CN102631927B - Double-hole carrier iron/ copper low-carbon alcohol synthesis catalyst and preparation method thereof - Google Patents
Double-hole carrier iron/ copper low-carbon alcohol synthesis catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a double-hole carrier iron/copper low-carbon alcohol synthesis catalyst with high activity and C<2+> alcohol selectivity, and a preparation method of the double-hole carrier iron/copper low-carbon alcohol synthesis catalyst. The double-hole carrier iron/copper low-carbon alcohol synthesis catalyst comprises Cu, Fe, K and M by weight percentage: 10-40% of Cu, 1-10% of Fe, 0.5-10% of K and 40-80% of M, wherein M is a double-hole carrier prepared from macroporous silica gel and ostiole colloidal silica. The preparation method comprises the steps of: dipping the ostiole colloidal silica in the macroporous silica gel in an isopyknic way, and preparing the double-hole carrier; then, dissolving metal in distilled water in a form of nitrate, and forming a mixed solution; and dipping the double-hole carrier in the mixed solution in an isopyknic way, and preparing the catalyst. The double-hole carrier iron/copper low-carbon alcohol synthesis catalyst prepared by the invention can be applied to the reaction for preparing low-carbon alcohol by synthesis gas, is simple in preparation technology, easy to operate, high in strength of the prepared catalyst and good in stability, and has high activity and C<2+> alcohol selectivity.
Description
Technical field
The present invention relates to a kind of iron/copper catalyst and preparation method thereof, a kind of for synthetic diplopore Supported Iron/copper catalyst of MAS and preparation method thereof specifically.
Technical background
The energy is the basis that modern society depends on for existence and development, and the supply capacity relation of clean fuel the sustainable development of national economy, is one of basis of national strategy safety guarantee.China's liquid fuel mainly comes from oil as (gasoline, diesel oil, LPG etc.) at present, and along with the exhaustion day by day of petroleum resources, the supply of liquid fuel will face huge threat.Since find pure building-up process in Fischer-Tropsch synthetic (F-T is synthetic) since, the CO hydrogenation selectivity catalyzes and synthesizes MAS and is considered to have industrial value and application prospect always.MAS can be used as the high-quality power fuel, although its calorific value a little less than vapour, diesel oil, due to the existence of oxygen in alcohol, its ratio of combustion vapour, diesel oil are abundant, in exhaust emissions, nuisance is less, is environmental friendliness fuel.Secondly, MAS has very high octane number, and it is explosion-proof, anti-seismic performance is superior, lead tetraethide and the controversial methyl tertiary butyl ether(MTBE) larger with the alternative toxicity of gasoline blending.Except above-mentioned act as a fuel and additive, can obtain first, second, third, fourth, penta, hexanol etc. after MAS separates, as the raw material of some chemical products such as solvent and esterifying agent.
Started from for 20 beginnings of the century by the direct synthesizing low-carbon mixed alcohol of synthesis gas; since seventies oil crisis; a large amount of research work are being done aspect the direct synthesis of low-carbon alcohol of synthesis gas by various countries; developed multiple catalyst systems, wherein representative have 4 classes: (1) modified methanol synthetic catalyst (Cu-ZnO/Al
2O
3, ZnO/Cr
2O
3), more typical patent has EP0034338A2 (people such as C.E.Hofstadt) and US Patent No. 4513100 (Snam company), this type of catalyst is added appropriate alkali metal or Modified With Alkali-earth Compounds and is got by methanol synthesis catalyst, activity is higher, in product, isobutanol content is high, but shortcoming is severe reaction conditions (temperature is 350-450 ℃, and pressure is 14-20MPa), water in products content is high, and mixed alcohol is selectively lower; (2) the Co-Cu catalyst of France Petroleum Institute (IFP) exploitation, only just obtained four catalyst patents (US4122110, US4291126, GB2118601, GB2158730) before 1985, and the main synthetic product of this type of catalyst is C
1-C
6Straight chain n-alkanol and C
1-C
6Hydro carbons, but catalyst stability is relatively poor; (3) MoS of U.S. DOW company exploitation
2Catalyst (US4882360), this type of catalyst has stronger sulfur tolerance, and product is moisture few, and higher alcohol content is higher.But shortcoming be wherein auxiliary element very easily and form carbonyls between carbon monoxide, cause the loss of auxiliary element, affect the activity of catalyst and selective, cause catalyst stability and life-span to be restricted; (4) Rh catalyst system (as US4014913 and US4096164), this type of catalyst are to add one to two kind of transition metal or metal oxide auxiliary agent in support type Rh catalyst, have higher activity and low-carbon alcohols selective.But the Rh compound is expensive, easily by CO
2Poison and be limited to use.Shanxi coalification institute of the domestic Chinese Academy of Sciences, Chinese Academy of Sciences's Dalian compound R﹠D institution such as China Science ﹠ Technology University has in one's power been carried out relevant research to low-carbon alcohol catalyst and technique, and a series of catalyst patent of invention (CN1225853 have been formed, CN1248492, CN1428192, CN101185899), but totally all exist total alcohol selectively on the low side, the shortcomings such as the distribution of higher alcohol product is relatively poor still have certain gap from industrial applications.
The diplopore carrier has different aperture structures, wherein macropore can promote reactant and the product diffusion rate in the duct, and aperture can provide large specific area and high metal dispersity, and all these characteristics make the diplopore carrier get a good chance of becoming novel catalyst carrier or promoter.At present, the diplopore carrier is mainly used in F-T synthetic (Zhang Y.Chem.Comn.11 (2002) 1216; Tsubaki N.Appl.Catal.A.292 (2005) 252; Xu B L.AIchE J.51 (2005) 2068) and CO
2The fields such as methanation (Inui T.J.Chem.Soc.Faraday 175 (1979) 787), but be applied to the synthetic report that there is not yet of low-carbon alcohols.
Summary of the invention
The present invention is directed to present low-carbon alcohols synthetic catalyst activity relatively poor, the higher alcohol selectivity of product is low, and the shortcomings such as severe reaction conditions provide a kind of active high and C that has
2 +Synthetic diplopore Supported Iron/copper catalyst of the selective high low-carbon alcohols of alcohol and preparation method thereof.
Catalyst of the present invention is comprised of Cu, Fe, K and M, and wherein M is the diplopore carrier of macropore silicon gel and the preparation of aperture Ludox, and each constituent content is respectively by weight percentage: Cu:10-40%; Fe:1-10%, K:0.5-10%, M:40-80%.
Method for preparing catalyst of the present invention adopts ultrasonic method and equi-volume impregnating, comprises the following steps:
(1) the diplopore carrier is that the aperture Ludox of 3-8nm and macropore silicon gel that pore diameter range is 40-70nm are mixed with and form by pore diameter range, concrete preparation method is: under ultrasound condition with the slow incipient impregnation of aperture Ludox in macropore silicon gel, constantly be stirred to and mix, the mixture that obtains is under ultrasound condition after standing 0.5-3h, vacuumize 0.5-2h under 60-100 ℃ of oil bath condition, then at 400-700 ℃ of roasting 1-5h, get final product to get the diplopore carrier.In carrier, the aperture Ludox is 10-20% with respect to macropore silicon gel percetage by weight.
(2) according to the requirement of aforementioned catalytic component content ratio, with cupric (Cu
2+), iron (Fe
3+) and potassium (K
1+) slaine (nitrate, sulfate or hydrochloride) be dissolved in and form mixed solution in distilled water, wherein the mantoquita concentration range is that 1.5-6.2mol/l, iron salt concentration scope are that 0.2-1.8mol/l, sylvite concentration range are 0.1-2.6mol/l.Adopt the method for incipient impregnation that mixed solution is incorporated in step (1) gained diplopore carrier under ultrasound condition, vacuumize 0.5-2h after standing 0.5-3h under 60-100 ℃ of oil bath condition, then put into drying box dry 5-24h under 100-130 ℃, at 400-700 ℃ of roasting 1-5h, obtain diplopore Supported Iron copper-based catalysts.
The catalyst that the present invention makes can be applicable in low carbon alcohol by synthetic gas reaction, application conditions be with catalyst filling in fixed bed reactors, at 0.1-0.5MPa, 260-320 ℃, 1000-3000h
-1Reduce 6-15h with pure hydrogen under condition, then be cooled to 180-200 ℃ and switch to the high pressure synthesis gas, at 230-340 ℃, 3.0-8.0MPa, 500-20000h
-1, H
2Carry out the low-carbon alcohols synthetic reaction under/CO=0.5-3.0 (mol ratio) reaction condition.
The present invention compared with prior art has following advantage:
1. raw material sources are extensive, and cost is low, and preparation technology is relatively simple, easy operating, and reaction condition is gentle, easily realizes the industry amplification.
2. the diplopore carrier of the present invention preparation has the active component high degree of dispersion, evenly distributes, and reactant and product are easy to the characteristics such as diffusion, can promote the activity of catalyst and higher alcohol product selectively.
3. catalyst mechanical strength of the present invention is high, and good stability has high activity and high C
2 +Alcohol is selective.
Description of drawings
Fig. 1 is the BET spectrogram of diplopore carrier of the present invention
The specific embodiment
The present invention is described further for the following examples, and protection scope of the present invention is not subjected to the restriction of these embodiment.
Choosing pore diameter range is the aperture Ludox of 3-5nm and the macropore silicon gel that pore diameter range is 50-60nm, under ultrasound condition with aperture Ludox incipient impregnation in macropore silicon gel, dipping process needs fully to stir.Dipping is standing 1h under ultrasound condition fully afterwards, then is positioned in oil bath and vacuumizes 1h under 80 ℃.The gained coagulum is crushed to after the 40-180 order at 600 ℃ of lower roasting 2h, obtains the diplopore carrier.Diplopore carrier texture character is seen Fig. 1, and in carrier, the aperture Ludox is 20% with respect to macropore silicon gel percetage by weight.
With 36 gram ferric nitrates, 152 gram copper nitrates and 1.3 gram potassium nitrate are dissolved in the mixed solution that forms in 100ml distilled water, adopt the incipient impregnation method to impregnated in the diplopore carrier under ultrasound condition, constantly stir until solution and diplopore carrier mix in dipping process.Dipping vacuumizes 2h after standing 0.5h after fully under 60 ℃ of conditions, then at 120 ℃ of dry 5h, then under 450 ℃ of air atmospheres roasting 3h, be crushed to the 40-60 order and obtain catalyst 1#.
Each composition percentage by weight of catalyst of preparation consists of: Cu 40%, and Fe 5%, and K 0.5%, diplopore carrier 54.5%.Reducing condition is: 300 ℃ of temperature, pressure 0.3MPa, air speed 1000h
-1, pure hydrogen 10h.Be applied in that in low carbon alcohol by synthetic gas reaction, reaction condition is: 300 ℃ of temperature, pressure 5.0MPa, air speed 6000h
-1, H
2/ CO=2.0, liquid product is collected with ice-water bath, and gas-phase product passes into gas-chromatography analysis, and reaction result sees Table 1.
Embodiment 2
Choosing pore diameter range is the aperture Ludox of 5-8nm and the macropore silicon gel that pore diameter range is 60-70nm, under ultrasound condition with aperture Ludox incipient impregnation in macropore silicon gel, dipping process needs fully to stir.Dipping is standing 3h under ultrasound condition fully afterwards, then is positioned in oil bath and vacuumizes 2h under 60 ℃.The gained coagulum is crushed to after the 40-180 order at 500 ℃ of lower roasting 4h, obtains the diplopore carrier.In carrier, the aperture Ludox is 10% with respect to macropore silicon gel percetage by weight.
With 15 gram ferric nitrates, 57 gram copper nitrates and 15 gram potassium nitrate are dissolved in the mixed solution that forms in 100ml distilled water and adopt the incipient impregnation method to impregnated in the diplopore carrier under ultrasound condition, constantly stir until solution and diplopore carrier dissolve fully in dipping process.Dipping vacuumizes 0.5h at 100 ℃ after standing 3.0h after fully, then at 100 ℃ of dry 24h, then under 700 ℃ of air atmospheres roasting 1h, be crushed to the 40-60 order and obtain catalyst 2#.Each composition percentage by weight of catalyst of preparation consists of: Cu15%, Fe2%, K6%, diplopore carrier 77%.Reducing condition is: 320 ℃ of temperature, pressure 0.1MPa, air speed 1000h
-1, pure hydrogen 10h.Be applied in that in low carbon alcohol by synthetic gas reaction, reaction condition is: 260 ℃ of temperature, pressure 4.0MPa, air speed 6000h
-1, H
2/ CO=1.0, liquid product is collected with ice-water bath, and gas-phase product passes into gas-chromatography analysis, and reaction result sees Table 1.
Comparative example 1
Each composition percentage by weight of catalyst of preparation consists of: Cu 34%, and Fe 8.5%, and K 0.5%, macropore silicon gel 57%.
With 61 gram ferric nitrates, 129 gram copper nitrates and 1.3 gram potassium nitrate are dissolved in the mixed solution that forms in 100ml distilled water and adopt the incipient impregnation method to impregnated in macropore silicon gel under ultrasound condition, constantly stir until mix in dipping process.Dipping is standing 1.0h under ultrasound condition fully afterwards, then vacuumizes 2h under 80 ℃ of oil bath conditions.The gained solidifying body is at 130 ℃ of dry 12h, and then roasting 3h under 500 ℃ of air atmospheres, be crushed to the 40-60 order and obtain catalyst 3#.Reducing condition is: 320 ℃ of temperature, pressure 0.5MPa, air speed 2000h
-1, pure hydrogen 12h.Be applied in that in low carbon alcohol by synthetic gas reaction, reaction condition is: 240 ℃ of temperature, pressure 5.0MPa, air speed 10000h
-1, H
2/ CO=1.0, liquid product is collected with ice-water bath, and gas-phase product passes into gas-chromatography analysis, and reaction result sees Table 1.
Comparative example 2
Each composition percentage by weight of catalyst of preparation consists of: Cu 15%, and Fe 8%, and K 4%, macropore silicon gel 73%.With 57 gram ferric nitrates, 57 gram copper nitrates and 10 gram potassium nitrate are dissolved in the mixed solution that forms in 100ml distilled water and adopt the incipient impregnation method to impregnated in macropore silicon gel under ultrasound condition, constantly stir until mix in dipping process.Dipping is standing 3.0h under ultrasound condition fully afterwards, then vacuumizes 3.0h under 100 ℃ of oil bath conditions.The gained solidifying body is at 110 ℃ of dry 24h, and then roasting 3h under 600 ℃ of air atmospheres, be crushed to the 40-60 order and obtain catalyst 4#.Reducing condition is: 340 ℃ of temperature, pressure 0.5MPa, air speed 1000h
-1, pure hydrogen 12h.Be applied in that in low carbon alcohol by synthetic gas reaction, reaction condition is: 340 ℃ of temperature, pressure 3.0MPa, air speed 10000h
-1, H
2/ CO=1.0,, liquid product is collected with ice-water bath, and gas-phase product passes into gas-chromatography analysis, and reaction result sees Table 1.
Comparative example 3
Each composition percentage by weight of catalyst of preparation consists of: Cu 42%, and Fe 10%, and K 2%, aperture silicon gel 46%.With 72 gram ferric nitrates, 160 gram copper nitrates and 5 gram potassium nitrate are dissolved in the mixed solution that forms in 100ml distilled water and adopt the incipient impregnation method to impregnated in aperture silicon gel under ultrasound condition, constantly stir until mix in dipping process.Dipping is standing 2.0h under ultrasound condition fully afterwards, then vacuumizes 3.0h under 60 ℃ of oil bath conditions.The gained solidifying body is at 110 ℃ of dry 12h, and then roasting 3h under 400 ℃ of air atmospheres, be crushed to the 40-60 order and obtain catalyst 5#.Reducing condition is: 300 ℃ of temperature, pressure 0.1MPa, air speed 2000h
-1, pure hydrogen 12h.Be applied in that in low carbon alcohol by synthetic gas reaction, reaction condition is: 280 ℃ of temperature, pressure 6.0MPa, air speed 10000h
-1, H
2/ CO=2.0,, liquid product is collected with ice-water bath, and gas-phase product passes into gas-chromatography analysis, and reaction result sees Table 1.
According to mutually relatively can finding out of embodiment and comparative example, adopt the Cu-Fe base low-carbon alcohols synthetic catalyst of diplopore carrier preparation to have higher low-carbon alcohols synthesizing activity and pure productive rate, particularly higher alcohol product (C
2 +OH) selectively be better than the low-carbon alcohols synthetic catalyst of conventional method preparation.
The reaction evaluating result of table 1 embodiment and comparative example
Claims (4)
1. diplopore Supported Iron copper low-carbon alcohols synthetic catalyst, it is characterized in that: catalyst is comprised of Cu, Fe, K and M, wherein M is the diplopore carrier of macropore silicon gel and the preparation of aperture Ludox, and each constituent content is respectively by weight percentage: Cu:10-40%; Fe:1-10%, K:0.5-10%, M:40-80%; Described diplopore carrier is that the aperture Ludox of 3-8nm and macropore silicon gel that pore diameter range is 40-70nm are mixed with and form by pore diameter range, step is: under ultrasound condition with the slow incipient impregnation of aperture Ludox in macropore silicon gel, constantly be stirred to and mix, the mixture that obtains is under ultrasound condition after standing 0.5-3h, vacuumize 0.5-2h under 60-100 ° of C oil bath condition, then at 400-700 ° of C roasting 1-5h, get final product to get the diplopore carrier.
2. the preparation method of diplopore Supported Iron copper low-carbon alcohols synthetic catalyst as claimed in claim 1 is characterized in that step is as follows:
(1) under ultrasound condition with the slow incipient impregnation of aperture Ludox in macropore silicon gel, constantly be stirred to and mix, the mixture that obtains is under ultrasound condition after standing 0.5-3h, vacuumize 0.5-2h under 60-100 ° of C oil bath condition, then at 400-700 ° of C roasting 1-5h, get final product to get the diplopore carrier;
(2) according to the requirement of claim 1 catalytic component content ratio, will contain Cu
2+, iron Fe
3+And K
+Slaine be dissolved in and form mixed solution in distilled water, wherein the mantoquita concentration range is that 1.5-6.2mol/L, iron salt concentration scope are that 0.2-1.8mol/L, sylvite concentration range are 0.1-2.6mol/L; Adopt the method for incipient impregnation to be incorporated in step (1) gained diplopore carrier under ultrasound condition, vacuumize 0.5-2h after standing 0.5-3h under 60-100 ° of C temperature conditions, then dry 5-24h under 100-130 ° of C, at 400-700 ° of C roasting 1-5h, obtain diplopore Supported Iron copper-based catalysts.
3. the preparation method of diplopore Supported Iron copper low-carbon alcohols synthetic catalyst as claimed in claim 2, it is characterized in that: described aperture Ludox pore diameter range is 3-8nm, macropore silicon gel pore diameter range is 40-70nm.
4. the application of diplopore Supported Iron copper low-carbon alcohols synthetic catalyst as claimed in claim 1 in the low carbon alcohol by synthetic gas reaction, it is characterized in that application conditions be with described catalyst filling in fixed bed reactors, at 0.1-0.5MPa, 260-320 ° C, 1000-3000h
-1Reduce 6-15h with pure hydrogen under condition, then be cooled to 180-200 ° of C and switch to the high pressure synthesis gas, at 230-340 ° of C, 3.0-8.0MPa, 500-20000h
-1, H
2Carry out the low-carbon alcohols synthetic reaction under/CO=0.5-3.0 reaction condition.
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| CN104148078B (en) * | 2014-07-17 | 2016-10-19 | 中国科学院广州能源研究所 | A kind of for biomass synthesis gas catalyst producing low-carbon alcohols and preparation method thereof |
| CN104258913B (en) * | 2014-08-06 | 2016-03-30 | 中国科学院广州能源研究所 | A kind of reduction apparatus of the catalyst for catalysis biomass synthesis gas synthesizing low-carbon mixed alcohol and method of reducing |
| CN105013503B (en) * | 2015-06-29 | 2017-10-27 | 中国科学院广州能源研究所 | A kind of preparation method and application of Fe base catalyst for F- T synthesis |
| CN110898848B (en) * | 2019-08-14 | 2023-04-21 | 新奥科技发展有限公司 | Catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN110898847B (en) * | 2019-08-14 | 2022-05-20 | 新奥科技发展有限公司 | Composite carrier type catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
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| CN101185899A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application |
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| US4473505A (en) * | 1980-02-12 | 1984-09-25 | Exxon Research And Engineering Co. | Phosphine and phosphonium compounds and catalysts |
| CN101185899A (en) * | 2007-12-21 | 2008-05-28 | 中国科学院山西煤炭化学研究所 | Copper base catalyst for producing low carbon mixed alcohol by synthesis gas and preparation method and application |
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