CN103084192A - Cobalt phosphide catalyst for preparing 3-pentanone and propanal from hydrogen, carbon monoxide and ethylene - Google Patents
Cobalt phosphide catalyst for preparing 3-pentanone and propanal from hydrogen, carbon monoxide and ethylene Download PDFInfo
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Abstract
The present invention provides a cobalt phosphide catalyst for preparing 3-pentanone and propanal from hydrogen, carbon monoxide and ethylene. Specifically the present invention provides an active carbon supported cobalt phosphide catalyst for preparing 3-pentanone and propanal from H2, CO and ethylene under a certain temperature and pressure reaction condition. The catalyst comprises a main active component, an additive and a carrier, wherein the main active component is a cobalt phosphide, the additive is one or a plurality of alkali metals or oxides thereof, and the carrier is selected from active carbon. In a fixed bed reactor, at a creation temperature, under a certain pressure and in the presence of the catalyst, high activity and high selectivity preparation of products such as 3-pentanone and propanal by using H2, CO and ethylene can be achieved.
Description
Technical field
The present invention relates to a kind of for prepare the phosphide catalyst of the supported cobalt of propione and propionic aldehyde take hydrogen, carbon monoxide and ethene as raw material.More specifically, the present invention relates under uniform temperature and pressure, with CO, H
2With the ethene gaseous mixture be the catalyst of the phosphide of the raw material activated carbon supported cobalt of efficiently producing propione and propionic aldehyde.
Technical background
Propione is important fine chemical material and high-grade solvent, is widely used in synthetic dyestuffs, medicine and agricultural chemicals and is used as organic solvent etc.As the key intermediate of producing pesticide herbicide Pendimethalin and anti-avian influenza medicine Tamiflu, the consumption of propione is increasing year by year.The method of synthetic propione has: 3-amylalcohol oxidizing process, methyl ethyl ketone and methanol by one-step method, methyl alcohol butanone one-step method, pentadiene method, acid-acid system etc.In recent years, China has researched and developed in industrial production and produced the method for propione by the 3-amylalcohol with the sodium chromate oxidation in sulfuric acid, but raw material dependence on import and process are seriously polluted.Acid-acid system is the propione synthetic method of present acknowledged tool application prospect, and wherein propione is transformed through decarboxylation by propionic acid, and the method not only conversion ratio is high, and without any three wastes problem, belongs to green clean preparation method.But propionic acid is to be that raw material directly or indirectly gets under the effect of noble metal catalyst by synthesis gas and ethene, and namely described method need to be used noble metal catalyst, and its cost is high.The propionic acid production method of current production rate maximum comprises following two steps: propionic aldehyde production and propionic aldehyde oxidation.At first adopt the ethene carbonylation method of Rh catalysis to produce propionic aldehyde, then make catalyst generation free-radical oxidation reaction generation propionic acid with manganese.This method technical maturity, but technological process is complicated, equipment is various, having relatively high expectations to the e-quipment and pipe material.New propionic acid production technology directly prepares propionic acid take ethene, carbon monoxide and hydrogen as raw material under carbonyl Rh catalysis, still due to the use of rhodium carbonyl catalyst, production cost is very high.
Startseva etc. (Kinet.Catal.25,424,1984)) find first: activated carbon supported Co
2(CO)
8Catalyst can make ethene, CO and H
2Catalytic reaction occurs in O, and the existence of propione detected in catalytic reaction products.Takahashi etc. (Chemistry Letter, pp205 1990, Journal of Catalysis 136,531 (1992)) have reported: under the effect of Rh/ activated-carbon catalyst, and CO, H
2Prepare propione and propionic aldehyde with the ethene gaseous mixture.Breysse etc. (Catalysis Letter, 32,55 (1995)) have reported: the catalyst of activated carbon supported Rh and Ir is used for the ethylene hydrogenation formylation reaction, and has measured the generation of propione.
But above-mentioned catalyst has all used noble metal.
Summary of the invention
It is a kind of for prepare the phosphide catalyst of the supported cobalt of propione and propionic aldehyde take hydrogen, carbon monoxide and ethene as raw material that one object of the present invention is to provide.Compared with prior art, catalyst of the present invention can not adopt rare precious metal, significantly reduces simultaneously energy consumption of reaction and improves processing safety, improves simultaneously CO, H
2Efficiently prepare the space-time yield of propione and propionic aldehyde with selective with the ethene gaseous mixture.
For achieving the above object, the invention provides a kind of for prepare the loaded catalyst of propione and propionic aldehyde take hydrogen, carbon monoxide and ethene as raw material, wherein: described catalyst is comprised of main active component, auxiliary agent and carrier, the weight of described main active component is 0.5~30.0% of described catalyst weight, and the weight of described auxiliary agent is 0~18.0% of described catalyst weight; Described main active component is the phosphide of cobalt; Described auxiliary agent is one or more alkali metal or its oxide; Described carrier is active carbon or CNT; The specific area of wherein said active carbon is 500~1350m
2/ g, and average pore size is 3~100nm; And the specific area of described CNT is 100~400m
2/ g, and average pore size is 2~20nm.
Described active carbon is preferably cocoanut active charcoal, almond active carbon.The specific area of described cocoanut active charcoal is 550~1350m
2/ g, and average pore size is 5~90nm.The specific area of described almond active carbon is 500~1250m
2/ g, and average pore size is 4~100nm.
Described hydrogen and carbon monoxide can be from synthesis gas.
Description of drawings:
Fig. 1 is the high resolution electron microscopy photo of the sample of embodiment 6 preparations.
Fig. 2 is ethene hydroformylation reaction unit schematic diagram.
The specific embodiment
The below elaborates content of the present invention.
Catalyst of the present invention is under uniform temperature and pressure, with CO, H
2With the ethene gaseous mixture be that raw material is efficiently produced the loaded catalyst of propione and propionic aldehyde by hydroformylation reaction.Catalyst is comprised of main active component, auxiliary agent and carrier three parts.Main active component is the phosphide of Co.Auxiliary agent is one or more in alkali metal such as K, Na and Li or its oxide.Carrier is selected active carbon or CNT etc.In fixed bed reactors by CO, H
2Hydroformylation reaction under this catalyst action, occurs in the reaction raw materials with ethene forms, but high activity, highly selective prepare propione and propionic aldehyde.
In reaction system of the present invention, can be directly with CO, H
2Be passed in the fixed bed reactors that pellet type catalyst of the present invention is housed with ethene, carry out hydroformylation reaction, with preparation propione and propionic aldehyde.
Based on the weight of catalyst of the present invention, the better weight percentage of main active component is 0.5~30.0%%, and better weight content is 1.0~25.0%; The better weight percentage of auxiliary agent is 0~18.0%, and better content is 0~15.0%; Carrier can be selected active carbon, and its specific area is preferably 500~1350m
2/ g, average pore size is 5~100nm, better specific area is 550~1300m
2/ g, average pore size is more preferred from 8~95nm; Carrier also can adopt CNT, and the better specific area of CNT is 100~400m
2/ g, average pore size is that the better specific area of 2~20nm is 110~300m
2/ g, better aperture is 5~10nm.
Described active carbon can be cocoanut active charcoal, and its specific area is 550~1350m
2/ g, and average pore size is 5~90nm.Preferably, the specific area of described cocoanut active charcoal is 750~1250m
2/ g, and average pore size is 8~85nm.
Described active carbon can be the almond active carbon, and its specific area is 500~1250m
2/ g, and average pore size is 4~100nm.Preferably, the specific area of described almond active carbon is 700~1150m
2/ g, and average pore size is 8~85nm.
Catalyst of the present invention one or more preparations in can be by the following method: infusion process, the precipitation method and hydrothermal synthesis method.
The shell carbon that adopts commodity is the active carbon that raw material is produced, and granularity is that the CNT of 20-40 order or commodity is as the carrier of catalyst.Such carrier before use through the deionized water cyclic washing to washing electrical conductivity of water in every meter of 20-25 milli Siemens (mS/m).This washing after carrier in baking oven 90-100 ℃ dry 8-10 hour.At first measure the water absorption of carrier, just to make the moistening water yield of carrier as water absorption.Need to add the red fuming nitric acid (RFNA) of 2-3ml and be heated to 40-50 ℃ of dissolving when configuring maceration extract in beaker, the liquid volume of adjusting maceration extract is the water absorption of carrier.Carrier is contained in culture dish, and the maceration extract that will contain active component and adjuvant component is poured in culture dish, and it is mixed in carrier.Sample after hybrid infusion is dried to substantially dry in the water-bath of 60 ℃, dried 8 hours for 80 ℃ in baking oven.At first this catalyst will carry out the reduction activation process before use, and its reduction activation condition is: H
2Stream (GHSV=3000h
-1), normal pressure, 5 ℃/min is warming up to 430 ℃ from room temperature, and 430 ℃ activate 8 hours.
Catalyst of the present invention can be used at fixed bed reactors, under uniform temperature and pressure, with CO, H
2With the ethene gaseous mixture be that raw material is efficiently produced propione and propionic aldehyde by hydroformylation reaction, in wherein said hydroformylation reaction, reaction temperature is 120 ℃, reaction pressure is 3.0MPa, CO/H
2/ ethene=1/1/1 (mol ratio), and air speed is 2000h
-1With CO, H
2With the ethene gaseous mixture be that raw material is produced the method for propione and propionic aldehyde by hydroformylation reaction, can be 15% left and right to the conversion ratio of ethene, and to propionic aldehyde selectively can be 45% left and right, selectively can be 43% left and right to propione.
The present invention will be further described below by specific embodiment.
Embodiment 1
The catalyst of embodiment 1 is 15%Co-0.66%P/ coconut husk charcoal (Co/P=12 mol ratio).(the 20-40 order, the BET specific area is: 1135m to take 10.0 gram coconut husk charcoals
2/ g, average pore size is 21nm), configuration 8ml contains 7.80 gram Co (NO
3)
2.6H
2O and 0.3 gram (NH
4)
2HPO
4The aqueous solution, drip the approximately dense HNO of 2ml
3, heating for dissolving, with the above-mentioned coconut husk charcoal carrier of this aqueous solution dipping, 60 ℃ of water-baths oven dry, 80 ℃ of oven for drying 8 hours.This moment, the weight of drying sample was about 18.45 grams.The product of preparing is the precursor of 15%Co-0.66%P/ coconut husk Pd/carbon catalyst.
The precursor of above-mentioned catalyst takes the above-mentioned catalyst of 5ml (3.4 gram) and is placed in φ 10 internal diameters before using,, length is the stainless steel reactor stage casing of 30 centimetres, fill with 20-40 purpose quartz sand at two ends.Catalyst is H in reactor
2(GHSV=3000h
-1) carry out the in-situ reducing activation in stream, condition is: normal pressure, 5 ℃/min is warming up to 430 ℃ from room temperature, keeps 8 hours at H
2Be cooled to reaction temperature in stream, thereby obtain 15%Co-0.66%P/ coconut husk Pd/carbon catalyst.
Embodiment 2
The catalyst of embodiment 2 is 15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio).(the BET specific area is: 1070m except adopting the almond charcoal
2/ g, average pore size is 25nm) outside, remaining preparation process is identical with embodiment 1.
Embodiment 3
The catalyst of embodiment 3 is 15%Co-0.66%P/ CNT (Co/P=12 mol ratio).(the BET specific area is: 254m except adopting CNT
2/ g, average pore size is 7.5nm) outside, remaining preparation process is identical with embodiment 1.
Embodiment 4
The catalyst of embodiment 4 is 0.4%Li15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio).Except add 0.4 gram LiNO in the aqueous solution identical with embodiment 2 configurations
3Outward, remaining preparation process is identical with embodiment 2.
Embodiment 5
The catalyst of embodiment 5 is 0.4%Na15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio).Except add 0.15 gram NaNO in the aqueous solution identical with embodiment 2 configurations
3Outward, remaining preparation process is identical with embodiment 2.
Embodiment 6
The catalyst of embodiment 6 is 0.5%K15%Co-0.66%P/ coconut husk charcoal (Co/P=12 mol ratio).Except add 0.12 gram KNO in the aqueous solution identical with embodiment 1 configuration
3Outward, remaining preparation process is identical with embodiment 1.
Embodiment 7
The catalyst of embodiment 7 is 1%Ni15%Co-0.66%P/ coconut husk charcoal (Co/P=12 mol ratio).Except add 0.52 gram Ni (NO in the aqueous solution identical with embodiment 1 configuration
3)
2.6H
2Outside O, remaining preparation process is identical with embodiment 1.
Embodiment 8
The catalyst of embodiment 8 is 1.0%La15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio).Except add 0.32 gram La (NO in the aqueous solution identical with embodiment 2 configurations
3)
3.6H
2Outside O, remaining preparation process is identical with embodiment 2.
Embodiment 9
The catalyst of embodiment 9 is 0.5%Ce15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio).Except add 0.16 gram Ce (NO in the aqueous solution identical with embodiment 2 configurations
3)
3.6H
2Outside O, remaining preparation process is identical with embodiment 2.
Embodiment 10
The catalyst of embodiment 10 is 1.0%Cu15%Co-0.66%P/ coconut husk charcoal (Co/P=12 mol ratio).Except add 0.38 gram Cu (NO in the aqueous solution identical with embodiment 1 configuration
3)
2.3H
2Outside O, remaining preparation process is identical with embodiment 1.
Embodiment 11
Embodiment 11 catalyst are 1.0%Mn15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except add 0.64 gram 50wt.%Mn (NO in the aqueous solution identical with embodiment 2 configurations
3)
2Outside the aqueous solution, all the other preparation processes are identical with embodiment 2.
Embodiment 12
The catalyst of embodiment 12 is 1.0%Mo15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except add 0.19 gram (NH in the aqueous solution identical with embodiment 2 configurations
4)
6Mo
7O
24.4H
2Outside O, remaining preparation process is identical with embodiment 2.
Embodiment 13
The catalyst of embodiment 13 is 0.5%Zr15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except add 0.24 gram Zr (NO in the aqueous solution identical with embodiment 2 configurations
3)
4.5H
2Outside O, remaining preparation process is identical with embodiment 2.
Embodiment 14
Embodiment 14 catalyst are 0.5%Fe15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except add 0.36 gram Fe (NO in the aqueous solution identical with embodiment 2 configurations
3)
3.6H
2Outside O, remaining preparation process is identical with embodiment 2.
Embodiment 15
Embodiment 15 catalyst are 0.5%Zn15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except add 0.22 gram Zn (NO in the aqueous solution identical with embodiment 2 configurations
3)
2.6H
2Outside O, remaining preparation process is identical with embodiment 2.
The high resolution electron microscopy photo of the sample of embodiment 6 preparation is seen accompanying drawing 1, can find that by Fig. 1 active component Co and P are that phosphide with metal Co and Co exists.
Select fixed bed reactors, the schematic diagram of its reaction unit is seen accompanying drawing 2.After opening stop valve 2,5 and 7, CO, H
2Show on Pressure gauge 3 with the stagnation pressure of ethene gaseous mixture, and purify through purification pot 4, by pressure regulator valve 6 conditioned reaction pressure, regulate the flow of gaseous mixture by mass flowmenter 15, check valve 16 is mainly to prevent that gaseous mixture from refluxing, gaseous mixture enters beds from reactor 17 tops, and reaction end gas enters water tourie 21, and the water in tourie is pumped into by pump 18.After product was absorbed by water, six-way valve 23 samplings were adopted in tail gas release after counterbalance valve 22, adopt 24 pairs of tail gas of chromatogram to carry out the original position analysis, and in tourie, water sample carries out off-line analysis.
Reaction temperature is 120 ℃, and reaction pressure is 3.0MPa, CO/H
2/ ethene=1/1/1, CO/H
2The air speed of/ethene gaseous mixture is 2000h
-1, reaction end gas fully absorbs with deionized water through cold-trap.After reacting the stationary phase of carrying out 10 hours, formally carry out reactivity worth and demarcate, the nominal time is 8 hours.Gas-phase product carries out on-line analysis, and chromatographic apparatus is Agilent 3000A Micro GC, molecular sieve, Plot Q, Al
2O
3With OV-1 four capillary posts, TCD detector.Water absorption product off-line analysis, FFAP capillary chromatographic column, fid detector.Internal standard method is analyzed, and n-amyl alcohol is internal standard compound.Reaction result is summarised in table 1.
Conversion ratio and optionally computational methods are as follows wherein:
n
i: every kind of contained ethene number of product, n
Ethane=1; n
Acetaldehyde=1; n
Propione=2; n
2 methyl pentanal=2; n
Propyl alcohol=1; n
2-ethyl-2-crotonaldehyde=2.
Table 1: ethene hydroformylation prepares the result of propione and propionic aldehyde
*Calculate based on the ethene molal quantity
Data can be found from table 1: along with adding of the alkali metal oxide auxiliary agents such as K, Na and Li, the ethene hydroformylation activity improves 50% left and right, and propione and propionic aldehyde selectively remains unchanged basically simultaneously.And the interpolation of the transition metal oxide auxiliary agents such as Mo is little on the impact of ethene hydroformylation reactivity worth.And reduced the ethene hydroformylation reactivity worth the adding of transition metal oxide auxiliary agent such as Mn, Zr, Fe, Zn, Cu, Ce and La.
Claims (10)
1. one kind is used for preparing the loaded catalyst of propione and propionic aldehyde take hydrogen, carbon monoxide and ethene as raw material, wherein:
Described catalyst is comprised of main active component, auxiliary agent and carrier, wherein
The weight of described main active component is 0.5~30.0% of described catalyst weight, and the weight of described auxiliary agent is 0~18.0% of described catalyst weight; Described main active component is the phosphide of cobalt; Described auxiliary agent is one or more alkali metal or its oxide; And described carrier is active carbon or CNT; The specific area of wherein said active carbon is 500~1350m
2/ g, and average pore size is 3~100nm; And the specific area of described CNT is 100~400m
2/ g, and average pore size is 2~20nm.
2. catalyst according to claim 1, wherein, the specific area of described active carbon is 550~1300m
2/ g, and average pore size is 8~95nm.
3. catalyst according to claim 1, wherein, described active carbon is cocoanut active charcoal, its specific area is 550~1350m
2/ g, and average pore size is 5~90nm.
4. catalyst according to claim 1, wherein, described active carbon is the almond active carbon, its specific area is 500~1250m
2/ g, and average pore size is 4~100nm.
5. catalyst according to claim 1, wherein, described auxiliary agent is that one or more select metal or its oxide in the group that free K, Na and Li form.
6. catalyst according to claim 1, wherein, described main active component percentage by weight is 1.0~25.0%.
7. catalyst according to claim 1, wherein, the percentage by weight of described auxiliary agent is 0~15.0%.
8. catalyst according to claim 3, wherein, the specific area of described cocoanut active charcoal is 750~1250m
2/ g, and average pore size is 8~85nm.
9. catalyst according to claim 4, wherein, the specific area of described almond active carbon is 700~1150m
2/ g, and average pore size is 8~85nm.
10. catalyst according to claim 1, wherein, the specific area of described CNT is 110~300m
2/ g, and average pore size is 5~10nm.
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Cited By (3)
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CN111420657A (en) * | 2020-04-16 | 2020-07-17 | 中国科学院上海高等研究院 | Ru-based catalyst for synthesizing 3-pentanone through ethylene conversion and preparation method and application thereof |
CN112979440A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Application of supported catalyst in reaction of synthesizing ketone by olefin carbonylation |
CN113385205A (en) * | 2021-07-16 | 2021-09-14 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
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CN112979440A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Application of supported catalyst in reaction of synthesizing ketone by olefin carbonylation |
CN112979440B (en) * | 2019-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Application of supported catalyst in reaction of synthesizing ketone by olefin carbonylation |
CN111420657A (en) * | 2020-04-16 | 2020-07-17 | 中国科学院上海高等研究院 | Ru-based catalyst for synthesizing 3-pentanone through ethylene conversion and preparation method and application thereof |
CN111420657B (en) * | 2020-04-16 | 2023-07-04 | 中国科学院上海高等研究院 | Ru-based catalyst for synthesizing 3-pentanone by ethylene conversion and preparation method and application thereof |
CN113385205A (en) * | 2021-07-16 | 2021-09-14 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
CN113385205B (en) * | 2021-07-16 | 2023-05-12 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
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