CN100556537C - The Catalysts and its preparation method of propionic acid synthesized by ethanol carboxylation - Google Patents
The Catalysts and its preparation method of propionic acid synthesized by ethanol carboxylation Download PDFInfo
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- CN100556537C CN100556537C CNB2008100704184A CN200810070418A CN100556537C CN 100556537 C CN100556537 C CN 100556537C CN B2008100704184 A CNB2008100704184 A CN B2008100704184A CN 200810070418 A CN200810070418 A CN 200810070418A CN 100556537 C CN100556537 C CN 100556537C
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- ethanol
- propionic acid
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Abstract
The Catalysts and its preparation method of propionic acid synthesized by ethanol carboxylation relates to a kind of catalyst, and especially relating to a kind of is propionic acid synthesized monometallic nickel-base catalyst of raw material reaction and preparation method thereof by ethanol and carbon monoxide.Provide a kind of ethanol conversion height, the Catalysts and its preparation method of the optionally active high propionic acid synthesized by ethanol carboxylation of purpose product propionic acid.Active component is the compound of nickel, and carrier is an active carbon.With active carbon boiling reflux in distilled water, the cooling after washing, dry under 100～120 ℃ then, get carrier active carbon; With the dissolved in distilled water nickel salt of 1/2 active carbon saturated water adsorptive value volume, add ammoniacal liquor or citric acid solution, the pH value transfers to 3.0～10.0, and makes the cumulative volume of solution just equal the required saturated water adsorptive value of active carbon; Disposable the pouring in the active carbon of equal-volume nickel salt solution of modulated good acidity flooded, dry, get the catalyst of propionic acid synthesized by ethanol carboxylation.
Description
Technical field
The present invention relates to a kind of catalyst, especially relating to a kind of is propionic acid synthesized monometallic nickel-base catalyst of raw material reaction and preparation method thereof by ethanol and carbon monoxide.
Background technology
Propionic acid is a kind of water white transparency, with the important industrial chemicals of intense stimulus flavor.The purposes of propionic acid and derivative thereof is very extensive, can be used for the production of chemical products such as cereal and food preservative, synthetic plastic, agricultural chemicals, medicine, spices.In recent years, along with the development of China's food, feed, medicine, printing-ink and coating industry, very fast to the demand growth of propionic acid and derivative thereof, it is very wide therefore to develop propionic acid project prospect.
External at present production propionic acid technology mainly contains three kinds: 1) the acetic acid synthesized accessory substance method of light oil direct oxidation, as U.S. Pat 4111982 disclosed technology; 2) the propionic acid method is produced in the propionic aldehyde liquid phase oxidation, as the disclosed technology of Chinese patent CN1569798A; 3) ethene oxo synthesis (Reppe technology).It is raw material that wherein German BASF joint-stock company (BASF) adopts with ethene, is reflected under 250～320 ℃, 10～30MPa condition to carry out, and generates propionic acid with carbon monoxide and water reaction under carbonyl nickel catalysis, and yield can reach 90%.
Ethanol carboxylated legal system propionic acid comes from du pont company the earliest, is raw material with ethanol, carbon monoxide and water, under 180～400 ℃, 35.5～70.9MPa, carries out the catalysis carboxylation in the acid medium and can get propionic acid.U.S. Pat 899691 disclosed a kind of H of using in 1962
3PO
4, Fe, Co, Ni complex compound be the research that catalyst carries out the ethanol carboxylated, reaction is under high pressure carried out.Chinese patent CN1736606A discloses a kind of Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation, it mainly is carrier active carbon to be washed through deionization earlier carry out preliminary treatment with the mode of pickling again, and by adsorbed gas in the vavuum pump eliminating active carbon hole, flood nickel and copper slaine again, make propionic acid synthesized bimetallic Ni-Cu/C catalyst, its ethanol conversion reaches 98%, and propionic acid and ethyl propionate combined selective are up to 62%.
Summary of the invention
The present invention aims to provide a kind of ethanol conversion height, the Catalysts and its preparation method of the optionally active high propionic acid synthesized by ethanol carboxylation of purpose product propionic acid.
The activity of such catalysts component of propionic acid synthesized by ethanol carboxylation of the present invention is the compound of nickel, and carrier is an active carbon, and the compound presoma of nickel is selected from NiSO
46H
2O, Ni (NO
3)
26H
2O, NiC1
26H
2O, Ni (HCOO)
22H
2O, Ni (CH
3COO)
24H
2O, Ni (C
2H
5COO)
2XH
2A kind of among the O, by atomic wts, nickel loading is 1%～20%.
The compound presoma of nickel preferably is selected from Ni (HCOO)
22H
2O, Ni (CH
3COO)
24H
2O, Ni (C
2H
5COO)
2XH
2A kind of in the O organic metal nickel compound.By atomic wts, nickel loading is preferably 5%～10%.
The Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation of the present invention can adopt incipient impregnation not have the roasting technology preparation, may further comprise the steps:
1) with active carbon boiling reflux in distilled water, the cooling after washing, dry under 100～120 ℃ then, get carrier active carbon;
2) with the dissolved in distilled water nickel salt of 1/2 active carbon saturated water adsorptive value volume, add ammoniacal liquor or citric acid solution, the pH value transfers to 3.0～10.0, and makes the cumulative volume of solution just equal the required saturated water adsorptive value of active carbon;
3) with step 2) in disposable the pouring in the active carbon of equal-volume nickel salt solution of modulated good acidity flood, oven dry, the catalyst of propionic acid synthesized by ethanol carboxylation.
In step 1), active carbon is preferably 20～30 purpose active carbons, and the time of boiling reflux is preferably 3h in distilled water, and the dry time is preferably 12h.
In step 2) in, the concentration of ammoniacal liquor is preferably 25%, and the concentration of citric acid solution is preferably 10mol/L.
In step 3), the time of dipping is preferably 20～30h, and the temperature of oven dry is preferably 100～120 ℃.
The catalyst of propionic acid synthesized by ethanol carboxylation of the present invention need not to carry out calcination process before use, adopts hydrogen reducing 2～3h, and the highest reduction temperature is 350 ℃.Activity of such catalysts is estimated on fixed-bed reactor and carried out, and loaded catalyst is 4g, and in molar ratio, raw material consists of carbon monoxide: ethanol: iodoethane=20: 10: 1, reaction pressure are 0.1MPa, and reaction temperature is 260 ℃.Condensate liquid adopts gas-chromatography hydrogen flame to detect.
The catalyst of propionic acid synthesized by ethanol carboxylation of the present invention adopts incipient impregnation not have the roasting technology preparation, technology is simple, with organic metal nickel is the propionic acid synthesized catalyst that presoma makes, and the selectivity of ethanol conversion, propionic acid and stability are all than with NiSO
46H
2O, Ni (NO
3)
26H
2O and NiCl
26H
2The catalyst effect that the O form makes will be got well, and ethanol conversion and propionic acid selectivity best result can not reach 98% and 96%.
The specific embodiment
Embodiment 1
Take by weighing 100g merchandise active carbon (20～30 order), boiling reflux 3h in 350ml distilled water, dry 12h under 100 ℃ is standby then.Adopt supersaturation suction method, the unit's of measuring gram number active carbon saturated water adsorptive value is 1.2ml.Getting the 10g active carbon, to put into the 12ml degree be 15.93%NiSO
46H
2In the O solution (its pH value transfers to 8.0 with the citric acid solution of 25% concentrated ammonia liquor and 10mol/l), dipping 24h, 120 ℃ of dry 12h obtain NiSO
4Load capacity is the catalyst of 8% ethanol carboxylated system propionic acid, and the gained catalyst is designated as Catl.
Take by weighing 4g Catl, after mixing with the quartz sand of amount is even, pack in the fixed bed reactors, in 350 ℃ of following hydrogen streams, reduce 3h, be cooled to 260 ℃ again, raw gas pressure is 0.1MPa, and then feeds carbon monoxide: ethanol: the unstripped gas of iodoethane=20: 10: 1 (mol ratio) begins reaction, the every h once sampling of cooling fluid, the flame analysis of gas-chromatography hydrogen.Activity rating the results are shown in Table 1.
The activity of such catalysts evaluation result that different nickel salt presomas of table 1 and pH value are made
Embodiment 2
Implementation step and condition are 15.93%NiSO with degree just with embodiment 1
46H
2O solution changes 20.61%Ni (NO into
3)
26H
2O solution obtains the Ni (NO of 8% load
3)
2The catalyst of ethanol carboxylated system propionic acid, the gained catalyst is designated as the Cat2. activity rating and the results are shown in Table 1.
Embodiment 3
Implementation step and condition are 15.93%NiSO with degree just with embodiment 1
46H
2O solution changes 21.26%NiCl into
26H
2O solution obtains the NiCl of 8% load
2The catalyst of ethanol carboxylated system propionic acid, the gained catalyst is designated as the Cat3. activity rating and the results are shown in Table 1.
Embodiment 4
Implementation step and condition are 15.93%NiSO with degree just with embodiment 1
46H
2O solution changes 17.35%Ni (HCOO) into
22H
2O solution obtains the Ni (HCOO) of 8% load
2The catalyst of ethanol carboxylated system propionic acid, the gained catalyst is designated as the Cat4. activity rating and the results are shown in Table 1.
Embodiment 5
Implementation step and condition are 15.93%NiSO with degree just with embodiment 1
46H
2O solution changes 19.82%Ni (C into
2H
5COO)
2XH
2O solution obtains the Ni (C of 8% load
2H
5COO)
2The catalyst of ethanol carboxylated system propionic acid, the gained catalyst is designated as the Cat5. activity rating and the results are shown in Table 1.
Embodiment 6
Implementation step and condition are 15.93%NiSO with degree just with embodiment 1
46H
2O solution changes 18.13% Ni (CH into
3COO)
24H
2O solution obtains the Ni (CH of 8% load
3COO)
2The catalyst of ethanol carboxylated system propionic acid, the gained catalyst is designated as the Cat6. activity rating and the results are shown in Table 1.
Comparative Examples 1
Implementation step and condition are with embodiment 5, just at N
2Under the protection, in 500 ℃ of calcining 3h, gained calcining rear catalyst is designated as the A. activity rating and the results are shown in Table 1 with Cat5.
Embodiment 7～10
Implementation step and condition be with embodiment 6, just is 18.13% Ni (CH with four parts of degrees with the citric acid solution of 25% concentrated ammonia liquor and 10mol/l
3COO)
24H
2The pH value of O solution is adjusted to 3.0,6.0,9.0 and 10.0 respectively, and the gained catalyst is designated as Cat7, Cat8, Cat9 and Cat10. activity rating successively and the results are shown in Table 1.
Embodiment 11～15
Implementation step and condition are with embodiment 5, and difference is the (CH with Ni
3COO)
24H
2O solution degree 18.13% changes 2.27%, 4.54%, 11.35%, 22.70% and 45.40% (its pH value all transfers to 8.0 with the citric acid solution of 25% concentrated ammonia liquor and 10mol/l) one by one into, obtains the Ni (CH of 1%, 2%, 5%, 10% and 20% load successively
3COO)
2Catalyst, gained catalyst are designated as Cat11, Cat12, Cat13, Cat14 and Cat15. activity rating respectively and the results are shown in Table 2.
Nickel salt Ni (the CH of table 2 different loads amount
3COO)
2Presoma activity of such catalysts evaluation result
Claims (7)
1. the Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation, the activity of such catalysts component of described propionic acid synthesized by ethanol carboxylation is the compound of nickel, and carrier is an active carbon, and the compound presoma of nickel is selected from Ni (HCOO)
22H
2O, Ni (CH
3COO)
24H
2O, Ni (C
2H
5COO)
2XH
2A kind of among the O, by atomic wts, nickel loading is 5%～10%; It is characterized in that its preparation method may further comprise the steps:
1) with active carbon boiling reflux in distilled water, the cooling after washing, dry under 100～120 ℃ then, get carrier active carbon;
2) with the dissolved in distilled water nickel salt of 1/2 active carbon saturated water adsorptive value volume, add ammoniacal liquor or citric acid solution, the pH value transfers to 3.0～10.0, and makes the cumulative volume of solution just equal the required saturated water adsorptive value of active carbon;
3) with step 2) in disposable the pouring in the active carbon of equal-volume nickel salt solution of modulated good acidity flood, oven dry, the catalyst of propionic acid synthesized by ethanol carboxylation.
2. the Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation as claimed in claim 1 is characterized in that in step 1), and active carbon is 20～30 purpose active carbons.
3. the Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation as claimed in claim 1 is characterized in that in step 1), and the time of boiling reflux is 3h in distilled water.
4. the Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation as claimed in claim 1 is characterized in that in step 1), and the dry time is 12h.
5. the Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation as claimed in claim 1 is characterized in that in step 2) in, the concentration of ammoniacal liquor is 25%.
6. the Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation as claimed in claim 1 is characterized in that in step 2) in, the concentration of citric acid solution is 10mol/L.
7. the Preparation of catalysts method of propionic acid synthesized by ethanol carboxylation as claimed in claim 1 is characterized in that in step 3), and the time of dipping is 20～30h, and the temperature of oven dry is 100～120 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1213585A (en) * | 1997-10-05 | 1999-04-14 | 中国科学院大连化学物理研究所 | Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application |
| CN1045429C (en) * | 1995-04-21 | 1999-10-06 | 南开大学 | Catalyzer for methanation of carbon dioxide and its preparation method |
| CN1548226A (en) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
| CN1736606A (en) * | 2005-07-20 | 2006-02-22 | 上海吴泾化工有限公司 | Process for synthesizing methyl acetic acid catalyst by ethanol carbonylation |
| CN1775671A (en) * | 2005-12-16 | 2006-05-24 | 中国科学院长春应用化学研究所 | Method for preparing carbon nano tube and its composite by nickel compound catalytic combustion of polyolefin |
| CN1876238A (en) * | 2006-07-07 | 2006-12-13 | 宁夏大学 | Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method |
-
2008
- 2008-01-03 CN CNB2008100704184A patent/CN100556537C/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045429C (en) * | 1995-04-21 | 1999-10-06 | 南开大学 | Catalyzer for methanation of carbon dioxide and its preparation method |
| CN1213585A (en) * | 1997-10-05 | 1999-04-14 | 中国科学院大连化学物理研究所 | Benzonitrile chlorination for preparing pentachlorobenzonitrile catalyst and its application |
| CN1548226A (en) * | 2003-05-14 | 2004-11-24 | 中国科学院大连化学物理研究所 | Catalyst for hydrodehalogenation of arene halide and its prepn and application |
| CN1736606A (en) * | 2005-07-20 | 2006-02-22 | 上海吴泾化工有限公司 | Process for synthesizing methyl acetic acid catalyst by ethanol carbonylation |
| CN1775671A (en) * | 2005-12-16 | 2006-05-24 | 中国科学院长春应用化学研究所 | Method for preparing carbon nano tube and its composite by nickel compound catalytic combustion of polyolefin |
| CN1876238A (en) * | 2006-07-07 | 2006-12-13 | 宁夏大学 | Catalyst for dehydrochlorination of chloralkane to produce chloroalkene and its preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 用于乙醇气相羰化反应的Ni/C催化剂研究. 冯景贤等.华南理工大学学报（自然科学版），第24卷第10期. 1996 * |
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