-MxOy/MWNTs) with carbon nanotube loaded rhodium and metal oxide auxiliary agent.Though this type of catalyst has very low alkane selectivity, the CNT price is very expensive and use is preceding will be through harsh complicated conditions such as the long-time high-temperature process of red fuming nitric acid (RFNA), and this makes this catalyst quite low in industrial possibility of its application.
Summary of the invention
One of technical problem to be solved by this invention is to exist low carbon alcohol by synthetic gas catalyst by-product alkane many in the conventional art, perhaps costs an arm and a leg, the harsh complicated problems of treatment conditions, and a kind of new catalyst that is used for low carbon alcohol by synthetic gas is provided.This catalyst is applicable to low carbon alcohol by synthetic gas reaction can keep higher low-carbon alcohols selectivity to have lower alkane selectivity again simultaneously, and preparation process mild condition, cost are relatively low, are fit to suitability for industrialized production.Two of technical problem to be solved by this invention provides one of a kind of and the technical solution problem corresponding Preparation of catalysts method that is used for low carbon alcohol by synthetic gas.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of catalyst that is used for low carbon alcohol by synthetic gas comprises following component by weight percentage:
A) 0.1～15% Rh;
B) 0～5% Mn;
C) 0～5% M, wherein M is selected among Li, Na or the K at least a;
D) 0～5% Fe;
E) 70.0～99.9% silica, described silica has composite pore structural, and it is mesoporous to have micron order macropore and nanoscale simultaneously, and wherein the macropore pore volume is 0.4～3.0 centimetre
3/ gram, mesoporous pore volume is 0.4～1.5 centimetre
3/ gram.
In the technique scheme, by weight percentage, the consumption preferable range of Rh is 0.3～10%, and more preferably scope is 0.4～8%; The consumption preferable range of Mn is 0.1～3%, and more preferably scope is 0.2～2.8%; The consumption preferable range of M is 0.01～4%, and more preferably scope is 0.02～2.7%; The consumption preferable range of Fe is 0.01～4%, and more preferably scope is 0.02～3.5%; The consumption preferable range of silica is 79.0～99.6%, and more preferably scope is 83.0～99.4%; Wherein the macropore pore volume preferable range of silica is 0.5～2.8 centimetre
3/ gram, more preferably scope is 0.5～2.5 centimetre
3/ gram; Mesoporous pore volume preferable range is 0.45～1.4 centimetre
3/ gram, more preferably scope is 0.49～1.38 centimetre
3/ gram.The specific area preferable range of described silica is 400～2000 meters
2/ gram, more preferably scope is 450～1500 meters
2/ gram, most preferred range is 460～1400 meters
2/ gram.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of Preparation of catalysts method that is used for low carbon alcohol by synthetic gas may further comprise the steps:
1) block copolymer and water soluble polymer are dissolved in the inorganic acid solution of 0.1～10 mol, form mixture A; Described block copolymer is selected from polyoxyethylene-poly-oxypropylene polyoxyethylene EOa-POb-EOa, a=10～200 wherein, b=10～100; Described water soluble polymer is selected from least a in polyvinyl alcohol, polyethylene glycol, poly-oxireme, polyacrylic acid, polyacrylamide or the polyvinylpyrrolidone; Described inorganic acid is selected from least a in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid or the tartaric acid;
2) under stirring, alkoxy silane is added among the mixture A, obtains sol B; Wherein alkoxy silane is selected from least a in trimethoxy silane, triethoxysilane, ethyl trimethoxy silane, MTES, dimethyldiethoxysilane, tetramethoxy-silicane or the tetraethoxysilane;
3) gas in the ultrasonic removal sol B;
4) the colloidal sol constant temperature through above processing leaves standstill, and produces sediment;
5) take out sediment, drying and roasting obtain the composite pore structural silica;
6) above-mentioned composite pore structural silica be impregnated in the metal salt solution that contains active constituent, dry then, roasting obtain described catalyst.
In the technique scheme, the time preferable range of ultrasonic processing in the step 3) is 30～600 seconds; The temperature preferable range that constant temperature leaves standstill in the step 4) is 20～120 ℃, and the time of repose preferable range is 1～120 hour; The sedimentary baking temperature preferable range of step 5) is 10～60 ℃, and drying time, preferable range was 0.1～30 day, and the sintering temperature preferable range is 300～800 ℃, and the roasting time preferable range is 1～30 hour.
Among the present invention, the inorganic salts of Rh are selected from least a in rhodium chloride, rhodium nitrate or the acetic acid rhodium, and the inorganic salts of Mn are selected from manganese nitrate, and the inorganic salts of M are selected from MNO
3Or at least a among the MCl, the inorganic salts of Fe are selected from least a in iron chloride, ferric nitrate, frerrous chloride or the ferrous nitrate.Can the slaine of active component is water-soluble, in methyl alcohol or the ethanol.During dipping, can be with one step of the common wiring solution-forming of the inorganic salts of each metal oxide impregnation silicon, also can be wherein one or both or three kinds of wiring solution-forming branches flood, dipping process can repeat 1～3 time.
It is carrier that the present invention adopts the composite pore structural silica, this carrier has micron-sized macroporous structure and nano level meso-hole structure simultaneously, make catalyst show high-specific surface area, large pore volume and excellent mass transfer-diffusion on the one hand, special composite pore structural has played facilitation to metal active constituent simultaneously, changed reaction process, made the present invention compare and show special catalytic effect and select performance preferably with normal load type catalyst; In addition, Preparation of catalysts mild condition easy operating of the present invention, and with low cost, be easy to suitability for industrialized production.Catalyst of the present invention is used for the low carbon alcohol by synthetic gas reaction, is H with the volume percent content
245～85%, the synthesis gas of CO15～55% is a raw material, and in reaction pressure 3.0 MPas, 310 ℃ of reaction temperatures are under 9000/ hour condition of air speed, and with common SiO
2For the catalyst of carrier is compared, up to 44%, the selectivity of methyl alcohol is up to 20% to the selectivity of ethanol for catalyst, and the selectivity of alkane can obtain better technical effect by being reduced to 24% more than 40%.
Description of drawings
Fig. 1 is the SEM figure of catalyst carrier composite pore structural silica among the present invention
Fig. 2 is the TEM figure of catalyst of the present invention
The present invention is further elaborated below by embodiment.
The specific embodiment
[embodiment 1]
1 gram triblock copolymer EO
20PO
70EO
20Join in the hydrochloric acid solution of 10 grams, 1 mol with 0.90 gram polyethylene glycol, stir and make its dissolving; In mixed solution, add 5 milliliters of tetramethoxy-silicanes then, continue to be stirred to the system stable homogeneous, ultrasonic then 100 seconds; Sol system after handling is transferred to constant temperature left standstill 48 hours for 60 ℃ in the mould, takes out sediment drying at room temperature 3 days, 450 ℃ of high-temperature roastings 5 hours, obtain the composite pore structural silica then, its specific area is up to 832 meters
2/ gram, 0.2 micron of macropore diameter, mesoporous aperture 4.8 nanometers, 2.1 centimetres of macropore pore volumes
3/ gram, 0.9 centimetre of mesoporous pore volume
3/ gram.
0.13 gram radium chloride (containing three crystallizations water), 0.18 gram manganese nitrate, 0.04 gram lithium nitrate and 0.01 gram iron chloride is soluble in water, and 10 gram composite pore structural silica were put into equal-volume mixed solution dipping 20 minutes, and drying at room temperature is flooded 2 times; And, obtain catalyst in 450 ℃ of roastings 2 hours, wherein Rh is 1% to each metallic element by weight percentage, Mn is 1%, Li is 0.075%, Fe is 0.075%.This catalyst is in H
2330 ℃ of in-situ reducing are 4 hours in the atmosphere, reduce to reaction temperature after logical synthesis gas begin reaction.Reaction pressure 3.0 MPas, 310 ℃ of reaction temperatures, air speed 9000/ hour.Measure its ethanol selectivity 44.2%, methyl alcohol 20.4%, alkane 23.1%.
[embodiment 2～4]
The consumption of polyethylene glycol (PEG) in the synthesis step of change catalyst, all the other operating procedures are all identical with [embodiment 1], and the catalyst structure parameter and the catalytic selectivity under the identical catalytic condition that obtain are as shown in table 1:
Table 1
[embodiment 5]
With triblock copolymer EO in the synthesis step of catalyst
20PO
70EO
20Change EO into
26PO
39EO
26, all the other operating procedures are all identical with [embodiment 1], and the catalyst structure parameter and the catalytic selectivity under the identical catalytic condition that obtain are as shown in table 2.
[embodiment 6]
1 gram triblock copolymer EO
20PO
70EO
20Join in the salpeter solution of 10 grams, 1 mol with the poly-oxireme of 0.75 gram, stir and make its dissolving; In mixed solution, add 5 milliliters of tetraethoxysilanes then.All the other operating procedures are all identical with [embodiment 1], and the catalyst structure parameter and the catalytic selectivity under the identical catalytic condition that obtain are as shown in table 2.
Table 2
[embodiment 7]
In the catalyst synthesis step, carrier floods twice in the solution that only contains 0.80 gram slaine radium chloride, and all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of a containing metal Rh who obtains is as shown in table 3.
[embodiment 8]
In the catalyst synthesis step, carrier floods twice in the solution that only contains 1.60 gram slaine radium chlorides, and all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of a containing metal Rh who obtains is as shown in table 3.
[embodiment 9]
In the catalyst synthesis step, carrier floods twice in the solution that contains 0.13 gram radium chloride and 0.63 gram manganese nitrate, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of containing metal Rh that obtains and Mn is as shown in table 3.
[embodiment 10]
In the catalyst synthesis step, carrier floods twice in the solution that contains 0.20 gram radium chloride and 0.06 gram lithium nitrate, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of containing metal Rh that obtains and Li is as shown in table 3.
[embodiment 11]
In the catalyst synthesis step, carrier floods twice in the solution that contains 0.40 gram radium chloride and 0.58 gram ferric nitrate, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of containing metal Rh that obtains and Fe is as shown in table 3.
[embodiment 12]
In the catalyst synthesis step, carrier floods twice in the solution that contains 0.07 gram radium chloride, 0.024 gram potassium nitrate and 0.13 gram iron chloride, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of containing metal Rh, K that obtains and Fe is as shown in table 3.
[embodiment 13]
In the catalyst synthesis step, carrier floods twice in the solution that contains 0.26 gram radium chloride, 0.18 gram manganese nitrate and 0.53 gram lithium nitrate, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of containing metal Rh, Mn that obtains and Li is as shown in table 3.
[embodiment 14]
In the catalyst synthesis step, carrier floods twice in the solution that contains 0.07 gram radium chloride, 0.054 gram manganese nitrate and 0.003 gram frerrous chloride, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of containing metal Rh, Mn that obtains and Fe is as shown in table 3.
[embodiment 15]
In the catalyst synthesis step, carrier floods twice in the solution that contains 0.28 gram rhodium nitrate, 0.36 gram manganese nitrate and 1.1 grams lithium chlorides, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of catalyst under identical catalytic condition of containing metal Rh, Mn that obtains and Li is as shown in table 3.
Table 3
[embodiment 16]
In the catalyst synthesis step, the dipping of carrier in metal salt solution once, all the other operating procedures are all identical with [embodiment 1], the catalytic selectivity of the catalyst that obtains under identical catalytic condition is as shown in table 4.
[embodiment 17]
In the catalyst synthesis step, the dipping of carrier in metal salt solution three times, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of the catalyst that obtains under identical catalytic condition is as shown in table 4.
Table 4
[embodiment 18]
In the impregnation steps, change aqueous solvent into methyl alcohol, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of the catalyst that obtains under identical catalytic condition is as follows: ethanol selectivity 43.7%, methyl alcohol 20.0%, alkane 28.4%.
[embodiment 19～22]
Change catalyst soakage step sintering temperature and the time afterwards, all the other operating procedures are all identical with [embodiment 1], and the catalytic selectivity of the catalyst that obtains under identical catalytic condition is as shown in table 5.
Table 5
[Comparative Examples 1]
Use the general commercial silica instead as carrier, all the other operating procedures are with [embodiment 1].The specific area of commercial silica is 340 meters
2/ gram, it is mesoporous only to contain nanoscale, and mesoporous aperture is 0.85 nanometer, and mesoporous pore volume is 10 centimetres
3/ gram.Its catalytic selectivity is an ethanol selectivity 26.5%, methyl alcohol 10%, alkane 44.5%.
Claims (8)
1. catalyst that is used for low carbon alcohol by synthetic gas comprises following component by weight percentage:
A) 0.1～15% Rh;
B) 0～5% Mn;
C) 0～5% M, wherein M is selected among Li, Na or the K at least a;
D) 0～5% Fe;
E) 70.0～99.9% silica, described silica has composite pore structural, and it is mesoporous to have micron order macropore and nanoscale simultaneously, and wherein the macropore pore volume is 0.4～3.0 centimetre
3/ gram, mesoporous pore volume is 0.4～1.5 centimetre
3/ gram.
2. according to the described catalyst that is used for low carbon alcohol by synthetic gas of claim 1, it is characterized in that by weight percentage that the consumption of Rh is 0.3～10%, the consumption of Mn is 0.1～3%, the consumption of M is 0.01～4%, and the consumption of Fe is 0.01～4%, and the consumption of silica is 79.0～99.6%; Wherein the macropore pore volume of silica is 0.5～2.8 centimetre
3/ gram, mesoporous pore volume is 0.45～1.4 centimetre
3/ gram.
3. according to the described catalyst that is used for low carbon alcohol by synthetic gas of claim 2, it is characterized in that by weight percentage, the consumption of Rh is 0.4～8%, the consumption of Mn is 0.2～2.8%, the consumption of M is 0.02～2.7%, the consumption of Fe is 0.02～3.5%, and the consumption of silica is 83.0～99.4%; Wherein the macropore pore volume of silica is 0.5～2.5 centimetre
3/ gram, mesoporous pore volume is 0.49～1.38 centimetre
3/ gram.
4. according to the described catalyst that is used for low carbon alcohol by synthetic gas of claim 1, the specific area that it is characterized in that described silica is 400～2000 meters
2/ gram.
5. according to the described catalyst that is used for low carbon alcohol by synthetic gas of claim 4, the specific area that it is characterized in that described silica is 450～1500 meters
2/ gram.
6. according to the described catalyst that is used for low carbon alcohol by synthetic gas of claim 5, the specific area that it is characterized in that described silica is 460～1400 meters
2/ gram.
7. the described Preparation of catalysts method that is used for low carbon alcohol by synthetic gas of claim 1 may further comprise the steps:
1) block copolymer and water soluble polymer are dissolved in the inorganic acid solution of 0.1～10 mol, form mixture A; Described block copolymer is selected from polyoxyethylene-poly-oxypropylene polyoxyethylene EOa-POb-EOa, a=10～200 wherein, b=10～100; Described water soluble polymer is selected from least a in polyvinyl alcohol, polyethylene glycol, poly-oxireme, polyacrylic acid, polyacrylamide or the polyvinylpyrrolidone; Described inorganic acid is selected from least a in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid or the tartaric acid;
2) under stirring, alkoxy silane is added among the mixture A, obtains sol B; Wherein alkoxy silane is selected from least a in trimethoxy silane, triethoxysilane, ethyl trimethoxy silane, MTES, dimethyldiethoxysilane, tetramethoxy-silicane or the tetraethoxysilane;
3) gas in the ultrasonic removal sol B;
4) the colloidal sol constant temperature through above processing leaves standstill, and produces sediment;
5) take out sediment, drying and roasting obtain the composite pore structural silica;
6) above-mentioned composite pore structural silica be impregnated in the metal salt solution that contains active constituent, dry then, roasting obtain described catalyst.
8. the Preparation of catalysts method that is used for low carbon alcohol by synthetic gas according to claim 7, the time that it is characterized in that ultrasonic processing in the step 3) is 30～600 seconds; The temperature that constant temperature leaves standstill in the step 4) is 20～120 ℃, and time of repose is 1～120 hour; The sedimentary baking temperature of step 5) is 10～60 ℃, and be 0.1～30 day drying time, and sintering temperature is 300～800 ℃, and roasting time is 1～30 hour.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294259A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon oxygen-containing compound by using synthesis gas and preparation method of catalyst |
| CN103418419A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for alkylation production of ethyl benzene, and preparation method thereof |
| CN103539622A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene through alkylation |
| CN109126818A (en) * | 2018-08-17 | 2019-01-04 | 新奥科技发展有限公司 | A kind of composite catalyst and preparation method thereof |
-
2009
- 2009-08-31 CN CN2009100578237A patent/CN101992099A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102294259A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Catalyst for preparing low-carbon oxygen-containing compound by using synthesis gas and preparation method of catalyst |
| CN103418419A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Catalyst for alkylation production of ethyl benzene, and preparation method thereof |
| CN103418419B (en) * | 2012-05-16 | 2016-01-13 | 中国石油化工股份有限公司 | The Catalysts and its preparation method of alkylation to prepare ethylbenzene |
| CN103539622A (en) * | 2012-07-12 | 2014-01-29 | 中国石油化工股份有限公司 | Method for preparing ethylbenzene through alkylation |
| CN109126818A (en) * | 2018-08-17 | 2019-01-04 | 新奥科技发展有限公司 | A kind of composite catalyst and preparation method thereof |
| CN109126818B (en) * | 2018-08-17 | 2021-12-07 | 新奥科技发展有限公司 | Composite catalyst and preparation method thereof |
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Application publication date: 20110330 |