CN103638933B - A kind of preparation method of the unstable state catalyst for low temperature methanol synthesis reaction - Google Patents
A kind of preparation method of the unstable state catalyst for low temperature methanol synthesis reaction Download PDFInfo
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Abstract
A kind of preparation method of the unstable state catalyst for low temperature methanol synthesis reaction, the preparation method relating to a kind of catalyst, first, synthesis gas is adsorbed on Cu/ZnO catalyst surface, generate first acid, then, ethanol attack Tubercuprose. or zinc formate in gas phase, generate Ethyl formate, this reaction is nucleophilic displacement of fluorine-elimination reaction, wherein, the ethanol with lone pair electrons exists as nucleopilic reagent, finally, the Ethyl formate hydrogenation with physical absorption of gaseous state generates ethanol and methanol, the first step of low temperature methanol synthesis mechanism reaction is to generate first acid, Tubercuprose. and zinc formate, the preparation process of catalyst can be directly synthesized astable catalyst, adopt unstable state catalyst prepared by the method after low temperature methanol synthesis reacts, the final form of remaining solid catalyst and structure and through roasting, conventional Cu/ZnO catalyst after reduction is completely the same。
Description
Technical field
The preparation method that the present invention relates to a kind of catalyst, the preparation method particularly relating to a kind of unstable state catalyst for low temperature methanol synthesis reaction。
Background technology
Metallic catalyst be solid catalyst is studied the earliest, the most deep, be also simultaneously obtain the most wide variety of a kind of catalyst。It is a most important class catalyst in Industrial Catalysis。By its effect classification, metallic catalyst can play the effects such as hydrogenation, dehydrogenation, oxidation, isomerization, cyclisation。According to price category, metallic catalyst includes base metal catalysts, as: Ni, Cu, Co, Fe etc.；And noble metal catalyst, as: Pt, Pd, Ru, Rh etc.。At present, the preparation method of metallic catalyst mainly includes chemical method and Physical。Chemical method wherein mainly has infusion process, coprecipitation, homogeneous precipitation method, sol-gel process and microemulsion method etc.；Physical has vapour deposition process, atom deposition method, sputtering method and solid-phase sequencing。In chemical method, it is gentle that coprecipitation method and homogeneous precipitation method prepare reaction condition in ground metallic catalyst preparation process, it is easy to controlling, and equipment investment is little, the metal particle size of preparation is uniformly dispersed controlled。And prepared catalyst activity in catalytic reaction is higher, therefore extensive use aborning。But, adopting coprecipitation method and homogeneous precipitation method to prepare in the process of metallic catalyst, owing to being widely used relatively inexpensive metal nitrate presoma, there is the substantial amounts of waste water containing nitrate anion to produce, the extreme influence that environment is caused, environment is unfriendly。Therefore, implementing Green Chemistry, advocating today of green synthetic chemistry, develop a kind of simple, free of contamination metallic catalyst preparation method is very necessary。
The synthesis gas prepared through methane reforming, biomass or coal gasification reacts mainly through methanol-fueled CLC and F-T synthesis two prepares large industrial chemicals, and previous reaction has more atom economy benefit, because the oxygen atom in synthesis gas is also contained in product。It is known that methanol is a kind of wide variety of industrial chemicals [1], can apply to the internal combustion engine [2] after improving simultaneously as a kind of important liquid fuel, or be directly used in methanol fuel cell (DMFC) [3]。Industrial, methanol is by synthesis gas (H2/CO/CO2) set out, under higher temperature and pressure (523-573K, 5-10MPa), by the Cu/ZnO/Al that ICI company develops2O3Catalyst preparing [4]。But, methanol-fueled CLC reaction is a strongly exothermic process, and its combined coefficient is strictly subject to thermodynamic (al) control。Industrialized methanol synthesizer, the conversion ratio of raw material (CO) step is only 14%。Therefore, exploitation low temperature methanol synthesis technique will obtain higher feed stock conversion, and greatly reduce energy consumption。Tsubaki team of Japan reports [5,6] a kind of slurry bed system low temperature methanol synthesis technique with alcoholic solution simultaneously as solvent and catalyst。Wherein, alcoholic solution plays the effect of heat transfer and heat-obtaining as solvent, the intermediate product Tubercuprose. that the lone pair electrons on the oxygen in alcoholic solvent react as nucleopilic reagent attack simultaneously, generates formic acid esters。Then formic acid esters hydrogenation generates again corresponding alcoholic solvent and Methanol product, plays the effect of catalyst。
The document grasped according to us and patent, in methanol-fueled CLC reaction, the copper-based catalysts that uses is the Nanometer Copper of metallic state or the copper of oxidation state, and after reduce, through hydrogen or synthesis gas, the metallic copper obtaining zeroth order。Research before, we once reported a kind of brand-new formic acid assisted Solid-state polishing one step and prepared nano metal Cu/ZnO catalyst [7], without extra reduction flow process。Paper proposes a kind of brand-new formic acid assisted Solid-state polishing first and prepares metal (Co, Ni, Ag, Cu) and metallic catalyst Cu/ZnO。When the metal formate presoma formed is in argon in the process of roasting, along with the progressively decomposition of formates, hydrogen and carbon monoxide progressively discharge and reducing agent as original position can the direct-reduction metal that goes out in presoma。Prepared Ni metal/ZnO catalyst is directly used in low-temp methanol reaction, shows the selectivity of good reactivity and methanol。But, owing to, in the process of solid-phase grinding, formic acid and nitrate generation redox reaction are excessively violent, cause that final metallic copper crystal grain is excessive。In patent later [8], we strictly control the ambient temperature in solid-phase grinding process so that it is carry out under mixture of ice and water and liquid nitrogen deep environment。When process of lapping carries out under liquid nitrogen environment-Cryogenic Conditions, nitrate and formic acid react very slow, and progressively discharge oxynitride, and the metal formate nucleus growth rate of formation is slow, and do not occur nucleus to reunite, ultimately form Nano grade superfine metal formates presoma。When the superfine metal formates presoma formed is in argon in the process of roasting, progressively decomposition along with formates, hydrogen and carbon monoxide progressively discharge and as original position reducing agent can the direct-reduction Ni metal that goes out in presoma, obtain wine-colored superfine nano Cu/ZnO catalyst。Selecting low temperature methanol synthesis reaction as probe reaction, under Cryogenic Conditions, the ultra-fine Cu/ZnO catalyst of preparation is compared with the Cu/ZnO catalyst of preparation under normal temperature condition, shows splendid reactivity and methanol selectivity。
List of references:
[1]Olah,G.A.;Goeppert,SuryaPrakash,A.;G.K.BeyondOilandGas:TheMethanolEconomy.(Wiley-VCH,Weinheim,Germany,2006).
[2]Breen,J.P.;Ross,J.R.H.Methanolreformingforfuel-cellapplications:developmentofzirconia-containingCu-Zn-Alcatalysts.Catal.Today1999,51,521-533.
[3]Liu,H.S.;Song,C.J.;Zhang,L.;Zhang,J.J.;Wang,H.J.;Wilkinson,D.P.Areviewofanodecatalysisinthedirectmethanolfuelcell.J.PowerSources2006,155,95-110.
[4]Behrens,M.;Studt,F.;Kasatkin,I.;Kühl,S.;H?vecker,M.;Pedersen,F.A.;Zander,S.;Girgsdies,F.;Kurr,P.;Kniep,B.L.;Tovar,M.;Fischer,R.W.;N?rskov,J.K.;Schl?gl,R.TheactivesiteofmethanolsynthesisoverCu/ZnO/Al2O3industrialcatalysts.Science2012,336,893-897.
[5]Tsubaki,N.;Ito,M.;Fujimoto,K.Anewmethodoflow-temperaturemethanolsynthesis.J.Catal.2001,197,224-227.
[6]Yang,R.Q.;Fu,Y.L.;Zhang,Y.;Tsubaki,N.InsituDRIFTstudyoflow-temperaturemethanolsynthesismechanismonCu/ZnOcatalystsfromCO2-containingsyngasusingethanolpromoter.J.Catal.2004,228,23-35
[7]Shi,L.;Shen,W.Z.;Jin,X.Z.;Zeng,C.Y.;Mastuda,K.;Tsubaki,N.;Formicaciddirectlyassistedsolid-statesynthesisofmetalliccatalystswithoutfurtherreduction:as-preparedCu/ZnOcatalystsforlow-temperaturemethanolsynthesis,J.Catal.2013,302,83-90.
[8] a kind of method preparing high activity metal Cu/ZnO catalyst under Cryogenic Conditions, application number: 201310187865.9, inventor: Shi Lei；Peaceful CHIGO；Xiao Linjiu。
Summary of the invention
The preparation method that it is an object of the invention to provide a kind of unstable state catalyst for low temperature methanol synthesis reaction, the method exists as highly active reaction intermediate, reaction rate can be significantly increased, ultimately generate catalyst, course of reaction only exists with reactive intermediates or two kinds of forms of catalyst。
It is an object of the invention to be achieved through the following technical solutions:
A kind of preparation method of the unstable state catalyst for low temperature methanol synthesis reaction, described method includes procedure below:
First, synthesis gas is adsorbed on Cu/ZnO catalyst surface, generate first acid, then, ethanol attack Tubercuprose. or zinc formate in gas phase, generate Ethyl formate, this reaction is nucleophilic displacement of fluorine-elimination reaction, wherein, the ethanol with lone pair electrons exists as nucleopilic reagent, finally, the Ethyl formate hydrogenation with physical absorption of gaseous state generates ethanol and methanol, the first step of low temperature methanol synthesis mechanism reaction is to generate first acid, Tubercuprose. and zinc formate, the preparation process of catalyst can be directly synthesized astable catalyst, react for low temperature methanol synthesis, first solid-state copper nitrate and zinc nitrate are adopted the method for physical mixed to grind uniformly by the synthesis flow of unstable state catalyst, it is subsequently adding formic acid solution, stir when room temperature or frozen water, reach critical point moment, violent redox reaction is there is in nitrate ion with formic acid, discharge the flue gas of substantial amounts of hot and substantial amounts of brown color, ultimately generate solid azury, after the solid precipitated out filters, moisture with the physical absorption in toluene solution extraction unstable state catalyst, then filter, again wash for several times with ethanol, finally filter, 120 degrees Celsius of baking ovens dry, the dried product taken out is directly used in low temperature methanol synthesis reaction。Using paste state bed reactor, low-temp methanol reaction condition is: reaction temperature 180 degrees Celsius, 50 atmospheric pressure of reaction pressure, unstable state catalyst quality 3g, solvent volume 40 milliliters, solvent species ethanol, mixing speed 2000 revs/min, 50 hours response time, synthesis gas composition Ar/CO/CO2/H2=3.13/33.00/5.23/58.64。
The preparation method of described a kind of unstable state catalyst for low temperature methanol synthesis reaction, the presoma of described copper and zinc is nitrate。
The preparation method of described a kind of unstable state catalyst for low temperature methanol synthesis reaction, the solvent used in described catalyst preparation process is formic acid。
The preparation method of described a kind of unstable state catalyst for low temperature methanol synthesis reaction, the molar ratio range of described formic acid and nitrate ion is 0-100。
The preparation method of described a kind of unstable state catalyst for low temperature methanol synthesis reaction, described extractant is toluene, washes some number of times through dehydrated alcohol after extraction。
The preparation method of described a kind of unstable state catalyst for low temperature methanol synthesis reaction, described baking temperature 80-150 degree Celsius, drying time is 0-200 hour。
Accompanying drawing explanation
Fig. 1 is low temperature methanol synthesis mechanism figure of the present invention；
Fig. 2 is necleophilic reaction schematic diagram of the present invention；
Fig. 3 is unstable state catalyst preparing flow chart of the present invention；
Fig. 4 is the photo figure of post catalyst reaction of the present invention, solvent and product；
The XRD phenogram of unstable state catalyst after Fig. 5 present invention reaction；
Fig. 6 low temperature methanol synthesis successive reaction of the present invention carries out CO, CO in time2, and total efficiency of carbon con version variation diagram。
Detailed description of the invention
Below in conjunction with accompanying drawing illustrated embodiment, the invention will be further described。
The present invention is on the basis studying [7,8] before, in conjunction with low temperature methanol synthesis route and mechanism, directly prepares the reactive intermediates class Tubercuprose. in low temperature methanol synthesis course of reaction and zinc formate material as astable catalyst。In the present invention, we have proposed the concept of a unstable state catalyst。It is known that the definition of catalyst is to significantly improve reaction rate, the chemical property of himself and quantity before the reaction after the material that all remains unchanged。And our the unstable state catalyst of definition is: itself exist as highly active reaction intermediate, reaction rate can be significantly increased, ultimately generate catalyst, course of reaction only exists with reactive intermediates or two kinds of forms of catalyst。
Such as accompanying drawing 1, proposed low temperature methanol synthesis mechanism is: first, and synthesis gas is adsorbed on Cu/ZnO catalyst surface, generates first acid。Then, ethanol attack Tubercuprose. or zinc formate in gas phase, its mechanism as shown in Figure 2, generates Ethyl formate。This reaction is nucleophilic displacement of fluorine-elimination reaction, and wherein, the ethanol with lone pair electrons exists as nucleopilic reagent。Finally, the Ethyl formate hydrogenation with physical absorption of gaseous state generates ethanol and methanol。From low temperature methanol synthesis mechanism it is observed that the first step of reaction is to generate first acid, Tubercuprose. and zinc formate。So, the preparation process of catalyst can be directly synthesized astable catalyst, react for low temperature methanol synthesis。The solid-state copper nitrate of certain molal quantity and zinc nitrate as shown in Figure 3, are first adopted the method for physical mixed to grind uniformly, are subsequently adding the formic acid solution of different molal quantity, stir when room temperature or frozen water by the synthesis flow of unstable state catalyst。When reaching critical point moment, there is violent redox reaction with formic acid in nitrate ion, discharges the flue gas of substantial amounts of hot and substantial amounts of brown color, ultimately generate solid azury。After the solid precipitated out is filtered, with the moisture of the physical absorption in toluene solution extraction unstable state catalyst, then filter, again wash for several times with ethanol, finally filter, dry a period of time in 120 degrees Celsius of baking ovens。The dried product taken out is directly used in low temperature methanol synthesis reaction。
Using paste state bed reactor, low-temp methanol reaction condition is: reaction temperature 180 degrees Celsius, 50 atmospheric pressure of reaction pressure, unstable state catalyst quality 3g, solvent volume 40 milliliters, solvent species ethanol, mixing speed 2000 revs/min, 50 hours response time, synthesis gas composition Ar/CO/CO2/H2=3.13/33.00/5.23/58.64。As shown in accompanying drawing 4 photo, the product and the catalyst that take out after reaction are claret, basically identical with the color of the metallic copper of high dispersive。After reaction through filtering, the XRD phenogram of dried catalyst as shown in Figure 5, its characteristic peak is attributed to metallic copper and zinc oxide completely。Illustrate that in course of reaction, astable catalyst has been fully converted to Cu/ZnO catalyst。
Use the method to prepare the advantage that unstable state catalyst react for low temperature methanol synthesis to be: 1., in the process of grinding, nitrate reacts with formic acid, discharges with the form of oxynitride gaseous state。And gaseous nitrogen oxygen compound deionized water adsorbs, it is possible to use as nitric recycle。Namely in the process of the preparation of catalyst, remain entirely without nitrate, and produce without the waste water containing nitric acid, environmental friendliness。2. the unstable state catalyst prepared by only need to through super-dry, it is not necessary to the flow process of roasting and reduction, saves the energy。3. the reducing agent formic acid used, a part is for reducing nitrate ion, and another part exists and in astable catalyst with the form of formates, and formates is the active intermediate kind of reaction, and atom economy efficiency is high。First, by 0.025mol copper nitrate and 0.025mol zinc nitrate physical mixed in mortar, and grind uniformly。Mixture is taken out to be put in crucible, is subsequently adding 0.6mol formic acid, with Glass rod stirring until copper nitrate and zinc nitrate are completely dissolved。After dissolving, crucible is placed in mixture of ice and water, and to keep ambient temperature be about zero degrees celsius, put。Initial reaction stage, it has been found that have minimum bubble formation in solution, and be gradually increased and increase, then there is violent redox reaction。Period has the flue gas of substantial amounts of brown color to generate, and discharges。Adopt deionized water absorptive collection, and recycle。After reaction, the light-blue solid product having color homogeneous precipitates out。Filter solid product, and repeatedly extract with toluene solution, ensure that less aqueous formic acid remains as far as possible。Use alcoholic solution alcohol wash solid product 3 times subsequently。Solid product after alcohol wash is placed in 120 degrees Celsius of baking ovens, dry 100 hours。Dried product becomes the bread-like of foaming, is ground to Powdered in mortar。Take 3 grams of this powder and join in 85 milliliters of reactors, add alcohol solvent 40 milliliters, reaction temperature 180 degrees Celsius, 50 atmospheric pressure of reaction pressure, mixing speed 2000 revs/min, 50 hours response time, synthesis gas composition Ar/CO/CO2/H2=3.13/33.00/5.23/58.64。The conversion ratio of reactant is such as shown in accompanying drawing six, and in the starting stage of reaction, owing to still having a small amount of water to remain in the duct of unstable state catalyst, the conversion ratio of CO gradually rises, and reaches about 80%, has substantial amounts of CO simultaneously2Generate。Along with the carrying out of reaction, in reactor, remaining water gradually decreases, and after 20 hours, reacts steady gradually。Conversion ratio stable for CO is about 27%, and total efficiency of carbon con version is stable about 23%。After reacting 50 hours, the liquid solvent of taking-up and product, through filtering post analysis, obtain the selectivity of methanol higher than 95%, and the balance of total carbon is more than 100%, owing to the formate in unstable state catalyst is converted into Methanol product。
Claims (1)
1. the preparation method for the unstable state catalyst of low temperature methanol synthesis reaction, described method includes procedure below: by 0.025mol copper nitrate and 0.025mol zinc nitrate physical mixed in mortar, and grind uniformly, mixture is taken out to be put in crucible, it is subsequently adding 0.6mol formic acid, with Glass rod stirring until copper nitrate and zinc nitrate are completely dissolved；After dissolving, crucible is placed in mixture of ice and water, and to keep ambient temperature be zero degrees celsius, put, initial reaction stage, it has been found that have minimum bubble formation in solution, and be gradually increased and increase, violent redox reaction then occurs, and period has the flue gas of substantial amounts of brown color to generate, and discharges；Adopting deionized water absorptive collection, and recycle, after reaction, the light-blue solid product having color homogeneous precipitates out；Filter solid product, and extract with toluene solution, use alcoholic solution alcohol wash solid product 3 times；Solid product after alcohol wash is placed in 120 degrees Celsius of baking ovens, dry 100 hours。
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| CN102019182A (en) * | 2010-12-16 | 2011-04-20 | 沈阳化工大学 | Preparation method of Cu/ZnO catalyst for preparing methanol from synthesis gas |
| CN103272602A (en) * | 2013-05-21 | 2013-09-04 | 沈阳化工大学 | Method for preparing high-activity metal Cu/ZnO catalyst under copious cooling condition |
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| CN102019182A (en) * | 2010-12-16 | 2011-04-20 | 沈阳化工大学 | Preparation method of Cu/ZnO catalyst for preparing methanol from synthesis gas |
| CN103272602A (en) * | 2013-05-21 | 2013-09-04 | 沈阳化工大学 | Method for preparing high-activity metal Cu/ZnO catalyst under copious cooling condition |
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| "Formic acid directly assisted solid-state synthesis of metallic catalysts without further reduction: as-prepared Cu/ZnO catalysts for low-temperature methanol synthesis";Lei Shi et al.;《Journal of Catalysis》;20130410;第302卷;第83-90页 * |
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