Indian Patents. 262992:PROCESS OF THE PREPARATION OF 22-BUTENE-1,4-DIOL

Title of Invention	PROCESS OF THE PREPARATION OF 22-BUTENE-1,4-DIOL
Abstract	2-Butene-1.4-diol can be prepared by hydrogenating 2-butyne-1,4-diol in the presence of a structured catalvst in the absence of a solvent.

Full Text	Process for the preparation of 2-butene-l .4-diol The present invention relates to the preparation of 2-butene-2.4-diol, which is an important industrial intermediate in the preparation of vitamin Be, Pharmaceuticals and insecticides, 2-butene-l,4-diol is usually prepared by catalytic hydrogenation of 2-butyne-l,4-diol in a solvejn, e.g., in an aqueous solution. In order to facilitate recovery of the catalyst it has been proposed to use filamentous woven cloths as a carrier for the catalyst in the hydrogenation of fequeous solutions of 2-butyne-l,4-diol, see Chem. Engineering Science 57 (2002), 3453-3460. According the present invention it has now been found that 2-butene-l,4-diol can be prepajred in high yield and selectivity by catalytic hydrogenation of 2-butyne-l,4-diol over a structured catalyst in the absence of a solvent. Since hydrogen is sparingly soluble in solvefts such as water the absence of such solvents increases the economy of the hydrogenation process in that it results in higher turnover per time unit. Further, the process of the present invention by avoiding separation and recycling of a solvent is preferred for reasons of environmental protection. Accordingly, the present invention relates to a process for the preparation of 2-butene-1.4-diol which comprises hydrogenating 2-butyne-l ,4-diol in the presence of a structured catalyst and in the:absence of a solvent. The term "structured catalyst" as used herein refers to catalysts wherein the spatial position of the catalyst is controlled. Structured catalysts are known in the art, see, e.g., Chimia 56(4), 2002, 159-J63. Examples of structured catalysts are ceramic carrier constructions and fibrous structures, especially filamentous woven cloths. All types of filamentous woven cloths can be used for use in the present invention. The fibers may be from organic or inorganic matter. Examples are fabrics from activated carbon fibers such as acrylonitri] fibers, glass fibers, ceramic fibers, metal fibers or fleece composite oxides of activated carbon fibers. Preferred are polyacrylonitril fabrics. The individual fibers of the filamentous wovan cloth preferably have a diameter of about 2 μm to about 100 μm especially a diameter of no more than about 20 μm. The fabrics are suitably be woven from threads consisting of a boundle of individual fibers, providing a porous size of the woven cloth of less than about 1 mm. They may be chemically treated , e.g., with nitric acid to modify the specific surface and may have a coating, e.g. of metals such as Al, Ti or Pb to improve selectivity. As the catalyst, ever)' hydrogenation catalyst which catalyzes the selective hydrogenation of 2-fcuryne-2,4-diol to 2-butene-2,4-diol can be used. Examples of such catalysts are noble metals such as palladium, platinum, iridium, rhodium, ruthenium or combinations thereof. The catalyst may be present on the carrier fabric in an amount up to about 10 mass%, suitally 1-10 mass%. The loading of the carrier fabric is accomplished by treating with a solution of a precursor of the catalyst, e.g. a salt of the catalyst metal and subsequent drying and heating in a hydrogen atmosphere and can be controlled by the concentration of the cftalyst precursor in the loading solution. The liydrogenation in accordance with the present invention can be carried out under conditions conventionally used for hydrogenations of 2-butin-2,4-diol to produce 2-butene-2,4-dfol. Suitably, the hydrogenation is carried out at a pressure of about 0.1 to about 6 MPa end at a temperature of about 350K to about 500K. The hydrogenation can be carried out bitch wise or in continuous mode. The fallowing Example illustrates the invention further without limiting it. Example Catalyst prepration Activated carbon fibres of polyacrylonitrile origin in the form of plain woven fabrics (Taiwan Carbon Technology Co) were used as supports for catalyst preparation. The fabrips are woven from the long threads of ca. 0,5 mm in diameter. These threads consist of a bundle of elementary filaments of 3-5 μm. The palladium deposition on the fabric was carried out via Join-exchange from aqueous solution of Na2PdCl4 as described in Chem. Eng, Sci. 2002, 57, 3453-3460. The loading of palladium was 4 mass% as determined by atorric absorption spectroscopy, and the catalysts were characterized via BET-method for specific surface area and pore size distribution. Pulse chemisorption of carbon monoxide was applied for the determination of Pd dispersion, see Chem. Eng. Sci., supra. Experimental set-up The experimental set-up is described in detail in Chem. Eng. Sci., supra. The reaction was carried out in a batch reactor (150 ml autoclave, Buechiglas, Uster, CH),iat isothermal conditions kept by a heating jacket. The autoclave was provided with a quantitative gas siapply system. . The fibrous caitalysts were placed between two metal gauzes (20 x 40 mm) fixed on the stirrer. The amount of catalyst placed in the reactor was varied between 150 and 35 mg. The agitation speed was kept at 1500 rpm to avoid mass transfer limitations. To achieve an efficient gas-liquid contact a self-gassing hollow shaft stirrer was used The autoclave was fed with hydrogen (>99.99%) under isobaric reaction conditions. Puie 2-butyne~I,4-diol was charged as a solid (mp 33IK) and molten under Argon to prevent degradation of the reactant. After the required temperature was reached, the reactor was flushed with hydrogen and pressurized to the desired level. During the course of the reaction, the pressure of Bj in the reactor was maintained constant by supplying hydrogen from the reservoir at the rate of consumption. The pressure in the Ha reservoir was monitored continuously allowing in situ measurement of the instantaneous hydrogen consumption. Samples of liquids withdrawn from the loop are analysed by gas chromatography (Auto System XL, PERSON ELMER) with He as a carrier gas and a HD-detector. Product separation was performed on a 30 m Perkin Elmer Elite Series 0.25 mm capillary column with a 0.25 micron coating, at temperature ramp of 20 K/min from 373 to 493K. Butan-1,3-diol was used as internal standard for quantitative GC analysis. The jesults of exferiments under varying reaction conditions can be seen from Figures 1 to i-s .3. Fig. I shows typical concentration time profiles for a reaction temperature of 352K. The measured and predicted selectivity for butenediol (B2) is ca. 98% up to butynediol (B3) conversions of 90% and drops to 95% at 99% conversion as shown in Fig. 2. The influence of teperature on the rate of reaction can be seen from Fig. 3, where the reactant concentration is shown as function of time. Based on the initial reaction rate, the dependence of thtt turnover frequency on temperature can be calculated. WE CLAIM 1 , Process for the preparation of 2-butene-1.4-dioJ which comprises hydrogenating 2-buty:ne-nl ,4-diol in tile presence of & structured catalyst and in the absence of a solvent. 2. A process as in claim 1 wherein the structured catalyst support is a filamentous woven cloth. 3 , A process as in claim 2 wherein filamentous woven cloth is made of activated carbon fibers. 4. A process as in claim 2 the activated carbon fibers are made from polyacrylonitril fibres. 5. A process at in any one of claim2 to 4 wherein the fibers have a diameter of about 2 μm to abou^ 100 um. 6. A process at in any one of claims 2 tor 5 wherein the fibers have a diameter of no more than 20 μm 7, A profcess as in arjy one of claims 2 to 6 wheiedn the porous size of the woven cloth is less thaS 1 mm, S, A process as in ariy oae of claims 2 to 7 wherein the catalyst metal is a palladium catalyst 9. A process as in any one of claims 1 to 8 wherein the catalyst loading of the carrier is about 1 to about 10 mass%. 10. A pipcess as in any one of claims 1 to 9 wherein the hydrogenation is carried out at a pressure} of about 0.1 to about 6 MPa. 1 1 . A process as in any one of claims 1 to 10 wherein the hydrogenation is carried out at a temperaiure of about 350K to about 500K.

Full Text

Process for the preparation of 2-butene-l .4-diol
The present invention relates to the preparation of 2-butene-2.4-diol, which is an important industrial intermediate in the preparation of vitamin Be, Pharmaceuticals and insecticides,
2-butene-l,4-diol is usually prepared by catalytic hydrogenation of 2-butyne-l,4-diol in a solvejn, e.g., in an aqueous solution. In order to facilitate recovery of the catalyst it has been proposed to use filamentous woven cloths as a carrier for the catalyst in the hydrogenation of fequeous solutions of 2-butyne-l,4-diol, see Chem. Engineering Science
57 (2002), 3453-3460.
According the present invention it has now been found that 2-butene-l,4-diol can be prepajred in high yield and selectivity by catalytic hydrogenation of 2-butyne-l,4-diol over a structured catalyst in the absence of a solvent. Since hydrogen is sparingly soluble in solvefts such as water the absence of such solvents increases the economy of the hydrogenation process in that it results in higher turnover per time unit. Further, the process of the present invention by avoiding separation and recycling of a solvent is preferred for reasons of environmental protection.
Accordingly, the present invention relates to a process for the preparation of 2-butene-1.4-diol which comprises hydrogenating 2-butyne-l ,4-diol in the presence of a structured catalyst and in the:absence of a solvent.
The term "structured catalyst" as used herein refers to catalysts wherein the spatial position of the catalyst is controlled. Structured catalysts are known in the art, see, e.g., Chimia 56(4), 2002, 159-J63. Examples of structured catalysts are ceramic carrier constructions and fibrous structures, especially filamentous woven cloths. All types of filamentous woven cloths can be used for use in the present invention. The fibers may be from organic or inorganic matter. Examples are fabrics from activated carbon fibers such as acrylonitri] fibers, glass fibers, ceramic fibers, metal fibers or fleece composite oxides of activated carbon fibers. Preferred are polyacrylonitril fabrics. The individual fibers of the filamentous wovan cloth preferably have a diameter of about 2 μm to about 100 μm especially a diameter of no more than about 20 μm. The fabrics are suitably be woven from threads consisting of a boundle of individual fibers, providing a porous size of the woven cloth of less than about 1 mm. They may be chemically treated , e.g., with nitric acid to modify the specific surface and may have a coating, e.g. of metals such as Al, Ti or Pb to improve selectivity.
As the catalyst, ever)' hydrogenation catalyst which catalyzes the selective hydrogenation of 2-fcuryne-2,4-diol to 2-butene-2,4-diol can be used. Examples of such catalysts are noble metals such as palladium, platinum, iridium, rhodium, ruthenium or combinations thereof. The catalyst may be present on the carrier fabric in an amount up to about 10 mass%, suitally 1-10 mass%. The loading of the carrier fabric is accomplished by treating with a solution of a precursor of the catalyst, e.g. a salt of the catalyst metal and subsequent drying and heating in a hydrogen atmosphere and can be controlled by the concentration of the cftalyst precursor in the loading solution.
The liydrogenation in accordance with the present invention can be carried out under conditions conventionally used for hydrogenations of 2-butin-2,4-diol to produce 2-butene-2,4-dfol. Suitably, the hydrogenation is carried out at a pressure of about 0.1 to about 6 MPa end at a temperature of about 350K to about 500K. The hydrogenation can be carried out bitch wise or in continuous mode.
The fallowing Example illustrates the invention further without limiting it.
Example
Catalyst prepration
Activated carbon fibres of polyacrylonitrile origin in the form of plain woven fabrics (Taiwan Carbon Technology Co) were used as supports for catalyst preparation. The fabrips are woven from the long threads of ca. 0,5 mm in diameter. These threads consist of a bundle of elementary filaments of 3-5 μm. The palladium deposition on the fabric was carried out via Join-exchange from aqueous solution of Na2PdCl4 as described in Chem. Eng, Sci. 2002, 57, 3453-3460. The loading of palladium was 4 mass% as determined by atorric absorption spectroscopy, and the catalysts were characterized via BET-method for specific surface area and pore size distribution. Pulse chemisorption of carbon monoxide was applied for the determination of Pd dispersion, see Chem. Eng. Sci., supra.
Experimental set-up
The experimental set-up is described in detail in Chem. Eng. Sci., supra.
The reaction was carried out in a batch reactor (150 ml autoclave, Buechiglas, Uster, CH),iat isothermal conditions kept by a heating jacket. The autoclave was provided with a quantitative gas siapply system.
. The fibrous caitalysts were placed between two metal gauzes (20 x 40 mm) fixed on the stirrer. The amount of catalyst placed in the reactor was varied between 150 and 35 mg. The agitation speed was kept at 1500 rpm to avoid mass transfer limitations. To achieve an efficient gas-liquid contact a self-gassing hollow shaft stirrer was used The autoclave was fed with hydrogen (>99.99%) under isobaric reaction conditions.
Puie 2-butyne~I,4-diol was charged as a solid (mp 33IK) and molten under Argon to prevent degradation of the reactant. After the required temperature was reached, the reactor was flushed with hydrogen and pressurized to the desired level. During the course of the reaction, the pressure of Bj in the reactor was maintained constant by supplying hydrogen from the reservoir at the rate of consumption. The pressure in the Ha reservoir was monitored continuously allowing in situ measurement of the instantaneous hydrogen consumption.
Samples of liquids withdrawn from the loop are analysed by gas chromatography (Auto System XL, PERSON ELMER) with He as a carrier gas and a HD-detector. Product separation was performed on a 30 m Perkin Elmer Elite Series 0.25 mm capillary column with a 0.25 micron coating, at temperature ramp of 20 K/min from 373 to 493K. Butan-1,3-diol was used as internal standard for quantitative GC analysis.
The jesults of exferiments under varying reaction conditions can be seen from Figures 1 to
i-s
.3.
Fig. I shows typical concentration time profiles for a reaction temperature of 352K. The measured and predicted selectivity for butenediol (B2) is ca. 98% up to butynediol (B3) conversions of 90% and drops to 95% at 99% conversion as shown in Fig. 2. The influence of teperature on the rate of reaction can be seen from Fig. 3, where the reactant concentration is shown as function of time. Based on the initial reaction rate, the dependence of thtt turnover frequency on temperature can be calculated.

WE CLAIM
1 , Process for the preparation of 2-butene-1.4-dioJ which comprises hydrogenating 2-buty:ne-nl ,4-diol in tile presence of & structured catalyst and in the absence of a solvent.
2. A process as in claim 1 wherein the structured catalyst support is a filamentous woven
cloth.
3 , A process as in claim 2 wherein filamentous woven cloth is made of activated carbon fibers.
4. A process as in claim 2 the activated carbon fibers are made from polyacrylonitril fibres.
5. A process at in any one of claim2 to 4 wherein the fibers have a diameter of about 2 μm
to abou^ 100 um.
6. A process at in any one of claims 2 tor 5 wherein the fibers have a diameter of no more
than 20 μm

7, A profcess as in arjy one of claims 2 to 6 wheiedn the porous size of the woven cloth is less thaS 1 mm,
S, A process as in ariy oae of claims 2 to 7 wherein the catalyst metal is a palladium catalyst
9. A process as in any one of claims 1 to 8 wherein the catalyst loading of the carrier is
about 1 to about 10 mass%.
10. A pipcess as in any one of claims 1 to 9 wherein the hydrogenation is carried out at a
pressure} of about 0.1 to about 6 MPa.
1 1 . A process as in any one of claims 1 to 10 wherein the hydrogenation is carried out at a temperaiure of about 350K to about 500K.

Documents:

4324-delnp-2007-Abstract-(27-09-2012).pdf

4324-delnp-2007-abstract.pdf

4324-delnp-2007-Claims-(27-09-2012).pdf

4324-delnp-2007-claims.pdf

4324-delnp-2007-correpondence-others (26-11-2008).pdf

4324-delnp-2007-Correspondence Others-(22-05-2012).pdf

4324-DELNP-2007-Correspondence Others-(27-09-2012).pdf

4324-delnp-2007-correspondence-others.pdf

4324-delnp-2007-description (complete).pdf

4324-delnp-2007-drawings.pdf

4324-DELNP-2007-Form-1-(27-09-2012).pdf

4324-delnp-2007-form-1.pdf

4324-delnp-2007-form-18 (26-11-2008).pdf

4324-delnp-2007-form-2.pdf

4324-delnp-2007-Form-3-(27-09-2012).pdf

4324-delnp-2007-form-3.pdf

4324-delnp-2007-form-5.pdf

4324-delnp-2007-GPA-(27-09-2012).pdf

4324-delnp-2007-gpa.pdf

4324-delnp-2007-pct-210.pdf

4324-delnp-2007-pct-304.pdf

4324-DELNP-2007-Petition-137-(27-09-2012).pdf

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Patent Number

262992

Indian Patent Application Number

4324/DELNP/2007

PG Journal Number

40/2014

Publication Date

03-Oct-2014

Grant Date

29-Sep-2014

Date of Filing

06-Jun-2007

Name of Patentee

DSM IP ASSETS B.V

Applicant Address

HET OVERLOON 1,NL-6411 TE HEERLEN, THE NETHERLANDS

Inventors:

#	Inventor's Name	Inventor's Address
1	JOANNET, ERIC	ROUTE DE MATHERENGES, CH-1510 MOUDON, SWITZERLAND
2	KIWI-MINSKER, LIOUBOV	CHEMIN DE LA RAMIERE 26, CH-1028 PREVERENGES, SWITZERLAND
3	RENKEN, ALBERT	CH.DES CHAMILLES 46, CH-1025 ST.SULPICE, SWITZERLAND

PCT International Classification Number

C07C 29/17

PCT International Application Number

PCT/EP2005/014103

PCT International Filing date

2005-12-29

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	05000227.8	2005-01-07	EUROPEAN UNION