CN106268856A - Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application - Google Patents
Rhodium base catalyst of one-step method from syngas ethanol and its preparation method and application Download PDFInfo
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Abstract
nullThe invention discloses rhodium base catalyst of a kind of one-step method from syngas ethanol and preparation method thereof，This catalyst includes active component、Auxiliary agent and carrier，Described active component is Rh，Auxiliary agent M is selected from alkali metal、One or more in alkaline-earth metal or transition metal，Carrier is ceria or cerium zirconium sosoloid，Preparation method be by the salt solution impregnation of active component and auxiliary agent on ceria or cerium zirconium sosoloid，Drying、Roasting、Described catalyst is i.e. obtained after reduction，Active component and auxiliary agent are dispersed on carrier，Between form stronger interaction，Catalyst is made to have high activity and stability，The rhodium base catalyst that the present invention prepares is applicable to synthesis gas and prepares ethanol process，Synthesis gas multistep processes can be substituted and prepare alcohol catalysis agent，Alcohols in product had higher selectivity，High degree is simplified synthesis gas and prepares ethanol route by this catalyst，Overcome the dependence to grain and petroleum resources in traditional ethanol synthetic route.
Description
Technical field
The invention belongs to noble metal catalyst and preparation field thereof, be specifically related to a kind of one-step method from syngas second
Rhodium base catalyst of alcohol and its preparation method and application.
Background technology
Ethanol as regenerative resource, can directly as liquid fuel or as gasoline additive with gasoline mix
Close and use, China's dependence to oil can be alleviated, ensure energy security；It addition, gasoline adds ethanol
After, the abundant burning of fuel can be promoted, reduce the discharge of harmful substance in vehicle exhaust, thus reduce right
The pollution of environment, meets China's energy substitution strategy and Renewable Energy Development direction.When ethanol in the oil
When mixing less than 10%, automobile engine, without carrying out big change, i.e. can be used directly ethanol petrol.
The method of industrial production ethanol is mainly fermentation method or ethylene direct hydration method, 2011, China's second
Alcohol total output is 6,700,000 tons, and what the most non-grain method produced only accounts for 200,000 tons, and often produces one ton of fuel second
Alcohol, needs to consume 3.03 tons of Semen Maydiss.As can be seen here, need every year to consume nearly 20,000,000 ton-grain foods.And China
Grain resource is the most abundant, to this end, in the case of grain alcohol project stops criticizing, need the technology that exploitation is new badly
Route meets domestic ever-increasing ethanol demand.And ethylene hydration ethanol technology, ethylene main source
In oil, also limit the development of this technology.Fermentation method and ethylene hydration method relatively, synthesis gas generates ethanol
There is abundant raw material sources such as coal, oven gas, biomass and other industrial process, so synthesis gas is raw
The technology of producing and ethanol, to substituting traditional grain fermentative routes, is alleviated the contradiction that petroleum resources are in short supply, is improved me
State's energy security, has important strategic importance and profound influence.
At present, the processing technology routine of synthesis gas ethanol mainly include synthesis gas through acetic acid preparation of ethanol by hydrogenating and
Synthesis gas ethanol the most processed.The former is from the perspective of atom economy, and processing technology routine is unreasonable, and
And it is limited to acetic acid production capacity；The latter needs solve to key challenge is how second in raising synthesizing low-carbon mixed alcohol
The yield of alcohol and selectivity, thus reduce later separation cost.The catalysis of MAS is prepared from synthesis gas
Agent is broadly divided into four classes: the methanol synthesis catalyst that (1) is modified；(2) modified fischer-tropsch synthetic catalyst；(3)
Mo base catalyst；(4) Rh base catalyst.Wherein carbon two is contained in being four kinds of catalyst by Rh base catalyst
The catalyst that oxide selectivity is the highest, but the price of its costliness and relatively low productivity so that it is be up till now
Only still without realizing industrialization.Therefore, catalyst cost is also the bottleneck restricting this technology industrialization.
Document report SiO2For the prioritizing selection of formate low-carbon alcohol catalyst, patent US4235801 discloses one
Plant Rh-Fe/SiO2Catalyst is used for synthesizing alcohol；Patent US4442228 discloses a kind of for synthesis gas system
The Rh-M catalyst of ethanol and process；CN 117549A and CN 1179993A also individually discloses
Rh-V-M/SiO2And M/Rh-Mn-Fe/SiO2Catalyst for synthesizing low-carbon mixed alcohol.Additionally, molecular sieve
The surface acidic-basic property excellent due to it and pore structure are also used as synthesizing the load of more than C2 oxygenatedchemicals catalyst
Body, as CN 102029173A discloses one with molecular sieve (SBA-15) as carrier, Fe, Mn are for helping
The Rh base catalyst of agent, the load capacity of its Rh is up to 5%, and ethanol selectivity only about 21%；It addition,
People also attempt CNT is applied to synthesis gas higher alcohols process, and CN 103537282A discloses one
Planting Rh-Mn/CNTs catalyst, the load capacity of Rh is 5～10%, and the highest selectivity of ethanol is 25%, CO
Conversion ratio reaches more than 20%.Although the Rh of high capacity amount improves second to a certain extent in above-mentioned catalyst
The selectivity of alcohol and yield, but severe reaction conditions (reaction pressure 100bar), catalyst cost are high greatly
Reduce the economy of this technology.
By analysis above, how reducing catalyst cost is also to realize synthesis gas ethanol the most processed skill
The key of art industrialization.To this end, patent CN 1175479A, CN 1175521A, CN 1225852A,
CN 1724151A, CN 103301849A discloses the catalyst that Rh load capacity is 1wt%, but ethanol
Selectivity and yield all do not report；And Ce excellent stores oxygen performance owing to having, it is widely used in stream
Change bed catalytic cracking, SOxRemoving, ethylbenzene dehydrogenation, three-effect catalysis reaction and water gas shift reaction etc..
The addition of Zr can promote the activity of the redox ability of Ce, heat stability and catalyst.And pertinent literature
Report Rh/CeO2-ZrO2Be excellent ethanol reforming catalysts (Applied Catalysis B:
Environmental, 2006, (3-4): 191 200；C.R.Chimie,2004,7:671-622.).Therefore, this
Bright it is intended to utilize it as carrier, carried noble metal rhodium, adds auxiliary agent as CO hydrogenation ethanol production simultaneously
Catalyst.
Summary of the invention
It is desirable to provide a kind of rhodium base catalyst and preparation thereof that can convert synthesis gas into ethanol efficiently
Methods and applications, this preparation method is easy and reproducible, and synthesis gas is turned by the rhodium base catalyst prepared
The catalytic selectivity of chemical conversion ethanol synthesis is high, and high to the selectivity of alcohols in product.
The invention discloses a kind of rhodium base catalyst for one-step method from syngas ethanol, by active component,
Auxiliary agent and carrier composition；Described active component is Rh, and auxiliary agent M is selected from alkali metal, alkaline-earth metal or transition
The combination of one or more in metallic element, carrier is ceria or a certain proportion of cerium zirconium sosoloid；
The load capacity of Rh is 0.1～the mass ratio of 10wt%, M and Rh is 0.05～10.
In rhodium base catalyst, add appropriate auxiliary agent can promote dissociating and inserting of CO in synthesis gas, improve
The conversion ratio of CO and the productivity of ethanol.When the load capacity of auxiliary agent is too high, excess auxiliary agent will cover noble metal
Rh, reduces the activity of catalyst and the selectivity to ethanol；Rh load capacity is too low, active sites lazy weight,
Catalyst activity is relatively low, and appropriateness improves load capacity and is conducive to improving activity and selectivity, but too high load
The gathering causing catalyst Rh granule is caused the reduction of active component dispersion by amount, thus affects catalytic
Can, the cost of catalyst also can be greatly improved simultaneously, in order to obtain high ethanol selectivity, need to control CO
Dissociative and the relative speed of the non-Dissociative of CO, it is therefore desirable to be adjusted to the ratio of auxiliary agent and Rh close
Suitable proportion, as preferably, the load capacity of described Rh is 1～9wt%, auxiliary agent and the mass ratio of Rh
When being 0.1～9, preferable result can be obtained.
Active component, auxiliary agent and carrier element are respectively from corresponding nitrate or acetate.
Described auxiliary agent M preferably is selected from Li, Na, K, Cs, La, Pr, Nd, Sm, Mn, Fe, Co,
The combination of one or more in Ni, Ru.
Cerium zirconium sosoloid has good heat stability and stores oxygen ability, is good catalyst carrier, but
It is the improper heat stability that not only can not improve catalyst of cerium zirconium ratio, also can affect catalyst simultaneously
Selectivity.Therefore, cerium that cerium zirconium sosoloid is comprised and the atomic ratio of zirconium are between 0.1～10, the most former
Son ratio is 1～4.
The preparation process of ceria or cerium zirconium sosoloid is: (a) utilizes homogeneous precipitation method synthetic vectors forerunner
Thing, (b) by resulting vehicle predecessor through filtering, wash, being dried, roasting, tabletting, sieving becomes dioxy
Change cerium or cerium zirconium sosoloid.
Homogeneous precipitation method described in step (a) is salt and the water-soluble slow-releasing alkali of metal needed for carrier to be dissolved in
In ionized water, being placed in there-necked flask by mixed solution, 60 DEG C～110 DEG C of oil bath heated and stirred are dissolved to solid,
Closing heating to be stirred for precipitation completely, wherein the usage amount of water-soluble slow-releasing type alkali is former needed for being synthetic vectors
1～60 times of each components precipitate institute alkali needed in material mixed solution；
Described homogeneous precipitation method utilizes suitable chemical reaction to make the configurational ion in solution by slow in solution
Generate equably, by controlling the concentration of precipitant in solution, be allowed to be slowly increased, make in solution
Precipitation is in poised state, and precipitation can the most uniformly generate, and this method avoid and directly adds precipitation
Agent and the uneven phenomenon of the system topical solutions that produces, make degree of supersaturation maintain in proper range, thus
Controlling the speed of growth of particle, precipitant used in the present invention is water-soluble slow-releasing type alkali.
Described water-soluble slow-releasing type alkali is water soluble, discharges OH after heat resolve-, high-temperature roasting without
Residual organic amine, described organic amine be carbamide, ethylenediamine, ethanolamine, diethanolamine, triethanolamine,
One or more of triethylene tetramine, wherein, carbamide is most commonly seen and cheap in water-soluble slow-releasing type alkali
Raw material, the most most preferably carbamide.Water-soluble slow-releasing type alkali is can to decompose to discharge OH in heating process-
Organic-inorganic compound, these compounds decompose after product noresidue after 500 DEG C of high-temperature roastings.OH-
There is during precipitation from homogeneous solution important effect, on the one hand for thermodynamics, only introduce OH-,
Reaction just can be carried out；On the other hand for aerodynamic point, OH-Just as catalyst, accelerate the crystalline substance of product
Change process.
Chemically seeing in reaction principle, the usage amount of alkali is minimum can sink equal to each component in raw material mixed solution
Alkali number needed for shallow lake；But there is a change in the degree of decomposition that the alkali used in the present invention is at a certain temperature
Learn balance, so the usage amount of alkali must be superfluous.
The usage amount of described water-soluble slow-releasing type alkali is that in synthesis catalytic agent carrier needed raw material mixed solution, each component is sunk
Shallow lake institute alkali needed is preferably 1～50 times, most preferably 10～30 times.
During precipitation from homogeneous solution, reaction temperature is the important factor in order of chemical reaction and crystal growth, instead
Answering temperature too low, precipitant decomposes not exclusively, and solution does not becomes certain degree of supersaturation, cannot react completely
Entirely, support precursor yield is low；When temperature raises, the yield of support precursor improves.Due to reaction temperature
Grain growth and nucleus formation speed are all had an impact, so the chi of the particle obtained under different reaction temperatures
Very little difference.From the point of view of prepared by industrial catalyst, it is not a gentle chemical process that temperature improves, meeting
It is greatly increased production cost, selects to be easier to decompose and cheap alkali, can effectively reduce reaction temperature, oil
Bath heating-up temperature is preferably 70 DEG C～100 DEG C, most preferably 80 DEG C～100 DEG C.
Response time with reaction temperature increase or the increase of base excess rate and shorten, or with reaction temperature with
Increase while base excess rate and shorten.Such as, temperature height high at some alkali concns, and easily decompose using
In the reaction system of alkali, the required sedimentation time can shorten to 1～10 hour, within usual 3～8 hours, compare through
Ji is rationally；And for low at some alkali concns, temperature is low, and use difficulty decompose alkali reaction system in,
The required sedimentation time can extend to 12 hours accordingly.
In step (a), the response time is 1～24 hour, preferably 1～10 hour, most preferably 3～8 hours.
In step (b), the solvent that washing uses is the organic solvent that surface tension is less, and organic solvent is different
Propanol, methanol, ethanol, pentane, be dried 6～24 under the conditions of 50～130 DEG C by carrier predecessor after washing
Hour, dried product exhibited is warming up to 300～800 DEG C of roastings 1～12 hours, gained with 1～10 DEG C/min speed
Product 10MPa compression molding, crushed 40～60 mesh sieves, obtained carrier.
Preferably baking temperature is 80～110 DEG C, and preferably sintering temperature is 400～600 DEG C.
The preparation process of described rhodium base catalyst is as follows:
1) Rh salt and the M salt mixed aqueous solution of certain proportioning are prepared；
2) by step 1) mixed aqueous solution of gained is added drop-wise on ceria or cerium zirconium sosoloid, drying,
Described rhodium base catalyst is obtained after roasting, reduction；
Rh salt, M salt and ceria or cerium zirconium sosoloid are based on the component proportion described in claim 2 and 4
Amount.
Drying process is: be dried 3～15 hours at 60～140 DEG C, is dried 6～12 little at preferably 80～120 DEG C
Time, dry temperature affects the distribution of active component and auxiliary agent, and dry rate is too fast, will cause active component
Major part is distributed in particle surface；
Roasting technique is: under nitrogen or air atmosphere, holding 1～10 hour at 200～700 DEG C, preferably
Keep 2～6 hours at 400～500 DEG C, the interaction relationship between sintering temperature appreciable impact Rh and auxiliary agent,
Thus affect the activity and selectivity of catalyst；Interaction between Rh and auxiliary agent is too strong or crosses weak to reacting all
It is disadvantageous, this active force can be made to be in suitable intensity by regulation sintering temperature, it is achieved C2Oxygen-containing
The maximization of compound yield；But when sintering temperature is too high, metal component will be caused to reunite and dispersion will decline,
Affect catalyst performance；
Reducing process is: under hydrogen atmosphere, holding 0.5～8 hour at 200～400 DEG C, preferably 250～350 DEG C
Lower holding 1～6 hours, due to the interaction between rhodium and auxiliary agent M component so that MxOyReduction temperature
Degree reduces, MxOyAt 50～250 DEG C, it is reduced to M, wherein reduces relatively difficult, would revert to relatively at a low price
State, rather than reduction-state.
When rhodium base catalyst of the present invention is applied in one-step method from syngas ethanol synthesis, the temperature of use
Scope is 200～400 DEG C, and preferable temperature is 250～350 DEG C；Using pressure limit is 0.1～8.0MPa, excellent
Selecting pressure limit is 1.0～5.0MPa；H2/ CO is 0.5～8.0, preferably H2/ CO is 1.0～4.0；When stablizing
Between be 3～48 hours, preferably stabilization time is 12～24 hours；Response time is 12～48 hours, the most instead
It is 20～28 hours between Ying Shi.
The evaluating catalyst of synthesis gas synthesizing alcohol reaction is carried out, instead on fixed-bed tube reactor
Answer procatalyst at high pressure, H2Air-flow keeps 1～6 hour at 250～350 DEG C, wherein H2Flow velocity is scope
25～100ml/min；Then being down to reaction temperature, be passed through CO and react, the gas reflected directly is used
Gas chromatogram carries out on-line analysis, and measures its flow, and liquid product collection gets up and is analyzed by chromatograph,
Selectivity and the space-time yield of the carbonaceous products such as alcohol, hydrocarbon are calculated by carbon back normalization method.
Beneficial effects of the present invention is embodied in:
(1) catalyst of the present invention is by ceria or cerium zirconium sosoloid and the activity being dispersed in its surfaces externally and internally
Component Rh and auxiliary agent M composition, by preparation catalyst, preparation is convenient and reproducible.
(2) catalyst of the present invention is interpolation auxiliary agent M in rhodium base catalyst, and impregnates in aqueous medium,
Each uniform component distribution, is beneficially formed between auxiliary agent and active component and interacts, prevent active component stream
Lose.
(3) catalyst of the present invention is used for one-step method from syngas ethanol synthesis, it is possible to substitute synthesis gas multistep
Method prepares alcohol catalysis agent, and alcohols in product is had higher selectivity, and high degree is simplified by the method
Synthesis gas prepares ethanol route, overcomes in traditional ethanol synthetic route and depends on grain and petroleum resources
Relying, in catalytic reaction process, reaction condition is gentle, and its reaction pressure is 1.0～5.0MPa, reaction temperature
Being 250～350 DEG C, described catalyst is higher to the selectivity of alcohols in product, and alcohol product yield is higher, and
In alcohol product, the ratio shared by ethanol is higher.
Detailed description of the invention
Embodiment 1
Weighing 81.06g ammonium ceric nitrate respectively, 14.54g nitrate trihydrate zirconium and 222.00g carbamide, by above-mentioned title
Ammonium ceric nitrate, nitrate trihydrate zirconium and the carbamide of amount are dissolved in deionized water and obtain 1500ml mixed solution, will
Mixed solution is placed in there-necked flask, 110 DEG C of oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours,
The precipitate with deionized water of gained is washed to neutral, then washs with isopropanol, filter, in vacuum drying oven 80 DEG C
Being dried 12 hours, dried solid is roasting 2 hours at 500 DEG C, by gained solid preform, grind,
It is screened to 40～60 mesh, by the Rh (NO that 1.03ml mass fraction is 97.25%3)3Solution, 0.45ml mole
Concentration is the Fe (NO of 2mol/L3)3Solution mixes with the deionized water of 2.44ml, is then dripped by this mixed solution
It is added on 10g solid.Gained solid is placed in 110 DEG C of baking ovens overnight.In air atmosphere, dry is consolidated
Body is roasting 3 hours at 450 DEG C, and 300 DEG C of hydrogen atmospheres reduce 1 hour, obtain
1%Rh-0.5%Fe/Ce0.8Zr0.2O2Catalyst.
Embodiment 2
Weighing 81.06g ammonium ceric nitrate respectively, 14.54g nitrate trihydrate zirconium and 222.00g carbamide, by above-mentioned title
Ammonium ceric nitrate, nitrate trihydrate zirconium and the carbamide of amount are dissolved in deionized water and obtain 1500ml mixed solution, will
Mixed solution is placed in there-necked flask, 110 DEG C of oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours,
The precipitate with deionized water of gained is washed to neutral, then washs with isopropanol, filter, in vacuum drying oven 80 DEG C
Being dried 12 hours, dried solid is roasting 2 hours at 500 DEG C, by gained solid preform, grind,
It is screened to 40～60 mesh, by the Rh (NO that 1.03ml mass fraction is 97.25%3)3Solution, 0.90ml mole
Concentration is the Fe (NO of 2mol/L3)3Solution mixes with the deionized water of 2.00ml, is then dripped by this mixed solution
It is added on 10g solid.Gained solid is placed in 110 DEG C of baking ovens overnight.In air atmosphere, dry is consolidated
Body is roasting 3 hours at 450 DEG C, and 300 DEG C of hydrogen atmospheres reduce 1 hour, obtain
1%Rh-1%Fe/Ce0.8Zr0.2O2Catalyst.
Embodiment 3
Weighing 81.06g ammonium ceric nitrate respectively, 14.54g nitrate trihydrate zirconium and 222.00g carbamide, by above-mentioned title
Ammonium ceric nitrate, nitrate trihydrate zirconium and the carbamide of amount are dissolved in deionized water and obtain 1500ml mixed solution, will
Mixed solution is placed in there-necked flask, 110 DEG C of oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours,
The precipitate with deionized water of gained is washed to neutral, then washs with isopropanol, filter, in vacuum drying oven 80 DEG C
Being dried 12 hours, dried solid is roasting 2 hours at 500 DEG C, by gained solid preform, grind,
It is screened to 40～60 mesh, by the Rh (NO that 1.03ml mass fraction is 97.25%3)3Solution, 2.24ml mole
Concentration is the Fe (NO of 2mol/L3)3Solution mixes with the deionized water of 0.65ml, is then dripped by this mixed solution
It is added on 10g solid.Gained solid is placed in 110 DEG C of baking ovens overnight.In air atmosphere, dry is consolidated
Body is roasting 3 hours at 450 DEG C, and 300 DEG C of hydrogen atmospheres reduce 1 hour, obtain
1%Rh-2.5%Fe/Ce0.8Zr0.2O2Catalyst.
Embodiment 4
Weigh 95.56g ammonium ceric nitrate and 209.38g carbamide respectively, by ammonium ceric nitrate and the carbamide of above-mentioned weighing
It is dissolved in deionized water and obtains 1500ml mixed solution, mixed solution is placed in there-necked flask, 110 DEG C
Oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours, the precipitate with deionized water of gained washed
To neutral, then washing with isopropanol, filter, in vacuum drying oven, 80 DEG C are dried 12 hours, dried solid
Roasting 2 hours at 500 DEG C, by gained solid preform, grind, are screened to 40～60 mesh, by 1.03ml
Mass fraction is the Rh (NO of 97.25%3)3Solution, 0.07ml molar concentration is the Fe (NO of 2mol/L3)3Molten
Liquid mixes with the deionized water of 2.56ml, is then added drop-wise on 10g solid by this mixed solution.Gained solid
It is placed in 110 DEG C of baking ovens overnight.In air atmosphere, by dry solid roasting 3 hours at 450 DEG C,
300 DEG C of hydrogen atmospheres reduce 1 hour, obtain 1%Rh-0.1%Fe/CeO2Catalyst.
Embodiment 5
Weigh 95.56g ammonium ceric nitrate and 209.38g carbamide respectively, by ammonium ceric nitrate and the carbamide of above-mentioned weighing
It is dissolved in deionized water and obtains 1500ml mixed solution, mixed solution is placed in there-necked flask, 110 DEG C
Oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours, the precipitate with deionized water of gained washed
To neutral, then washing with isopropanol, filter, in vacuum drying oven, 80 DEG C are dried 12 hours, dried solid
Roasting 2 hours at 500 DEG C, by gained solid preform, grind, are screened to 40～60 mesh, by 1.03ml
Mass fraction is the Rh (NO of 97.25%3)3Solution, 0.22ml molar concentration is the Fe (NO of 2mol/L3)3Molten
Liquid mixes with the deionized water of 3.07ml, is then added drop-wise on 10g solid by this mixed solution.Gained solid
It is placed in 110 DEG C of baking ovens overnight.In air atmosphere, by dry solid roasting 3 hours at 450 DEG C,
300 DEG C of hydrogen atmospheres reduce 1 hour, obtain 1%Rh-0.25%Fe/CeO2Catalyst.
Embodiment 6
Weigh 95.56g ammonium ceric nitrate and 209.38g carbamide respectively, by ammonium ceric nitrate and the carbamide of above-mentioned weighing
It is dissolved in deionized water and obtains 1500ml mixed solution, mixed solution is placed in there-necked flask, 110 DEG C
Oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours, the precipitate with deionized water of gained washed
To neutral, then washing with isopropanol, filter, in vacuum drying oven, 80 DEG C are dried 12 hours, dried solid
Roasting 2 hours at 500 DEG C, by gained solid preform, grind, are screened to 40～60 mesh, by 1.03ml
Mass fraction is the Rh (NO of 97.25%3)3Solution, 0.45ml molar concentration is the Fe (NO of 2mol/L3)3Molten
Liquid mixes with the deionized water of 2.84ml, is then added drop-wise on 10g solid by this mixed solution.Gained solid
It is placed in 110 DEG C of baking ovens overnight.In air atmosphere, by dry solid roasting 3 hours at 450 DEG C,
300 DEG C of hydrogen atmospheres reduce 1 hour, obtain 1%Rh-0.5%Fe/CeO2Catalyst.
Embodiment 7
Weigh 95.56g ammonium ceric nitrate and 209.38g carbamide respectively, by ammonium ceric nitrate and the carbamide of above-mentioned weighing
It is dissolved in deionized water and obtains 1500ml mixed solution, mixed solution is placed in there-necked flask, 110 DEG C
Oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours, the precipitate with deionized water of gained washed
To neutral, then washing with isopropanol, filter, in vacuum drying oven, 80 DEG C are dried 12 hours, dried solid
Roasting 2 hours at 500 DEG C, by gained solid preform, grind, are screened to 40～60 mesh, by 1.03ml
Mass fraction is the Rh (NO of 97.25%3)3Solution, 0.21ml molar concentration is the La (NO of 2mol/L3)3Molten
Liquid mixes with the deionized water of 3.08ml, is then added drop-wise on 10g solid by this mixed solution.At air gas
Under atmosphere, by dry solid roasting 3 hours at 450 DEG C, 300 DEG C of hydrogen atmospheres reduce 1 hour, obtain
1%Rh-1.35%La/CeO2Catalyst.
Embodiment 8
Weigh 95.56g ammonium ceric nitrate and 209.38g carbamide respectively, by ammonium ceric nitrate and the carbamide of above-mentioned weighing
It is dissolved in deionized water and obtains 1500ml mixed solution, mixed solution is placed in there-necked flask, 110 DEG C
Oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours, the precipitate with deionized water of gained washed
To neutral, then washing with isopropanol, filter, in vacuum drying oven, 80 DEG C are dried 12 hours, dried solid
Roasting 2 hours at 500 DEG C, by gained solid preform, grind, are screened to 40～60 mesh, by 1.03ml
Mass fraction is the Rh (NO of 97.25%3)3Solution, 0.13ml mass concentration is the Mn (NO of 50%3)2Solution
Mix with the deionized water of 3.16ml, then this mixed solution is added drop-wise on 10g solid.Gained solid is put
In 110 DEG C of baking ovens overnight.In air atmosphere, by dry solid roasting 3 hours at 450 DEG C, 300 DEG C
Hydrogen atmosphere reduces 1 hour, obtains 1%Rh-0.3%Mn/CeO2Catalyst.
Embodiment 9
Weigh 95.56g ammonium ceric nitrate and 209.38g carbamide respectively, by ammonium ceric nitrate and the carbamide of above-mentioned weighing
It is dissolved in deionized water and obtains 1500ml mixed solution, mixed solution is placed in there-necked flask, 110 DEG C
Oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours, the precipitate with deionized water of gained washed
To neutral, then washing with isopropanol, filter, in vacuum drying oven, 80 DEG C are dried 12 hours, dried solid
Roasting 2 hours at 500 DEG C, by gained solid preform, grind, are screened to 40～60 mesh, by 1.03ml
Mass fraction is the Rh (NO of 97.25%3)3Solution, 0.26ml mass concentration is the Mn (NO of 50%3)2Solution
Mix with the deionized water of 3.03ml, then this mixed solution is added drop-wise on 10g solid.Gained solid is put
In 110 DEG C of baking ovens overnight.In air atmosphere, by dry solid roasting 3 hours at 450 DEG C, 300 DEG C
Hydrogen atmosphere reduces 1 hour, obtains 1%Rh-0.6%Mn/CeO2Catalyst.
Embodiment 10
Weigh 95.56g ammonium ceric nitrate and 209.38g carbamide respectively, by ammonium ceric nitrate and the carbamide of above-mentioned weighing
It is dissolved in deionized water and obtains 1500ml mixed solution, mixed solution is placed in there-necked flask, 110 DEG C
Oil bath heated and stirred 2 hours, closes heating and is stirred for 2 hours, the precipitate with deionized water of gained washed
To neutral, then washing with isopropanol, filter, in vacuum drying oven, 80 DEG C are dried 12 hours, dried solid
Roasting 2 hours at 500 DEG C, by gained solid preform, grind, are screened to 40～60 mesh, by 1.03ml
Mass fraction is the Rh (NO of 97.25%3)3Solution, 1.05ml mass concentration is the Mn (NO of 50%3)2Solution
Mix with the deionized water of 2.25ml, then this mixed solution is added drop-wise on 10g solid.Gained solid is put
In 110 DEG C of baking ovens overnight.In air atmosphere, by dry solid roasting 3 hours at 450 DEG C, 300 DEG C
Hydrogen atmosphere reduces 1 hour, obtains 1%Rh-2.4%Mn/CeO2Catalyst.
Performance test
Catalyst packing embodiment 1～10 prepared carries out synthesis gas synthesis second in fixed bed reactors
The reaction test of alcohol.Test process is: the internal diameter of rustless steel fixed bed reactors is 15mm, inside adds internal diameter and is
The corundum bushing pipe of 8mm, the consumption of catalyst is 1ml.Synthesis gas is passed through fixed bed reactors after mixing and enters
Row reaction, reaction temperature is 250～350 DEG C, and reaction pressure is 1.0～5.0MPa, n (H2)/n (CO)=1.0～4.0,
V (CO)=28ml/min.Off-line analysis is sampled after liquid product collection a period of time that condensation obtains, uncooled
Gas on-line chromatographic analysis.Result is shown in table 1.
Table 1
Knowable to upper table result, the catalyst activity that the present invention prepares is preferable, and the selectivity of alcohol is relatively
Height, close to 60% under more excellent composition, the selectivity of ethanol reaches as high as 26.6%.
Claims (10)
1. a rhodium base catalyst for one-step method from syngas ethanol, is made up of active component, auxiliary agent and carrier,
It is characterized in that, described active component is Rh, and auxiliary agent M is selected from alkali metal, alkaline-earth metal or transition metal
The combination of one or more in element, carrier is ceria or a certain proportion of cerium zirconium sosoloid.
2. rhodium base catalyst as claimed in claim 1, it is characterised in that the load of described active component Rh
Amount is 0.1～10wt%, preferably 1～9wt%；The mass ratio of described auxiliary agent M Yu Rh is 0.05～10, excellent
Elect 0.1～9 as.
3. rhodium base catalyst as claimed in claim 1, it is characterised in that active component, auxiliary agent and carrier unit
Element is respectively from corresponding nitrate or acetate；Auxiliary agent M is selected from Li, Na, K, Cs, La, Pr, Nd,
The combination of one or more in Sm, Mn, Fe, Co, Ni, Ru.
4. rhodium base catalyst as claimed in claim 1, it is characterised in that cerium zirconium sosoloid institute in described carrier
The cerium comprised and the atomic ratio of zirconium are between 0.1～10, and preferably atomic ratio is 1～4.
5. rhodium base catalyst as claimed in claim 1, it is characterised in that
The preparation process of ceria or cerium zirconium sosoloid is: (a) utilizes homogeneous precipitation method synthetic vectors forerunner
Thing, (b) by resulting vehicle predecessor through filtering, wash, being dried, roasting, tabletting, sieving becomes dioxy
Change cerium or cerium zirconium sosoloid.
6. rhodium base catalyst as claimed in claim 5, it is characterised in that
Homogeneous precipitation method described in step (a) is salt and the water-soluble slow-releasing alkali of metal needed for carrier to be dissolved in
In ionized water, being placed in there-necked flask by mixed solution, 60 DEG C～110 DEG C of oil bath heated and stirred are dissolved to solid,
Closing heating to be stirred for precipitation completely, wherein the usage amount of water-soluble slow-releasing type alkali is former needed for being synthetic vectors
1～60 times of each components precipitate institute alkali needed in material mixed solution；
In step (b), the solvent that washing uses is the organic solvent that surface tension is less, and organic solvent is different
Propanol, methanol, ethanol, pentane, be dried 6～24 under the conditions of 50～130 DEG C by carrier predecessor after washing
Hour, dried product exhibited is warming up to 300～800 DEG C of roastings 1～12 hours, gained with 1～10 DEG C/min speed
Product 10MPa compression molding, crushed 40～60 mesh sieves, obtained carrier.
7. rhodium base catalyst as claimed in claim 6, it is characterised in that described water-soluble slow-releasing alkali be carbamide,
Ethylenediamine, ethanolamine, diethanolamine, triethanolamine, triethylene tetramine one or more.
8. the preparation method of the arbitrary described rhodium base catalyst of claim 1-7, it is characterised in that step is such as
Under:
1) Rh salt and the M salt mixed aqueous solution of certain proportioning are prepared；
2) by step 1) mixed aqueous solution of gained is added drop-wise on ceria or cerium zirconium sosoloid, drying,
Described rhodium base catalyst is obtained after roasting, reduction；
Rh salt, M salt and ceria or cerium zirconium sosoloid are based on the component proportion described in claim 2 and 4
Amount.
9. preparation method as claimed in claim 8, it is characterised in that described step 2) in drying process be:
It is dried 3～15 hours at 60～140 DEG C, is dried 6～12 hours at preferably 80～120 DEG C；Roasting technique is: nitrogen
Under gas or air atmosphere, keep 1～10 hour at 200～700 DEG C, keep 2～6 hours at preferably 400～500 DEG C；
Reducing process is: under hydrogen atmosphere, holding 0.5～8 hour at 200～400 DEG C, preferably 250～350 DEG C
Lower holding 1～6 hours.
10. the application of rhodium base catalyst as described in claim 1-7 is arbitrary, it is characterised in that this rhodium base is catalyzed
Agent is in one-step method from syngas ethanol synthesis, and the temperature range of use is 200～400 DEG C, and preferable temperature is
250～350 DEG C；Using pressure limit is 0.1～8.0MPa, and preferred pressure range is 1.0～5.0MPa；H2/CO
It is 0.5～8.0, preferably H2/ CO is 1.0～4.0；Stabilization time is 3～48 hours, and preferably stabilization time is 12～24
Hour；Response time is 12～48 hours, and the preferably response time is 20～28 hours.
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| CN110898847A (en) * | 2019-08-14 | 2020-03-24 | 新奥科技发展有限公司 | Composite carrier type catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
| CN111282571A (en) * | 2020-03-20 | 2020-06-16 | 北京工业大学 | Preparation method and application of praseodymium-neodymium-palladium doped cerium-manganese composite catalyst |
| CN114425362A (en) * | 2020-10-14 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin and preparation method and application thereof |
| CN114570423A (en) * | 2021-12-27 | 2022-06-03 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing ethanol and propanol from synthesis gas and preparation method and application thereof |
| CN115382541A (en) * | 2022-08-19 | 2022-11-25 | 天津大学 | Method for regulating existence form of Rh species in rhodium-based catalyst |
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| CN110898847A (en) * | 2019-08-14 | 2020-03-24 | 新奥科技发展有限公司 | Composite carrier type catalyst for preparing low-carbon alcohol from synthesis gas and preparation method thereof |
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| CN111282571A (en) * | 2020-03-20 | 2020-06-16 | 北京工业大学 | Preparation method and application of praseodymium-neodymium-palladium doped cerium-manganese composite catalyst |
| CN111282571B (en) * | 2020-03-20 | 2022-06-21 | 北京工业大学 | Preparation method and application of praseodymium-neodymium-palladium doped cerium-manganese composite catalyst |
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| CN114425362B (en) * | 2020-10-14 | 2023-10-31 | 中国石油化工股份有限公司 | Catalyst for synthesizing low-carbon olefin, preparation method and application thereof |
| CN114570423A (en) * | 2021-12-27 | 2022-06-03 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing ethanol and propanol from synthesis gas and preparation method and application thereof |
| CN114570423B (en) * | 2021-12-27 | 2023-09-15 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing ethanol and propanol from synthesis gas, and preparation method and application thereof |
| CN115382541A (en) * | 2022-08-19 | 2022-11-25 | 天津大学 | Method for regulating existence form of Rh species in rhodium-based catalyst |
| CN115382541B (en) * | 2022-08-19 | 2024-02-02 | 天津大学 | Method for regulating existence form of Rh species in rhodium-based catalyst |
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