CN103084192B - 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 phosphide catalyst of the supported cobalt for preparing propione and propionic aldehyde for raw material with hydrogen, carbon monoxide and ethene.More specifically, the present invention relates under uniform temperature and pressure, with CO, H
2be the catalyst that the phosphide of the activated carbon supported cobalt of propione and propionic aldehyde efficiently produced by raw material with ethene gaseous mixture.
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 producing pesticide herbicide Pendimethalin and anti-avian influenza medicine Tamiflu, the consumption of propione is increasing year by year.The method of synthesis 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 the industrial production and in sulfuric acid, has been oxidized the method for propione produced by 3-amylalcohol with sodium chromate, but raw material dependence on import and process contamination is serious.Acid-acid system is the propione synthetic method of generally acknowledging most application prospect at present, 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 that raw material directly or indirectly gets under the effect of noble metal catalyst by synthesis gas and ethene, namely described method needs to use noble metal catalyst, and its cost is high.The maximum propionic acid production method of current production rate comprises following two steps: propionic aldehyde is produced and propionic aldehyde is oxidized.First adopt the ethenecarbonyl 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, higher to the requirement of e-quipment and pipe material.New propionic acid production technology for raw material, directly prepares propionic acid with ethene, carbon monoxide and hydrogen under carbonyl Rh catalysis, but due to the use of rhodium carbonyl catalyst, production cost is very high.
Startseva etc. (Kinet.Catal.25,424,1984)) Late Cambrian: activated carbon supported Co
2(CO)
8catalyst can make ethene, CO and H
2there is catalytic reaction in O, and in catalytic reaction products, detects the existence of propione.Takahashi etc. (Chemistry Letter, pp205 1990, Journal of Catalysis 136,531 (1992)) report: under the effect of Rh/ activated-carbon catalyst, CO, H
2propione and propionic aldehyde is prepared with ethene gaseous mixture.Breysse etc. (Catalysis Letter, 32,55 (1995)) report: the catalyst of activated carbon supported Rh and Ir is used in ethylene hydrogenation formylation reaction, and has measured the generation of propione.
But above-mentioned catalyst all employ noble metal.
Summary of the invention
One object of the present invention is the phosphide catalyst providing a kind of supported cobalt for preparing propione and propionic aldehyde for raw material with hydrogen, carbon monoxide and ethene.Compared with prior art, catalyst of the present invention can not adopt rare precious metal, significantly reduces energy consumption of reaction simultaneously and improves processing safety, improving CO, H simultaneously
2the space-time yield of propione and propionic aldehyde and selective is efficiently prepared with ethene gaseous mixture.
For achieving the above object, the invention provides a kind of for hydrogen, carbon monoxide and ethene for the loaded catalyst of propione and propionic aldehyde prepared by raw material, wherein: described catalyst is made up 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 from synthesis gas.
Accompanying drawing illustrates:
Fig. 1 is the high resolution electron microscopy photo of sample prepared by embodiment 6.
Fig. 2 is ethene hydroformylation reaction unit schematic diagram.
Detailed description of the invention
Elaborate content of the present invention below.
Catalyst of the present invention is under uniform temperature and pressure, with CO, H
2be that raw material efficiently produces the loaded catalyst of propione and propionic aldehyde by hydroformylation reaction with ethene gaseous mixture.Catalyst by main active component, auxiliary agent and carrier three part form.Main active component is the phosphide of Co.Auxiliary agent is that alkali metal is as one or more in K, Na and Li or its oxide.Carrier selects active carbon or CNT etc.By CO, H in fixed bed reactors
2with the reaction raw materials of ethene composition, under this catalyst action, there is hydroformylation reaction, high activity, highly selective can prepare propione and propionic aldehyde.
In reaction system of the present invention, can directly by 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, to prepare 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 select active carbon, and its specific area is preferably 500 ~ 1350m
2/ g, average pore size is 5 ~ 100nm, and 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 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 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 can by the following method in one or more preparation: infusion process, the precipitation method and hydrothermal synthesis method.
Adopt the shell carbon of commodity to be the active carbon that raw material is produced, granularity is the carrier of CNT as catalyst of 20-40 order or commodity.Such carrier extremely washs electrical conductivity of water in 20-25 Mei meter Hao Siemens (mS/m) through deionized water cyclic washing before use.Carrier after this washing is 90-100 DEG C of dry 8-10 hour in an oven.First the water absorption of carrier is measured, with the water yield just making carrier moistening for water absorption.Need to add the red fuming nitric acid (RFNA) of 2-3ml when configuring maceration extract in beaker and be heated to 40-50 DEG C of dissolving, the liquid volume of adjustment maceration extract is the water absorption of carrier.Carrier is contained in culture dish, the maceration extract containing active component and adjuvant component is poured in culture dish, make it mix in carrier.Sample after hybrid infusion is dried to substantially dry in the water-bath of 60 DEG C, dries 8 hours for 80 DEG C in baking oven.First this catalyst will carry out reduction activation process before use, and its reduction activation condition is: H
2stream (GHSV=3000h
-1), normal pressure, 5 DEG C/min is from room temperature to 430 DEG C, and 430 DEG C activate 8 hours.
Catalyst of the present invention may be used in fixed bed reactors, under uniform temperature and pressure, with CO, H
2be that raw material efficiently produces propione and propionic aldehyde by hydroformylation reaction with ethene gaseous mixture, in wherein said hydroformylation reaction, reaction temperature is 120 DEG C, and reaction pressure is 3.0MPa, CO/H
2/ ethene=1/1/1 (mol ratio), and air speed is 2000h
-1.With CO, H
2be that raw material produces the method for propione and propionic aldehyde by hydroformylation reaction with ethene gaseous mixture, can be about 15% to the conversion ratio of ethene, and can be about 45% to the selective of propionic aldehyde, can be about 43% to the selective of propione.
Below by specific embodiment, the present invention will be further described.
Embodiment 1
The catalyst of embodiment 1 is 15%Co-0.66%P/ coconut husk charcoal (Co/P=12 mol ratio).(20-40 order, BET specific surface area is: 1135m to take 10.0 grams of coconut husk charcoals
2/ g, average pore size is 21nm), configuration 8ml is containing 7.80 grams of Co (NO
3)
2.6H
2o and 0.3 gram (NH
4)
2hPO
4the aqueous solution, drip the dense HNO of about 2ml
3, heating for dissolving, with the above-mentioned coconut husk high-area carbon of this aqueous impregnation, 60 DEG C of water-baths are dried, 80 DEG C of oven for drying 8 hours.Now the weight of drying sample is about 18.45 grams.The product prepared is the precursor of 15%Co-0.66%P/ coconut husk Pd/carbon catalyst.
Before the precursor use of above-mentioned catalyst, take 5ml (3.4 grams) above-mentioned catalyst and be placed in φ 10 internal diameter, length is the stainless steel reactor stage casing of 30 centimetres, and two ends 20-40 object quartz sand is filled.Catalyst is H in the reactor
2(GHSV=3000h
-1) carry out in-situ reducing activation in stream, condition is: normal pressure, and 5 DEG C/min, from room temperature to 430 DEG C, keeps 8 hours at H
2be cooled to reaction temperature in stream, thus 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).Except adopting almond charcoal, (BET specific surface area is: 1070m
2/ g, average pore size is 25nm) outward, 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).Except adopting CNT, (BET specific surface area is: 254m
2/ g, average pore size is 7.5nm) outward, 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 adding 0.4 gram of LiNO configuring in the identical aqueous solution with embodiment 2
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 adding 0.15 gram of NaNO configuring in the identical aqueous solution with embodiment 2
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 adding 0.12 gram of KNO configuring in the identical aqueous solution with embodiment 1
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 adding 0.52 gram of Ni (NO configuring in the identical aqueous solution with embodiment 1
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 adding 0.32 gram of La (NO configuring in the identical aqueous solution with embodiment 2
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 adding 0.16 gram of Ce (NO configuring in the identical aqueous solution with embodiment 2
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 adding 0.38 gram of Cu (NO configuring in the identical aqueous solution with embodiment 1
3)
2.3H
2outside O, remaining preparation process is identical with embodiment 1.
Embodiment 11
Embodiment 11 catalyst is 1.0%Mn15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except adding 0.64 gram of 50wt.%Mn (NO configuring in the identical aqueous solution with embodiment 2
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 adding 0.19 gram of (NH configuring in the identical aqueous solution with embodiment 2
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 adding 0.24 gram of Zr (NO configuring in the identical aqueous solution with embodiment 2
3)
4.5H
2outside O, remaining preparation process is identical with embodiment 2.
Embodiment 14
Embodiment 14 catalyst is 0.5%Fe15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except adding 0.36 gram of Fe (NO configuring in the identical aqueous solution with embodiment 2
3)
3.6H
2outside O, remaining preparation process is identical with embodiment 2.
Embodiment 15
Embodiment 15 catalyst is 0.5%Zn15%Co-0.66%P/ almond charcoal (Co/P=12 mol ratio), except adding 0.22 gram of Zn (NO configuring in the identical aqueous solution with embodiment 2
3)
2.6H
2outside O, remaining preparation process is identical with embodiment 2.
Accompanying drawing 1 is shown in by the high resolution electron microscopy photo of sample prepared by embodiment 6, can find that active component Co and P exists with the phosphide of metal Co and Co by Fig. 1.
Select fixed bed reactors, accompanying drawing 2 is shown in by the schematic diagram of its reaction unit.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, reaction pressure is regulated by pressure regulator valve 6, the flow of gaseous mixture is regulated by mass flowmenter 15, check valve 16 mainly prevents gaseous mixture from refluxing, gaseous mixture enters beds from reactor 17 top, and reaction end gas enters water tourie 21, and the water in tourie is pumped into by pump 18.After product is only absorbed by the water, tail gas release after counterbalance valve 22, adopts six-way valve 23 to sample, and adopt chromatogram 24 pairs of tail gas to carry out in-situ study, in tourie, water sample carries out off-line analysis.
Reaction temperature is 120 DEG C, 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 through cold-trap deionized water.After the stationary phase of 10 hours is carried out in reaction, formally carry out reactivity worth demarcation, 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 tetra-capillary post, TCD detector.Aqueous phase 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 summed up in Table 1.
Wherein conversion ratio and optionally computational methods are as follows:
N
i: ethene number contained by often kind 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 ethylene molar number
From table 1, data can find: along with adding of the alkali metal oxide auxiliary agents such as K, Na and Li, and ethene hydroformylation activity improves about 50%, and propione and the selective of propionic aldehyde remain unchanged substantially simultaneously.And the interpolation of the transition metal oxide auxiliary agents such as Mo, little on the impact of ethene hydroformylation reactivity worth.And adding of the transition metal oxide auxiliary agents such as Mn, Zr, Fe, Zn, Cu, Ce and La reduces ethene hydroformylation reactivity worth.
Claims (8)
1. for hydrogen, carbon monoxide and ethene for the loaded catalyst of propione and propionic aldehyde prepared by raw material, wherein:
Described catalyst is made up 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 be described catalyst weight be greater than 0 to 15.0%; Described main active component is the phosphide of cobalt; Described auxiliary agent is that one or more are selected from metal in the group be made up of K, Na and Li 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, and 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 almond active carbon, and its specific area is 500 ~ 1250m
2/ g, and average pore size is 4 ~ 100nm.
5. catalyst according to claim 1, wherein, described main active component percentage by weight is 1.0 ~ 25.0%.
6. 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.
7. 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.
8. 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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| 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 |
| 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 |
| CN113385205B (en) * | 2021-07-16 | 2023-05-12 | 清华大学 | Metal phosphide catalyst for heterogeneous hydroformylation reaction |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075902A (en) * | 1993-01-09 | 1993-09-08 | 厦门大学 | High carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine is water soluble catalyst loaded |
| CN1666817A (en) * | 2004-03-12 | 2005-09-14 | 中国科学院大连化学物理研究所 | Method for preparing transition metal phosphide |
| CN102029169A (en) * | 2009-09-29 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for preparing loaded transitional metal phosphide catalyst |
| CN102600871A (en) * | 2012-03-07 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Transition metal phosphide catalyst for synthesizing alcohol, preparation method thereof and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6084239A (en) * | 1983-10-14 | 1985-05-13 | Agency Of Ind Science & Technol | Preparation of acetaldehyde |
-
2011
- 2011-10-28 CN CN201110334984.3A patent/CN103084192B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1075902A (en) * | 1993-01-09 | 1993-09-08 | 厦门大学 | High carbon aldehyde by hydrogen formylating high carbon nuber terminal olefine is water soluble catalyst loaded |
| CN1666817A (en) * | 2004-03-12 | 2005-09-14 | 中国科学院大连化学物理研究所 | Method for preparing transition metal phosphide |
| CN102029169A (en) * | 2009-09-29 | 2011-04-27 | 中国科学院大连化学物理研究所 | Method for preparing loaded transitional metal phosphide catalyst |
| CN102600871A (en) * | 2012-03-07 | 2012-07-25 | 中国科学院山西煤炭化学研究所 | Transition metal phosphide catalyst for synthesizing alcohol, preparation method thereof and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| "Effects of Chlorine on Formation of 3-Pentanone during Ethene Hydroformylation over Rh/Active-Carbon Catalyst;Nobuo Takahashi et.al.;《Journal of catalysis》;19961231;第159卷;第491页左栏第2段、右栏第2-3段以及第493页表3 * |
| 马占华 等.助剂对合成异壬醛用负载铑基催化剂性能的影响.《中国石油大学学报(自然科学版)》.2009,第33卷(第2期), * |
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