CN104772150A - Cobalt-based catalyst for synthesis gas one-step preparation of mixed alcohol and aldehyde, and preparation method and application thereof - Google Patents
Cobalt-based catalyst for synthesis gas one-step preparation of mixed alcohol and aldehyde, and preparation method and application thereof Download PDFInfo
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- CN104772150A CN104772150A CN201410017037.5A CN201410017037A CN104772150A CN 104772150 A CN104772150 A CN 104772150A CN 201410017037 A CN201410017037 A CN 201410017037A CN 104772150 A CN104772150 A CN 104772150A
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Abstract
The invention discloses a cobalt-based catalyst for synthesis gas one-step preparation of mixed alcohol and aldehyde, and a preparation method and an application thereof. The catalyst comprises Co, Mn, Cu, an alkali metal and an auxiliary agent. The preparation method includes the following steps: 1) according to the composition ratio of the catalyst, preparing a mixed salt solution from nitrates of Cu, Co, Mn and the auxiliary agent; 2) according to the composition ratio of the catalyst, preparing a precipitant solution from an alkali metal containing precipitant; 3) carrying out parallel flow of the mixed salt solution of the step 1) and the precipitant solution of the step 2), and co-precipitating; and 4) after precipitation is finished, aging, separating, washing, drying and calcinating, and thus obtaining the catalyst; or after precipitation is finished, aging, separating, washing, drying, calcinating, then impregnating in an alkali metal solution, drying, calcinating, and thus obtaining the catalyst. The obtained catalyst has the advantages of high mixed alcohol and aldehyde selectivity, low cost, simple and convenient preparation, easy industrial amplification and the like.
Description
Technical field
The present invention relates to a kind of catalyst and method for making thereof and application, particularly relate to a kind of cobalt-base catalyst for the synthesis of gas one-step method mixed alcohol, aldehyde and method for making thereof and application.
Background technology
C with the research that coal and natural gas are primary raw material Synthesis of mixed alcohols
1one of important content of chemistry.The application prospect of mixed alcohol is increasingly bright and clear, and as fuel additive, it has good dissolubility, volatility, driver behavior and higher octane number.In addition, it can also use as the raw material of some chemical products and clean fuel.
At present, existing directly by the report of synthesis gas Synthesis of mixed alcohols, in this kind of catalyst, most is representational following four kinds:
(1) modified methanol synthetic catalyst (Cu/ZnO/A1
2o
3, ZnO/Cr
2o
3): more typical patent has EP0034338A2 and U.S. US4513100.Such catalyst is developed by Italian Snam company and German Lugi company the earliest.
(2) modification F-T synthesizes Cu-Co catalyst: IFP (IFP) developed in the first Cu-Co co-precipitation low-carbon alcohol catalyst, has patent US4122110,4291126 and GB2118061,2158730.
(3) sulfur resistive MoS
2catalyst: molybdenum system sulfide catalyst (patent US4882360) of DOW company of U.S. exploitation.
(4) noble metal Rh catalyst based (as US4014913 and 4096164): after adding one to two kinds of transition metal or metal oxide auxiliary agent in support type Rh catalyst, have higher activity and selectivity, particularly to C to higher alcohols synthesis
2 +alcohol selective higher, product is based on ethanol.
Above catalyst system all can obtain the OXO products of certain content, and substantially all exists with the form of mixed alcohol in OXO products, but rarely has report for the research simultaneously containing a large amount of aldehyde in OXO products.Aldehydes is with a wide range of applications in fine chemistry industry, and the method that tradition prepares aldehydes is hydroformylation reaction, and namely alkene and synthesis gas directly react and prepare aldehydes, but due to raw material olefin more expensive, economy is subject to certain restrictions.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of cobalt-base catalyst for the synthesis of gas one-step method mixed alcohol, aldehyde and method for making thereof and application.Utilize this catalyst can prepare mixed alcohol, aldehyde by the one-step method from syngas that price is more cheap, there is advantage economically and industrial application value.
For solving the problems of the technologies described above, the cobalt-base catalyst for the synthesis of gas one-step method mixed alcohol, aldehyde of the present invention, comprising: cobalt (Co), manganese (Mn), copper (Cu), alkali metal and auxiliary agent;
Wherein, the mol ratio of Mn/Co is 0 ~ 10 (namely the mol ratio x of Mn/Co is 0≤x≤10, preferably 0.5≤x≤2); Alkali-metal content is the mass percent calculating accounting for catalyst with alkali metal oxide, and its scope y is 0 < y≤10%, preferably 0.5% < y≤2%;
The molar ratio range of Cu/Co is 0 ~ 10, preferably 0.1 ~ 1;
Auxiliary agent is selected from least one in transition metal, rare earth metal or alkaline-earth metal, and the molar ratio range of auxiliary agent and Co is 0 ~ 10, and preferably 0.1 ~ 1.
Described alkali metal is selected from the one in lithium (Li), sodium (Na), potassium (K) or caesium (Cs), is preferably sodium.
Described transition metal comprises: Fe, Ni, Zr, Zn, Ru, Rh or Pd etc.;
Described rare earth metal comprises: La or Ce etc.;
Affiliated alkaline-earth metal comprises: Mg, Ca or Ba etc.;
In addition, the invention also discloses the preparation method of above-mentioned catalyst, comprise the steps:
(1) according to the composition and ratio of catalyst, the nitrate of Cu, Co, Mn and auxiliary agent is mixed with mixing salt solution (i.e. certain density homogeneous mixture solotion);
(2) according to the composition and ratio of catalyst, the precipitating reagent of alkali metal containing is mixed with precipitant solution (i.e. certain density homogeneous solution);
Wherein, precipitating reagent is selected from least one in sodium carbonate, sodium acid carbonate, NaOH, potash, saleratus or potassium hydroxide;
(3) 10 ~ 100 DEG C, pH6 ~ 12 time, by the precipitant solution co-precipitation of the mixing salt solution of step (1) and step (2), namely the precipitant solution of the mixing salt solution of step (1) and step (2) is added dropwise in settling vessel simultaneously;
(4) after precipitation terminates, at 10 ~ 100 DEG C, aging 0.5 ~ 24h; After aging end, operate according to following step (5A) or (5B), obtain catalyst:
(5A), after aging, after separation, washing, drying and roasting, catalyst is obtained;
(5B) after aging, through being separated, washing, after dry and roasting, obtain the presoma of catalyst, after the presoma of this catalyst floods above-mentioned alkali metal soln, drying, roasting, obtain catalyst.
In described step (1), total metal molar concentration range of mixing salt solution is 0.01 ~ 10mol/L.
In described step (2), precipitating reagent is preferably sodium carbonate; The molar concentration scope of precipitant solution is 0.01 ~ 10mol/L.
In described step (3), the mixed volume ratio of mixing salt solution and precipitant solution is 1: 5 ~ 5: 1, preferably 1: 2 ~ 2: 1; And preferably 50 ~ 80 DEG C, pH7 ~ 9 time, by the precipitant solution co-precipitation of the mixing salt solution of step (1) and step (2).
In described step (4), preferably at 50 ~ 80 DEG C, aging 1 ~ 5h.
In described step (5A) or (5B), baking temperature is 50 ~ 150 DEG C, preferably 100 ~ 120 DEG C; Drying time is 1 ~ 24h, preferably 10 ~ 12h; Sintering temperature is 200 ~ 800 DEG C, preferably 300 ~ 400 DEG C; Roasting time is 0.5 ~ 24h, preferably 2 ~ 5h.
In described step (5B), the concentration range of alkali metal soln is 0.1mol/L ~ 4.0mol/L, preferred 0.5mol/L ~ 1.0mol/L; Dipping temperature is generally room temperature, and dip time can be 1 ~ 24h; Presoma incipient impregnation (namely according to water absorption rate 1: the 1) alkali metal soln of preferred catalyst.
Moreover, the invention discloses the application of this catalyst, in the catalytic reaction namely for the synthesis of gas one-step method mixed alcohol, aldehyde.
Wherein, catalytic reaction condition is: reaction temperature is 150 ~ 350 DEG C, preferably 200 ~ 300 DEG C; Operating pressure is 0.1 ~ 13Mpa, preferably 2 ~ 6Mpa, especially preferably 6Mpa; Reaction velocity is 100 ~ 10000h
-1, preferably 2000 ~ 6000h
-1, especially preferably 6000h
-1; Synthesis gas is by H
2form with CO, and H
2the mol ratio of/CO is 0.1 ~ 10, preferably 1 ~ 3.
Before the catalytic reaction of described catalyst for the synthesis of gas one-step method mixed alcohol, aldehyde, need to activate, wherein, activation condition is: in the atmosphere of hydrogen of dilution, gradient increased temperature to 150 ~ 600 °, preferably 200 ~ 400 DEG C; Activation 1 ~ 24h, preferably 6 ~ 12h.
The atmosphere of hydrogen of described dilution is the gaseous mixture of hydrogen and inert gas, the gaseous mixture of preferred hydrogen and nitrogen, and wherein mol ratio shared by hydrogen is 10% ~ 50%, preferably 10%; The air speed of the atmosphere of hydrogen of dilution is 1000 ~ 20000h
-1, preferred 20000h
-1.
In the present invention, mixed alcohol comprises positive structure and the isomery alcohol that methyl alcohol, ethanol and carbon number are more than 2, and carbon number reaches as high as more than 20; Mixed aldehyde comprises positive structure and the isomery aldehyde that acetaldehyde and carbon number are more than 3, and carbon number reaches as high as more than 10.
Gained catalyst of the present invention has high mixed alcohol, aldehyde is selective, with low cost, prepare easy and be easy to advantage such as industry amplification etc., and wherein, the selective of total oxygenatedchemicals can reach more than 50C%, C
2the ratio of above oxygenatedchemicals in total oxygenatedchemicals can up to more than 90wt%, and by changing the ratio of active component in catalyst, in oxygenatedchemicals mixed alcohol and mixed aldehyde mass ratio can between 0.5 and 2 modulation.
Detailed description of the invention
In following examples, the synthesis gas related to is by CO and H
2formed.
Embodiment 1
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.2/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L.By Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 224mL mixed solution and 136mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, obtain catalyst.
In the reaction of this catalyst for the synthesis of gas mixed alcohol, aldehyde, reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h
-1, reduction temperature (can gradient increased temperature) is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature (namely 220 DEG C), with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 2
By Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Co/Mn=1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L.By Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 210mL mixed solution and 215mL precipitant solution are carried out co-precipitation, and wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 120 DEG C of oven dry 12h, with temperature programming to 330 DEG C roasting 3h after grinding evenly, obtain the presoma of catalyst.
Adopt incipient impregnation method, by the presoma of this catalyst dipping Na
2cO
3the aqueous solution, the content of Na is 1% (with Na
2the quality of O is relative to the quality meter of catalyst Precursors), wherein, dipping temperature is room temperature, and dip time is 24h, then, be placed in fume hood to spend the night, the baking oven being placed in 60 DEG C spends the night oven dry (namely drying 12h), after grinding evenly, with temperature programming to 330 DEG C roasting 3h, compressing tablet is also crushed to 40 ~ 60 orders, obtains catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h
-1, reduction temperature (can gradient increased temperature) is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 240 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 3
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=1.5/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L.By Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 187mL mixed solution and 204mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, obtain the presoma of catalyst.
Adopt incipient impregnation method, by the presoma of this catalyst dipping Na
2cO
3the aqueous solution, the content of Na is 1% (with Na
2the quality of O is relative to the quality meter of catalyst Precursors), wherein, dipping temperature is room temperature, dip time is 20h, is then placed in fume hood and spends the night, and the baking oven being placed in 60 DEG C spends the night oven dry (namely drying 12h), after grinding evenly, with temperature programming to 330 DEG C roasting 3h, compressing tablet is also crushed to 40 ~ 60 orders, obtains catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 1.5ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h
-1, reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 230 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 4
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.2/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 323mL mixed solution and 125mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, obtain the presoma of catalyst.
Adopt incipient impregnation method, by the presoma of this catalyst dipping Na
2cO
3the aqueous solution, the content of Na is 3% (in the quality of the quality of Na2O relative to catalyst Precursors), wherein, dipping temperature is room temperature, and dip time is 10h, then be placed in fume hood to spend the night, the baking oven being placed in 60 DEG C spends the night oven dry (namely drying 12h), after grinding evenly, with temperature programming to 330 DEG C roasting 3h, compressing tablet is also crushed to 40 ~ 60 orders, obtains catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 1.5ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h
-1, reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 230 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 5
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.2/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 254mL mixed solution and 183mL precipitant solution are carried out co-precipitation, and wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 120 DEG C of oven dry 12h, with temperature programming to 330 DEG C roasting 3h after grinding evenly, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h-1, and reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 12000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 6
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.1/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 218mL mixed solution and 163mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 8000h
-1, reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 7
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.6/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 217mL mixed solution and 135mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 8000h
-1, reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 8
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.2/1/2 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 176mL mixed solution and 221mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 8000h
-1, reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 9
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=1.2/1/2 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 169mL mixed solution and 201mL precipitant solution are carried out co-precipitation, and wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 120 DEG C of oven dry 12h, with temperature programming to 330 DEG C roasting 3h after grinding evenly, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 8000h
-1, reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 10
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o, Mn (NO
3)
2(50%) with Zr (NO
3)
45H
2o is dissolved in a certain amount of deionized water by Cu/Co/Mn/Zr=0.2/1/1/0.15 (mol ratio) and forms the mixed solution that total metal concentration is 1mol/L.By K
2cO
3be dissolved in a certain amount of deionized water and form K
+concentration is the precipitant solution of 1mol/L.
Adopt two coprecipitations, above-mentioned for 243mL mixed solution and 231mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 9, controls titration temperature at 80 DEG C, after titration completely, with aging 12h at 80 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 400 DEG C roasting 5h, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 10000h
-1, reduction temperature is 300 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 6000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=1.8 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 11
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o, Mn (NO
3)
2(50%) with Ce (NO
3)
36H
2o is dissolved in a certain amount of deionized water by Cu/Co/Mn/Ce=0.2/1/1/0.1 (mol ratio) and forms the mixed solution that total metal concentration is 2mol/L.By Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 167mL mixed solution and 224mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (50ml), controlling titration environment pH is 7, controls titration temperature at 65 DEG C, after titration completely, with aging 24h at 80 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 100 DEG C and dry 12h, after grinding evenly, with temperature programming to 400 DEG C roasting 8h, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 3000h
-1, reduction temperature is 350 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 240 DEG C, and reaction velocity is 5000h
-1, operating pressure is 4.0MPa, the H in synthesis gas
2mol ratio=1.8 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 12
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o, Mn (NO
3)
2(50%) with Mg (NO
3)
26H
2o is dissolved in a certain amount of deionized water by Cu/Co/Mn/Mg=0.4/1/1.2/0.05 (mol ratio) and forms the mixed solution that total metal concentration is 0.5mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 0.5mol/L.
Adopt two coprecipitations, above-mentioned for 356mL mixed solution and 412mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (150ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 4h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 24h, after grinding evenly, with temperature programming to 350 DEG C roasting 12h, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 15000h
-1, reduction temperature is 300 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% synthesis gas (mol ratio) by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 5000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2.0 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 13
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.2/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L, by Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 254mL mixed solution and 183mL precipitant solution are carried out co-precipitation, and wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, control titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, through centrifugal, washing 6 times after, be placed in baking oven Program and be warming up to 120 DEG C of oven dry 12h, with temperature programming to 330 DEG C roasting 3h after grinding evenly, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h-1, and reduction temperature is 250 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 240 DEG C, and reaction velocity is 12000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 14
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.2/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L.By Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 224mL mixed solution and 136mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 8, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 65 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 12h, after grinding evenly, with temperature programming to 400 DEG C roasting 3h, obtain catalyst.
In the reaction of this catalyst for the synthesis of gas mixed alcohol, aldehyde, reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h
-1, reduction temperature (can gradient increased temperature) is 300 DEG C, and the time is 5h.
After reduction process terminates, be down to goal response temperature (namely 220 DEG C), with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 6000h
-1, operating pressure is 8.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Embodiment 15
By Cu (NO
3)
23H
2o, Co (NO
3)
26H
2o and Mn (NO
3)
2(50%) be dissolved in a certain amount of deionized water by Cu/Co/Mn=0.6/1/1 (mol ratio) and form the mixed solution that total metal concentration is 2mol/L.By Na
2cO
3be dissolved in a certain amount of deionized water and form Na
+concentration is the precipitant solution of 2mol/L.
Adopt two coprecipitations, above-mentioned for 217mL mixed solution and 135mL precipitant solution are carried out co-precipitation, wherein, mother liquor selects deionized water (100ml), controlling titration environment pH is 9, controls titration temperature at 65 DEG C, after titration completely, with aging 2h at 80 DEG C in mother liquor, after centrifugal, washing 6 times, be placed in baking oven Program and be warming up to 120 DEG C and dry 24h, after grinding evenly, with temperature programming to 330 DEG C roasting 3h, obtain catalyst.
This catalyst is for the synthesis of in gas mixed alcohol, aldehyde reaction, and reaction unit is fixed bed reactors, and loaded catalyst is 1.5ml, and with the dilution of 3ml fine quartz sand, first carry out the reduction (namely activating) of catalyst, wherein, reducing atmosphere is H
2with N
2gaseous mixture, H
2/ gaseous mixture=10% (mol ratio), reduction air speed is 20000h
-1, reduction temperature is 250 DEG C, and the time is 10h.
After reduction process terminates, be down to goal response temperature, with 10% (mol ratio) synthesis gas by reactor pressure back pressure to 6.0MPa, emptying after about 24h.Reaction temperature is 220 DEG C, and reaction velocity is 5000h
-1, operating pressure is 6.0MPa, the H in synthesis gas
2mol ratio=2 of/CO, use kind and the content of various component contained by gas-chromatography (Shimadzu GC-2014, GC-2010plus) assay products, and correspondingly calculate the conversion ratio of this reaction and selective, and reaction result is in table 1 and table 2.
Table 2 embodiment catalyst reaction product distribution results
From the data of table 1 and table 2, synthesis gas can one-step method mixed alcohol, aldehyde, prepared by regulating catalyst and change reaction process condition, product distribution can free modulation, specific as follows: selective between 30% to 70% in gross product of oxygenatedchemicals (comprising mixed alcohol and mixed aldehyde), and C
2+product reaches as high as more than 90% in oxygenatedchemicals distribution, and mixed alcohol accounts for the ratio of total oxygenatedchemicals (ratio of corresponding mixed aldehyde is then between 70% to 30%) between 30% to 70%.
Claims (15)
1. for the synthesis of a cobalt-base catalyst for gas one-step method mixed alcohol, aldehyde, it is characterized in that, comprising: Co, Mn, Cu, alkali metal and auxiliary agent;
Wherein, the mol ratio of Mn/Co is 0 ~ 10;
Alkali-metal content is the mass percent calculating accounting for catalyst with alkali metal oxide, and its scope y is 0 < y≤10%;
The molar ratio range of Cu/Co is 0 ~ 10;
Auxiliary agent is selected from least one in transition metal, rare earth metal or alkaline-earth metal, and the molar ratio range of auxiliary agent and Co is 0 ~ 10.
2. cobalt-base catalyst as claimed in claim 1, is characterized in that: the mol ratio of described Mn/Co is 0.5 ~ 2;
Alkali-metal content is the mass percent calculating accounting for catalyst with alkali metal oxide, and its scope y is 0.5% < y≤2%;
The molar ratio range of Cu/Co is 0.1 ~ 1;
The molar ratio range of auxiliary agent and Co is 0.1 ~ 1.
3. cobalt-base catalyst as claimed in claim 1, is characterized in that: described alkali metal is selected from the one in Li, Na, K or Cs;
Described transition metal comprises: Fe, Ni, Zr, Zn, Ru, Rh or Pd;
Described rare earth metal comprises: La or Ce;
Affiliated alkaline-earth metal comprises: Mg, Ca or Ba.
4. cobalt-base catalyst as claimed in claim 3, is characterized in that: described alkali metal is Na.
5. a preparation method for the cobalt-base catalyst as described in any one of claim 1-4, is characterized in that, comprises step:
(1) according to the composition and ratio of catalyst, the nitrate of Cu, Co, Mn and auxiliary agent is mixed with mixing salt solution;
(2) according to the composition and ratio of catalyst, the precipitating reagent of alkali metal containing is mixed with precipitant solution;
Wherein, precipitating reagent is selected from least one in sodium carbonate, sodium acid carbonate, NaOH, potash, saleratus or potassium hydroxide;
(3) 10 ~ 100 DEG C, pH6 ~ 12 time, by the precipitant solution co-precipitation of the mixing salt solution of step (1) and step (2);
(4) after precipitation terminates, at 10 ~ 100 DEG C, aging 0.5 ~ 24h; After aging end, operate according to following step (5A) or (5B), obtain catalyst:
(5A), after aging, after separation, washing, drying and roasting, catalyst is obtained;
(5B) after aging, through being separated, washing, after dry and roasting, obtain the presoma of catalyst, after the presoma of this catalyst floods above-mentioned alkali metal soln, drying, roasting, obtain catalyst.
6. method as claimed in claim 5, it is characterized in that: in described step (1), total metal molar concentration range of mixing salt solution is 0.01 ~ 10mol/L.
7. method as claimed in claim 5, it is characterized in that: in described step (2), precipitating reagent is sodium carbonate; The molar concentration scope of precipitant solution is 0.01 ~ 10mol/L.
8. method as claimed in claim 5, is characterized in that: in described step (3), and the mixed volume of mixing salt solution and precipitant solution is than being 1:5 ~ 5:1;
In step (3), 50 ~ 80 DEG C, pH7 ~ 9 time, by the precipitant solution co-precipitation of the mixing salt solution of step (1) and step (2).
9. method as claimed in claim 8, is characterized in that: the mixed volume of described mixing salt solution and precipitant solution is than being 1:2 ~ 2:1.
10. method as claimed in claim 5, is characterized in that: in described step (4), at 50 ~ 80 DEG C, aging 1 ~ 5h.
11. methods as claimed in claim 5, is characterized in that: in described step (5A) or (5B), baking temperature is 50 ~ 150 DEG C; Drying time is 1 ~ 24h; Sintering temperature is 200 ~ 800 DEG C; Roasting time is 0.5 ~ 24h;
In step (5B), the concentration range of alkali metal soln is 0.1mol/L ~ 4.0mol/L; Dipping temperature is room temperature, and dip time is 1 ~ 24h, and with the presoma incipient impregnation alkali metal soln of catalyst.
12. methods as claimed in claim 11, is characterized in that: in described step (5A) or (5B), baking temperature is 100 ~ 120 DEG C; Drying time is 10 ~ 12h; Sintering temperature is 300 ~ 400 DEG C; Roasting time is 2 ~ 5h.
In step (5B), the concentration range of alkali metal soln is 0.5mol/L ~ 1.0mol/L.
The application of 13. 1 kinds of cobalt-base catalysts as described in any one of claim 1-4, is characterized in that: in the catalytic reaction for the synthesis of gas one-step method mixed alcohol, aldehyde;
Wherein, catalytic reaction condition is: reaction temperature is 150 ~ 350 DEG C; Operating pressure is 0.1 ~ 13Mpa; Reaction velocity is 100 ~ 10000h
-1; Synthesis gas is by H
2form with CO, and H
2the mol ratio of/CO is 0.1 ~ 10.
14. apply as claimed in claim 13, it is characterized in that: described catalytic reaction condition is: reaction temperature is 200 ~ 300 DEG C; Operating pressure is 2 ~ 6Mpa; Reaction velocity is 2000 ~ 6000h
-1; Synthesis gas is by H
2form with CO, and H
2the mol ratio of/CO is 1 ~ 3.
15. apply as claimed in claim 13, it is characterized in that: before the catalytic reaction of described catalyst for the synthesis of gas one-step method mixed alcohol, aldehyde, need to activate, and wherein, activation condition is: in the atmosphere of hydrogen of dilution, are warming up to 150 ~ 600 DEG C; Activation 1 ~ 24h;
The atmosphere of hydrogen of described dilution is the gaseous mixture of hydrogen and inert gas, and wherein, mol ratio shared by hydrogen is 10% ~ 50%; The air speed of the atmosphere of hydrogen of dilution is 1000 ~ 20000h
-1.
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| CN111420674B (en) * | 2020-04-09 | 2023-03-21 | 中国科学院上海高等研究院 | Catalyst for directly synthesizing alcohol aldehyde oxygen-containing product by synthesis gas one-step method and application |
| CN115400763A (en) * | 2022-09-02 | 2022-11-29 | 上海盛剑环境系统科技股份有限公司 | For CO 2 Catalyst for preparing higher alcohol by hydrogenation, and preparation method and application of catalyst |
| CN115400763B (en) * | 2022-09-02 | 2024-07-12 | 上海盛剑环境系统科技股份有限公司 | For CO2Catalyst for preparing higher alcohol by hydrogenation, preparation method and application of catalyst |
| CN115999555A (en) * | 2022-12-02 | 2023-04-25 | 内蒙古鄂尔多斯电力冶金集团股份有限公司 | For CO 2 Catalyst for preparing higher alcohol by hydrogenation, preparation method and application thereof |
| CN116943662A (en) * | 2023-06-13 | 2023-10-27 | 北京海望氢能科技有限公司 | Heterogeneous catalyst and preparation method and application thereof |
| CN116943662B (en) * | 2023-06-13 | 2024-02-20 | 北京海望氢能科技有限公司 | Heterogeneous catalyst and preparation method and application thereof |
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Application publication date: 20150715 |