CN102417437A - Catalyst for low-carbon mixed alcohol synthesis from syngas, and preparation method and application thereof - Google Patents
Catalyst for low-carbon mixed alcohol synthesis from syngas, and preparation method and application thereof Download PDFInfo
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- CN102417437A CN102417437A CN2011102360633A CN201110236063A CN102417437A CN 102417437 A CN102417437 A CN 102417437A CN 2011102360633 A CN2011102360633 A CN 2011102360633A CN 201110236063 A CN201110236063 A CN 201110236063A CN 102417437 A CN102417437 A CN 102417437A
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Abstract
The invention provides a molybdenum carbide-based catalyst for low-carbon alcohol synthesis from syngas, and a preparation method and reaction conditions thereof. The catalyst uses surface carbon-modified SBA-15 as the carrier. The surface carbon-modified SBA-15 mesoporous material is prepared by using low-cost ethyl orthosilicate as the silicon source and saccharide as the carbon source, and is used as the carrier; and by using the carbon on the surface as the reducer and carbonizer, the molybdenum carbide-based catalyst for alcohol synthesis from syngas is prepared through high-temperature carbonization under inert gas atmosphere. The introduction of the carrier improves the dispersion degree of active components of the catalyst; and the prepared catalyst has the characteristics of high total alcohol selectivity, high C2+ alcohol selectivity and good reaction stability.
Description
Technical field
The present invention relates to a kind ofly, belong to the derived energy chemical field by synthetic gas catalyzed conversion preparing liquid fuel or Chemicals technology.Mainly be applicable to by synthetic gas (carbon monoxide and hydrogen) catalyzed conversion preparing low-carbon mixed alcohol, Preparation of catalysts method and catalytic reaction condition are provided.
Background technology
MAS (abbreviation low-carbon alcohol) is meant by C
1-C
6The liquid mixture that alcohol constitutes starts from nineteen twenty by the research of the direct synthesizing low-carbon mixed alcohol of synthetic gas.The influence of twice oil crisis of the seventies in 20th century and the enhancing of people's environmental consciousness, making with coal or biomass is that raw material is produced low-carbon alcohol through synthetic gas and become C
1One of research content of chemistry.Alcohol fuel has sufficient combustion, efficient height, CO and NO
xAnd advantage such as hydro carbons discharging is few (Chianelli R R, et al.Catal.Today.1994,22,361-396).
Software engineering researchers invent goes out multiple different low-carbon alcohol catalyst system since 20 beginnings of the century, and wherein representative have four kinds of catalyzer.(1) methanol synthesis catalyst of modification (Cu-Zn/Al, Zn-Cr); This type catalyzer is added an amount of basic metal or earth alkali metal and is got (related patent U.S. Patent No. EP-0034338-A2, US Patent 4513100 etc.) by catalyst for methanol.Cu-Zn/Al series catalysts reaction conditions is gentle, but active ingredient Cu is easy to sintering, and methanol content is high in the product.Zn-Cr series catalysts primary product is methyl alcohol and side chain isopropylcarbinol, and reaction conditions is harsh (pressure 14-20Mpa, temperature 350-450 ℃) comparatively.(2) Cu-Co catalyzer; The Cu-Co series catalysts is representative (US Patent4122110,4291126) with France Petroleum Institute (IFP), and operational condition is relatively gentleer, and primary product is the straight chain n-alkanol, reactive behavior and C
2+The selectivity of OH alcohol is higher, but total pure selectivity is lower and water in products is more.(3) noble metal-based catalysts (comprising Rh, Ru and Re); Wherein Rh is catalyst based owing to have higher ethanol and select active and by a large amount of research, but its raw materials cost height and catalyzer are prone to poison (US Patent 4014913,4096164).(4) catalyst with base of molybdenum (US Patent 4882360); Catalyst with base of molybdenum has unique sulfur resistance and is difficult for carbon distribution, and the product water cut is few, is regarded as very promising catalyst system.
In catalyst with base of molybdenum, molybdenum carbide is catalyst based as one type of new catalytic material, receives widely paying close attention to.The desk study research of CO field of hydrogenation shows that molybdenum carbide mainly generates light hydrocarbon, CO
2With a small amount of alcohol; After the potassium modification, MAS is higher alcohols (C particularly
2+OH) selectivity obviously improves.Utilize F-T catalysts (Fe, Co, Ni) to modify K-β-Mo
2The C catalyzer is found the K-β-Mo that is modified by Co or Ni element
2The C catalyzer has high reactivity and selectivity to alcohol mixture, especially to C
2+Alcohol all the more so, Fe then inhibited (Xiang M L, et al.Fuel, 2008,87,599-606), they are Ni＞Co＞Fe to the reactive behavior of higher alcohols in proper order; The alcohol selectivity is: Ni＞Co＞Fe.Therefore in recent years, the catalyst based low carbon alcohol by synthetic gas that is used to of the unsupported molybdenum carbide of auxiliary agent Ni modification reacted, and such catalyzer has higher C
2+The alcohol selectivity (Xiang M L, et al.Catal.Comm, 2007,8,503-507.Xiang M L, et al.Catal.Comm, 2007,8,513-518.).But the total pure selectivity of this type catalyzer generally has only 45%, and the product major part is hydro carbons and other compounds.Therefore through the modulation of auxiliary agent, the introducing of carrier, the methods such as optimization of synthesis technique, might obtain having concurrently high total pure selectivity and C
2+Alcohol is catalyzer optionally.
Summary of the invention
The object of the invention is primarily aimed at the problem of the catalyst based active ingredient serious agglomeration of non-loading type molybdenum carbide, is carrier with the SBA-15 of surface carbon modification, and a kind of Catalysts and its preparation method and application with well dispersed property is provided.Such catalyst preparation process is simple, and is with low cost, has good synthol selectivity and C
2+The alcohol selectivity has tangible using value.
The present invention mainly comprises steps such as load and the catalyst reaction evaluation of preparing carriers, carrier surface modification, active ingredient and auxiliary agent.Below be operation steps of the present invention and schematic illustration:
(1) preparation of carrier:
(TEOS) slowly is added drop-wise in the aqueous solution that is dissolved with template P123 with tetraethoxy, and stirs 23h, obtains white mixed solution.Move into mixed solution in the stainless steel cauldron (Teflon bottle) of band polytetrafluoroethylsubstrate substrate, in 100 ℃ of thermostatic drying chambers, leave standstill crystallization 24h.Reaction is carried out suction filtration, gained throw out water repetitive scrubbing suction filtration after finishing.After 120 ℃ of oven dry, 500 ℃ of roastings in retort furnace obtain white mesoporous SBA-15 powder with filter cake.
(2) surface-treated of carrier:
In the aqueous solution of sugar, is carburization agent with the concentrated acid with exsiccant SBA-15 powder impregnation, and certain temperature is handled certain hour.Products therefrom high-temperature roasting under noble gas atmosphere obtains SBA-15 (C-SBA-15) black powder of surface carbon modification.
(3) Preparation of catalysts
With C-SBA-15 is carrier, adopts the incipient impregnation method to use molybdate solution, and inorganic nickel solution, potassium salt soln flood certain hour and oven dry respectively.High-temperature roasting under noble gas atmosphere obtains molybdenum carbide base synthol catalyzer.
The present invention also provides the reaction conditions of said catalyzer in the reaction of CO hydrogenation synthol.
Advantage of the present invention:
(1) in molybdenum carbide is catalyst based, introduce the SBA-15 carrier, improve dispersion degree of active components, the molybdenum carbide that obtains having high-specific surface area is catalyst based.
(2) being raw material with cheap tetraethoxy, is template with polyoxyethylene-poly-oxypropylene polyoxyethylene (P123), prepares the narrow mesoporous material SBA-15 of pore size distribution through hydrothermal synthesis method.With sucrose, glucose or fructose is carbon source, and the carbon modification is carried out on the SBA-15 surface, obtains surperficial carbonaceous mesoporous material.
(3) carbon that utilizes carrier surface is as reductive agent and carburization agent, and high-temperature roasting under the noble gas atmosphere obtains molybdenum carbide base synthol catalyzer.
(4) the synthetic catalyzer has: total pure selectivity is high, C
2+The alcohol selectivity is high, the characteristics of good operation stability.
Description of drawings
Fig. 1 is transmission electron microscope (TEM) figure of the C-SBA-15 of preparation
Fig. 2 is catalyst based X-ray diffraction (XRD) collection of illustrative plates of molybdenum carbide of preparation
Fig. 3 is catalyst based transmission electron microscope (TEM) figure of the molybdenum carbide of preparation
Embodiment
Below in conjunction with embodiment the present invention is further described, the present invention includes but be not limited to following embodiment.
The P123 that takes by weighing 4.0g adds deionized water and the stirring of 90mL in the beaker of 250mL, pour in the 500mL there-necked flask after treating to dissolve fully, moves into the hydrochloric acid (4M) of 60g, in 40 ℃ of waters bath with thermostatic control, continues to stir 0.50h.Take by weighing the TEOS of 8.50g, slowly be added drop-wise to TEOS in the there-necked flask with constant pressure funnel, the dropping time is 1h; After dripping, continue to stir 23h.Move into the solution in the there-necked flask in the stainless steel cauldron (Teflon bottle) of band polytetrafluoroethylsubstrate substrate, in 100 ℃ of thermostatic drying chambers, leave standstill crystallization 24h.Take out the Teflon bottle, naturally cool to room temperature, solution in the bottle is carried out suction filtration, and be neutrality until pH value of filtrate, to the seasoning of gained white solid with deionized water wash (about 5 times).Dried solid moves in the retort furnace and under air atmosphere, carries out roasting, and calcination procedure is raised to 550 ℃ for the temperature rise rate with 1 ℃/min from room temperature, keeps 360min at 550 ℃, naturally cools to room temperature then, and the gained solid is SBA-15 (white powder).
Get the dry SBA-15 1g for preparing, be impregnated in the aqueous solution that 5ml is dissolved with 1g sucrose, and add the 0.14g vitriol oil.With the ultrasonic 30min of this mixture, handle 6h at 100 ℃ subsequently, temperature is increased to 160 ℃ and handles 6h again.Final sample is heated to 900 ℃ under argon shield atmosphere, keep 5h, obtains the SBA-15 of surface carbon modification.Fig. 1 is the transmission electron microscope photo of surface carbon modified SBA-15.
Adopt equi-volume impregnating to prepare catalyzer, concrete steps are: get 1g C-SBA-15 carrier, drip zero(ppm) water to just wetting, write down its water regain, promptly soak the needed minimum amount of carrier.According to the proportionlity of water regain that records and carrier quality, according to the charge capacity 10wt% of molybdenum, the ammonium molybdate with the dissolved in distilled water calculated amount of certain volume obtains steeping fluid.Carrier is dipped in the steeping fluid that contains active ingredient, covers and seal film, leave standstill 24h, its active ingredient is carried on the carrier through wicking action, again through 120 ℃ of oven dry.Above-mentioned sample carries out incipient impregnation (nickel molybdenum mol ratio n with nickel nitrate solution again
Ni/ n
Mo=1/6), product dry 24h under 120 ℃.The gained sample is in Ar atmosphere, and 900 ℃ of constant temperature 300min drop to room temperature rapidly, then with 1%O
2/ N
2Obtain black powder behind the gas mixture passivation 2h.The gained black powder is with solution of potassium carbonate dipping (mol ratio n
K/ n
Mo=1/5), the sample that obtains is dry 24h under 120 ℃, and last, sample is in the Ar air-flow, and 900 ℃ of constant temperature 120min can make load type molybdenum carbide catalyst.Catalyst weight per-cent is formed: Mo content is 10%, and Ni content is 1.45%, and K content is 0.80%, and C-SBA-15 content is 87.75%.
K-Ni-β-Mo with method for preparing
2The C/C-SBA-15 catalyzer carries out the evaluation of synthol reacting catalytic performance in the stainless steel fixed-bed reactor.Reactor inside diameter is about 8mm, and catalyst levels is 2ml, and particle diameter is the 40-60 order, 300 ℃ of temperature of reaction, pressure 8Mpa, synthetic gas CO/H
2=1: 1, air speed 2000h
-1Reaction behind the stable equilibrium, the alcohols in the tail gas, by Tianjin, island GC2014C gas chromatograph that capillary chromatographic column is housed, hydrogen flame detector (FID) on-line analysis; Hydro carbons in the tail gas is by Tianjin, island GC2014C gas chromatograph that Propack-Q stationary phase chromatographic column is housed, fid detector on-line analysis; H in the tail gas
2, CO, CH
4And CO
2By Tianjin, island GC2014C gas chromatograph that carbonaceous molecular sieve post TDX-01 is housed, the on-line analysis of TCD detector.
Above catalyzer is carried out synthol catalytic performance test result show this Catalyst for CO transformation efficiency 16.1%, hydrocarbon-selective 19.5%, total pure selectivity 80.5%, C
2+Alcohol selectivity 42.3%.Total pure selectivity of this catalyzer and C
2+The alcohol selectivity is high, and reaction stability is good, is good synthol catalyzer.
Claims (7)
1. method by synthetic gas (carbon monoxide and hydrogen) catalyzed conversion preparing low-carbon mixed alcohol is characterized in that composition, preparation method and the reaction conditions of catalyzer.
2. method according to claim 1 is characterized in that support of the catalyst is the SBA-15 (C-SBA-15) of surface carbon modification.
3. method according to claim 2 is characterized in that among the support of the catalyst C-SBA-15 that the massfraction of carbon is 1-20%.
4. method according to claim 1; The massfraction that it is characterized in that consisting of of catalyzer: active ingredient Mo is 5-80%; The massfraction of auxiliary agent Ni is 1.0-5.0%, and the massfraction of auxiliary agent K is 0.50-2.0%, and the massfraction of support C-SBA-15 is 95-20%.
5. method according to claim 1; It is characterized in that the preparation method of the SBA-15 support of the catalyst (C-SBA-15) of surface carbon modification, wherein carbon source is sucrose, glucose, fructose, and carburization agent is the vitriol oil, concentrated nitric acid, concentrated hydrochloric acid or its mixture; Treatment temp is 50 ℃-180 ℃; Treatment time is 2-8h, products therefrom roasting under nitrogen or argon gas atmosphere, and maturing temperature is 600-1000 ℃.
6. method according to claim 1 is characterized in that the Preparation of catalysts method, is carrier with C-SBA-15; Adopt the incipient impregnation method to use ammonium molybdate solution, nickel nitrate solution floods 20-25h respectively successively, 100-150 ℃ of oven dry; The gained sample is in argon gas atmosphere; 800-1000 ℃ of constant temperature 100-400min drops to room temperature rapidly, then with 0.5-2%O
2/ N
2Gas mixture passivation 1-3h floods 20-25h with solution of potassium carbonate then, 100-150 ℃ of oven dry, and product is 700-900 ℃ of roasting 1-3h under argon gas atmosphere, obtains load type molybdenum carbide base synthol catalyzer.
7. method according to claim 1 is characterized in that the reaction conditions of catalyzer, and temperature of reaction is 270-370 ℃, and pressure is 5-12Mpa, synthetic gas H
2/ CO=2: 1-1: 2, air speed 1000-10000h
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107464938A (en) * | 2017-07-31 | 2017-12-12 | 中南大学 | A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery |
| CN109201096A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | CO2Add the catalyst and application thereof of hydrogen preparing low-carbon mixed alcohol |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | Preparation method and application of catalyst for preparing low-carbon alcohol from synthesis gas |
| CN113522344A (en) * | 2021-07-22 | 2021-10-22 | 太原理工大学 | Ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof |
| WO2022166084A1 (en) * | 2021-02-04 | 2022-08-11 | 厦门大学 | Preparation method for and use of solvent coordination metal catalyst |
| CN115569663A (en) * | 2021-06-21 | 2023-01-06 | 中国石油化工股份有限公司 | Preparation method of novel sulfur-resistant shift catalyst |
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Cited By (10)
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| CN109201096A (en) * | 2017-07-03 | 2019-01-15 | 中国石油化工股份有限公司 | CO2Add the catalyst and application thereof of hydrogen preparing low-carbon mixed alcohol |
| CN109201096B (en) * | 2017-07-03 | 2021-08-03 | 中国石油化工股份有限公司 | CO2Catalyst for preparing low-carbon mixed alcohol by hydrogenation and application thereof |
| CN107464938A (en) * | 2017-07-31 | 2017-12-12 | 中南大学 | A kind of molybdenum carbide/carbon composite with core shell structure and preparation method thereof and the application in lithium-air battery |
| CN107464938B (en) * | 2017-07-31 | 2020-02-04 | 中南大学 | Molybdenum carbide/carbon composite material with core-shell structure, preparation method thereof and application thereof in lithium air battery |
| CN111420689A (en) * | 2020-03-26 | 2020-07-17 | 内蒙古大学 | Preparation method and application of catalyst for preparing low-carbon alcohol from synthesis gas |
| WO2022166084A1 (en) * | 2021-02-04 | 2022-08-11 | 厦门大学 | Preparation method for and use of solvent coordination metal catalyst |
| CN115569663A (en) * | 2021-06-21 | 2023-01-06 | 中国石油化工股份有限公司 | Preparation method of novel sulfur-resistant shift catalyst |
| CN115569663B (en) * | 2021-06-21 | 2023-10-20 | 中国石油化工股份有限公司 | Preparation method of novel sulfur-tolerant shift catalyst |
| CN113522344A (en) * | 2021-07-22 | 2021-10-22 | 太原理工大学 | Ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof |
| CN113522344B (en) * | 2021-07-22 | 2022-03-11 | 太原理工大学 | Ordered mesoporous KIT-6 loaded sulfated zirconium-aluminum composite oxide solid acid material and preparation and application thereof |
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Application publication date: 20120418 |