WO2010044092A1 - Procédé d’hydrogénation sélective d’alcynes en alcènes sur des catalyseurs sur support de métal simple avec une activité élevée - Google Patents

Procédé d’hydrogénation sélective d’alcynes en alcènes sur des catalyseurs sur support de métal simple avec une activité élevée Download PDF

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Publication number
WO2010044092A1
WO2010044092A1 PCT/IN2009/000043 IN2009000043W WO2010044092A1 WO 2010044092 A1 WO2010044092 A1 WO 2010044092A1 IN 2009000043 W IN2009000043 W IN 2009000043W WO 2010044092 A1 WO2010044092 A1 WO 2010044092A1
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Prior art keywords
catalyst
range
butynediol
hydrogenation
catalysts
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PCT/IN2009/000043
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English (en)
Inventor
Amod Madhukar Sathe
Bapurao Sidram Shinde
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Hindustan Organic Chemicals Limited
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Publication of WO2010044092A1 publication Critical patent/WO2010044092A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/08—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds
    • C07C5/09—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of carbon-to-carbon triple bonds to carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium

Definitions

  • US Patent # 5,583,274 claims selective hydrogenation of alkynes present in alkenes streams along with sulphur containing compounds, by using Pd/Ag catalysts containing fluorides in the form of potassium fluoride on alumina supports, whereas US Patent # 6,127,310 claims the use of Pd along with Pb and alkali metal or alkali metal halide as selectivity enhancers.
  • US Patents # 7,045,670 and 7,408,091 claim liquid phase selective hydrogenation of alkynes absorbed in liquid stream on Zn promoted Pd catalyst on alumina support, with hydrogen containing more than 2000 ppm CO.
  • US Patent #6,054,409 reports selective hydrogenation of unsaturated hydrocarbons in olefins with a Pd/Ag catalyst on a low surface area (2-20 mVg) alumina carrier with pore volumes greater than 0.4 cc/g and a particular size range of the pores.
  • a Pd/Ag catalyst on a low surface area (2-20 mVg) alumina carrier with pore volumes greater than 0.4 cc/g and a particular size range of the pores.
  • As per US Patent #5,750,806 selective hydrogenation of alkynes (acetylenes) to alkenes is reported on Pd/Bi monoliths in Trickle bed, and as per US Patent # 6,365,790 B 2 for Pd/Bi and Pd/Ag monoliths on Kanthal fabric.
  • Recent US Patent # 7,288,686 reveals complete removal of acetylenic compounds from hydrocarbon streams by using Pd with Ag/Zn/Bi/K in a fixed bed reactor.
  • Palladium catalysts containing one or more additional metal are also reported in prior art for selective hydrogenation of 1,4 butynediol to 1,4 butenediol/ 1,4 butanediol: Canadian Patent # 1,090,829 mentions palladium with lead in the form of lead acetate hydrate dozing to the reactor (autoclave). US Patent # 4,438,285 mentions use of Pd/Ru in a batch process, on activated carbon as well as alumina supports. US Patent
  • Ca, Mg, Ba carbonates (US Patents# 5,714,644; 6,469,221 Bl; 2006/0094910 Al); MgO (US Patent# 5,714,644); activated carbon (US Patent# 4,438,285); apart from the monoliths or fibers (US Patents# 5, 521,139; 5,750,806; 6,365,790 B2; Ind. Eng. Chem. Res., 44, 2005, 6148-6153) etc. are also reported in prior art. Reaction parameters, types of reactors etc.
  • Alkynes in the form of gases or gases absorbed in liquids are reported in prior art.
  • 1,4 butynediol is in the form of aqueous solution up to 50% concentration, excepting in one case (Ind.Eng.Chem.Res.44, 2005, 6148-6153), wherein molten pure 1,4 butynediol (from solid state) hydrogenation is reported in prior art.
  • the hydrogen gas reported in prior art is generally pure hydrogen; however controlled carbon monoxide addition to hydrogen for better selectivity towards double bond, is also reported in US patents # 5,750,806 and 6,365,730 B 2 .
  • Catalyst activity expressed in g of alkyne (or particularly 1,4 butynediol, as the case may be) reacted per day per gram of (total) metal contents in the catalyst is calculated typically for the following cases mentioned in prior art:
  • an activity in the range of 130 to 260 g butynediol/(day-g metal) can be calculated for the ranges Ni/Mo on AI 2 O 3 catalyst.
  • an activity of 75 g butanediol per hour i.e. 108 g butynediol reacted per hour can be calculated for 20 g Raney Ni/Mo catalyst used, which works out equivalent to 13O g butynediol reacted/ (day-g metal).
  • an activity in the range of 80 to 260 g butynediol reacted/ (day-g metal) can be calculated for the 1% Pt/ CaCO3 catalyst.
  • the catalyst activity works out to 160 g butynediol reacted/ (day-g metal).
  • the object of the present invention is to provide an efficient, commercially attractive process for the preparation of alkenes, particularly 1, 4 butenediol with high selectivity and activity per unit of metal contents, by hydrogenating the corresponding alkynes, particularly pure or technical grade 1,4 butynediol, under low pressure and temperature, in the absence of any additives for improving selectivity (e.g. CO), by a commercially available suitably supported catalyst containing a single metal component, prepared in any conventional manner and achieving a longer catalyst life.
  • selectivity e.g. CO
  • the object of the present invention is achieved by a process for the hydrogenation of alkynes, particularly technical grade 1 ,4 butynediol, in a reactor, in the presence of a standard commercial catalyst prepared in any conventional manner, working under hydrogenation pressure from 1 to 20 bar, at a temperature range of 15 to 250 0 C, under hydrogen pressure from 1 to 20 bar, under space velocity ranging from: GHSV 1 to 10,00Oh '1 , and LHSV 0.001 to 1Oh "1 .
  • the process is preferably carried out using pure or technical grade 1 ,4 butynediol- synthesized by various alternate routes correspondingly , from acetylene and aqueous formaldehyde.
  • the strength of butynediol solution is 20 to 60%, preferably aqueous solution.
  • the hydrogen gas is in pure form and in particular, carbon monoxide or any other compound is not periodically added to the same for controlling the selectivity.
  • the hydrogenation reaction is carried out in a continuous single tube bubble column up flow reactor.
  • the hydrogenation catalysts are capable of hydrogenating triple to double and subsequently to single bond compounds, which may contain very low amount of a single active metal, chosen from palladium, nickel, molybdenum, copper or platinum.
  • the active metal content may vary from 0.0001 to 1%, preferably from 0.0005 to 0.01%.
  • the catalyst support can be selected from alumina, alumino silicates, silica gel or activated carbons. More efficient utilization of the active metal results in high activity per unit of metal contents , at the same time giving very high selectivity.
  • typical physical properties of the catalyst being: the surface area between 3 to 300 mVg, preferably 5 to 10 m 2 /g; the pore volume between 0.05 to 0.6 cc/g, preferably 0.15 to 0.50 cc/g; the side crushing strength between 2 to 20 kg, preferably 5 to 15 kg.
  • the most preferred catalyst being palladium supported on alumina in a wide range of palladium contents offered within the range of these physical properties. Catalysts of this type are commercially available under the various grades as follows:
  • Li another embodiment of the invention the process is carried out under hydrogen pressures from 5 to 15 bar.
  • the process is carried out at a temperature in the range of 50-150 0 C.
  • the gas hourly space velocity (GHSV) for the process is in the range of 10 to 1000 h "1 .
  • liquid hourly space velocity (LHSV) for the process is in the range of 0.01 to 1 h '1 .
  • the catalyst is run consecutively for more than 5000 hours.
  • the process is scaled up 1: 10 times in a similar single tube reactor, without adversely affecting the selectivity of alkenes.
  • Hydrogenation reactor for the present study consisted of a standard stainless steel continuous single tube reactor, with an outside jacket arrangement for heat removal. Gas & liquid were introduced at the bottom of the reactor in co-current up flow manner. At the reactor outlet from the top, the two phases were separated in a gas- liquid separator. The hydrogenation runs were carried out once through for the liquid as well as gas. In an industrial set up, gas recycle arrangement after the gas-liquid separator is easily possible.
  • the reactor was packed with PCI/AI 2 Q 3 catalysts containing Pd in various proportions from amongst the commercially available catalysts of various grades from different suppliers mentioned earlier. Pure industrial hydrogen gas as such was used. Carbon monoxide (CO) or any other components were not added at any time to the hydrogen to influence on the hydrogenation process selectivity.
  • CO Carbon monoxide
  • Example 2 The catalyst activity for various PdZAl 2 Oj catalysts is described in Example 2, as a function of LHSV for constant value of GHSV.
  • Technical grade 1,4 butynediol produced under different catalysts (typically Catalyst #1 and Catalyst #2) at Malawistan Organic Chemicals Limited, Rasayani, Maharashtra, India, was employed for the study.
  • the catalyst activity expressed per unit mass of the catalyst shows inconsistency, however the activity based on unit mass of the active metal is found to increase with lower active metal containing (typically palladium) catalysts, under all conditions. Hence this was selected as a proper basis for all further comparisons.
  • Example 3 showing the variation of GHSV with LHSV confirms that the reaction is influenced by mass transfer effects. Further study, illustrated by Examples 4 to 8 focuses on the selectivity for l,4butenediol.
  • Example 4 It can be seen from Example 4 that there is a threshold catalytic activity, beyond which the selectivity to 1,4 butenediol is adversely affected.
  • Example 5 illustrates that with lowering of active metal (palladium) contents of the catalysts, selectivity towards 1,4 butenediol (desirable) improves significantly at complete conversions of 1,4 butynediol, by suppressing the formation of 1,4 butanediol (undesirable).
  • Example 6 further reaffirms this selectivity trend, where pure 1,4 butynediol is used.
  • the process selectivity improves with lower active metal contents for 1,4 butynediol prepared by various techniques.
  • Example 7 wherein pure 1,4 butenediol product in aqueous solution was introduced as feed, hydrogenated and the outlet product showed consistency in the assay content of 1,4 butenediol, under similar hydrogenation process conditions as for 1,4 butynediol. This was further established in the 1 : 10 scaled up version of the bubble column up flow reactor by Example 8.
  • the gas hourly space velocity (GHSV) was maintained at about 31O h '1 and the liquid hourly space velocity (LHSV) kept at about 0.075 h "1 .
  • Catalyst activity obtained at full conversion of butynediol was 504 g butynediol/ (day- kg catalyst).
  • the hydrogenation reactor containing 0.1% Pd/ AUC ⁇ catalyst as described in part (a) was used for this study.
  • Zinc 60- to 500 ppm was introduced in the form of zinc acetate dihydrate by addition to the technical grade 35% butynediol solution , as described in part (a).
  • Example 2 The same continuous single tube bubble column up flow reactor as referred to in Example 1, was used for hydrogenation studies of technical grade aqueous butynediol solutions prepared from aqueous formaldehyde and acetylene under two different catalysts (Catalysts #1 and #2 respectively) of butynediol synthesis at Malawistan Organic Chemicals Limited, Rasayani, Maharashtra, India, under the same pressure and temperature conditions as mentioned in Example 1, except that the hydrogenation reactor was packed with standard industrial PdZAl 2 Q 3 catalysts containing palladium contents in varying amounts. The runs were carried out under varying liquid hourly space velocities (LHSV), keeping Gas hourly space velocity (GHSV) constant The results are tabulated in Table 2.
  • LHSV liquid hourly space velocities
  • GHSV Gas hourly space velocity
  • the catalyst activity in part (A) is expressed as grams of butynediol reacted per day- per kilogram of the catalyst. However, to get a better comparison of the activity, the same is also expressed in terms of grams of palladium contents in the catalyst in part (B).
  • Example 2 The same continuous single tube bubble column up flow reactor as referred to in Example 1 was used for hydrogenation of various technical grade aqueous butynediol solutions with standard industrial Pd/Al 2 Qj catalysts containing palladium contents in varying amounts, as referred to in Example 2 and was operated at the same temperature and pressure conditions as mentioned in Example 1, except that the runs were carried out under varying GHSVs, at constant LHSVs.
  • the results are tabulated in Table 3.
  • the catalyst activity is expressed here as grams of butynediol reacted per day- per gram of palladium contents in the catalyst.
  • Example 2 The same continuous single tube bubble column up flow reactor as referred to in Example 1 was used for hydrogenation of various technical grade aqueous butynediol solutions with standard industrial Pd/Al 2 C>3 catalysts containing palladium contents in varying amounts, under the same range of GHSV and LHSV as referred to in example 2 and 3, and was operated at the same temperature and pressure conditions as mentioned in Example 1.
  • the results are tabulated in Table 4.
  • the catalyst activity, as in Example 3 is expressed as grams of butynediol reacted per day- per gram of palladium contents in the catalyst.
  • Example 2 The same continuous single tube bubble column up flow reactor as referred to in Example 1 was used for hydrogenation of various technical grade aqueous butynediol solutions with standard industrial Pd/AfeOs catalysts containing palladium contents in varying amounts, under the same range of GHSV and LHSV as referred to in example 2 and 3, and was operated at the same temperature and pressure conditions as mentioned in Example 1. Hydrogenation in tins case, was carried out such that complete conversion of 1,4 butynediol is achieved. Selectivities for the desired product (1,4 butenediol) and the undesired product (1,4 butanediol) are expressed. The results are tabulated in Table 5.
  • Example 2 The same continuous single tube bubble column up flow reactor as referred to in Example 1 was used for hydrogenation studies of pure Butynediol ('Aldrich * make) dissolved in demineralized water to make a 35% solution and was operated at the same temperature and pressure conditions as mentioned in Example 1.
  • the hydrogenation reactor was packed with standard industrial Pd/AkQj catalysts containing 0.002% Pd contents, and was operated under the same range of GHSV and LHSV as mentioned in Examples 2 and 3. Hydrogenation was carried out just near complete conversion of butynediol.
  • the catalyst activity achieved was 13,100 of butynediol/day-g palladium. Selectivities for the desired product (1,4 butenediol) and the undesired product (1,4 butanediol) are expressed. The results are tabulated in Table 6.
  • Example 7 The same continuous single tube bubble column up flow reactor as referred to in Example 1 was used for hydrogenation studies of industrially available pure 1,4 butenediol, dissolved in demineralized water to make a 35% solution and was operated at the same temperature and pressure conditions as mentioned in Example 1.
  • the hydrogenation reactor was packed with standard industrial PdVAfeQj catalysts containing 0.002% Pd contents (as in example 6), and was operated under the same range of GHSV and LHSV as mentioned in Examples 2 and 3. The results are tabulated in Table 7.
  • Example 7 Hydrogenation study for over hydrogenation of pure butenediol, as illustrated in Example 7, was repeated in a 1:10 scaled up version of the continuous single tube bubble column up flow reactor, as described in Example 1, and maintained at the same temperature and pressure conditions in Example 1 and operated under the same range of GHSV and LHSV as mentioned in Examples 2 and 3.
  • the hydrogenation reactor was packed with standard industrial PdZAl 2 O 3 catalysts containing 0.002% Pd contents (as in Examples 6 and 7). The results are tabulated in Table 8.
  • the process can utilize 1,4 butynediol right from highly pure grade to any technical grade, which may be synthesized by various alternative processes using different catalysts, from the reaction of formaldehyde and acetylene.
  • the influence of mass transfer on the present process can be advantageously used for achieving high activity, by choosing a right combination of GHSV and LHSV, which will result in more throughputs.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention a pour objet un procédé d’hydrogénation sélective d’alcynes en alcènes sur des catalyseurs de métal simple sur support approprié avec une activité élevée par unité de teneur en métal. Elle élabore en outre une hydrogénation sélective de grades techniques de 2-butyne-1,4-diol produit à partir de la synthèse de Reppe en 2-butène-1,4-diol, avec essentiellement moins de catalyseur contenant du Pd, parmi divers catalyseurs Pd/Al2Q3 disponibles commercialement, sous des pressions d’hydrogène inférieures situées dans la plage de 1 à 20 bars, à des températures inférieures entre 15 et 250° C, avec une GHSV de 1 à 10000 h‑1 et une LHSV de 0,001 à 10 h-1, qui peuvent être augmentées proportionnellement jusqu’à plus de 10 fois dans un réacteur à tube simple continu ou multitubulaire.
PCT/IN2009/000043 2008-10-15 2009-01-13 Procédé d’hydrogénation sélective d’alcynes en alcènes sur des catalyseurs sur support de métal simple avec une activité élevée WO2010044092A1 (fr)

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IN2215/MUM/2008 2008-10-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115739077A (zh) * 2022-10-13 2023-03-07 厦门大学 一种高选择性钯基催化剂及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4831200A (en) * 1986-12-30 1989-05-16 Labofina, S.A. Process for the selective hydrogenation of alkynes
US6262317B1 (en) * 1996-10-10 2001-07-17 Basf Aktiengesellschaft Process for preparing 1,4-butanediol by catalytic hydrogenation of 1,4-butinediol
US6469221B1 (en) * 2000-11-20 2002-10-22 Council Of Scientific And Industrial Research Process for the conversion of 1, 4 butynediol to 1, 4 butanediol, or a mixture of 1, 4 butenediol and 1,4 butanediol
US7045670B2 (en) * 2003-09-03 2006-05-16 Synfuels International, Inc. Process for liquid phase hydrogenation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4831200A (en) * 1986-12-30 1989-05-16 Labofina, S.A. Process for the selective hydrogenation of alkynes
US6262317B1 (en) * 1996-10-10 2001-07-17 Basf Aktiengesellschaft Process for preparing 1,4-butanediol by catalytic hydrogenation of 1,4-butinediol
US6469221B1 (en) * 2000-11-20 2002-10-22 Council Of Scientific And Industrial Research Process for the conversion of 1, 4 butynediol to 1, 4 butanediol, or a mixture of 1, 4 butenediol and 1,4 butanediol
US7045670B2 (en) * 2003-09-03 2006-05-16 Synfuels International, Inc. Process for liquid phase hydrogenation

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115739077A (zh) * 2022-10-13 2023-03-07 厦门大学 一种高选择性钯基催化剂及其应用

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