CN102626638A - Catalyst for preparation of 1,2-pentanediol - Google Patents
Catalyst for preparation of 1,2-pentanediol Download PDFInfo
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- CN102626638A CN102626638A CN2012100752057A CN201210075205A CN102626638A CN 102626638 A CN102626638 A CN 102626638A CN 2012100752057 A CN2012100752057 A CN 2012100752057A CN 201210075205 A CN201210075205 A CN 201210075205A CN 102626638 A CN102626638 A CN 102626638A
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Abstract
The invention discloses a catalyst for the preparation of 1,2-pentanediol. The catalyst contains one or more elements of IB, VIB, VIIB and VIIIB families in the periodic table of elements; the catalyst also contains one or more elements selected from IA, IIA, IIIA, IVA and VA families in the periodic table of elements; the copper-containing catalyst which is prepared through a precipitation method comprises 30-70wt% of copper oxide; and the copper-containing catalyst which is prepared through carrier material dipping or coating comprises 10-25wt% of copper oxide. The copper-based catalyst of the invention has the advantages of product yield improvement, catalyst production cost reduction, resource saving, and product competitiveness improvement.
Description
Technical field
The present invention relates to catalyst, be specifically related to a kind of catalyst through hutanal and Cymag Synthetic 2-hydroxypentanoic acid methyl ester hydrogenation preparation 1,2 pentanediols.
Technical background
2-hydroxypentanoic acid methyl esters in preference temperature, reacts on the hydrogenation catalyst under gas phase, hydrogen condition.In fact all heterogeneous catalysts that are suitable for the two keys of hydrogenized carbonyl, carbon can be used.Hydrogenation catalyst can be used in fixed bed, slurry attitude bed and the fluidized-bed reactor.
Summary of the invention
The objective of the invention is to: a kind of catalyst of preparation 1,2 pentanediols is provided, adopts copper-based catalysts, improve product yield, reduce the Catalyst Production cost, economize on resources.
Technical solution of the present invention is: this catalyst contains one or more elements of IB in the periodic table of elements, II B, VI B, VII B and VIII B family; Catalyst can also contain the element that one or more are selected from IA in the periodic table of elements, II A, III A, IV A and V A family according to catalyst activity and optionally requirement; Preferred catalyst is such; Include as the activity of such catalysts component: the mixture of the multiple element in copper, chromium, cobalt, nickel, zinc, rhenium, rhodium, calcium, iridium, palladium, iron, platinum or these elements; And as its activity auxiliary agent optionally: cobalt, potassium, tin, special what select is the cupric hydrogenation catalyst.
As the heterogeneous catalyst in this method, not only can use the sedimentation type catalyst, and the immersion-type carried catalyst can adopt also.
The sedimentation type catalyst can be pressed method preparation: with catalytic active component from their salting liquid; Especially from their solution of nitrate and/or acetate, through adding alkali metal and/or alkaline earth metal hydroxide solution and/or carbonate solution, come out as hydroxide, oxide hydrate, basic salt or the carbonate deposition of indissoluble; The sediment that obtains filters subsequently, washs, dry and calcining; Usually at 250-700 ℃, especially transfer the oxide of corresponding oxide, mixed oxide and/or mixed valence to 300-500 ℃ of calcining, they pass through with hydrogen or hydrogeneous gas; Usually at 50-700 ℃; Especially handle for 100-400 ℃, be reduced into corresponding metal and/or, and change into the form of their real catalytic activity than the oxide of suboxides valency; Suitable reducing agent: formaldehyde, hydrazine have economic worth or hydrogen most certainly to replace hydrogen, under certain reducing condition, are reacted to not consuming hydrogen, or the generation water yield does not become principle.
Supported catalyst preparation: adopt carrier direct impregnation active constituent, perhaps from relevant salting liquid, be precipitated out active component simultaneously with carrier; The suitable carriers material is: aluminium and titanyl compound, zinc oxide, zirconium dioxide, silica, kaolinite, magnesium silicate, alumina silicate, zeolite, also can use the mixture of these carrier materials; The sediment that drying is crossed before calcining, grind with shaping assistant graphite, talcum or stearic acid and/or with blowing agent cellulose, methylcellulose, starch, wax, paraffin and/or PAG and, suppress or finished form garden cylindricality, sphere, annular, the strip of extrusioning catalyst.
In the present invention; Adopt following hydrogenation catalyst, it contains the metal or the metallic compound of the ability catalytic hydrogenation that is deposited on a kind of carrier material, and following this carried catalyst is specially adapted to method of the present invention usually; In carried catalyst, active component gets on through infusion process; The mode that catalytic active component is coated onto on the carrier is not critical usually, and method reaches in various manners; Activity component metal loads to a kind of carrier material through following method and gets on: flood through the salt of coherent element or the solution or the suspension of oxide; Dry then with use a kind of reducing agent hydrogen, hydrogeneous gas or hydrazine subsequently; The most handy hydrogeneous gas; Metallic compound is reduced into corresponding metal or than the compound of suboxides valency, the reduction reaction that is deposited on the metallic compound on the carrier material can carried out under described the same terms about precipitated catalyst with the front; Active component is coated onto the another kind possibility method that carrier gets on is: carrier floods with labile salting liquid: with the nitrate or the complex of thermal decomposition easily; Be carbonyl or hydride complex solution impregnated carrier, the impregnated carrier that heating makes makes the metallic compound of absorption carry out thermal decomposition to 300-600 ℃; This thermal decomposition is preferably carried out under protective gas covers, and suitable protective gas is nitrogen, carbon dioxide, hydrogen or inert gas; In addition, catalytically-active metals also can be deposited to catalyst carrier through evaporation or flame-spraying and get on, in this case, and can be as carrier material with wire screen or metal forming.
The content of the catalytically-active metals in these supported catalysts of the present invention is said in principle, is not critical for the success of the method for the invention; To those skilled in the art, carried catalyst has the advantages of high catalytic activity tenor, produces higher space-time conversion ratio during compared with lower content; Usually the catalytically-active metals of carried catalyst accounts for the 0.01-85wt% of catalyst total amount, the supported catalysts of preferred 0.1-40wt%; Because these content data relate to the total catalyst that comprises carrier, different carrier mass has different proportion and specific area, so actual value can be higher or lower than said value, but this does not damage the result who obtains through the inventive method; Certainly if need, can multiple catalytically-active metals be applied on the corresponding carrier mass; Simultaneously, through being described in DE-A2,519,817, EP-A1, the method in 477,219 and EP-A285,420 is applied to reactive metal on the carrier; In the catalyst described in the above-mentioned document, catalytically-active metals exists with alloy form, and said alloy is through to the salt of above-mentioned metal or complex heat-treating or reduce preparation through immersion deposition after on the carrier with said salt or complex.
The activation of precipitated catalyst and carried catalyst is carried out through the hydrogen scene that is present in wherein in reactant mixture; Yet these catalyst are activation separately before use preferably.
Used carrier mass is generally oxide, zirconium dioxide, silica, diatomite, silica gel, shale soil montmorillonite, magnesium or aluminosilicate, ZSM-5 or ZSM-10 zeolite, the active carbon of aluminium and titanyl compound, zinc; Preferred carrier is aluminium oxide, titanium dioxide, zinc oxide, zirconium dioxide, active carbon, silica; Certainly if need, the mixture of various carriers also can be used as the carrier of the catalyst that uses in the present invention.
In the methods of the invention, the hydrogenation catalyst that is adopted: palladium/active carbon, platinum/active carbon, palladium/aluminium oxide, cobalt/active carbon, cobalt/silica, cobalt/aluminium oxide, iron/active carbon, manganese/active carbon, rhenium/active carbon, rhenium/aluminium oxide, rhenium/palladium/active carbon, copper/active carbon, Cu/SiO 2, copper/aluminium oxide, copper/zinc oxide, copper/palladium/aluminium oxide, copper/aluminium oxide.
Preferred especially catalyst comprises a kind of metal in the copper metal at least; The precipitated catalyst that contains copper contains the 20-70%wt that accounts for total catalyst weight usually, and preferred content 35-50%wt calculates with CuO; Through the dipping of carrier material or the copper containing carrier catalyst of coating preparation, the CuO weight content is 10-30%, is preferably 15-25%.
The present invention has the following advantages: it is the copper-based catalysts system that 2-hydroxypentanoic acid methyl ester hydrogenation preparation 1,2 pentanediols adopt, and has improved product yield, has reduced the Catalyst Production cost, has practiced thrift resource, has improved product competitiveness.
The specific embodiment
Further specify technical solution of the present invention below in conjunction with specific embodiment, these embodiment can not be interpreted as it is the restriction to technical scheme.
Among the embodiment below, the conversion ratio, the selectivity that provide are measured with gas chromatography.
Embodiment 1:
A Fixed Bed Gas Phase reactor that external heat, flow-control arranged (in the Φ 12 * 600mm), the 20-40 purpose of packing into 10g copper, palladium/aluminium oxide catalyst (CuO content 50%wt, Pd content 0.08%, Al
2O
349.92%), method for making: take by weighing needed copper nitrate, aluminum nitrate and palladium liquid, with sodium carbonate liquor neutralization, sediment is through filtration, washing, drying, 480 ℃ of calcinings, adds the moulding of sieving of 1% graphite powder at last; At 2MPa, liquid air speed 0.09hr
-1Under hydrogen ester mol ratio 100 conditions, when 170 ℃ of reaction temperatures, 2-hydroxypentanoic acid methyl ester conversion rate 97.5%, 1,2-pentanediol selectivity 99.5%; When 200 ℃ of reaction temperatures, 2-hydroxypentanoic acid methyl ester conversion rate 100%, 1,2-pentanediol selectivity 97.5%.
Embodiment 2:
Press the same method of embodiment 1, in fixed bed reactors, the 10g 20-40 order Cu-Cr catalyst of packing into, the copper of its catalyst is with the CuO restatement, and CuO 51%, and Cr is with Cr
2O
3Meter 49%; The catalyst method for making: copper nitrate solution and chromic acid solution neutralize, and regulate Acidity of Aikalinity with ammoniacal liquor simultaneously, obtain that deposition is washed, drying, and roasting adds bonding agent and carries out moulding; At 180 ℃, 2MPa, liquid air speed 0.08hr
-1Under hydrogen ester mol ratio 120 conditions, 2-hydroxypentanoic acid methyl ester conversion rate 99.2%, 1,2-pentanediol selectivity 98%.
Embodiment 3:
Press embodiment 1 same quadrat method, the 10g Cu-Cr-Ca catalyst of packing into, it forms percentage by weight CuO 49%, CaO 2%, Cr
2O
348%, bonding agent 1%; Its method for making is with embodiment 2, at 180 ℃, 2.2MPa, liquid air speed 0.1hr
-1Under hydrogen ester mol ratio 140 conditions, 2-hydroxypentanoic acid methyl ester conversion rate 100%, 1,2-pentanediol selectivity 98.5%.
Embodiment 4:
Press embodiment 1 same quadrat method, the 10g copper-Si catalyst of packing into, it consists of CuO 25%, SiO
275%; The preparation method: with the copper carbonate solution impregnating carrier of dropping ammonia, the carrier of dipping is at 110 ℃, 450 ℃ of roastings; At 210 ℃, 2MPa, liquid air speed 0.07hr
-1Under hydrogen ester mol ratio 90 conditions, 2-hydroxypentanoic acid methyl ester conversion rate 100%, 1,2-pentanediol selectivity 96.3%.
Embodiment 5:
Press embodiment 1 same quadrat method, the 10g copper/activated-carbon catalyst of packing into, it consists of, and CuO is 15%, active carbon 85%; The preparation method: with the copper liquid impregnated carrier that drips sal volatile, the carrier of dipping is protected 400 ℃ of roastings 110 ℃ of dryings in the nitrogen; At 170 ℃, 2MPa, liquid air speed 0.08hr
-1Under hydrogen ester mol ratio 130 conditions, 2-hydroxypentanoic acid methyl ester conversion rate 92.5%, 1,2-pentanediol selectivity 97.6%.
Embodiment 6:
Press embodiment 1 same quadrat method, the 10g palladium/activated-carbon catalyst of packing into, it consists of Pd 4%; The preparation method: with the palladium solution impregnating carrier that has dripped carbonic hydroammonium, soaked carrier is 110 ℃ of dryings, and nitrogen is protected 450 ℃ of roastings; At 210 ℃, 1.8MPa, liquid air speed 0.1hr
-1Under hydrogen ester mol ratio 90 conditions, 2-hydroxypentanoic acid methyl ester conversion rate 100%, 1,2-pentanediol selectivity 97.8%.
Embodiment 7:
Press embodiment 1 same quadrat method, the 10g cobalt/activated-carbon catalyst of packing into, it forms cobalt oxide 10%; The preparation method: cobalt nitrate carries out the acidity allotment with ammoniacal liquor earlier, pours required absorbent charcoal carrier into then, and soaked carrier is protected 430 ℃ of roastings 110 ℃ of dryings in nitrogen gas; At 205 ℃, 2.1MPa, liquid air speed 0.06hr
-1Under hydrogen ester mol ratio 110 conditions, 2-hydroxypentanoic acid methyl ester conversion rate 94.5%, 1,2-pentanediol selectivity 96.3%.
Claims (6)
1. prepare 1, the catalyst of 2-pentanediol is characterized in that: this catalyst contains one or more elements of IB in the periodic table of elements, II B, VI B, VII B and VIII B family.
2. prepare 1, the catalyst of 2-pentanediol is characterized in that: this catalyst also contains one or more elements that is selected from IA in the periodic table of elements, II A, III A, IV A and V A family.
3. preparation 1 according to claim 1 and 2, the catalyst of 2-pentanediol is characterized in that: described catalyst is a Cu-contained catalyst.
4. preparation 1 according to claim 3; The catalyst of 2-pentanediol is characterized in that: described catalyst is palladium/active carbon, platinum/active carbon, palladium/aluminium oxide, cobalt/active carbon, cobalt/silica, cobalt/aluminium oxide, rhenium/palladium/active carbon, copper/active carbon, Cu/SiO 2, copper/aluminium oxide, copper/zinc oxide, copper/palladium/aluminium oxide, copper/aluminium oxide.
5. preparation 1 according to claim 3, the catalyst of 2-pentanediol is characterized in that: described Cu-contained catalyst is prepared by the precipitation method, and the cupric oxide content of cupric precipitated catalyst accounts for the 30-70%wt of total catalyst weight.
6. preparation 1 according to claim 3, the catalyst of 2-pentanediol is characterized in that: described Cu-contained catalyst is through carrier material dipping or coating preparation, and the cupric oxide content of copper containing carrier catalyst accounts for the 10-25%wt of total catalyst weight.
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| CN2012100752057A CN102626638A (en) | 2012-03-21 | 2012-03-21 | Catalyst for preparation of 1,2-pentanediol |
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| CN2012100752057A CN102626638A (en) | 2012-03-21 | 2012-03-21 | Catalyst for preparation of 1,2-pentanediol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336345A (en) * | 2015-07-10 | 2017-01-18 | 华东理工大学 | Method for preparing 1,3-propylene glycol |
| CN108558700A (en) * | 2018-06-08 | 2018-09-21 | 潍坊伽玛化学有限公司 | A kind of synthetic method of 1,2- pentanediols |
| CN111978148A (en) * | 2019-05-21 | 2020-11-24 | 中石化南京化工研究院有限公司 | Process for preparing 1, 6-hexanediol by reducing 1, 6-adipic acid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1723180A (en) * | 2002-12-13 | 2006-01-18 | 巴斯福股份公司 | Method for the production of 1,6-hexanediol |
| CN101225022A (en) * | 2008-02-13 | 2008-07-23 | 上海华谊丙烯酸有限公司 | Method for preparing 1,5-pentadiol by hydrogenation of 1,5-glutaraldehyde |
-
2012
- 2012-03-21 CN CN2012100752057A patent/CN102626638A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1723180A (en) * | 2002-12-13 | 2006-01-18 | 巴斯福股份公司 | Method for the production of 1,6-hexanediol |
| CN101225022A (en) * | 2008-02-13 | 2008-07-23 | 上海华谊丙烯酸有限公司 | Method for preparing 1,5-pentadiol by hydrogenation of 1,5-glutaraldehyde |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336345A (en) * | 2015-07-10 | 2017-01-18 | 华东理工大学 | Method for preparing 1,3-propylene glycol |
| CN108558700A (en) * | 2018-06-08 | 2018-09-21 | 潍坊伽玛化学有限公司 | A kind of synthetic method of 1,2- pentanediols |
| CN111978148A (en) * | 2019-05-21 | 2020-11-24 | 中石化南京化工研究院有限公司 | Process for preparing 1, 6-hexanediol by reducing 1, 6-adipic acid |
| CN111978148B (en) * | 2019-05-21 | 2023-02-17 | 中石化南京化工研究院有限公司 | Process for preparing 1, 6-hexanediol by reducing 1, 6-adipic acid |
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Application publication date: 20120808 |