CN104039747B - For producing cobalt and the tin catalyst of ethanol - Google Patents

Abstract

The method that the present invention relates to be formed alcohol by alkanoic acid, the step of the method includes: making at elevated temperatures to contact with the hydrogenation catalyst of the 3 25wt.% active metals being included on carrier with the feed stream of hydrogen containing alkanoic acid, wherein said active metal comprises cobalt and stannum.

Description

For producing cobalt and the tin catalyst of ethanol

Cross-Reference to Related Applications

This application claims the priority of following application: the U.S. of December in 2011 submission on the 29th faces Time application No.61/581,290, and on February 29th, 2012 submit to U.S. Patent application No. The U.S. Patent application No.13/418 that on March 13rd, 13/408,240,2012 submits to, 749； The U.S. Patent application No.13/480,187 submitted to on May 24th, 2012.By quote by Full content and the disclosure of above-mentioned application are expressly incorporated herein.

Invention field

The present invention relates to cobalt and tin catalyst, the method preparing such catalyst, and use The method that alkanoic acid is reduced by such catalyst.In one embodiment, can pass through By acetic acid also original production ethanol in the presence of catalyst containing cobalt and stannum.

Background of invention

For industrial use ethanol according to routine by petrochemical materials such as oil, natural gas or Coal produces, raw material midbody such as synthesis gas produce, or by starchiness material or cellulose Material such as Semen Maydis (corn) or sugarcane production.By petrochemical materials and by cellulosic material The conventional method producing ethanol includes that the acid-catalyzed hydration of ethylene, methanol homologization, direct alcohol close Become and Fiscber-Tropscb synthesis.The unstability of petrochemical materials price promotes the second produced according to routine Alcohol cost fluctuation, make when cost of material raises alcohol production is substituted the needs in source than with Toward bigger.Starchiness material and cellulose material are ethanol by microbe conversion.But, Fermentation is generally used for being suitable for the consumer of the ethanol of fuel or human consumption and produces.Additionally, form sediment The fermentation of opaque or cellulose material and food sources constitute competition and to for industrial use The amount of producible ethanol be applied with restriction.

Extensively ground by the also original production ethanol of alkanoic acid and/or other carbonyl containing compound Study carefully, be referred to the various combinations of catalyst, carrier and operating condition in the literature.EP0175558 The reduction on an metal oxide of various carboxylic acid is had been proposed that with U.S. Patent number 4,398,039. " Carboxylic acids and derivatives " in:Fine of Yokoyama et al. Chemicals Through Heterogeneous Catalysis, provides in 2001,370-379 For converting the summary of some development results of the hydrogenation catalyst of various carboxylic acid.

U.S. Patent number 6,495,730 describe the method for using catalyst to make hydrogenation of carboxylic acids, This catalyst comprises load containing ruthenium and the activated carbon of the active metal substance of stannum.U.S. Patent number 6,204,417 describe for making aliphatic carboxylic acid or acid in the presence of comprising the catalyst of Pt and Re Acid anhydride or its ester or interior ester through hydrogenation thus prepare the other method of fatty alcohol.U.S. Patent number 5,149,680 describe for making carboxylic acid and their anhydride catalytic hydrogenation in the presence of a catalyst For alcohol and/or the method for ester, this catalyst comprises group VIII metal, such as palladium, energy and VIII At least one in the metal that race is metallic alloying, and rhenium metal, tungsten or molybdenum.United States Patent (USP) No. 4,777,303 describe for producing alcohol by making hydrogenation of carboxylic acids in the presence of a catalyst Method, this catalyst comprise the first component for molybdenum or tungsten on high surface area graphite carbon and Second component for VIII noble metal.United States Patent (USP) 4,804,791 describes for urging Producing the other method of alcohol by making hydrogenation of carboxylic acids in the presence of agent, this catalyst comprises VIII noble metal and rhenium.United States Patent (USP) 4,517,391 describes by using main containing cobalt Catalyst method at a pressure exceeding the atmospheric pressure and raise temperature time make acetic acid hydrogenation Thus prepare ethanol.

Existing method is subjected to hinder the various problems of commercial viability, including: (i) catalyst is not There is the necessary choice to ethanol；(ii) catalyst is the most prohibitively expensive and/or life to ethanol Become in non-selective and produce unwanted by-product；(iii) excessive operation temperature and pressure are needed Power, and/or the catalyst life that (iv) is not enough.

Summary of the invention

In the first embodiment, the present invention relates to urge for the hydrogenation that alkanoic acid is reduced to alcohol Agent, the 3-25wt.% active metal that this catalyst is included on carrier, wherein said activity Metal comprises cobalt and stannum.In some embodiments, active metal press 1.2:1-1:1.2 mole Exist than with 5-20wt.%.Carrier also comprises the support modification agent existed with 0.1-50wt.%. This catalyst can comprise the nickel less than 2wt.%, ferrum, ruthenium, rhodium, palladium, osmium, iridium or platinum. This catalyst not cupric and/or zinc.

In this second embodiment, the present invention relates to urge for the hydrogenation that alkanoic acid is reduced to alcohol Agent, cobalt that this catalyst is included on carrier, stannum, and selected from nickel, ferrum, ruthenium, rhodium, The metal of palladium, osmium, iridium and platinum, wherein said metal exists with the amount less than 2wt.%.Substantially First-class mol ratio is 1.2:1-1:1.2.

In the 3rd embodiment, the present invention relates to urge for the hydrogenation that alkanoic acid is reduced to alcohol Agent, the 3-25wt.% active metal that this catalyst is included on carrier, wherein said activity Metal comprises cobalt and the stannum of substantially equimolar ratio.

In the 4th embodiment, the method that the present invention relates to be formed ethanol by acetic acid, the method Including the feed stream made at elevated temperatures containing acetic acid and hydrogen be included on carrier 3-25wt.% active metal hydrogenation catalyst contact, wherein said active metal comprise cobalt and Stannum.In some embodiments, active metal presses the mol ratio of 1.2:1-1:1.2 with 5-20wt.% Exist.Carrier comprises the support modification agent existed with 0.1-50wt.%.Described feed stream can be led to Cross and make oil, coal, natural gas and/or gasification of biomass produce.Acetic acid is big for the selectivity of ethanol In 60%.Carry out ethanol after hydrogenation separating to produce finished product second in one or more towers Alcohol product.

In the 5th embodiment, the method that the present invention relates to be formed ethanol by acetic acid, the method Including the feed stream made at elevated temperatures containing acetic acid and hydrogen be included on carrier The hydrogenation catalyst contact of 3-25wt.% active metal, wherein said active metal comprises substantially The cobalt of equimolar ratio and stannum.

In a sixth embodiment, the method that the present invention relates to be formed ethanol by acetic acid, the method Including the feed stream made at elevated temperatures containing acetic acid and hydrogen be included on carrier Cobalt, stannum, and urge selected from nickel, ferrum, ruthenium, rhodium, palladium, osmium, the hydrogenation of metal of iridium and platinum Agent contacts, and wherein said metal exists with the amount less than 2wt.%.

In the 7th embodiment, the method that the present invention relates to be formed ethanol by mixed feeding, should The step of method includes: make at elevated temperatures feed stream containing mixed feeding and hydrogen with The cobalt of the substantially equimolar ratio of 3-25wt.% or 5-20wt.% being included on carrier and stannum Hydrogenation catalyst contacts, and wherein said mixed feeding comprises 5-40wt.% ethyl acetate and 60-95 Wt.% acetic acid.In some embodiments, hydrogenation catalyst does not comprise other metal.At some In embodiment, mixture flow comprises 30wt.% ethyl acetate and 70wt.% acetic acid.Catalysis Agent can comprise cobalt and the stannum of the substantially equimolar ratio of 20wt.%.Substantially equimolar ratio Cobalt and stannum can be 1.2:1-1:1.2.Carrier material can be existed and carrier by 25-97wt.% Material can be selected from silicon dioxide, silica/alumina, calcium metasilicate (calcium Metasilicate), pyrolytic silicon dioxide, high-purity silicon dioxide, carbon, aluminium oxide and they Mixture.Carrier can also comprise the support modification agent of 0.1-50wt.%.Support modification agent can With selected from (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkali earth metasilicate, (iv) alkali metal silicate, (v) Group IIB metal oxide, (vi) Group IIB metal metasilicate, (vii) IIIB family metal oxide, (viii) IIIB race's metal metasilicates and their mixture. In other embodiments, support modification agent can be calcium metasilicate.In still other embodiment In, support modification agent can be selected from TiO₂、ZrO₂、Nb₂O₅、Ta₂O₅、Al₂O₃、B₂O₃、 P₂O₅、Sb₂O₃、WO₃、MoO₃、Fe₂O₃、Cr₂O₃、V₂O₅、Nb₂O₅、MnO₂、 CuO、Co₂O₃And Bi₂O₃.Described feed stream can produce by making gasification of carbonaceous materials, its Described in carbonaceous material can be oil, coal, natural gas or biomass.Acetic acid is for the choosing of ethanol Selecting property can be more than 60%.Then ethanol can be separated further in one or more towers with Produce finished product ethanol product.

In the 8th embodiment, the present invention relates to the hydrogenation for being formed ethanol by mixture flow Catalyst, this catalyst be included in selected from silicon dioxide, silica/alumina, calcium metasilicate, Pyrolytic silicon dioxide, high-purity silicon dioxide, carbon, aluminium oxide and the carrier of their mixture On the cobalt of substantially equimolar ratio of 3-25wt.% and stannum, wherein said mixed feeding comprises 5-40wt.% acetic acid and 60-95wt.% ethyl acetate.Substantially cobalt and the stannum of equimolar ratio is permissible For 1.2:1-1:1.2.

In the 9th embodiment, the present invention relates to urge for the hydrogenation that alkanoic acid is reduced to alcohol Agent, the active metal of the 3-25wt.% that this catalyst is included on carrier and 0.05-2wt.% Accelerator, wherein said active metal comprises cobalt and stannum, and wherein said accelerator is selected from First metal and noble metal.Noble metal can exist by 0.1-0.7wt.% and active metal is permissible Exist by 5-20wt.%.Active metal can be by substantially equimolar than existing.This catalyst Also comprise carrier and support modification agent.

In the tenth embodiment, the present invention relates to urge for the hydrogenation that alkanoic acid is reduced to alcohol Agent, the active metal of the 3-25wt.% that this catalyst is included on carrier and 0.05-2wt.% The first metal, wherein said active metal comprises cobalt and stannum, and wherein the first metal is selected from Barium, potassium, caesium and combinations thereof.Carrier can comprise support modification agent.When the first metal is During caesium, before dipping active metal, caesium is impregnated on carrier.When the first metal is potassium, After dipping active metal, potassium is impregnated on carrier.

In the 11st embodiment, the present invention relates to the hydrogenation for alkanoic acid being reduced to alcohol Catalyst, the active metal of the 3-25wt.% that this catalyst is included on carrier and 0.05-2 The noble metal of wt.%, wherein said active metal comprises cobalt and stannum, and wherein said noble metal Selected from rhodium, ruthenium, palladium, gold, iridium and combinations thereof.

In the 12nd embodiment, the method that the present invention relates to be formed ethanol by acetic acid, the party Method includes: makes feed stream containing acetic acid and hydrogen at elevated temperatures and is included on carrier 3-25wt.% active metal contact, wherein with the hydrogenation catalyst of 0.05-2wt.% accelerator Described active metal comprises cobalt and stannum, and wherein said accelerator is selected from the first metal and your gold Belong to.First metal can be barium, potassium, caesium or combinations thereof, and noble metal can be with 0.1-0.7 The rhodium of wt.% existence or gold.First metal can be existed by 0.05-0.5wt.%.This catalyst is also Comprise carrier and support modification agent.Acetic acid is more than 60% for the selectivity of ethanol.Then one Ethanol is separated to produce finished product ethanol product by individual or multiple tower further.

In the 13rd embodiment, the method that the present invention relates to be formed ethanol by acetic acid, the party Method includes: makes feed stream containing acetic acid and hydrogen at elevated temperatures and is included on carrier 3-25wt.% active metal contact with the hydrogenation catalyst of 0.05-2wt.% the first metal, its Described in active metal comprise cobalt and stannum, and wherein said first metal is selected from barium, potassium, caesium And combinations thereof.Carrier also comprises support modification agent.When the first metal is caesium, at dipping Before active metal, caesium is impregnated on carrier.When the first metal is potassium, at dipping activity gold After genus, potassium is impregnated on carrier.

In the 14th embodiment, the method that the present invention relates to be formed ethanol by acetic acid, the party Method includes: makes feed stream containing acetic acid and hydrogen at elevated temperatures and is included on carrier 3-25wt.% active metal contact, wherein with the hydrogenation catalyst of 0.05-2wt.% noble metal Described active metal comprises cobalt and stannum, and wherein said noble metal selected from rhodium, ruthenium, palladium, gold, Iridium and combinations thereof.

Detailed Description Of The Invention

Introduction

In general, the present invention relates to for alkanoic acid and/or its ester are reduced, be preferred for by Acetic acid and/or the catalyst of ethyl acetate reduction.The activity gold that this catalyst is included on carrier Belong to.Described active metal comprises cobalt and stannum.Without being bound by theory, in catalyst, the existence of stannum can With the activity promoting catalyst to make acetic acid convert, improve the selectivity for ethanol, and make to urge Agent is stable in longer validity period.Stannum (its represent when being used alone go on business add Hydrogen Energy Power) unexpected and unexpectedly can improve the performance of the catalyst comprising cobalt.Additionally, The combination of cobalt and stannum is unexpected and advantageously produces the low selectivity for methane.Therefore, cobalt It is favourable with the combination of the bimetallic of stannum in by acetic acid production ethanol.

In preferred embodiments, total metal ladings is 3-25wt.%, more preferably 5-20wt.% Or 10-20wt.%.In some embodiments, total metal ladings is 20wt.%.At some In embodiment, cobalt can be existed by the amount of at least 1.5wt%, for example, at least 3wt.%.When When metal ladings is relatively low, acetic acid conversion can be reduced.Cobalt and/or stannum can be deposited as oxide It is on catalyst.In one embodiment, the mol ratio of cobalt and stannum can be 1.9:1-1:1.9, such as 1.5:1-1:1.5 or 1.4:1-1:1.4.In a more preferred embodiment, Mol ratio and the more preferably 1:1 of of substantially equal mol ratio, i.e. 1.2:1-1:1.2 can be had on carrier The cobalt of mol ratio and stannum.

In some embodiments, can have can be other with what cobalt/tin catalyst was applied in combination Active metal.Exemplary other active metal include nickel, ferrum, ruthenium, rhodium, palladium, osmium, Iridium and platinum.In one embodiment, other active metal is platinum.Other active metal In the presence of, preferably exist with the amount of the total metal ladings less than cobalt and stannum.An embodiment party In case, the metal ladings of active metal is less than 2wt.%, e.g., less than 1.75wt.% or is less than 1.5wt.%.For the scope, the metal ladings of active metal is 0.4wt.%-1wt.%, example Such as 0.4wt.%-0.7wt.% or 0.4wt.%-0.6wt.%.In a preferred embodiment, Cobalt/tin catalyst does not contains any copper or zinc.

In some embodiments, the combination of cobalt and stannum can be carried out by the first metal or noble metal Promote.Promoter metals can be by 0.05-2wt.%, such as 0.1-1.5wt.% or 0.2-0.4 Wt.% exists.First metal can be selected from barium, potassium, caesium and combinations thereof.First metal can With by 0.05-2wt.%, such as 0.05-0.5wt.% or 0.1-0.4wt.% exists.Noble metal can With selected from rhodium, ruthenium, palladium, gold, iridium and combinations thereof.In certain preferred embodiments, expensive Metal can be with selected from rhodium and gold.Noble metal can be by 0.05-2wt.%, such as 0.1-0.7wt.% Or 0.1-0.4wt.% exists.

In other embodiments, catalyst comprises the cobalt as active metal and stannum, and not Containing other metal any.Therefore, catalyst can without include ferrum, copper, palladium, rhenium, rhodium and The metal of ruthenium.

Carrier

The catalyst of the present invention can be on any suitable carrier.In one embodiment, Carrier can be inorganic oxide.In one embodiment, carrier can be selected from silicon dioxide, Silica/alumina, calcium metasilicate, pyrolytic silicon dioxide, high-purity silicon dioxide, carbon, Aluminium oxide, titanium dioxide, zirconium oxide, graphite, zeolite and their mixture.At another In embodiment, carrier can be selected from silicon dioxide, silica/alumina, calcium metasilicate, Pyrolytic silicon dioxide, high-purity silicon dioxide, carbon, aluminium oxide and their mixture.Preferably Ground, carrier comprises silicon dioxide.In one embodiment, carrier with 25wt.%-97wt.%, The amount of such as 30wt.%-95wt.% or 35wt.%-80wt.% exists.

Surface area containing silicon carrier such as silicon dioxide is preferably at least about 50m²/ g, for example, at least About 100m²/ g, at least about 150m²/ g, at least about 200m²/ g or most preferably at least about 250 m²/g.For the scope, preferably there is 50-600m containing silicon carrier²/ g, such as 100-500m²/g Or 100-300m²The surface area of/g.As the application uses in the whole text, high surface titanium dioxide Silicon refers to have at least about 250m²The silicon dioxide of the surface area of/g.For the purpose of this specification, Surface area refers to BET Nitrogen surface area, refers to by ASTM D6556-04 (by drawing With being incorporated by herein) surface area that measures.

Further preferably have containing silicon carrier as by pressure hydrargyrum hole measurement method (mercury intrusion Porosimetry) 5-100nm measured, such as 5-30nm, 5-25nm or about 5-10nm Average pore size, and as by pressure hydrargyrum hole measurement method measure 0.5-2.0cm³/ g, such as 0.7-1.5cm³/ g or about 0.8-1.3cm³The average pore sizes of/g.

The form of the carbon monoxide-olefin polymeric of carrier and thus gained can vary widely.At some In exemplary, the form of carrier and/or carbon monoxide-olefin polymeric can be pill, extrusion Thing, ball, the microsphere of spray drying, ring, five spoke wheels (pentaring), trilobal thing, Quatrefoil thing, multi-leaf-shaped thing or thin slice, although pref. cylindrical pill.Preferably, siliceous load It is 0.1-1.0g/cm that body has permission bulk density³, such as 0.2-0.9g/cm³Or 0.3-0.8 g/cm³Form.For size, silica supports preferably has 0.01-1.0cm, example Such as the mean diameter of 0.1-0.7cm or 0.2-0.5cm, mean diameter such as refers to spheroidal particle Diameter or the equivalent spherical diameter of aspherical particle.Because be positioned on carrier or within one Kind or the size of various active metal generally the least, these active metals should the most not shadow Ring the size of overall catalyst granule.Therefore, above-mentioned particle diameter is commonly available to carrier and final The size of catalyst granules.

Preferably silica supports is high from the SS61138 of Saint-Gobain NorPro Surface area (HSA) silica catalyst supports.Saint-Gobain NorPro SS61138 bis- Silicon oxide contains the high surface area silica of about 95 weight %；About 250m²The surface area of/g； The mean pore sizes of about 12nm；The about 1.0cm measured by pressure hydrargyrum hole measurement method³/ g's is average Pore volume and about 0.352g/cm³Bulk density.

Preferably silica/alumina carrier is KA-160 (S ü d Chemie) silicon dioxide Ball, it has the density of the nominal diameter of about 5mm, about 0.562g/ml, about 0.583g H₂O/g The absorbance of carrier, about 160-175m²The surface area of/g and the pore volume of about 0.68ml/g.

Support modification agent

Carrier can also comprise support modification agent.In one embodiment, support modification agent with Based on overall catalyst weight gauge 0.1wt.%-50wt.%, such as 0.2wt.%-25wt.%, 0.5 The gross weight of wt.%-15wt.% or 1wt.%-8wt.% exists.

Support modification agent can regulate the acidity of carrier material.Such as, the sour position on carrier is such asAcid position can be adjusted being conducive to during acetic acid hydrogenation by support modification agent Selectivity to ethanol.The acidity of carrier can be by reducing on carrier materialAcid position Quantity or reduce on this carrierThe availability of acid position is adjusted.Carrier is also Can be adjusted by the pKa making support modification agent change carrier.Unless context is additionally Indicating, surface acidity thereon or number of acid sites can be edited by F.Delannay, “Characterization of Heterogeneous Catalysts”；Chapter III:Measurement of Acidity of Surfaces, 370-404 page；Marcel Dekker, Inc., the technology described in N.Y.1984 is measured, and is incorporated by this by quoting Literary composition.Especially, use regulation support acidity so that carrier has less acid or bigger alkalescence Modified support, is more beneficial for the formation of ethanol compared with other hydrogenation products.

In some embodiments, support modification agent can be that the acidity improving catalyst acidity changes Property agent.Suitably acid modification agent can be selected from the oxide of Group IVB metal, VB race metal Oxide, the oxide of group vib metal, the oxide of VIIB race metal, VIII gold Oxide, aluminum oxide and their mixture belonged to.Acid carrier modifying agent includes being selected from TiO₂、ZrO₂、Nb₂O₅、Ta₂O₅、Al₂O₃、B₂O₃、P₂O₅And Sb₂O₃Those. Preferably acid carrier modifying agent includes selected from TiO₂、ZrO₂、Nb₂O₅、Ta₂O₅And Al₂O₃ Those.Acid modification agent can also include selected from WO₃、MoO₃、Fe₂O₃、Cr₂O₃、 V₂O₅、Nb₂O₅、MnO₂、CuO、Co₂O₃And Bi₂O₃Those.

In another embodiment, support modification agent can be to have low volatility or non-volatile The basic modifier of property.This kind of basic modifier such as can be selected from: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkali earth metasilicate, (iv) alkali metal silicate, (v) IIB Family metal oxide, (vi) Group IIB metal metasilicate, (vii) IIIB family metal oxide, (viii) IIIB race metal metasilicates and their mixture.Outside deoxygenation compound and metasilicate, Can use including nitrate, nitrite, acetate and lactate is other type of Modifying agent.Preferably, support modification agent is appointed in sodium, potassium, magnesium, calcium, scandium, yttrium and zinc The oxide of meaning element and metasilicate, and aforesaid any mixture.It is highly preferred that alkali Property support modification agent is calcium silicates, more preferably calcium metasilicate (CaSiO₃).Calcium metasilicate can be in Crystallization or amorphous.

In a preferred embodiment, catalyst comprises 0.25-1.25wt.% platinum and 0.25-3 Wt.% stannum.These preferred active metals are on silica supports.Preferably, titanium dioxide Silicon carrier also comprises support modification agent such as CaSiO₃.In some embodiments, can have Basic modifier and acid modification agent.WO₃And CaSiO₃All can be used in silicon dioxide or two On silicaalumina carrier material.

The method preparing catalyst

The invention still further relates to the method for preparing this catalyst.Optionally, it is also possible to by one Or variety carrier modifying agent by mixing or joins on carrier via dipping.Modification can be carried The dusty material of body or its precursor carries out pelletize, crushes, sieves and join on carrier.Can So that solvent is preferably used, such as water, glacial acetic acid, strong acid example hydrochloric acid, nitric acid or sulphuric acid, or Organic solvent.Gained mixture can be stirred and use the profit dipping technique that such as begins to add it to In other carrier, described beginning, the precursor of support modification agent is joined hole by profit dipping technique In the carrier material that volume is identical with the volume of solution.Then capillarity is by support modification agent Precursor suck in the hole in carrier.Then can by be dried the water removed in carrier solution and Any volatile component also makes stannum be deposited on carrier to form the load containing support modification agent precursor Body.Being dried can be such as at 50 DEG C-300 DEG C, such as 100 DEG C-200 DEG C or the temperature of about 120 DEG C Under carry out optional 1-24 hour, such as 3-15 hour or the period of 6-12 hour.

Once being formed, modified support can be shaped to the granule with required size distribution, such as Forming mean diameter is the granule of 0.2-0.4cm.Can carry out carrier extruding, pelletize, pressure Sheet, suppress, crush or sieve into required size be distributed.Can use and carrier is shaped to required chi Any known method of very little distribution.

In the method for optimizing preparing catalyst, cobalt and stannum is made to be impregnated on carrier.Active metal Precursor be preferred for metal impregnation step, described precursor such as includes the water about the first metal Soluble compound or water-dispersible compound/complex.Depend on used metal precursor, Such as water, glacial acetic acid or the solvent of organic solvent can be preferably used.Second active metal precursor.In It is also preferred that be impregnated in carrier by the second metal precursor.

By by the first metal precursor and/or the second metal precursor and/or additionally metal precursor (excellent Be selected in suspension or solution) in any one or two kinds of add (optionally dropping) to dry load Body impregnates.Then gained mixture can be heated such as optionally under vacuo to remove Solvent.Then can optionally along with the heating of oblique line ascending manner carry out other be dried and calcining thus Form final carbon monoxide-olefin polymeric.When heating and/or applying vacuum, the metal of metal precursor is excellent Choosing is decomposed into their simple substance (or oxide) form.In some cases, throw at catalyst Enter before using and calcine the high temperature such as standing to meet with during operation, liquid can not be completed The removal of carrier such as water.During calcining step, or at least using the initial of catalyst During stage, these compounds are made to be converted into catalysis activity form or its catalysis active oxygen of metal Compound.

Being immersed on carrier by active metal can simultaneously (co-impregnation) or in succession carry out.Same Time dipping time, active metal precursor.In mixed and it joined in carrier together, connecing And be dried and calcine to form final carbon monoxide-olefin polymeric.For impregnating simultaneously, if institute State two kinds of precursors incompatible with desired solvent such as water, then be desirable to dispersant, Surfactant or solubilizing agent such as ammonium oxalate is to promote dividing of described first and second metal precursors Dissipate or dissolve.

When serial impregnation, first the first active metal precursor.In is joined in carrier, then enter Row is dried and calcining, then with the second active metal precursor.In dipping resulting materials, then carries out another Outer is dried with calcining step to form final carbon monoxide-olefin polymeric.

Suitably metal precursor include such as metal halide, amine solubilising metal hydroxides, Metal nitrate or metal oxalate.Such as, the suitable compound of stannum precursor and cobalt precursors includes Potassium stannate, sodium stannate, butter of tin, stannous chloride, nitric acid stannous, stannous oxalate and six water Close cobalt nitrate.The suitable compound of the first metal and noble metal precursor includes but not limited to nitrosyl Base nitric acid ruthenium (III), Palladous nitrate. (II), nitric acid gold (III), dehydration rhodium nitrate (III), cesium nitrate, Potassium nitrate and barium nitrate.Generally, the viewpoint in terms of economics and environment simultaneously from the point of view of, preferably The aqueous solution of soluble compound.Precursor particularly preferred for stannum is stannous oxalate, i.e. SnC₄H₄O₆·xH₂O.Precursor particularly preferred for cobalt is cabaltous nitrate hexahydrate, i.e. Co(NO₃)₂·6H₂O.Being calcined together with carrier and active metal by solution can be such as at 250 DEG C -800 DEG C, such as carry out at a temperature of 300-700 DEG C or 350 DEG C-500 DEG C optional 1-12 hour, Such as 2-10 hour, 4-8 hour or the period of about 6 hours.

On the one hand, first stannum precursor is joined on carrier, be followed by cobalt metal precursor.When It can also be so contrary addition sequence.As it appears from the above, in sequent embodiment, preferably Followed by it is dried in each impregnation steps and calcines.To produce the purest second wherein In those situations of alcohol, it is usually preferred to use based on nitrogenous amine and/or the precursor of nitrate.

When promoter metals includes in the catalyst, dipping continuously can be used to add accelerator Metal or promoter metals precursor, to add promoter metals for starting, be followed by relating to cobalt and Second impregnation steps of the co-impregnation of stannum.The exemplary precursors of promoter metals includes metal halide Metal hydroxides, metal nitrate or the metal oxalate of thing, amine solubilising.

The Co-Sn catalyst that barium promotes

In one embodiment, accelerator is barium.The carrier of cobalt-tin catalyst that barium promotes is excellent Choosing comprises support modification agent.Especially, support modification agent is selected from following basic modifier: (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkali earth metasilicate, (iv) alkali Metal metasilicates, (v) Group IIB metal oxide, (vi) Group IIB metal metasilicate, (vii) IIIB Family metal oxide, (viii) IIIB race metal metasilicates and their mixture.Most preferably, Calcium metasilicate is the basic supports modifying agent of the cobalt-tin catalyst promoted for barium.Support modification agent It is used together with barium and can improve acetic acid conversion and/or ethanol selectivity.

The Co-Sn catalyst that caesium promotes

In some embodiments, caesium accelerator can be immersed on carrier before active metal. This impregnation sequence can improve the alcohol choosing of the cobalt-tin catalyst of alkanoic acid conversion ratio and/or caesium promotion Selecting property.

The Co-Sn catalyst that potassium promotes

In some embodiments, potassium accelerator can be immersed on carrier after active metal. This impregnation sequence can improve the alcohol choosing of the cobalt-tin catalyst of alkanoic acid conversion ratio and/or potassium promotion Selecting property.

Catalyst makes the purposes of acetic acid hydrogenation

One advantage of catalyst of the present invention is that this catalyst is for producing stability or the work of ethanol Property.Therefore, it can be appreciated that, the catalyst of the present invention is fully able to for acetic acid hydrogenation Commercial size commercial Application, particularly alcohol production.Especially, it is possible to obtain such stable Property degree, the catalyst that this extent of stability makes catalyst activity can have every 100 hours makes With less than 6%, within the most every 100 hours, it is less than 3% or every 100 hour productivity less than 1.5% Fall off rate.Preferably, once catalyst realizes lower state, just measures yield decline rates.

In one embodiment, have by the presence of a catalyst by alkanoic acid and/or its Ester, and the method for more preferably acetic acid and/or ethyl acetate also original production ethanol.Some embodiment party In case, raw material comprises acetic acid.In other embodiments, raw material be mixing raw material and can To comprise acetic acid in addition to the hydrogen and ethyl acetate.Raw material can comprise 5-40wt.% acetic acid second Ester and 60-95wt.% acetic acid, such as 5-30wt.% ethyl acetate and 70-95wt.% acetic acid. In some embodiments, raw material comprises 30wt.% ethyl acetate and 70wt.% acetic acid.Institute Stating hydrogenation reaction can be by being expressed as:

HOAc+2H₂→EtOH+H₂O

What relevant the inventive method was used is fed to the raw material of primary reactor, acetic acid, acetic acid Ethyl ester and hydrogen can be derived from any suitable sources, including natural gas, oil, coal, life Material etc..As an example, methanol carbonyl, oxidation of acetaldehyde, ethane oxidation, oxygen can be passed through Change fermentation and production of acetic acid by anaerobic fermentation.The methanol carbonylation process being suitable for acetic acid production describes In United States Patent (USP) No.7,208,624,7,115,772,7,005,541,6,657,078,6,627,770, 6,143,930,5,599,976,5,144,068,5,026,908,5,001,259 and 4,994,608 In, their complete disclosure is incorporated herein by.It is optionally possible to ethanol is raw Produce and integrate with this methanol carbonylation process.

Due to oil and natural gas price fluctuation, more or less become expensive, so by substituting carbon Source produces the method for acetic acid and intermediate such as methanol and carbon monoxide and the most gradually causes concern.Special Not, when oil is relatively costly, by derived from more can carbon source forming gas (" close Become gas ") produce acetic acid may become favourable.Such as, United States Patent (USP) No.6,232,352 (pass through Quote and be incorporated by herein) teach transformation methanol device in order to the method manufacturing acetic acid. By transformation methanol device, for new acetic acid device, the substantial contribution relevant with CO generation Expense is significantly reduced or eliminates to a great extent.Make all or part synthesis gas from methanol Synthesis loop carries out shunting and be supplied to separator unit to reclaim CO, then uses it for giving birth to Produce acetic acid.In a similar manner, the hydrogen for hydrogenation step can be supplied by synthesis gas.

In some embodiments, the some or all of raw materials for above-mentioned acetic acid hydrogenation method can With partly or entirely derived from synthesis gas.Such as, acetic acid can be formed by methanol and carbon monoxide, Methanol and carbon monoxide all can be derived from synthesis gas.Synthesis gas can pass through partial oxidative steam reforming Or steam reformation is formed, and carbon monoxide can be isolated from synthesis gas.Similarly, may be used So that the hydrogen being used for acetic acid hydrogenation formation crude ethanol product step is isolated from synthesis gas.And then, Synthesis gas can be derived from several kinds of carbon source.Carbon source such as can be selected from natural gas, oil, oil, Coal, biomass and combinations thereof.Synthesis gas or hydrogen can also derive from biologically-derived methane Gas, the biology such as produced by refuse landfill refuse (landfill waste) or agricultural wastes spreads out Raw methane gas.

In another embodiment, the acetic acid for hydrogenation step can be by biomass ferment shape Become.Fermentation process is preferably by producing acetic acid (acetogenic) method or the microorganism of homoacetogenesis Carbohydrate fermentation is made to obtain acetic acid and produce seldom (if any) carbon dioxide as by-product. Compared with the conventional yeasts method being generally of about 67% carbon efficiencies, the carbon efficiencies of described fermentation process Preferably greater than 70%, more than 80% or more than 90%.Optionally, sweat uses Microorganism is selected from following genus: fusobacterium (Clostridium), Lactobacillus (Lactobacillus), Moore Bordetella (Moorella), hot anaerobic bacillus(cillus anaerobicus) belong to (Thermoanaerobacter), propionibacterium (Propionibacterium), propanoic acid Spirillum (Propionispera), Anaerobiospirillum (Anaerobiospirillum) and Bacteroides (Bacteriodes), it is especially selected from following material: formic acid clostridium aceticum (Clostridium Formicoaceticum), Clostridium butyricum (Clostridium butyricum), hot vinegar Moore Salmonella (Moorella thermoacetica), Kai Wure anaerobe (Thermoanaerobacter kivui), Deshi Lactobacillus (Lactobacillus delbrukii), product propionibacterium acide-propionici (Propionibacterium acidipropionici), tree propanoic acid spirillum (Propionispera of dwelling Arboris), Anaerobiospirillum succinoproducens (Anaerobiospirillum succinicproducens), Bacteroides amylophilus (Bacteriodes amylophilus) and bacteroides ruminicola (Bacteriodes ruminicola).Optionally, in this process, can by all or part of come authigenic material The gasification of non-fermentation residues such as lignan can be used for the hydrogen of hydrogenation step of the present invention to be formed Gas.It is disclosed in United States Patent (USP) No.6,509,180 for forming the exemplary fermentation process of acetic acid； 6,927,048；7,074,603；7,507,562；7,351,559；7,601,865；7,682,812； With 7, in 888,082, they are incorporated by herein by quoting.No. is announced referring further to the U.S. 2008/0193989 and 2009/0281354, they are incorporated by herein by quoting.

The example of biomass includes but not limited to agricultural wastes, forestry products, grass and other fibre Dimension cellulosic material, harvesting of wood residue, soft wood fragment, hardwood fragment, branch, tree root, Leaf, bark, sawdust, defective paper pulp, Semen Maydis (corn), corn straw, Wheat Straw, Rice straw, bagasse, switch grass, Miscanthus, animal wastes, municipal garbage, municipal sludge (municipal Sewage), commercial waste, grape skin, almond shell, Semen Caryae Cathayensis shell, coconut husk, coffee grounds, Grass grain, Radix Glycyrrhizae grain, wood substance grain, cardboard, paper, plastics and cloth.See for example United States Patent (USP) No.7,884,253, it is incorporated by herein by quoting.Another kind of biomass sources is black liquor, The thickest dark liquid, its for convert wood into paper pulp, then by pulp dryer to manufacture paper The by-product of Kraft method.Black liquor is lignin residue, hemicellulose and inorganic chemistry The aqueous solution of material.

United States Patent (USP) No.RE35,377 (being incorporated into herein also by quoting) provides one Plant by making carbonaceous material such as oil, coal, natural gas and conversion of biomass material produce methanol Method.The method includes making solid and/or liquid carbon-containing material hydrogasification to obtain process gas Body, with other natural gas by this process gas steam pyrolysis to form synthesis gas.By this synthesis Gas is converted into the methanol that can turn to acetic acid with carbonyl.The method produces as above-mentioned equally about this Bright spendable hydrogen.United States Patent (USP) No.5,821,111 discloses one and useless biomass is led to Crossing the method that gasification is converted into synthesis gas, and United States Patent (USP) No.6,685,754 disclose production Hydrogen-containing gas composition such as comprises the method for the synthesis gas of hydrogen and carbon monoxide, by quoting They are incorporated by herein.

Be fed to the acetic acid of hydrogenation reactor and can also comprise other carboxylic acid and anhydride, and aldehyde and/ Or ketone such as acetaldehyde and acetone.Preferably, suitable acetic acid feed stream comprises one or more choosings From acetic acid, acetic anhydride, acetaldehyde, ethyl acetate and the compound of their mixture.At this These other compounds can also be hydrogenated with by bright method.In some embodiments, third In alcohol production, the existence of carboxylic acid such as propanoic acid or its anhydride can be useful.Acetic acid feed also may be used There is water.

Or, can be directly from United States Patent (USP) No.6,657,078 (by quoting by it the most also Enter herein) described in the flash vessel of a class methanol carbonylation unit take out the second of vaporous form Acid is as crude product.For example, it is possible to by thick vapor product directly to enter hydrogenation reactor and not Need condense acetic acid and light fraction or remove water, thus save overall craft expense.

Acetic acid can be made to gasify at the reaction temperatures, then can be by the acetic acid of gasification in company with the dilutest Release state or dilute with the carrier gas of relative inertness such as nitrogen, argon, helium, carbon dioxide etc. Hydrogen feed together.For making reaction run in the gas phase, the temperature in control system is answered to make It does not drop below the dew point of acetic acid.In one embodiment, can be at a particular pressure Make acetic acid gasify at acetic acid boiling point, then the acetic acid of gasification can be further heated to reactor Inlet temperature.In another embodiment, acetic acid is mixed with other gas before gasification, Then mixed vapour is always heated to reactor inlet temperature.Preferably, by make hydrogen and/ Or circulating air passes the acetic acid at a temperature of at or below 125 DEG C and makes acetic acid be changed into steam State, is then heated to reactor inlet temperature by the gaseous stream of merging.

Reactor can include using fixed bed reactors or fluid bed anti-in some embodiments Answer the various structures of device.In many embodiments of the present invention, it is possible to use " adiabatic " reacts Device；That is, have to come with little or no the internal pipe arrangements (plumbing) needed through reaction zone Add or remove heat.In other embodiments, it is possible to use a reactor of Radial Flow Or multiple reactor is as reactor, or can use with or without heat exchange, chilling Or introduce the series reactor of additionally charging.Or, it is possible to use it is equipped with heat transmission medium Shell-tube type reactor.In many cases, during reaction zone can be contained in single container or between Have in the series containers of heat exchanger.

In preferred embodiments, catalyst is anti-in the fixed bed of such as pipeline or catheter shape Answering in device and use, the most typically the reactant of vaporous form is across or through described catalyst. Other reactor, such as fluid bed or fluidized bed reactor can be used.In some cases, add Hydrogen catalyst can be used in combination with inert material to regulate reactant streams by catalyst bed The time of contact of pressure drop and reactant compound and catalyst granules.

Hydrogenation in reactor can be carried out in liquid phase or gas phase.Preferably, in the gas phase in This reaction is carried out under the conditions of Ru Xia.Reaction temperature can be 125 DEG C-350 DEG C, such as 200 DEG C-325 DEG C, 225 DEG C-300 DEG C or 250 DEG C-300 DEG C.Pressure can be 10 kPa-3000 KPa, such as 50kPa-2300kPa, 100kPa-2100kPa or 200kPa-2100kPa. Can be by reactant with more than 500hr^-1, it is greater than 1000hr^-1, more than 2500hr^-1Or Even greater than 5000hr^-1Gas hourly space velocity (GHSV) be fed to reactor.For the scope, GHSV can be 50hr^-1-50,000hr^-1, such as 500hr^-1-30,000hr^-1、1000 hr^-1-10,000hr^-1Or 1000hr^-1-6500hr^-1。

Optionally just be enough to overcome under the pressure of the pressure drop of catalytic bed with selected GHSV is hydrogenated with, although being not intended to use higher pressure, it should be appreciated that at high sky Speed such as 5000hr^-1Or 6,500hr^-1The lower possible experience sizable pressure by reactor beds Fall.

Although the every mole of acetic acid of this reaction consumes 2 mol of hydrogen thus produce 1 moles ethanol, but In feed stream, hydrogen can be about 100:1-1:100, such as with the actual mol ratio of acetic acid 50:1-1:50,20:1-1:2 or 18:1-8:1.Most preferably, hydrogen is more than with the mol ratio of acetic acid 2:1, is greater than 4:1 or more than 8:1.Generally, reactor can use excess when necessary Hydrogen, and secondary hydrogenation reactor can use the hydrogen of q.s to be hydrogenated with by impurity.? On the one hand, a part for the excess hydrogen of autoreactor guides the secondary reaction for hydrogenation in the future Device.In some optional embodiments, secondary reactor can be higher compared with hydrogenation reactor Pressure under operation and can will comprise the high pressure gas stream of hydrogen in adiabatic pressure reduction vessel Separate with secondary reactor product liquid, and gas streams can be guided hydrogenation reactor system.

Contact or the time of staying can also vary widely, and these depend on the amount such as acetic acid, urge Agent, reactor, the variable of temperature and pressure.When using the antigravity system in addition to fixed bed Time, typical time of contact be part the second to more than some hours, anti-at least for gas phase Should, preferred time of contact is the 0.1-100 second, such as 0.3-80 second or 0.4-30 second.

Especially, the hydrogenation of acetic acid can obtain the advantageous conversion rate of acetic acid and favourable to ethanol Selectivity and productivity.For the present invention, term " conversion ratio " is separately converted in referring to charging The amount of the acetic acid of compound in addition to acetic acid.Conversion ratio is with based on acetic acid or acetic acid in charging The percent of ethyl ester meter represents.The conversion ratio of acetic acid or ethyl acetate can be at least 10%, example Such as at least 20%, at least 40%, at least 50%, at least 60%, at least 70% or at least 80%. The conversion ratio of ethyl acetate (ethyl acetate acid) is preferably greater than 0%, it means that consume Ethyl acetate more than produce ethyl acetate.During acetic acid hydrogenation, acetic acid second can be produced Ester.Do not having in the case of mixing vapor-phase reactant consumes any ethyl acetate, ethyl acetate Conversion ratio can be negative.But, for the present invention, consume enough ethyl acetate with At least offset produced ethyl acetate.It is therefore preferred that the conversion ratio of ethyl acetate is permissible It is at least 0%, for example, at least 5%, at least 10%, at least 20% or at least 35%.Although Expect to have the high conversion of at least 80% or at least 90%, the catalysis of particularly acetic acid conversion Agent, but acetic acid low when the selectivity height of ethanol in some embodiments or ethyl acetate Conversion ratio can also accept.Certainly, should fully understand, in many cases, can be by suitably Recycle stream or use bigger reactor to make up low acetate conversion ratio, but more difficult In making up poor selectivity.

Selectivity is represented by mole percent based on the acetic acid converted and/or ethyl acetate.Ying Li Every kind of compound that solution is converted by acetic acid and/or ethyl acetate has independent selectivity and is somebody's turn to do Selectivity does not relies on conversion ratio.Such as, if the 60 of the acetic acid converted moles of % are converted into Ethanol, then ethanol selectivity is 60%.Preferably, the selectivity that ethanol is had by catalyst It is at least 50%, for example, at least 60% or at least 70%.Preferably, the selectivity of ethanol can Being high and at least 75%, for example, at least 80% or at least 85%.This hydrogenation process Preferred embodiment also have less desirable product such as methane, ethane and carbon dioxide Low selectivity.The selectivity of these less desirable products is preferably smaller than 4%, e.g., less than 2% Or less than 1%.It is highly preferred that these less desirable products exist with the amount that can't detect.Alkane The formation of hydrocarbon can be low, it is desirable that the acetic acid through catalyst is less than 2%, less than 1% Or it being converted into alkane less than 0.5%, this alkane has the least value in addition to being a fuel.At some In embodiment, catalyst has based on acetic acid and ethyl acetate for the overall selectivity of alcohol meter. Overall selectivity can be at least 60%, for example, at least 70%, at least 80%, at least 85% or At least 88%.

As used herein, the term " productivity " refer to hydrogenation during based on used catalyst thousand Gram grams of regulation product such as ethanol that meter is formed per hour.Preferably productivity is every kilogram Catalyst at least 100 grams of ethanol per hour, such as every kg catalyst at least 400 grams per hour Ethanol or every kg catalyst at least 600 grams of ethanol per hour.For the scope, described productivity It is preferably every kg catalyst 100-3 per hour, 000 gram of ethanol, such as 400-2,500 grams of ethanol Every kg catalyst per hour or the 600-2,000 gram of every kg catalyst of ethanol per hour.

In the various embodiments of the present invention, reactor the crude ethanol product produced, in office Before what is with post processing such as purification and separation, unreacted acetic acid, ethanol will be typically comprised And water.Provide the exemplary compositing range of crude ethanol product in Table 1.Table 1 is determined " other " such as ester, ether, aldehyde, ketone, alkane and carbon dioxide can be included.

In one embodiment, crude ethanol product can comprise less than 20wt.%, the least In 15wt.%, less than 10wt.% or the acetic acid of the amount less than 5wt.%.For the scope, The acetic acid concentration of table 1 can comprise 0.1wt.%-20wt.%, such as 0.2wt.%-15wt.%, 0.5-10wt.% or 1wt.%-5wt.%.In the embodiment with relatively low acetate amount, second The conversion ratio of acid is preferably greater than 75%, is greater than 85% or more than 90%.Additionally, ethanol Selectivity is preferably also high, more than 75%, is greater than 85% or more than 90%.

Can use some different technology from use catalyst of the present invention time reactor produce thick Ethanol product reclaims ethanol product.

Alcohol product can be technical grade ethanol, comprises based on this alcohol product gross weight meter 75-96 Weight % ethanol, such as 80-96 weight % or 85-96 weight % ethanol.Some embodiment party In case, when using water to separate further, ethanol product preferably comprises more than 97wt.%, example Such as larger than 98wt.% or the ethanol of the amount more than 99.5wt.%.Preferred at this aspect alcohol product Comprise less than 3wt.%, e.g., less than 2wt.% or the water less than 0.5wt.%.

The finished product ethanol composition produced by embodiment of the present invention may be used for various application, bag Include fuel, solvent, chemical raw material, drug products, cleaning agent, disinfectant, hydrogen conversion Or consumption.In fuel applications, this finished product ethanol composition and gasoline concoction can be made for machine Motor-car such as automobile, ship and small-sized piston engine aircraft.In on-fuel is applied, should Finished product ethanol composition can serve as cosmetics and cosmetic formulations, detersive, disinfectant, painting Material, ink and the solvent of medicine.This finished product ethanol composition can also be at medicinal product, food With dealing with solvent in the manufacture process that preparation, dyestuff, photochemistry and latex process.

This finished product ethanol composition is also used as chemical raw material to prepare other chemicals such as Vinegar, ethyl acrylate, ethyl acetate, ethylene, glycol ethers, ethamine, ethylbenzene, aldehyde, fourth two Alkene and higher alcohol, particularly butanol.In the preparation of ethyl acetate, can be by this finished product ethanol Compositions acid esterification.In another is applied, this finished product ethanol composition can be made to be dehydrated To produce ethylene.Any of dehydration catalyst, such as zeolite catalyst or phosphorus tungsten can be used Acid catalyst, makes ethanol dehydration, and described dehydration catalyst is such as at the open No. of copending United States 2010/0030002, those described in 2010/0030001 and WO2010146332, Their full content and disclosure are expressly incorporated herein by this by quoting.Such as, zeolite catalysis Agent can serve as dehydration catalyst.Preferably, described zeolite has the aperture of at least about 0.6nm, Preferably zeolite includes the catalytic dehydration selected from modenite, ZSM-5, X zeolite and zeolite Y Agent.Such as X zeolite is described in United States Patent (USP) No.2, and in 882,244, zeolite Y is described in U.S. State's patent No.3, in 130,007, passes through at this to quote they to be incorporated by herein.

Following examples set forth the behaviour for preparing the various catalyst used in the inventive method Make.

Embodiment

Embodiment A

50mol.% cobalt and the preparation of 50mol.% stannum on silicon dioxide

By the silicon dioxide of even particle size distribution at 120 DEG C in baking oven in a nitrogen atmosphere (1.0g) it is dried overnight, and is then cooled to room temperature to form carrier material.Preferably Silica support materials is the SS61138 high surface from Saint-Gobain NorPro (HSA) silica catalyst supports.Preparation 0.5g in 8M nitric acid_Salt/mL Co(NO₃)₂·6H₂The material liquid (stock solution) of O (Alfa Aesar).With SnC₄H₄O₆·xH₂O (Alfa Aesar) preparation 0.25g in 8M nitric acid_SaltThe raw material of/mL Sn Liquid.Prepare 193.05 μ L raw material cobalt liquid, 1060.4 μ L raw material tin liquors and 66.55 μ L nitric acid also And by 1200 these impregnation mixtures of μ L on 1g carrier.The dipping repeating active metal makes Gross activity metal ladings is 20wt.%.Co and Sn adds with equimolar amounts.By urging of dipping Agent is dried at 50 DEG C, then with 2 DEG C/min with the oblique line speed of 1 DEG C/min in atmosphere Oblique line speed is up to 120 DEG C.Catalyst is kept 2 hours and the most in atmosphere at 120 DEG C Maintain 4 hours at 450 DEG C with the rates of heat addition of 2 DEG C/min.

Embodiment B

50mol.% cobalt and the preparation of 50mol.% stannum on silica-alumina

Silicon dioxide-the oxygen at 120 DEG C, uniform particle sizes being distributed in baking oven in a nitrogen atmosphere Change aluminum (1.0g) to be dried overnight, and be then cooled to room temperature.Carrier contains 13.4wt.% Al₂O₃.Prepare 457.6 μ L from the raw material cobalt liquid of embodiment A, 564.3 μ L from enforcement The raw material tin liquor of example A and 518.1 μ L water and by this impregnation mixture 1g silicon dioxide- On alumina support.Repeated impregnations makes the gross activity metal ladings of cobalt and stannum be 20wt.%. For this catalyst material, repeat being dried and calcining of embodiment A.

Embodiment C-contrasts

The preparation of 100mol.% cobalt on silicon dioxide

Use the silicon dioxide (1.0g) of embodiment A.Preparation 0.5g salt/mL in 8M nitric acid Co(NO₃)₂·6H₂The material liquid of O (Alfa Aesar).Prepare 193.05 μ L raw material cobalt liquid and 66.55 μ L nitric acid and by 1200 these impregnation mixtures of μ L on 1g carrier.Repeat cobalt It is 20wt.% that dipping makes total metal ladings.For this catalyst material, repeat embodiment A Be dried and calcining.

Embodiment D-contrasts

The preparation of 100mol.% cobalt on silica-alumina

Silicon dioxide-the oxygen at 120 DEG C, uniform particle sizes being distributed in baking oven in a nitrogen atmosphere Change aluminum (1.0g) to be dried overnight, and be then cooled to room temperature.Preparation is in 8M nitric acid 0.5 g_Salt/mL Co(NO₃)₂·6H₂The material liquid of O (Alfa Aesar).Prepare 193.05 μ L raw material cobalts Liquid and 66.55 μ L nitric acid and by 1200 these impregnation mixtures of μ L at 1g silica-zirconia On alumina supporter.The dipping repeating cobalt makes total metal ladings be 20wt.%.For this catalyst Material, repeats being dried and calcining of embodiment A.

Embodiment E-contrasts

50mol.% cobalt and the preparation of 50mol.% copper on silicon dioxide

Repeating the catalyst of embodiment A, difference is to replace stannum with copper and replace nitre with water Acid.0.5g_Salt/mL Cu(NO₃)₂·3H₂The material liquid of O (Alfa Aesar).By former for 457.6 μ L Material copper liquid is immersed on carrier with cobalt.For this catalyst material, repeat embodiment A It is dried and calcining.

Embodiment F-contrasts

50mol.% cobalt and the preparation of 50mol.% copper on silica-alumina

Repeating the catalyst of embodiment B, difference is to replace stannum with copper and replace nitre with water Acid.0.5g_Salt/mL Cu(NO₃)₂·3H₂The material liquid of O (Alfa Aesar).By former for 457.6 μ L Material copper liquid is immersed on carrier with cobalt.For this catalyst material, repeat embodiment A It is dried and calcining.

Embodiment G

50mol.% cobalt and 50mol.% stannum on silicon dioxide-calcium metasilicate (10wt.%) carrier Preparation

Uniform grading distribution is about 0.2mm's at 120 DEG C by baking oven in a nitrogen atmosphere 2.7g silicon dioxide and 0.3g calcium metasilicate are dried overnight, and be then cooled to room temperature with Form carrier.Preparation 0.5g in 8M nitric acid_Salt/mL Co(NO₃)₂·6H₂O(Alfa Aesar) Material liquid.Use SnC₄H₄O₆·xH₂O (Alfa Aesar) preparation 0.25g in 8M nitric acid_Salt The material liquid of/mL Sn.Prepare 193.05 μ L raw material cobalt liquid, 1060.4 μ L raw material tin liquors and 66.55 μ L nitric acid and by 1200 these impregnation mixtures of μ L on 1g modified support.Repeat The dipping of active metal makes gross activity metal ladings be 20wt.%.Co and Sn is with equimolar Amount adds.For this catalyst material, repeat being dried and calcining of embodiment A.

Embodiment H-contrasts

75mol.% cobalt and the preparation of 25mol.% stannum on silica supports

Use the silicon dioxide (1.0g) of embodiment A.Preparation 0.5g salt/mL in 8M nitric acid Co(NO₃)₂·6H₂The material liquid of O (Alfa Aesar).Use SnC₄H₄O₆·xH₂O(Alfa Aesar) Preparation 0.25g in 8M nitric acid_SaltThe material liquid of/mL Sn.Prepare 193.05 μ L raw material cobalt liquid, 1060.4 μ L raw material tin liquors and 66.55 μ L nitric acid and by 1200 these impregnation mixtures of μ L 1 On g carrier.The dipping of heavy active metal makes gross activity metal ladings be 20wt.%, its Middle 75mol.%Co and 25mol.%Sn.For this catalyst material, repeat embodiment A Be dried and calcining.

Embodiment I-contrasts

75mol.% cobalt and 25mol.% stannum on silicon dioxide-calcium metasilicate (10wt.%) carrier Preparation

Use the modified support containing calcium metasilicate of embodiment G.Preparation 0.5g in 8M nitric acid_Salt/mL Co(NO₃)₂·6H₂The material liquid of O (Alfa Aesar).Use SnC₄H₄O₆·xH₂O(Alfa Aesar) preparation 0.25g in 8M nitric acid_SaltThe material liquid of/mL Sn.Prepare 193.05 μ L former Expect cobalt liquid, 1060.4 μ L raw material tin liquors and 66.55 μ L nitric acid and by 1200 these mixing of μ L Thing is immersed on 1g modified support.The dipping of heavy active metal makes gross activity metal carry Amount is 20wt.%, wherein 75mol.%Co and 25mol.%Sn.For this catalyst material Material, repeats being dried and calcining of embodiment A.

Comparative example J-contrasts

25mol.% cobalt and 75mol.% stannum on silicon dioxide-calcium metasilicate (10wt.%) carrier Preparation

Use the modified support containing calcium metasilicate of embodiment G.Preparation 0.5g in 8M nitric acid_Salt/mL Co(NO₃)₂·6H₂The material liquid of O (Alfa Aesar).Use SnC₄H₄O₆·xH₂O(Alfa Aesar) preparation 0.25g in 8M nitric acid_SaltThe material liquid of/mL Sn.Prepare 193.05 μ L former Expect cobalt liquid, 1060.4 μ L raw material tin liquors and 66.55 μ L nitric acid and by 1200 these mixing of μ L Thing is immersed on 1g modified support.The dipping repeating active metal makes gross activity metal ladings For 20wt.%, wherein 25mol.%Co and 75mol.%Sn.For this catalyst material, Repeat being dried and calcining of embodiment A.

The gas chromatogram (GC) of product is analyzed

The analysis of product is carried out by online GC.Use equipped with 1 flame ion detection The integrated GC of triple channel of device (FID) and 2 thermal conductivity detector (TCD)s (TCD) comes analytical reactions thing and product Thing.Prepass is equipped with FID and CP-Sil5 (20m)+WaxFFap (5m) pillar and is used for Quantify: acetaldehyde；Ethanol；Acetone；Methyl acetate；Vinyl acetate；Ethyl acetate；Acetic acid； Ethylene acetate；Ethylene glycol；Ethylidene diacetate；And paraldehydum.Center-aisle is joined Have TCD and Porabond Q pillar and for quantifying: CO2；Ethylene；And ethane.After Passage is equipped with TCD and Porabond Q pillar and is used for quantifying: helium；Hydrogen；Nitrogen； Methane；And carbon monoxide.

Make acetic acid feed liquid evaporation and in company with hydrogen with together with the helium of carrier gas with about 2430hr^-1Average total gas hourly space velocity (GHSV) at the temperature of about 250 DEG C and 2500kPa Install in reactor under pressure.Make partial vapor effluent through gas chromatogram for carrying out this stream Go out the analysis of thing content.

Embodiment 1-hydrogenation catalyst

The catalyst of testing example A-J.Report in table 2 in 20 and 60 TOS (fortune During row m-in hours) time acetic acid conversion and selectivity.As shown in table 2, embodiment A with B show the comparative catalyst the most stanniferous with comparative example C-F compared with in conversion ratio and choosing The performance of the raising in terms of selecting property.Additionally, 50-50 mol ratio demonstrates with right in embodiment G In ratio H-J, other mol ratio compares the performance of improvement.

Embodiment K

50mol.% cobalt and the preparation of 50mol.% stannum in the case of there is platinum on silicon dioxide.

Use the catalyst of embodiment A.It is being dried and before calcining by Pt (NO₃)₂(Sigma Aldrich) join in this carrier.There is different amounts of platinum used；0wt.%, 0.2wt.%, 0.4wt.% and 0.6wt.%.

Embodiment L

On silicon dioxide-calcium metasilicate (10wt.%) carrier in the case of there is platinum 50mol.% Cobalt and the preparation of 50mol.% stannum

Use the catalyst of embodiment G.It is being dried and before calcining by Pt (NO₃)₂(Sigma Aldrich) join in this carrier.There is different amounts of platinum used；0wt.%, 0.2wt.%, 0.4wt.% and 0.6wt.%.The catalyst of testing example A-J.

Embodiment 2

Testing example K and the catalyst of L under the same conditions as example 1.Such as table 3 Shown in, platinum adds the performance demonstrating improvement with higher carrying capacity.

The noble metal promoted agent of embodiment 3-

The nitrate precursors of noble metal is immersed on the catalyst of embodiment A.The gold of noble metal Genus loading levels is 0.4wt.%.

Make acetic acid feed liquid evaporation and in company with hydrogen with together with the helium of carrier gas with about 2430 hr^-1Average total gas hourly space velocity (GHSV) at the temperature of about 250 DEG C and 2500 kPa Install in reactor under pressure.Make partial vapor effluent through gas chromatogram for carrying out this stream Go out the analysis of thing content.

Report 20 and 60TOS acetic acid time (during operation m-in hours) in table 4 Conversion ratio and selectivity.

The the first noble metal promoted agent of embodiment 4--before impregnation

By the nitrate precursors of the first metallic promoter agent before dipping active metal such as cobalt and stannum It is immersed in embodiment A (SiO₂) and embodiment L (SiO₂-CaSiO₃) catalyst on.First metal The metal ladings level of accelerator is 0.2wt.%.

Report 20 and 60TOS acetic acid time (during operation m-in hours) in table 5 Conversion ratio and selectivity.

The the first noble metal promoted agent of embodiment 5--after immersion

By the nitrate precursors of the first metallic promoter agent after dipping active metal such as cobalt and stannum It is immersed in embodiment A (SiO₂) catalyst and embodiment L (SiO₂-CaSiO₃) catalyst on. The most do not test barium.The metal ladings level of the first metallic promoter agent is 0.2 Wt.%.

Acetic acid when 20 and 60TOS (during operation m-in hours) reported in table 6 Conversion ratio and selectivity.

Embodiment M

The preparation of 100mol.% cobalt on silicon dioxide-calcium metasilicate (10wt.%) carrier

Uniform grading distribution is about 0.2mm's at 120 DEG C by baking oven in a nitrogen atmosphere 2.7g silicon dioxide and 0.3g calcium metasilicate are dried overnight, and be then cooled to room temperature with Form carrier material.Preparation 0.5g in distilled water_SaltThe material solution of/mL Co.Prepare 2413.4 μ L raw material cobalt liquid and 1524.6 μ L distilled water and by this impregnation mixture of 3.58mL On 2g modified support.Repeat cobalt dipping making total metal ladings is 20wt.%.By dipping Catalyst is dried at 50 DEG C, then with 2 DEG C/min with the oblique line speed of 1 DEG C/min in atmosphere Oblique line speed until 120 DEG C.Catalyst is kept 2 hours and then at air at 120 DEG C In maintain 4 hours at 450 DEG C with the rate of heat addition of 2 DEG C/min.

Embodiment N

The preparation of 100mol.% cobalt on silicon dioxide-calcium metasilicate (15wt.%) carrier

Uniform grading distribution is about 0.2mm's at 120 DEG C by baking oven in a nitrogen atmosphere 2.55g silicon dioxide and 0.45g calcium metasilicate are dried overnight, and are then cooled to room temperature To form carrier material.Preparation 0.5g in distilled water_SaltThe material solution of/mL Co.Prepare 2413.4 μ L raw material cobalt liquid and 1524.6 μ L distilled water and by this impregnation mixture of 3.58mL On 2g modified support.Repeat cobalt dipping making total metal ladings is 20wt.%.By dipping Catalyst is dried at 50 DEG C, then with 2 DEG C/min with the oblique line speed of 1 DEG C/min in atmosphere Oblique line speed until 120 DEG C.Catalyst is kept 2 hours and then at air at 120 DEG C In maintain 4 hours at 450 DEG C with the rate of heat addition of 2 DEG C/min.

First metallic promoter agent on comparative example 6-Co catalysts

By the nitrate precursors of the first metallic promoter agent before dipping active metal such as cobalt and stannum It is immersed in embodiment M (SiO₂-CaSiO₃) catalyst on.The metal of the first metallic promoter agent carries Amount level is 0.2wt.%.

Report 20 and 60TOS acetic acid time (during operation m-in hours) in table 7 Conversion ratio and selectivity.

Embodiment 7

Catalyst is 50mol.% cobalt on silica prepared by the operation according to embodiment A With 50mol.% stannum.

Be made of stainless steel have 30mm internal diameter and can rise to control temperature tubular type anti- Answer in device, dispose 50ml 50mol.% cobalt on silica and 50mol.% stannum.After charging The length of catalyst bed is about 70mm approx.

Feed liquid is substantially made up of 70wt.% acetic acid and 30wt.% ethyl acetate.Make into Feed liquid evacuator body and in company with hydrogen with together with the helium of carrier gas with about 2430hr^-1Average total Gas hourly space velocity (GHSV) installs to reactor at the temperature of about 250 DEG C and the pressure of 2500kPa In.Make partial vapor effluent through gas chromatogram for carrying out the analysis of this effluent content. Ethyl acetate is 4.1%-10.8% for the selectivity of ethanol.

Embodiment 8

The catalyst used be the operation according to embodiment M prepare at the silicon of silicon dioxide-partially 100mol.% cobalt on acid calcium (10wt.%) carrier.

It is essentially repeated in embodiment 1 operation provided.Make partial vapor effluent through gas phase Chromatograph is for carrying out the analysis of this effluent content.Ethyl acetate for the selectivity of ethanol is 0.6%-7.1%.

Embodiment 9

The catalyst used be the operation according to embodiment N prepare at the silicon of silicon dioxide-partially 100mol.% cobalt on acid calcium carrier.

It is essentially repeated in embodiment 1 operation provided.Make partial vapor effluent through gas phase Chromatograph is for carrying out the analysis of this effluent content.Ethyl acetate for the selectivity of ethanol is 0.6%-7.1%.

Although the present invention of describing in detail, but various amendments within the spirit and scope of the present invention Will be apparent to those skilled in the art.By quoting institute discussed above Publication and list of references is had to be expressly incorporated herein.Further, it should be understood that each of the recited present invention The various piece of aspect and multiple embodiment and multiple feature can partly or entirely be carried out Combination or exchange.In the description of each embodiment aforementioned, such as those skilled in the art institute It can be appreciated that, the embodiment quoting another embodiment can be fitted with other embodiment Local combination.Additionally, it would be recognized by those skilled in the art that described above is only way of example, And it is not intended to limit the present invention.

Claims (14)

1. the method being formed ethanol by acetic acid, the method includes: make at elevated temperatures Feed stream containing acetic acid and hydrogen be included in containing the 10-20wt.% active metal on silicon carrier Hydrogenation catalyst contact, wherein said active metal comprises cobalt and stannum, and wherein said activity Metal exists with the cobalt of 1.9:1-1:1.9 and the mol ratio of stannum.

2. the method being formed ethanol by acetic acid, the method includes: make at elevated temperatures Feed stream containing acetic acid and hydrogen be included in containing the 10-20wt.% active metal on silicon carrier Hydrogenation catalyst contact, wherein said active metal comprises cobalt and stannum, and wherein said activity Metal exists with the cobalt of 1.2:1-1:1.2 and the mol ratio of stannum.

3. the method any one of claim 1-2, wherein said containing silicon carrier selected from titanium dioxide Silicon, silica/alumina, calcium metasilicate and their mixture.

4. the method any one of claim 1-2, wherein said carrier also comprises with 0.1 The support modification agent that the amount of wt.%-50wt.% exists.

5. the method any one of claim 1-2, wherein said carrier also comprises support modification Agent, support modification agent is selected from (i) alkaline earth oxide, (ii) alkali metal oxide, (iii) alkaline earth Metal metasilicates, (iv) alkali metal silicate, (v) Group IIB metal oxide, (vi) Group IIB Metal metasilicates, (vii) IIIB family metal oxide, (viii) IIIB race metal metasilicates and Their mixture.

6. the method any one of claim 1-2, wherein said carrier also comprises support modification Agent, support modification agent comprises calcium metasilicate.

7. the method any one of claim 1-2, wherein said carrier also comprises support modification Agent, support modification agent is selected from TiO₂、ZrO₂、Nb₂O₅、Ta₂O₅、Al₂O₃、B₂O₃、P₂O₅、 Sb₂O₃、WO₃、MoO₃、Fe₂O₃、Cr₂O₃、V₂O₅、Nb₂O₅、MnO₂、CuO、 Co₂O₃And Bi₂O₃。

8. the method any one of claim 1-2, wherein said raw material also comprises 5-40wt.% Ethyl acetate.

9. the method any one of claim 1-2, wherein said catalyst is without other work Property metal.

10. the method any one of claim 1-2, wherein said active metal also comprises choosing From the first metal and the promoter metals of noble metal, wherein the first metal selected from barium, potassium, caesium and Combinations thereof, and wherein said noble metal selected from rhodium, ruthenium, palladium, gold, iridium and they Combination.

The method of 11. claim 10, wherein said promoter metals is deposited with 0.05-2wt.% ?.

Method any one of 12. claim 1-2, the method also includes making carbonaceous material gas Changing to produce feed stream, wherein said carbonaceous material is selected from oil, coal, natural gas and biomass.

Method any one of 13. claim 1-2, wherein acetic acid is for the selectivity of ethanol More than 60%.

The method of 14. claim 3, wherein said silicon dioxide selected from pyrolytic silicon dioxide, High-purity silicon dioxide and their mixture.