CN101341110A - Alcohol synthesis from co or co2 - Google Patents

Abstract

Methods for producing alcohols from CO or CO2 and H2 utilizing a palladium-zinc on alumina catalyst are described. Methods of synthesizing alcohols over various catalysts in microchannels are also described. Ethanol, higher alcohols, and other C2<+> oxygenates can be produced utilizing Rh-Mn or a Fisher-Tropsch catalyst.

Description

With CO or CO 2Synthol

Related application

According to 35U.S.C. the 119th (e) bar, the application requires 60/823093 right of priority of the US provisional application number application on August 21st, 60/751144 and 2006 of on December 16th, 2005 application.

Official's right

The part of the research is by U.S.Department Energy, and Office ofBiomass Program subsidizes, and contract number is DE-AC06-76RL01830.

Technical field

The present invention relates to pure synthetic method, pure synthetic catalyst and pure synthesis system.A part of the present invention comprises that also reaction generates the method for alcohol.

Introduction

The catalyzer of aluminium oxide loaded Pd/Zn is a kind of known pure steam reforming reaction catalyzer.For example referring to " Steam Reforming ofMethanol over Pd/ZnO:Effect of the formation of Pd/Zn alloysupon the reaction, " Appl.Catal.A:General 125 (1995) 145-147 of application 20040223908 of US publication and Iwasa etc.Takezawa etc. " Steam Reforming and dehydrogenation ofmethanol:Difference in the catalytic functions of copper andGroup VIII metals; " Cat.Today has discussed the mechanism and the methanol dehydrogenation of steam reformation among 36 (1997) 45-56.Though by CO ₂Mechanism the unknown of synthesizing alcohol on Pd/Zn, but the synthesis mechanism on Cu/ZnO Fujita etc. " Mechanisms ofMethanol Synthesis from Carbon Dioxide and from Carbon Monoxideat Atmospheric Pressure over Cu/ZnO; " discuss among the J.Catal.157,403-413 (1995).

By CO ₂Synthesizing alcohol and higher alcohols can comprise that the composite catalyst of Fisher-Tropsch catalyzer finishes by use.Inui and Yamamoto exist " Effective synthesis ofethanol from CO2 on polyfunctional composite catalysts; " Catalysis Today vol.45, reported the combination of using catalyzer among the pp.209-214 (1998), mix or pass through continuously, come synthesizing alcohol and higher alcohols.

Summary of the invention

On the one hand, the present invention includes hydrogen and C ₁ ⁺The oxygenate reaction forms C ₂ ⁺The segmentation reaction of oxygenate.This segmentation reaction can be carried out along the length direction of microchannel, and/or by carrying out hydrogen and C in first microchannel or in the first part of microchannel ₁ ⁺The reaction of oxygenate provides other hydrogen subsequently and once more reaction mixture is exposed under the reaction conditions in the microchannel." reaction conditions " is included in has catalyzer to exist under the suitable temperature.In some preferred embodiments, reaction comprises the hydrogen segmentation is added in the incoming flow that contains CO.As substituting of segmentation hydrogenation, CO and/or CO ₂Can add in the sectional mode; Similarly, C ₁ ⁺Oxygenate can adopt the sectional mode to add, and, the mixing of these materials, for example H ₂And CO ₂Mixture can join in the microchannel reaction passage in the sectional mode and (be called reaction chamber, microchannel again).In preferred embodiments, reaction chamber in microchannel has pure synthetic catalyst described here.The micro-channel device of other segmentation reaction is known, and can be suitable in the methods of the invention.For example referring to 2005/026915 of the US publication application 2006/0129015 of Tonkovich etc. (hydrogen peroxide synthetic) and Tonkovich, at this in conjunction with above document.

On the other hand, the invention provides pure synthetic method, comprising: in the microchannel, in the presence of alcohol catalyst, hydrogen is contacted with CO.The feature of this method also is effects more described herein.For example, at least 20% CO transformation efficiency, present method unexpectedly obtains at least 30% C ₂ ⁺Oxygenate selectivity (selectivity of preferred alcohol), preferably at least 40%, more preferably at least 50%, and selectivity is that 40-is about 60% in some embodiments, in certain embodiments can be up to about 56%.That reports in this and the document only 20% has formed contrast.Preferably, this method can be moved under high relatively output, for example 1000h at least ^-1GHSV, more preferably 3000h at least ^-1, be 2000-100000h in some embodiments ^-1, be 2000-4000h in certain embodiments ^-1The use of micro passage reaction makes the CO hydrogenation reaction of high heat release to carry out under the isothermal mode, to obtain high productive rate.The integrated permission of catalyzer in micro passage reaction hydrogenation under high-throughput and high volume-time yield is produced alcohol, and has improved selectivity of product significantly.From the preferred 5W/cc at least of the effusive heat flow of microchannel, and be 5-8W/cc in certain embodiments, wherein " cc " volume is meant the volume (being catalyzer with the microchannel part that flows through or the mode of (flow-by or flow through) of passing exists) of reaction chamber.Catalyzer can also comprise that the Fisher-Tropsch catalyzer is to improve the output of ethanol and higher alcohols.

On the other hand, the invention provides method, comprising: contain CO and H by the CO synthol ₂Reaction gas mixtures contact with catalyzer, wherein catalyzer comprises Pd and the Zn that is dispersed on the aluminum oxide; With one or more alcohol of formation.In certain embodiments, one or more alcohol that form in forming one or more pure steps mainly are made up of methyl alcohol.Catalyzer can also comprise the Fisher-Tropsch catalyzer, makes one or more alcohol contain a large amount of ethanol and higher alcohols becomes possibility.

On the other hand, the invention provides a kind of by CO ₂The novel method of synthol comprises: contain CO and H ₂Reaction gas mixtures contact with catalyzer, wherein catalyzer comprises Pd and the Zn that is dispersed on the aluminum oxide; With one or more alcohol of generation.

In a related aspect, the invention provides a kind of by CO ₂The method of synthesizing alcohol and higher alcohols comprises: CO and H are arranged ₂Reaction gas mixtures contact with catalyzer, wherein catalyzer comprises that (a) is dispersed in Pd-Zn and (b) the Fisher-Tropsch catalyzer on the aluminum oxide; With generation ethanol or higher alcohols.

On the other hand, the invention provides a kind of synthetic C ₂ ⁺The method of oxygenate comprises: in first step, the composition that will contain Rh or Pd carries out RedOx to be handled to form catalyzer; Then, in step subsequently, under the situation that catalyzer exists with C ₁ ⁺Oxygenate contacts with hydrogen to form C ₂ ⁺Oxygenate.Under the situation that catalyzer exists with C ₁ ⁺The step that oxygenate contacts with hydrogen is preferably carried out in the microchannel.Preferred Rh catalyzer is because it has higher selectivity.The Rh that is carried on the silicon-dioxide is especially preferred.RedOx handles and comprises that reduction at high temperature contains the first step of Rh (or the less preferred Pd of containing) composition.Preferably in the presence of hydrogen, reduce.RedOx handles and also comprises the second follow-up step: oxidation at high temperature.High temperature is meant and is higher than room temperature, preferably at least 100 ℃, and more preferably at least 200 ℃.In certain embodiments, reduction is carried out under the temperature higher than oxidation.In some embodiments, carry out in the temperature range of reduction between 300-400 ℃.In some embodiments, carry out in the temperature range of oxidation between 200-300 ℃.A loop cycle has a reduction step and an oxidation step, and the RedOx processing comprises at least one circulation, preferably at least 2 circulations.For catalyst system, for example by CuZnAl and Rh-MnZSiO with Rh and/or Pd ₂The mixed catalyst system that forms, surprising discoverys RedOx processing can improve total CO transformation efficiency, and keeps or improve product selectivity.

On the other hand, the invention provides a kind of method of synthol, comprising: under the situation that alcohol catalyst exists, hydrogen is contacted in the microchannel with CO under the high temperature.In this case, " high temperature " is meant the temperature that temperature is reported in the prior art.For example, for the catalyzed reaction in the presence of the Cu catalyzer, the present invention carries out under at least 250 ℃ temperature, is at least 270 ℃ in some embodiments, yet report Cu catalyzer should be above 230 ℃ in the document.Equally, in the present invention, can carry out under the temperature at least 300 ℃, be at least 320 ℃ in some embodiments in the reaction on the Rh catalyzer that loads on the silicon-dioxide.

On the other hand, present invention resides in hydrogen and C on the thin layer catalyst ₁ ⁺The oxygenate reaction generates C ₂ ⁺Oxygenate.Preferably, described being reflected in the microchannel carried out.The catalytically active material thin layer can be applied directly on reaction chamber (preferred microchannel) wall, or is applied directly on the support of the catalyst of insertion reaction chamber (preferred microchannel reaction chamber).The preferred 100 μ m or littler of thin layer, more preferably 50 μ m or littler are 30 μ m or littler in some embodiments, are 20 μ m or littler in some embodiments, be 10 μ m or littler in some embodiments, and be 5 μ m-50 μ m in some embodiments.

The present invention also comprises the combination of these methods.For example by in the microchannel, on thin layer catalyst, reacting the ethanol selectivity that can be improved; Preferably carry out with hydroformylation stage.Hydroformylation stage has kept gratifying reactant and hydrogen ratio in entire reaction.

In some respects, the present invention's method of being described to react.These methods can be described to " system " by alternate, and the present invention also comprises the system with any method described here.System of the present invention can be described to comprise and reactant and/or product bonded device and/or catalyzer.Randomly, system is further characterized in that its operational condition.

Various embodiments of the present invention can provide multiple advantage, comprise one or more following advantages: high carbon monoxide or carbon dioxide conversion; High pure selectivity; Low methyl alcohol or methane selectively; Under very short duration of contact, operate; Can under than the higher temperature of conventional system (for example CuZnAl catalyzer), operate, even because the not ignition quality of the speed of reaction that at high temperature improves, catalyzer and under relative high temperature high stability for a long time, make it possible to obtain bigger turnout.

Term

" alcohol catalyst " is meant catalysis hydrogen and C ₁ ⁺The oxygenate reacted composition.It is known that multiple composition is arranged is alcohol catalyst.Preferred alcohol catalyst comprises Rh, preferably is carried on the Rh on the silicon-dioxide, and in some embodiments, Rh is dispersed on zirconium white and/or magnesium oxide, the moly-sulfide, preferably is doped with K, and is mixed with Co, Pd/Zn in some embodiments; And Cu, preferred copper catalyst is formed and is comprised Cu/ZnO/Cr ₂O ₃-Cs and Cu-CoO-ZrO ₂-K; And mixed catalyst, for example contain the mixed catalyst of the mixture of Cu and Rh.

For purpose of the present invention, C ₁ ⁺Oxygenate is defined as CO, CO ₂, methyl alcohol (CH ₃OH) or formaldehyde (CH ₂O) and composition thereof.Its wider aspect, the present invention includes to use and contain C ₁ ⁺The incoming flow of oxygenate.In some preferred embodiments, incoming flow (reactant) contains CO.Can in incoming flow, there be hydrogen (H ₂) or can add during the course.

For purpose of the present invention, C ₂ ⁺Oxygenate is defined as containing the compound of at least 2 carbon atoms and 1 Sauerstoffatom.This definition can be understood the scope of these compounds concerning the chemical industry personnel of this area, these compounds are suitably formed by method described here and (that is, pass through C ₁ ⁺The catalyzed reaction of oxygenate).In some preferred embodiments, the product of expection can be defined as ethanol or higher alcohols.In some embodiments, alcoholic acid is synthetic especially preferred.

Patent term as routine, " comprise " and be meant and contain, and when using this term, the present invention can (in the little embodiment of some relative scope) can be described to " mainly by ... form " or in the scope minimum implementation, can be described as " by ... form ".The aspect of being described by " comprising " of the present invention is not restricted to single component, and can contain other component.The composition of " being made up of one group of component basically " can contain other component that feature of the present invention is not had basically influence.Equally, " basically " composition of not having a specific components does not have this kind group component that influence basically requires attribute.

Gas hourly space velocity (" GHSV ") is defined as (0 ℃ and 1 normal atmosphere) under the normal conditions total hour flow velocity (L/h) divided by reaction zone volume (L).Under the situation of the packed-bed reactor that uses fine catalyst, the reaction zone volume equals catalyst volume.In micro passage reaction, reaction zone also comprise the volume in the bulk flow path of flowing through catalyzer-promptly with the vertical cross section that flows in have the microchannel volume (for example, comprising the volume that the wall coating is above) of catalyzer.

" microchannel " is to have at least one interior dimensions (between wall and the wall, do not contain catalyzer) be 1cm or littler passage, be preferably 2mm or littler (in certain embodiments for about 1.0mm or littler) and, be 50-500 μ m in certain embodiments greater than 100nm (being preferably greater than 1 μ m).The microchannel also is restricted to has at least one inlet, and this inlet is different with at least one outlet.The microchannel not merely is the passage that is full of zeolite or neutral hole material.The length of microchannel is corresponding with the direction that flows through passage.To flow through the direction of passage vertical with fluid basically for microchannel height and width.Under the situation of laminated device, the microchannel has two major surfacess (for example piling up the surface that forms with the bonded thin slice), highly be the distance between from the major surfaces to the major surfaces, and width is with highly vertical.

In some preferred embodiments, use micro passage reaction, preferably contact with a plurality of adjacent heat exchange micro channel heats with a plurality of microchannel reaction passages.A plurality of microchannels for example can comprise 2,10,100,1000 or more passage.In preferred embodiments, the planar microchannels that the microchannel is configured to be arranged in parallel, for example at least 3 row planar microchannels.In some preferred embodiments, a plurality of microchannels inlet links to each other with a total head and/or a plurality of microchannel exports and links to each other with a total afterbody.In operating process, alternative heat exchange layers (if existence) has comprised mobile fluid in heating and/or the cooling microchannel.The indefiniteness embodiment of such known reactor of Shi Yonging comprises microelement layer structure (laminated plate that for example has the microchannel) in the present invention, this structure is at US6, and 200,536 and US6, example goes out (passing through reference in conjunction with above two pieces of documents at this) in 219,973.Use the feature performance benefit of such structure to comprise: heat transfer that they are big relatively and rate of mass transfer.The advantage that micro passage reaction can minimize etc. in conjunction with good heat transfer and rate of mass transfer, superior temperature control performance, the residence time and by product.Pressure drop can be very low, makes to have high turnout.And, to compare with conventional system, the use of micro passage reaction can obtain better temperature control, and has kept many relatively isothermal surfaces.Except the process microchannel, can also have other parts, for example microchannel or non-micro channel heat exchanger.Micro channel heat exchanger is more preferably.Heat exchange fluid can flow through adjacent heat exchange microchannel, and heat exchange fluid can and can have steam, liquid metal or other known heat exchange fluid for gas or liquid, and this system can most preferably have phase change in heat exchanger.In some preferred embodiments, a plurality of heat exchange layers and a plurality of reaction channel staggered (for example at least 10 heat exchange layers are staggered with at least 10 process microchannel layers).The microchannel is defined by microchannel wall.

Description of drawings

Fig. 1 is the synoptic diagram of reactor, and wherein this reactor comprises the viewgraph of cross-section of the water-gas shift reactor with micro channel heat exchanger.

Fig. 2 is cross one another micro passage reaction synoptic diagram, and wherein this reactor is and flow structure.

Fig. 3: the methyl alcohol composite diagram that commercial CuZnAl catalyzer is compared with not preferred PdZnAl catalyzer.Synthesis condition is P=1170psig, charging=125sccm, 70%H ₂, 25%CO ₂, 5%Ar.

Fig. 4: under the condition identical, contain the CuZnAl catalyzer and contain the methyl alcohol composite diagram that the PdZnAl catalyzer is compared with Fig. 3.

Fig. 5: reaction pressure is to Rh catalyzer (Rh-Mn-WSiO ₂Catalyzer, GHSV=1700h ^-1, H ₂/ CO=1: 1) the upward influence of CO transformation efficiency and selectivity of product.

Fig. 6: H ₂/ CO ratio is to the influence (Rh-Mn/SiO of transformation efficiency and selectivity of product ₂Catalyzer, P=5.4Mpa, T=280 ℃, GHSV=3750h ^-1).

Fig. 7: RedOx handles influence (CuZnAl and the Rh-Mn/SiO to the mixed catalyst system performance ₂Blending ratio is 1: 2, P=5.4MPa, GHSV=3750h ^-1, T=280 ℃).

Detailed description of the Invention

In catalyst more of the present invention, the Pd-Zn alloy is dispersed on the alumina support. Aluminium oxide is a kind of especially desirable carrier because its low cost, high surface and and Pd/Zn between good interaction. In some preferred embodiments, catalyst contain the 2-10 % by weight Pd (weight that comprises aluminium oxide, wherein Pd/Zn is dispersed on the aluminium oxide, but does not comprise the material below any, for example metal felt or foam), be 5-10wt% in some embodiments. In some preferred embodiments, pure synthetic catalyst has the mol ratio of the Pd of 0.1-0.5: Zn, and more preferably 0.2-0.45 most preferably is 0.25-0.39. It preferably, does not basically have non-alloy Pd, because can reduce the output of alcohol. In some preferred embodiments, prepare the Pd/Zn catalyst by co-precipitation Pd and Zn, these components can be used inorganic or the Organometallic precursor co-precipitation. Before operation, steam reforming catalyst can advantageously carry out activation process, preferably reduces under 350-500 ℃ of temperature. The Pd-Zn catalyst is better than the Pd catalyst, in some embodiments, has crystalline solid ZnO in catalyst. Similarly catalyst is disclosed among the US patent application 200400223908A1, is used for the catalytic alcohol steam reformation.

In some preferred embodiments, Rh and Mn are dispersed on silica, titanium dioxide or the Zirconia carrier. In preferred embodiments, the amount of Rh existence is 1wt%-10wt %, more preferably 4-6%. The amount that Mn exists is 1-6wt%, more preferably 3-4wt%. In some preferred embodiments, catalyst is comprised of Rh, Mn and silica substantially.

Catalyst can be the form of any routine, such as powder, bead, coating etc. Preferably, catalyst is catalyst fixing rather than mobile or fluidisation. In addition, in some preferred structures, catalyst comprises the macropore carrier of bottom. The embodiment of preferred macropore carrier comprises commercial metal foam and preferred metal felt. Before Pd-Zn was deposited to aluminium oxide catalyst, the large aperture carrier had at least 5% porosity, more preferably 30-99%, more preferably 70-98%. Preferably, carrier has 1: m-1000: the average cell size of m (sum of bore dia/hole number), wherein this hole dimension is measured by optics and electronic scanner microscope. The preferred form of porous carrier is foam and felt. Foam is for having the continuous structure of the continuous wall that defines the hole in total. Felt is for to have the fiber of hole between fiber, and comprises snarly silk thread, for example steel wool. Other carrier can be monolithic, for example honeycomb. Equally, catalyst can be arranged on the wall of the passage of microreactor or microchannel (passage with 5mm or smaller szie) sequence. Various carriers and carrier structure are described in the US patent 6680044, pass through reference in conjunction with the document at this. At this also in conjunction with US patent 6488838 (submission on August 17th, 1999).

Catalyst of the present invention can be combined with macropore carrier. Catalyst with macropore carrier preferably has (comprising catalytically-active metals) pore volume of the 5-98% that accounts for total porous material volume, more preferably 30-95 %. Preferably, the material hole volume of at least 20% (preferably at least 50%) is comprised of the hole of 0.1-300 micron-scale (diameter), and more preferably hole dimension is the 0.3-200 micron, more preferably the 1-100 micron. Pore volume and pore size distribution are by mercury void determination instrument (determining the cylindrical geometry body in hole) and nitrogen absorption measurement. Known, mercury void determination instrument and nitrogen are adsorbed as complementary technology, and mercury void determination instrument is more accurate for measuring large hole dimension (greater than 30nm), and nitrogen absorption is more accurate for the aperture of aperture (less than 50nm). 0.1-300 the micron hole dimension can so that molecule under most gas phase catalysis conditions, be distributed in the material.

In order to form ethanol and higher alcohol, the Fisher-Tropsch catalyst can use with pure synthetic catalyst, for example Pd-Zn alloy or conventional Cu/Zn/Al catalyst and Fisher-Tropsch catalyst. Conventional Fischer-Tropsch catalyst is based on following material: iron (Fe), cobalt (Co), nickel (Ni), ruthenium (Ru), rhenium (Re), osmium (Os) and combination thereof; And above any material can use in the present invention. Except these catalyst metals, can also add co-catalyst. Co-catalyst can comprise transition metal and metal oxide, lanthanide series metal or metal oxide and IA family element (except H). Known, Fisher-Tropsch metal and optional co-catalyst can be dispersed in (for example aluminium oxide) on the carrier material and can comprise the carrier (for example metal felt) of bottom.

Some aspect of catalyst is characterised in that the attribute measured of alcohol synthesis reaction. In some preferred embodiments, under by other condition that catalyst is placed on reaction chamber (describing in such as embodiment) and contacts with reaction gas mixtures and in such as embodiment, describe during detecting catalyst, can be by the attribute definition catalyst of measuring, for example, the attribute of any selective determination in about 10% (or about 5%) in an embodiment; Or in a certain scope that shows of a certain at least amount that shows in an embodiment or embodiment or the attribute with stability that shows among the embodiment. For an embodiment, catalyst can be restricted to pure productive rate in the productive rate of about 10% (or about 5%) of describing among the embodiment (when catalyst during for the catalyst measured according to the process of listing in an embodiment). In this case, can think that catalyst is by the attribute " definition " in the lower mensuration of specific condition (phase can draw) from embodiment. The feature of method also characterizes by the value that shows among the embodiment.

In some creationary methods of synthol, contain carbon monoxide (or carbon dioxide or CO and CO₂Mixture) contact with pure synthetic catalyst with the reaction gas mixtures of hydrogen. Can also have for example nitrogen of inert gas. In certain preferred aspects, admixture of gas comprises, in mol% (being equal to dividing potential drop), (CO+CO₂)∶H ₂Ratio be 1: 1.5-1: 4, more preferably 1: 2-1: 3. When reacting gas mainly was comprised of CO and hydrogen, ratio was preferably 1: 1.5-1: 3, and reacting gas is mainly by CO₂When forming with hydrogen, ratio is preferably 1: 2-1: 4. In methyl alcohol is synthetic, in the reacting middle catalyst temperature preferably less than 500EC, 220-450EC more preferably; Being in some embodiments 280 ℃ or higher, is 350 ℃ or higher in some embodiments, and the preferred attribute of measuring did not have to carry out catalytic reaction, more preferably at least 10 days in the situation of significant change (less than about 5%) at least 20 hours. Stable reaction moves under substantially the same productive rate. For methyl alcohol, minimum yield should minimum be 400g/hr/L cat. Same, when Pd-Zn catalyst and FT catalyst mix, temperature is preferably less than 500EC, 280-450EC more preferably, and more preferably 350-400EC, and preferred catalytic stable reaction is moved at least 20 hours, more preferably at least 10 days. For ethanol, minimum yield should be at least 200g/hr/L cat. When pure synthetic catalyst and FT catalyst series connection use, the FT reaction should be carried out under than the high temperature and pressure of the reaction on the pure synthetic catalyst. For the FT district, temperature has the preferred range of above-mentioned ethanol; For the Pd-Zn district, be preferably 280-330EC, and in some embodiments, temperature range is 290-310EC. Pressure is 1Mpa at least preferably, and more preferably 5Mpa at least is 1-30MPa in some embodiments, is 2-15MPa in some embodiments, and is 3-10MPa in some embodiments. Flow velocity (GHSV) by reaction channel is preferably at least 1000hr^-1, more preferably 10000hr at least^-1, be 10000-360000hr in some embodiments^-1, be 25000-100000hr in some embodiments^-1, be 25000-81000hr in some embodiments^-1, be 25000-50000hr in some embodiments^-1 Preferably short time of contact (being defined as the cumulative volume of the reaction chamber that contains catalyst divided by the cumulative volume of the reacting gas under 273K and the 1atm (being assumed to the perfect gas state)) is to minimize reactor volume, and time of contact is preferably less than 0.4s, more preferably 10-140ms. Carbon monoxide conversion ratio (be defined as change between reactant and the product CO molal quantity divided by CO molal quantity in the reactant) or carbon dioxide conversion, usually in above-mentioned scope, measure, be preferably at least 50%, and conversion ratio is 10-80% in some preferred embodiments. Selectively preferably at least 80% of methyl alcohol, more preferably at least 90%.

Synthetic for the ethanol on the catalyst with Rh and Mn, can preferred following scope:

T=240-340 ℃ (being preferably 260-280 ℃);

P=10-100atm (preferred＞50atm);

GHSV＝1000-100000h ^-1(more preferably being at least 2000, is 2000-10000h in some embodiments^-1)；

CO ₂Conversion ratio=20-80% (being 40-50% in some embodiments);

Ethanol selective=20-80% (being 40-60% in some embodiments).

For comprising that the ethanol of conventional Cu/Zn/Al catalyst on catalyst that the FT catalyst is combined is synthetic, can preferred following scope:

T=240-420 ℃ (being preferably 280-370 ℃);

P=10-120atm (preferred＞50atm);

GHSV＝1000-100000h ^-1(preferred 20000-50000h^-1)；

CO ₂Conversion ratio=20-80% (being 40-50% in some embodiments);

Ethanol selective=10-60% (being 20-40% in some embodiments).

The alcohol formation reaction can be carried out in one step or a plurality of step.In one embodiment, this method has first step, and this step is to carry out cryogenic relatively methyl alcohol to synthesize on the Pd-Zn catalyzer; And second step subsequently, the high-temperature step of carrying out on for example based on the catalyzer of Fe at the Fisher-Tropsch catalyzer.Temperature head (based on the medial temperature of each step) can be 20EC at least (or 40EC) at least.This polystep reaction can carry out in a plurality of reactors that separate or have in the single reactor in a plurality of districts and carry out, for example the first relative cryogenic reaction zone and high temperature FT reaction zone subsequently.

In preferred embodiments, the temperature of each step, for example alcohol is synthetic or Fischer-Tropsch is reflected at that isothermal carries out in the microchannel.In preferred embodiments, temperature is changed to 10 ℃ or littler on catalyst length, and more preferably 5 ℃ or littler, more preferably 2 ℃ or littler.

Alcohol or other C of in any the inventive method, making ₂ ⁺Oxygenate can be converted into unsaturated compound, for example passes through dehydration reaction.For example, ethanol can dehydrated formation ethene on aluminium or zeolite (for example ZSM-5), and temperature is preferably 200-300 ℃ (more preferably 260-280 ℃), and pressure is preferably the about 5atm of about 1-, preferred GHSV=1000-100,000h ^-1(preferred 2000-10,000h ^-1), and preferred at least 90% ethanol conversion, and preferred ethylene selectivity is 95% or higher.Another optional method is hydrogenation deoxidation reaction (HDO), wherein H ₂With C ₂₊Oxygenate water generation reaction and unsaturated compound, preferred condition comprise that NiMo or CoMo catalyzer, pressure are 240-330 ℃, GHSV=1000-100000h for about 1-20atm, temperature ^-1, and the preferred alcohol transformation efficiency is at least 90%, and the optimal ethylene selectivity is 95% or higher.In some preferred embodiments, be reflected in the identical microchannel and take place, in the same area of microchannel or successive zone, carry out, in some preferred embodiments without any the step of inserting, as separating step.

As discussing in US patent application 200400223908A1, the Pd-Zn catalyzer can be prepared by a method comprising the following steps: alumina supporter is provided; Add on the solid metal oxide carrier having soluble zinc solution; Add alkaline matter to increase the pH value; In a part that adds the alkali step at least, deposit Pd then.Alumina supporter can self deposit to (before or after other step) on the macropore carrier.This method is especially favourable to the aqueous solution, and wherein metal oxide carrier has acidic surface usually.Dissolved Zn preferably all is dissolved in the solvent to small part.The solution that contains dissolved zinc contains zinc at least, but all right other component of implication comprises metal; In zinc solution, there is not other metal in some preferred embodiments; Solution has the Zn of 0.1-3M in some preferred embodiments.The order of adding joins aluminium in the Zn solution or Zn solution is joined in the aluminium unimportant, and the inventive method comprises any order.Alkali can be able to add before adding zinc solution, in the process or afterwards.Preferably, alkali adds after zinc solution, more preferably slowly adds so that zinc precipitates gradually.Preferably, alkali is ammonia soln.In some preferred embodiments, adding alkali is 7 or higher up to the pH value.When after adding part alkali at least, adding Pd, can be improved.Preferably, Pd all adds the back at alkali to be added, and the Pd of feasible so the highest per-cent deposits on the surface of catalyzer.Pd is preferably depositing to behind the deposition zinc on the catalyzer, in some preferred embodiments, is containing zinc layer drying and optional by calcining back deposition Pd.In some preferred embodiments, Pd is impregnated in solution (preferred aqueous solutions) and contains on the zinc carrier.

Optionally, catalyzer can be by just wet impregnation technology preparation, and this technology is by using the solution impregnation aluminum oxide of Pd and Zn.The material that generates is dried subsequently and is calcined, preferably under 350-450EC.

Catalyzer should be reduced, to form the Pd-Zn alloy.In some preferred embodiments, catalyzer is at H ₂Have reduction down, temperature is 350EC at least, is higher than 400EC in some preferred embodiments, and is 400-500EC in some embodiments.In some preferred embodiments, there is reduction in the preparation catalyzer at hydrogen, and temperature is for being no more than 400EC.Preferably, the calcining of carrying out before or after deposition Pd that contains the Zn catalyzer is carried out under 200-400EC, more preferably 250-350EC.When reduction (with operation) catalyzer, can use identical temperature range.Subzero treatment has increased catalyst life and surface-area.

The present invention also comprises the catalyzer by the preceding method preparation.

An embodiment of reactor 2 shows with cross section in Fig. 1.Reaction chamber 4 contains catalyzer 6 and has inlet 8 and outlet 10.The catalyzer 6 that shows in Fig. 1 is positioned on the top and bottom of reaction chamber, and this chamber of the reactor has the open channels from reactor inlet to outlet: this structure is known as " flowing through " form.Other structure, for example fluid directly passes " passing " form of porous catalyst, also is possible certainly.Heat passage in order to improve, micro channel heat exchanger 12 can contact with reaction chamber.Micro channel heat exchanger 12 has the passage 14 that flows through heat exchange fluid.These passage 14 at least one sizes are less than 1cm, preferably less than 1mm.Distance from passage 14 to catalyzer preferably minimizes, to reduce heat passage distance.Micro channel heat exchanger can be by known technology preparation, for example electrodischarge machining(E.D.M.) (EDM).

The preferred reaction chamber of alcohol synthesis reaction can be any length and height.Preferred reaction chamber has 5mm or littler width, more preferably 2mm or littler, and in some embodiments, the width of reaction chamber is 1mm or littler.Reaction chamber preferably with the heat exchanger chambers heat transfer contact, to remove thermopositive reaction heat.Can be any length or width with the heat exchanger chambers of reaction chamber heat exchange.The length of preferred heat exchanger chambers and the size that width approaches reaction chamber.More preferably heat exchanger chambers and reaction chamber are to intersect the localized mode of chamber adjacent (referring to Fig. 2: the reaction chamber and the heat exchanger chambers of intersecting are piled up) on width, wherein have at least 3 reaction channels and at least 3 hot switching paths alternate (in this embodiment, term passage and chamber can be used alternatingly).The width of heat exchanger chambers is preferably 5mm or littler, more preferably 2mm or littler, and in some embodiments, the width of heat exchanger chambers is 1mm or littler.Flow direction in the heat exchanger chambers can for and stream, adverse current or cross-stream.The mass transfer of micro-channel device short-distance and medium-distance and the feasible superior performance that has of conducting heat.

Reactor can also be designed to reaction chamber and link to each other with heat exchanger chambers, and wherein reaction chamber is made up of a series of microchannels, rather than single microchannel.In this structure, the width of reaction chamber can surpass 5mm, but at least one gravel size decision of the single passage in the series of channel is less than 5mm.Preferred this size is less than 2mm.The width that reaction chamber needs can produce very strong effect to the net heat conduction of catalyzer.The net heat conduction of catalyzer is high more, and the width of catalyzer is big more, and removal heat that still can be very fast.In known references, also have a lot of micro passage reaction designs in the document, and those skilled in the art can select suitable being designed for to carry out alcohol synthesis reaction in micro-channel device.

Embodiment

Based on the normal condition that is used to prepare a plurality of samples following examples are described.Listed the preferred value of specific temperature etc. for carrying out each step.

Use the common dipping method in a step to prepare Al ₂O ₃The Pd-Zn catalyzer of load.Particularly, spissated palladium nitrate solution (20.19wt%Pd is from Engelhard Corp.) and Zn (NO ₃) ₂6H ₂O (99.5%, Aldrich) mix down at 60 ℃.Has 230m ²The neutral Al of/gBET surface-area and 70-100 order particle size ₂O ₃Carrier (Engelhard Corp) 500 ℃ of following precalcinings 2 hours and before first wet impregnation steps 110 ℃ of preservations.Carrier under 60 ℃ by the nitrate solution of the premixed Pd of appropriate amount and Zn dipping, with the final product of obtain having different Pd carrying capacity (being 8.9% among this embodiment) and Pd/Zn mol ratio (being 0.38 among this embodiment).The wetted sample under 110 ℃ air drying keep before evening 60 ℃ 1 hour.The sample that is dried was calcined 3 hours down at 350 ℃ subsequently.

In methyl alcohol is synthetic, Pd/ZnO-Al ₂O ₃Catalyzer is used alone.Yet, at ethanol and C ₂ ⁺In alcohol synthetic, Pd/ZnO-Al ₂O ₃Catalyzer uses with the FeCuAlK catalyzer (Fe: Cu: Al: K=1: 0.03: 2: 0.7) as C-C chain combination catalyzer (F-T catalyzer).Latter's catalyzer is prepared by their corresponding nitrate by co-precipitation.In active testing, above-mentioned two kinds of catalyzer mix by their powder of physical mixed, use the film-making mechanical preparation to be of a size of diameter 10mm and high 2mm subsequently.The small pieces that obtain are pulverized and the scope between the 70-100 order of looking over so as to check.Experimentize in fixed-bed reactor, wherein said reaction bed is 316 stainless steel tube preparations of 4mm by diameter.Reactor is designed to the dirty operator scheme of high pressure.For the methanation reaction in the stainless steel reactor is minimized, be coated in the silicon-dioxide (SiO on the stainless steel tube ₂) use in the high temperature preheating district.All experiments experimentize under the isothermal condition that shows the homogenization temperature distribution along catalyst bed.Catalyzer under 400 ℃ and environmental stress in 10% hydrogen in-situ reducing.After the reduction, N ₂/ H ₂Mixture is fed in start-up course to form steady flow and reactor to be heated to the temperature that needs.When catalytic bed temperature reaches the value that needs, a certain proportion of premixed CO ₂/ H ₂Gas is fed in the reactor.At 260-400 ℃ of temperature, pressure is that 2-8.1MPa and GHSV are 25000-81000h ^-1Under carry out above experiment.Conventional feed component is CO ₂: H ₂=1: 3.For each use fine catalyst, in reactor, load the catalyzer of 0.2g, and measure its volume.Set the gas hourly space velocity (GHSV) of total charging flow velocity needing to obtain, it is by the reaction channel cubing.By online gas chromatographic analysis gaseous product, wherein said gas-chromatography has TCD and fid detector.Under-3 ℃, in prolong, collect product liquid and pass through the GC mass spectrum and the GC analysis.Calculate the transformation efficiency and the selectivity of product of carbonic acid gas based on charging and product flow velocity and carbon balance.

Method for preparing catalyst and the activation that contains the Rh-Mn catalyzer

SiO ₂This SiO is provided by Davison ₂(BET surface-area=the 400m of precalcining in air under 550 ℃ of temperature ²/ g).The rhodium nitrate solution that contains the 10%Rh metal available from Engelhard is used as precursor.Although Rh/SiO ₂Self can promote that synthetic gas is converted into ethanol, but the use of suitable promotor (for example Mn, V etc.) can improve active and alcoholic acid selectivity.Mn (NO ₃) ₂(99%) and NH ₄VO ₃(＞98%) from Aldrich, and is used separately as the precursor of Mn and V.Rh-Mn/SiO ₂Catalyzer is impregnated into SiO by using just wet technology altogether with Rh and Mn precursor ₂Prepare on the carrier.The ultimate density of Rh and Mn is controlled to be the amount of 6wt% and 1.5wt% respectively.Behind the dipping, all catalyzer were all calcined 3 hours in the air under 350 ℃ of temperature.Methanol synthesis catalyst, F51-8PPT (Katalco Corporation) improves by the Cs that uses just wet technology dipping 3%.This catalyzer is as the synthetic catalyst of relative higher alcohols.Catalyzer is tested under the form of powder type and regular monomer type structure.When under powder type, testing, the particulate powders catalyzer before being placed to micro passage reaction by granulating, pulverize and cross and be sieved to the 70-100 order.Purpose is a minimum pressure drop.Regular Rh-Mn/SiO ₂Catalyzer prepares by washcoated technology.The Rh-Mn/SiO of powdered ₂By ball milling 24 hours, wherein water was as medium, afterwards the catalyst slurry behind the ball milling by washcoated to the FeCrAlY metal felt.Sign by SEM shows that the catalyst particle size on the regular catalyst changes between the 0.5-2 micron.Washcoated felt catalyzer (regular catalyst) is loaded in the micro passage reaction after the weight gain that needs, and wherein this reactor has active refrigerating function.

Catalyzer reduces under the helium flow that is containing 10% hydrogen under 220-350 ℃ of temperature range and the barometric point.The specific catalyst treating processes is developed, and catalyzer is handled by reduction-oxidation circulation (RedOx) in this process.In the RedOx treating processes, catalyzer at first under 350 ℃ of temperature by 10% hydrogen reduction 12 hours, cool to room temperature then.Reactor imports the helium that contains 2% oxygen after by nitrogen purging, and temperature of reactor is elevated to 250 ℃ with the temperature rise rate of 1 ℃/min.The time length of oxidation is 2 hours, afterwards reactor cool to room temperature under helium flow.Repeat once above reduction and oxidising process again, and feed gas mixtures import before the catalyzer helium that contained 10% hydrogen finally reduce.

Micro passage reaction and operation

Experiment (316 stainless steel) in the micro passage reaction with 5.08cm * 0.94cm * 0.15cm channel size is carried out.Micro passage reaction is designed to the high pressure downflow mode.The synoptic diagram of reactor assembly and micro passage reaction assembly with in reference paper 12, describe similar.In order to minimize the methanation reaction in the stainless steel reactor, coating silicon dioxide (SiO ₂) stainless steel tube as the high temperature preheating district.Experiment is that 260-300 ℃ of pressure is to carry out under the 2-504Mpa in temperature.All experiments are all carried out under isothermal condition, as shown in being distributed by the uniform temperature along catalyst bed.

N ₂/ H ₂Mixture is charging in start-up course, to set up stable-state flow and reactor to be heated to the temperature that needs.When reaction bed temperature reaches target value, be fed in the reactor with the pre-synthetic gas that needs mixed.Typical feed component is CO: H ₂: CO ₂: Ar=30: 62: 4: 4.The internal standard of purpose is calculated in the existence of Ar as transformation efficiency and selectivity.Set the gas hourly space velocity (GHSV) of total charging flow velocity needing to obtain.Reaction product is analyzed by online gas-chromatography (HP 5890GC), and wherein gas-chromatography has TCD and fid detector.The GC post that uses is GS-Q 30m, is prepared by JW Scientific.For analysis, select temperature to be elevated to 300 ℃ with the speed of 5/min.Under-3 ℃, in prolong, collect product liquid, and by the GC mass spectroscopy.Calculate carbon monoxide transformation efficiency and selectivity of product based on charging and product flow velocity and carbon balance.

Temperature of reaction and pressure are to Rh-Mn/SiO ₂The influence of catalyzer

Temperature of reaction, pressure and feed composition are to Rh-Mn/SiO ₂The influence of catalyst activity is described in table 1 and 2.Primary product is by methane, CO ₂, MeOH, EtOH and C ₂ ⁺Hydrocarbon and oxygenate are formed.In order to study Temperature Influence, reactor is operated under the isothermal pattern.In the catalysis lathe, install by a plurality of thermopairs and regulate furnace temperature with the control catalyst bed tempertaure.The top of the beds of measuring and the temperature head between the bottom have shown the superior heat abstraction ability of micro passage reaction between ± 2 ℃.As shown in table 1, when catalyst temperature when 280 ℃ are increased to 300 ℃, the CO transformation efficiency increases (condition 1 and 2) along with temperature and increases.Yet the methane selection rate is increased to 48.1% from 38.4%, and the alcoholic acid selectivity obviously reduces simultaneously.This shows at Rh-Mn/SiO ₂Alcohol on the catalyzer is synthetic preferably to carry out being lower than under 280 ℃ the temperature.In order to further specify Temperature Influence, under lesser temps and low GHSV condition, experimentize.By the result who is obtained by condition 3 and 4 that shows in the comparison sheet 1 as can be known, cold operation obtains higher ethanol selection rate and lower methane forms.Under Rh catalyzer condition, the formation of methane is very responsive to variation of temperature.

Pressure is to Rh-Mn/SiO ₂The influence of catalyzer is at 300 ℃ of constant temperature and GHSV=3750h ^-1Under study, the results are shown in table 2.When reaction process from condition 1 during to condition 2, wherein pressure is reduced to 3.8Mpa from 5.4, transformation efficiency reduces and selectivity of product remains unchanged substantially.As if this shown when carrying out that mainly by temperature of reaction control rather than pressure, therefore change pressure can not produce any remarkable influence to selectivity of product to selectivity of product under being reflected at 300 ℃ high temperature.In order to further specify the influence of pressure, be reflected under 270 ℃ the low relatively temperature and carry out selectivity of product.Drawn the reaction result figure under differential responses pressure among Fig. 5.In the time of 270 ℃, the CO transformation efficiency raises when rising pressure.The selectivity of total oxygenate also raises, although be not very obvious.Yet, compare with operation under the high temperature, along with reaction pressure raises, the selectivity of methane has downtrending.According to theory of mechanics, high pressure helps CO and enters into metal-(CHx) _AdThe surface is to form C ₂ ⁺Oxygenate has reduced (CH _x) _AdForm the hydrogenation speed of methane.This means that methane selectively can be suppressed when reactor is being lower than under about 270 ℃ temperature operation.In 60 hours operate continuously processes, Rh-Mn/SiO ₂The catalytic activity of catalyzer is highly stable, and can not observe the inactivation of catalyzer.

Table 1, temperature of reaction is to Rh-Mn/SiO ₂The influence of catalyst activity

Condition	1	2	3	4
					Temperature, ℃	280	300	280	265
Pressure, MPa	5.4	5.4	5.4	5.4
					GHSV，h -1	3750	3750	1700	1700
H 2/CO，mol/mol	2	2	2	2
					The CO transformation efficiency	24.6	40.5	38.7	25.1
Selectivity, %
					CO 2	0.0	3.4	1.3	0

CH 4	38.4	48.1	40.2	34.2
					MeOH	3.9	1.9	2.8	2.6
EtOH	56.1	44.5	53.9	61.4
					C 2 +HC and Oxy	1.6	2.1	1.8	1.8

Table 2, reaction pressure and feeding rate are to Rh-Mn/SiO ₂The influence of catalyst performance

Condition	1	2	3	4
					Temperature, ℃	300	300	300	300
Pressure, MPa	5.4	3.8	3.8	3.8
					GHSV，h -1	3750	3750	3750	3750
H 2/CO，mol/mol	2	2	1	3
					The CO transformation efficiency	40.5	32.1	18.7	35.4
Selectivity, %
					CO 2	3.4	2.1	8.5	1.9
CH 4	48.1	48.0	48.3	54.4
					MeOH	1.9	3.2	2.1	1.9
EtOH	44.5	44.4	34.8	40.9
					C 2 +HC and Oxy	2.1	2.3	6.3	0.9

H ₂/ CO ratio is to the influence of selectivity of product

Table 2 shows different H ₂/ CO ratio is to the influence of transformation efficiency and selectivity (condition 3-5).Experiment is respectively at 300 ℃, 3.8MPa and GHSV=3750h ^-1Under carry out.Work as H ₂/ CO is than being reduced to (table 2, condition 2-3) at 1 o'clock from 2, and the CO transformation efficiency sharply descends, and CO ₂Selectivity increases, and means that water gas shift reaction is at lower H ₂It is obvious to become under/CO the ratio.The alcoholic acid selectivity also can reduce and unwanted product C ₂ ⁺Hydrocarbon increases.When condition 3 changes to condition 4, H ₂/ CO ratio is elevated to 3 from 1, and the CO transformation efficiency increases and CO ₂Selectivity is as the reduction of expection.The alcoholic acid selectivity increases a little.Yet the product methane selectively of not expecting also can increase.This shows at Rh-MnZSiO ₂On the catalyzer, high temperature and/or the low voltage operated ethanol that is unfavorable for form.Therefore, in order to use Rh-MnZSiO ₂Catalyst test, ethanol is synthetic to have limited very narrow H ₂/ CO ratio range.Therefore, experiment is still carried out under the cryogenic condition at high pressure.Purpose is to be disclosed in H under the condition that helps ethanol formation ₂/ CO ratio is to the influence of selectivity of product.Fig. 6 has provided CO transformation efficiency, methane selectively, CO ₂Selectivity and specific activity are to H ₂The response of/CO ratio.With H ₂/ CO is than being reduced to the reduction of CO selectivity, CO at 0.6 o'clock from 2 ₂Selectivity raises, and the corresponding reduction of the selectivity of methane.Specific activity is according to the mmol CO meter of per hour every gram catalyzer conversion, along with H ₂The reduction of/CO ratio and increasing.Because GHSV remains unchanged in these experiments, although total CO transformation efficiency therefore descends, still actual efficiency of carbon conversion raises.

The influence of RedOx circular treatment

The process that is used for deactivated catalyst has very strong influence to the RH catalyzer of load.Different treating processess can produce Rh at SiO ₂Different degrees of scatter on the carrier.Dispersity has become some research topics to the Rh activity of such catalysts of load and the influence of product selectivity ^13-14Theme.This research is devoted to illustrate important catalyst reactivation process.One of suitable activating technology is called the redox circulation, and this will be described at experimental section.In industrial treatment, gasoline reforming for example, this process has been applicable to the precious metal of activation load, to obtain very high metal dispersion and stability.

Two kinds of catalyzer Rh-Mn/SiO ₂And Rh-Mn-V/SiO ₂Handle by the RedOx process, its result lists in table 3 and 4.Compare with conventional hydrogen reduction processing, the Rh catalyzer that RedOx handles demonstrates very high initial conversion.In starting stage (TOS was less than 12 hours), the methane selectively of two kinds of catalyzer changes within 1%.Improved total transformation efficiency although RedOx handles, it does not produce favorable influence to the formation of methane.Therefore under steady state operation (TOS=72 hour), for the catalyzer that RedOx handles, the CO transformation efficiency is still high by 4% than conventional processing, and methane selectively has also increased about 2%.

The mixed catalyst system that is made up of Cu base methanol synthetic catalyst and load Rh catalyzer also can handle with RedOx.Using the reason of this mixed catalyst system is to be in following expectation: the carbinol precursor (C that produces on the Cu catalyzer ₁ ⁺Material) thus can promote carbochain growth to generate C ₂The oxygenate intermediate helps alcoholic acid and forms.After RedOx handles, detect the time of the air current flow of mixed catalyst system.The result has been shown among Fig. 3.Surprisingly, after RedOx handled, the CO transformation efficiency increased continuously and just settles out after operation in 200 hours.Simultaneously, CO ₂Selectivity demonstrates uptrend and settles out later at 200 hours air-flows.CO ₂Formation expect that this mainly gives the credit to the catalyst based known aqueous vapor transformation function of Cu.In operating process, methane selectively is reduced to 10% from 20%.Calculate based on absolute value, what the independent load Rh catalyzer of the methyl alcohol selectivity ratios on the mixed catalyst will be low is many.In whole 250 hours operation, the selectivity of different oxygenate (mainly containing methyl alcohol and ethanol) was moderate fully, near constant level: TOS=100 hour.The performance of this catalyzer can be optimized by the ratio of adjusting two kinds of catalyzer.

Add alkali-metal influence

For formation and the promotion alcoholic acid selectivity that suppresses methane, to Rh-Mn/SiO ₂Add potassium in the catalyzer.Know, basic metal promotes the growth of carbochain on Cu is catalyst based.Table 5 has shown that adding Cs in methanol synthesis catalyst has increased C ₂ ⁺The selectivity of alcohol.Yet, do not prove clearly also in the document whether basic metal has promoted C ₂The generation of alcohol on load Rh catalyzer.As shown in table 5, when to Rh-Mn/SiO ₂In when adding 3%K, the CO transformation efficiency reduces.Interpolation K or other alkali-metal negative impact that the CO transformation efficiency is produced are observed at other catalyzer that some are used for the synthetic gas conversion.With primary Rh-Mn/SiO ₂Compare, add K and cause the selectivity of methane obviously to reduce.Though methyl alcohol and alcoholic acid are mixed selectivity owing to the methane selectively reduction increases, and the alcoholic acid selectivity reduces.Net increase be the output of methyl alcohol.As if the existence of K does not promote the growth of carbochain on the catalyzer of load Rh, and these are catalyst based different with Cu.This may be because obviously different with the response path on the Rh based catalyst system at Cu.

The performance of regular catalyst under high-throughput

As mentioned above, preparation is the test regular catalyst also, in order to compare with identical fine catalyst.Regular catalyst is coated in to have on the high heat conducting material, on the promptly thin FeCrAlY metal felt.Regular catalyst has very effective cooling attached on the reaction channel wall on this conduit wall.Use the identical Rh-Mn/SiO of powder type ₂Catalyzer carries out controlled experiment (reference experiment), and operates in the micro passage reaction of identical geometrical dimension.As shown in table 6, in the Run EC-02 that uses regular catalyst to carry out, can be at GHSV=10000h at least ^-1Flow velocity under react, with the identical inversion quantity of the controlled experiment that obtains and under the flow velocity of low 7 times of GHSV, operate (operation ET-32).Because the use of regular catalyst (catalyzer that promptly has the wide aperture carrier) and effective heat abstraction, temperature of reaction and methane selectively be not under high yield " out of control ".

Table 3: the redox circular treatment is to Rh-Mn/SiO ₂Effect on Performance

GHSV＝1700h ^-1，P＝5.4MPa，T＝270℃，H ₂/CO＝2∶1。

Table 4: the redox circular treatment is to Rh-Mn-V/SiO ₂Effect on Performance

GHSV＝1700h ^-1，P＝5.4MPa，T＝270℃，H ₂/CO＝2∶1。

Table 5: the performance of different pure synthetic catalysts relatively

T＝280℃，P＝5.4MPa，GHSV＝3750h ^-1，H ₂/CO＝2∶1。

Catalyst performance relatively

Reaction conditions and performance	Data of the present invention (table 5)	Data in literature *
			GHSV，h -1	3750	180
T，℃	280	200
			P，MPa	5.4MPa	0.1
Catalyzer	Rh-Mn/SiO 2	Rh 2MnO 4/SiO 2
			The CO transformation efficiency, %	24.6	20.2
Selectivity
			CH 4	38.4	42.3
CO 2	0	3.0
			MeOH	3.9	2.0
EtOH and C 2Oxygenate	56.1	20.4
			Other HCs	1.6	32.3

*S.Ishiguro，S.Ito，K.Kunimori，Catalysis Today 45，197-201，1998(Table 1)。

Can see, use micro passage reaction to make us under high yield, to operate, thereby obtain high transformation efficiency and improved selectivity.

Table 6: regular Rh-Mn/SiO ₂Catalyzer compares with the identical performance of powder type catalyzer in micro passage reaction

The operation code name	Run EC-02	Run ET 32
			Catalyst structure	Be coated in the Rh-Mn/SiO on the FeCrAlY felt 2	Powdered Rh-Mn/SiO 2
GHSV，h -1	20000	2700
			Transformation efficiency mol%	20.4	22.7
Selectivity %
			CH 4	36.5	31.1
CO 2	2.3	4.7
			C 2 +HC	3.2	1.7
Pure and mild C 2 +Oxy	58.0	62.4
			Concrete active, the CO/gh that mmol is transformed	46.0	26.8

H2/CO＝1∶1，T＝300℃。

Claims (32)

1, a kind of with CO or CO ₂The method of synthol comprises:

To comprise H ₂With CO or CO ₂Reactive gas mixture current moving contact with catalyzer,

Wherein catalyzer comprises Pd and the Zn that is dispersed on the aluminum oxide; With

Form one or more alcohol.

2, method as claimed in claim 1, wherein one or more alcohol form in forming one or more pure steps of mainly being made up of methyl alcohol.

3, method as claimed in claim 1, wherein catalyzer also comprises the Fisher-Tropsch catalyzer, and one or more alcohol form in steps at one or more alcohol that contain higher alcohols and form, wherein said higher alcohols contains 2 or more carbon atoms.

4, method as claimed in claim 3, wherein one or more alcohol form in forming one or more alcohol formation steps, comprising being mainly the alcoholic acid alcohol mixture.

5, method as claimed in claim 3, wherein catalyzer comprises the Pd-Zn alloy that is dispersed on the aluminium oxide catalyst, and the Fisher-Tropsh catalyzer, described two kinds of catalyst mix are together.

6, method as claimed in claim 3, wherein catalyzer comprises mainly by the first part that is dispersed in the Pd-Zn alloy composition on the aluminium oxide catalyst and comprises the second section of Fisher-Tropsh catalyzer.

7, method as claimed in claim 3 is wherein controlled described flow step, makes duration of contact less than 1 second.

8, method as claimed in claim 7, wherein catalyst arrangement is in the reaction channel with 5mm or littler width, and the temperature variation of striding on the catalyzer is 10 ℃ or littler.

9, method as claimed in claim 6, wherein first part and second section are arranged in the reaction channel with 5mm or littler width.

10, method as claimed in claim 6, wherein reaction gas mixtures with contact with first part before second section contacts.

11, method as claimed in claim 1, wherein catalyzer comprises crystal ZnO.

12, method as claimed in claim 2, wherein reaction gas mixtures comprises CO, and CO and H ₂Reaction forms methyl alcohol.

13, method as claimed in claim 1, wherein reaction gas mixtures comprises CO and CO ₂

14, method as claimed in claim 1, wherein reaction gas mixtures is mainly by CO and H ₂Form.

15, a kind of by CO ₂The method of synthesizing alcohol or higher alcohols comprises:

Make and contain CO ₂And H ₂Reactive gas mixture current moving contact with catalyzer;

Wherein catalyzer comprises: (a) be dispersed in Pd-Zn alloy and (b) Fisher-Tropsh catalyzer on the aluminum oxide; With

Form ethanol or higher alcohols.

16, a kind of method of synthol comprises: in the microchannel hydrogen is contacted on alcohol catalyst with CO;

At least 20% CO is converted into product, and C ₂ ⁺The selectivity of oxygenate is at least 30%.

17,, comprise that the alcoholic acid selectivity is at least 30% as the method for claim 16.

18, as the method for claim 16, catalyst arrangement flowing through in the structure wherein in the microchannel.

19, as the method for claim 16, wherein catalyzer comprises pure synthetic catalyst and Ficher-Tropsch catalyzer.

20, as the method for claim 19, wherein pure synthetic catalyst is in the same place with the Ficher-Tropsch catalyst mix.

21, as the method for claim 19, wherein pure synthetic catalyst and Ficher-Tropsch catalyzer are successively set in the microchannel.

22, as the method for claim 16, wherein catalyzer comprises Rh and the Mn that is arranged on silicon-dioxide, titanium dioxide or the zirconium white.

23, a kind of synthetic C ₂ ⁺The method of oxygenate comprises:

The composition that contains Rh or Pd is carried out RedOx to be handled to form the first step of catalyzer;

Then in step subsequently, under the situation that catalyzer exists with C ₁ ⁺Oxygenate contacts with hydrogen to form C ₂ ⁺Oxygenate;

Wherein RedOx handle reduction under the temperature be included at least 25 ℃ contain Rh or Pd composition first step and

Second step of oxidation under at least 25 ℃ temperature then.

24, as the method for claim 23, wherein there is C under the situation of catalyzer ₁ ⁺The contact procedure of oxygenate and hydrogen is carried out in the microchannel.

25, as the method for claim 24, wherein catalyzer comprises the Rh on silicon-dioxide.

26, a kind of method of synthol comprises:

In the microchannel, hydrogen is contacted on catalyzer with CO;

Reaction by hydrogen and CO forms alcohol; With

Wherein catalyzer comprises Cu, and contact procedure carries out under at least 250 ℃ of temperature, or wherein catalyzer comprises that the Rh and the contact procedure that load on the silicon-dioxide carry out under at least 300 ℃ of temperature.

27, a kind of synthetic C ₂ ⁺The method of oxygenate comprises:

With hydrogen and C ₁ ⁺Oxygenate contacts on the Fisher-Tropsch catalyst film;

By hydrogen and C ₁ ⁺Oxygenate is reacted on the Fisher-Tropsch catalyst film and is formed C ₂ ⁺Oxygenate;

Wherein thickness of thin layer is 100 μ m or littler.

28, as the method for claim 27, wherein thin layer is included in the coating on the microchannel wall.

29, as the method for claim 28, wherein hydrogen is to add in the mode that distributes along microchannel length.

30, as the method for claim 27, wherein thin layer catalyst comprises the coating that is coated on metal felt or the metal foam.

31, a kind of method that forms unsaturated compound comprises:

Method by claim 16 prepares C ₂ ⁺Oxygenate, and with C ₂ ⁺Oxygenate is dewatered or the hydrogenation deoxidation reaction, to form unsaturated compound.

32, as the method for claim 31, C wherein ₂ ⁺Oxygenate is an ethanol, and wherein dehydration or hydrogenation deoxidation are reflected at and form in the same microchannel of alcoholic acid and carry out.

Images