CN102040470A - Method for preparing low carbon alcohol by using synthesis gas - Google Patents
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- CN102040470A CN102040470A CN2009102016658A CN200910201665A CN102040470A CN 102040470 A CN102040470 A CN 102040470A CN 2009102016658 A CN2009102016658 A CN 2009102016658A CN 200910201665 A CN200910201665 A CN 200910201665A CN 102040470 A CN102040470 A CN 102040470A
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Abstract
The invention relates to a method for preparing low carbon alcohol by using synthesis gas, which mainly solves the problems of much alkane byproduct, high cost of used catalyst and high production cost during preparing the low carbon alcohol by using the synthesis gas in the prior art. The synthesis gas is used as a raw material; the reaction raw material is contacted with a catalyst to generate the low carbon alcohol under the conditions that the reaction temperature is between 150 and 450 DEG C, the reaction pressure is 0.08 to 6.0 MPa and the volume space velocity is 500 to 15,000 per hour; wherein the raw material comprises the following components in percentage by volume: 45 to 85 percent of hydrogen and 15 to 55 percent of CO; the raw material comprises the following components in percentage by weight: a) 0.1 to 15 percent of Rh, b) 0 to 5 percent of Mn, c) 0 to 5 percent of M, d) 0 to 5 percent of Fe and e) 70.0 to 99.9 percent of silicon oxide, wherein the M is selected from at least one of Li, Na and K; the silicon oxide has a composite pore structure and meanwhile has micro macropores and nano mesopores, wherein the volume of the macropores is 0.4 to 3.0 cubic centimeters per gram, and the volume of the mesopores is 0.4 to 1.5 cubic centimeters per gram. According to the technical scheme, the method well solves the problems, and can be used in the industrial production of preparing the low carbon alcohol by using the synthesis gas.
Description
Technical field
The present invention relates to a kind of 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 mixture of lower alcohols by synthetic gas is the problem that has important research meaning and wide application prospect in the C1 chemical field.Be suitable as very much gasoline dope and use because of having high-performances such as octane value height, explosion-proof, antidetonation by the low-carbon alcohol of coal, natural gas via synthesis gas preparation, simultaneously, low-carbon alcohol still is important chemical material and the free of contamination vehicle fuel of ideal high-octane rating.If can directly make low-carbon alcohol from Sweet natural gas, then both can save food, also can make full use of the coal and the natural gas source 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.
Catalyzer is the core content of catalyzed reaction, and in decades, the countries in the world scientific research personnel produces at synthetic 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 alcohol 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 oxygenatedchemicalss 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 active 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 catalyzer need adopt the preparation method of step impregnation and substep hydrogen high temperature reduction to obtain, caused the increase greatly of catalyzer cost and the loss of energy on the one hand, Fu Za preparation process also makes this catalyzer 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 carbon nanotube be carrier loaded Rh-Mn-Li-Fe active ingredient, found that pre-treatment makes the carbon nanotube opening, active ingredient is introduced in the hole of carbon nanotube, the catalyzer 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 catalyzer has very low alkane selectivity, the carbon nanotube price is very expensive and use is preceding will be through harsh complicated conditions such as the long-time pyroprocessing of concentrated nitric acid, and this makes this catalyzer quite low in industrial possibility of its application.
Summary of the invention
Technical problem to be solved by this invention is to exist low carbon alcohol by synthetic gas by-product alkane many in the conventional art, and the problem that perhaps catalyst system therefor costs an arm and a leg, production cost is high provides a kind of new method that is used for low carbon alcohol by synthetic gas.This method can keep higher low-carbon alcohol selectivity to have lower alkane selectivity again simultaneously, and the catalyst system therefor cost is relatively low, is fit to suitability for industrialized production.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method that is used for low carbon alcohol by synthetic gas, with the synthetic gas is raw material, in temperature of reaction is 150～450 ℃, reaction pressure is 0.08～6.0 MPa, volume space velocity is under 500～15000/ hours conditions, and reaction raw materials contacts with catalyzer and generates low-carbon alcohol; Wherein in the raw material each component in volume percent: hydrogen is 45～85%, and CO is 15%～55%; Described catalyzer 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% silicon oxide, described silicon oxide has composite pore structural, and it is mesoporous to have micron order macropore and nano level 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 silicon oxide is 79.0～99.6%, and more preferably scope is 83.0～99.4%; Wherein the macropore pore volume preferable range of silicon oxide 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 surface area preferable range of described silicon oxide is 400～2000 meters
2/ gram, more preferably scope is 450～1500 meters
2/ gram, most preferred range is 460～1400 meters
2/ gram.The temperature of reaction preferable range is 200～400 ℃, and the reaction pressure preferable range is 0.1～5.0 MPa, and the volume space velocity preferable range is 800～12000/ hours.In volume percent, the preferable range of each component is that hydrogen is 50～80% in the raw material, and CO is 20%～50%.
The preparation method of catalyst system therefor is as follows among the present invention:
1) segmented copolymer and water soluble polymer are dissolved in the inorganic acid solution of 0.1～10 mol, form mixture A; Described segmented 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, polyoxyethylene glycol, poly-oxyethylene, polyacrylic acid, polyacrylamide or the polyvinylpyrrolidone; Described mineral acid is selected from least a in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, citric acid or the tartrate;
2) under whipped state, organoalkoxysilane is added among the mixture A, obtains sol B; Wherein organoalkoxysilane is selected from least a in Trimethoxy silane, triethoxyl silane, ethyl trimethoxy silane, Union carbide A-162, 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 throw out;
5) take out throw out, drying and roasting obtain the composite pore structural silicon oxide;
6) above-mentioned composite pore structural silicon oxide be impregnated in the metal salt solution that contains active constituent, dry then, roasting obtain described catalyzer.
Wherein, the time preferable range of supersound process is 30～600 seconds in the step 3); 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 drying temperature preferable range of step 5) is 10～60 ℃, and time of drying, preferable range was 0.1～30 day, and the maturing temperature preferable range is 300～800 ℃, and the roasting time preferable range is 1～30 hour.The inorganic salt of Rh are selected from least a in Trichlororhodium, rhodium nitrate or the acetic acid rhodium, and the inorganic salt of Mn are selected from manganous nitrate, and the inorganic salt of M are selected from MNO
3Or at least a among the MCl, the inorganic salt of Fe are selected from least a in iron(ic) chloride, iron nitrate, iron protochloride or the Iron nitrate.Can the metal-salt of active ingredient 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 salt of each metal oxide impregnation silicon, also can be wherein one or both or three kinds of wiring solution-forming branches flood, steeping process can repeat 1～3 time.
It is carrier that the present invention adopts the composite pore structural silicon oxide, this carrier has micron-sized macroporous structure and nano level meso-hole structure simultaneously, make catalyzer show high-specific surface area, large pore volume and excellent mass transfer-diffusion on the one hand, special composite pore structural has played promoter action 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 catalyzer; In addition, the Preparation of catalysts mild condition easy handling that the present invention is used, and with low cost, be easy to suitability for industrialized production.Adopting the inventive method, is H with the volume percent content
245～85%, the synthetic gas of CO15～55% is a raw material, and in reaction pressure 3.0 MPas, 310 ℃ of temperature of reaction are under 9000/ hour condition of air speed, and with common SiO
2For the catalyzer of carrier is compared, up to 44%, the selectivity of methyl alcohol is up to 20% to the alcoholic acid selectivity for catalyzer, 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 support of the catalyst composite pore structural silicon oxide among the present invention
Fig. 2 is the TEM figure of catalyzer among the present invention
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
1 gram triblock copolymer EO
20PO
70EO
20Join in the hydrochloric acid soln of 10 grams, 1 mol with 0.90 gram polyoxyethylene glycol, stir and make its dissolving; In mixing solutions, 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 throw out drying at room temperature 3 days, 450 ℃ of high-temperature roastings 5 hours, obtain the composite pore structural silicon oxide then, its specific surface 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 rhodium chloride (containing three crystal water), 0.18 gram manganous nitrate, 0.04 gram lithium nitrate and 0.01 gram iron(ic) chloride is soluble in water, and 10 gram composite pore structural silicon oxide were put into equal-volume mixing solutions dipping 20 minutes, and drying at room temperature is flooded 2 times; And, obtain catalyzer 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 catalyzer is in H
2330 ℃ of in-situ reducing are 4 hours in the atmosphere, reduce to temperature of reaction after logical synthetic gas begin reaction.Reaction pressure 3.0 MPas, 310 ℃ of temperature of reaction, air speed 9000/ hour.Measure its ethanol selectivity 44.2%, methyl alcohol 20.4%, alkane 23.1%.
[embodiment 2]
With triblock copolymer EO in the synthesis step of catalyzer
20PO
70EO
20Change EO into
26PO
39EO
26, all the other operation stepss 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.
[embodiment 3]
1 gram triblock copolymer EO
20PO
70EO
20Join in the salpeter solution of 10 grams, 1 mol with the poly-oxyethylene of 0.75 gram, stir and make its dissolving; In mixing solutions, add 5 milliliters of tetraethoxysilanes then.All the other operation stepss 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 4]
In the catalyzer synthesis step, carrier floods twice in the solution that only contains 0.80 gram metal-salt rhodium chloride, and all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of a containing metal Rh who obtains is as shown in table 2.
[embodiment 5]
In the catalyzer synthesis step, carrier floods twice in the solution that only contains 1.60 gram metal-salt rhodium chlorides, and all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of a containing metal Rh who obtains is as shown in table 3.
[embodiment 6]
In the catalyzer synthesis step, carrier floods twice in the solution that contains 0.13 gram rhodium chloride and 0.63 gram manganous nitrate, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of containing metal Rh that obtains and Mn is as shown in table 3.
[embodiment 7]
In the catalyzer synthesis step, carrier floods twice in the solution that contains 0.20 gram rhodium chloride and 0.06 gram lithium nitrate, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of containing metal Rh that obtains and Li is as shown in table 3.
[embodiment 8]
In the catalyzer synthesis step, carrier floods twice in the solution that contains 0.40 gram rhodium chloride and 0.58 gram iron nitrate, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of containing metal Rh that obtains and Fe is as shown in table 3.
[embodiment 9]
In the catalyzer synthesis step, carrier floods twice in the solution that contains 0.07 gram rhodium chloride, 0.024 gram saltpetre and 0.13 gram iron(ic) chloride, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of containing metal Rh, K that obtains and Fe is as shown in table 3.
[embodiment 10]
In the catalyzer synthesis step, carrier floods twice in the solution that contains 0.26 gram rhodium chloride, 0.18 gram manganous nitrate and 0.53 gram lithium nitrate, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of containing metal Rh, Mn that obtains and Li is as shown in table 3.
[embodiment 11]
In the catalyzer synthesis step, carrier floods twice in the solution that contains 0.07 gram rhodium chloride, 0.054 gram manganous nitrate and 0.003 gram iron protochloride, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of containing metal Rh, Mn that obtains and Fe is as shown in table 3.
[embodiment 12]
In the catalyzer synthesis step, carrier floods twice in the solution that contains 0.28 gram rhodium nitrate, 0.36 gram manganous nitrate and 1.1 grams lithium chlorides, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of catalyzer under identical catalytic condition of containing metal Rh, Mn that obtains and Li is as shown in table 3.
Table 3
[embodiment 13]
In the impregnation steps, change aqueous solvent into methyl alcohol, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of the catalyzer that obtains under identical catalytic condition is as follows: ethanol selectivity 43.7%, methyl alcohol 20.0%, alkane 28.4%.
[embodiment 14～17]
Change catalyst soakage step maturing temperature and the time afterwards, all the other operation stepss are all identical with [embodiment 1], and the catalytic selectivity of the catalyzer that obtains under identical catalytic condition is as shown in table 3.
[embodiment 18～20]
The Preparation of catalysts method is identical with [embodiment 1], and the reaction procatalyst is at H
2Original position reductive temperature and time changes in the atmosphere, and other condition is all identical with [embodiment 1], and the catalytic selectivity of the catalyzer that records under identical catalytic condition is as shown in table 3.
Table 3
[embodiment 21～26]
The Preparation of catalysts method is identical with [embodiment 1], only changes H in reaction pressure, temperature of reaction, reaction velocity, the raw material
2With the ratio of CO, other condition is all as shown in table 4 with embodiment 1 identical catalytic selectivity.
Table 4
[Comparative Examples 1]
Use the general commercial silicon oxide instead as carrier, all the other operation stepss are with [embodiment 1].The specific surface area of commercial silicon oxide is 340 meters
2/ gram, it is mesoporous only to contain nano level, 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. a method that is used for low carbon alcohol by synthetic gas is a raw material with the synthetic gas, is 150～450 ℃ in temperature of reaction, and reaction pressure is 0.08～6.0 MPa, and volume space velocity is under 500～15000/ hours conditions, and reaction raw materials contacts with catalyzer and generates low-carbon alcohol; Wherein in the raw material each component in volume percent: hydrogen is 45～85%, and CO is 15%～55%; Described catalyzer 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% silicon oxide, described silicon oxide has composite pore structural, and it is mesoporous to have micron order macropore and nano level 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 method 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 silicon oxide is 79.0～99.6%; Wherein the macropore pore volume of silicon oxide is 0.5～2.8 centimetre
3/ gram, mesoporous pore volume is 0.45～1.4 centimetre
3/ gram.
3. according to the described method 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 silicon oxide is 83.0～99.4%; Wherein the macropore pore volume of silicon oxide is 0.5～2.5 centimetre
3/ gram, mesoporous pore volume is 0.49～1.38 centimetre
3/ gram.
4. according to the described method that is used for low carbon alcohol by synthetic gas of claim 1, the specific surface area that it is characterized in that described silicon oxide is 400～2000 meters
2/ gram.
5. according to the described method that is used for low carbon alcohol by synthetic gas of claim 4, the specific surface area that it is characterized in that described silicon oxide is 450～1500 meters
2/ gram.
6. according to the described method that is used for low carbon alcohol by synthetic gas of claim 5, the specific surface area that it is characterized in that described silicon oxide is 460～1400 meters
2/ gram.
7. the described method that is used for low carbon alcohol by synthetic gas of claim 1 is characterized in that temperature of reaction is 200～400 ℃, and reaction pressure is 0.1～5.0 MPa, and volume space velocity is 800～12000/ hours.
8. the described method that is used for low carbon alcohol by synthetic gas of claim 1, it is characterized in that in the raw material that each component is in volume percent: hydrogen accounts for 50～80%, and CO accounts for 20%～50%.
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Cited By (5)
| 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 |
| CN102872882A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst for preparing low carbon alcohol, as well as preparation method and application of copper-based catalyst |
| CN105418440A (en) * | 2015-07-24 | 2016-03-23 | 张家港吉慕特化工科技有限公司 | Method for synthesizing 2- amino-2-methyl-1-propanol from isopropylamine |
| CN106268856A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application |
| CN106669732A (en) * | 2015-11-06 | 2017-05-17 | 中国科学院大连化学物理研究所 | Catalyst for direct synthesis of ethanol by hydrogenation of CO as well as preparation and application thereof |
-
2009
- 2009-10-13 CN CN2009102016658A patent/CN102040470A/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 |
| CN102872882A (en) * | 2012-09-17 | 2013-01-16 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst for preparing low carbon alcohol, as well as preparation method and application of copper-based catalyst |
| CN102872882B (en) * | 2012-09-17 | 2014-11-26 | 中国科学院山西煤炭化学研究所 | Copper-based catalyst for preparing low carbon alcohol, as well as preparation method and application of copper-based catalyst |
| CN106268856A (en) * | 2015-05-22 | 2017-01-04 | 中国科学院大连化学物理研究所 | Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application |
| CN105418440A (en) * | 2015-07-24 | 2016-03-23 | 张家港吉慕特化工科技有限公司 | Method for synthesizing 2- amino-2-methyl-1-propanol from isopropylamine |
| CN106669732A (en) * | 2015-11-06 | 2017-05-17 | 中国科学院大连化学物理研究所 | Catalyst for direct synthesis of ethanol by hydrogenation of CO as well as preparation and application thereof |
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Application publication date: 20110504 |