Method for producing pentanediol through selective hydrogenolysis of furan derivative

A technology of furan derivatives and pentanediol, which is applied in the fields of chemical instruments and methods, chemical/physical processes, and the reduction and preparation of oxygen-containing functional groups. Uniform distribution, simple preparation method, good economic benefits

Inactive Publication Date: 2015-12-09
LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Chinese patent (CN102627526A) discloses a method of directly hydrogenating α-hydroxy n-valerate to 1,2-pentanediol. Although the yield of this method can reach 95%, the raw material is very scarce and the production cost is high
(2) N-pentene epoxidation method: use n-pentene as raw material, prepare 1,2-epoxypentane through epoxidation, and then hydrolyze and open the ring to obtain 1,2-pentanediol (CN1552684, CN104177230A, US4605795A), this method has problems such as easy generation of by-products, low product yield and serious equipment corrosion
The synthesis methods of 1,5-pentanediol mainly include: (1) Epoxypentenal is prepared by photooxidation of cyclopentadiene, and then obtained by catalytic hydrogenation at 70-100°C under a pressure of about 7MPa, but the cyclopentadiene The low photooxidation efficiency of pentadiene makes this method not economical; (2) Using glutaric acid as raw material, it is first esterified to obtain 1,5-methyl glutarate, and then under the action of CuZnAl catalyst Hydrogenation at 150-350°C and 3-5MPa to produce 1,5-pentanediol (Chinese patents CN03137598.7, CN1565728A)
The conversion rate of this process and the selectivity of 1,5-pentanediol can both be greater than 95%, but the process flow is long and the cost of raw materials is high
(3) Using 1,5-glutaraldehyde as a raw material, hydrogenation is carried out at 60-120°C and 2-8MPa through a supported Ni-based catalyst (CN101225022) or Ru-based catalyst (CN101270032). The selectivity of this method is good, Mild conditions, the disadvantage is that the raw material resources are not abundant and the price is high
Chinese patent CN102872897A discloses a method of using hydrogen-type ultrastable molecular sieve (H-USY) to support Pt to catalyze the hydrogenolysis of furfuryl alcohol to produce 1,5-pentanediol. This method can obtain a yield of nearly 80% of the target product, but the reaction A large amount of precious metal Pt catalyst needs to be added in the process, and the production cost is high
However, the catalyst contains the toxic element Cr, which causes great environmental pollution and harsh reaction conditions.

Method used

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  • Method for producing pentanediol through selective hydrogenolysis of furan derivative
  • Method for producing pentanediol through selective hydrogenolysis of furan derivative

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Embodiment 1

[0028] A method for selective hydrogenolysis of furan derivatives to prepare pentanediol: 1) Preparation of active catalyst 1: Weigh 7.61g of copper nitrate trihydrate and 139.46g of aluminum nitrate tetrahydrate and dissolve them in 300mL of distilled water to form a salt solution, and weigh 40g Sodium hydroxide and 21.2g of anhydrous sodium carbonate were added to 200mL of water to make a mixed alkali solution, and the salt solution and mixed alkali solution were added dropwise to the three-necked flask under vigorous stirring to maintain the pH of the system at 10. Aged for 24 hours, suction filtered and washed with distilled water until neutral, and dried at 110°C for 12 hours to obtain a catalyst precursor with a layered structure of hydrotalcite. The precursor was calcined in a muffle furnace at 500° C. for 4 hours, and then reduced and activated in a hydrogen atmosphere at 350° C. for 3 hours to obtain the active catalyst 1 provided by the present invention.

[0029] 2)...

Embodiment 2

[0031] A method for selective hydrogenolysis of furan derivatives to prepare pentanediol: 1) Preparation of active catalyst 2: the operation is the same as in Example 1, replacing 139.46g of aluminum nitrate nonahydrate with 62.73g of zirconium nitrate tetrahydrate, and obtaining this product after reduction and activation Active catalyst 2 provided by the invention.

[0032] 2) Selective hydrogenolysis reaction of furfuryl alcohol: the same as in Example 1, and the test results are shown in Table 1.

Embodiment 3

[0034] A method for selective hydrogenolysis of furan derivatives to prepare pentanediol: 1) Preparation of active catalyst 3: the operation is the same as in Example 1, except that 47.84g of lanthanum nitrate hexahydrate is used instead of 139.46g of aluminum nitrate nonahydrate, and the product is obtained after reduction and activation The active catalyst 3 provided by the present invention.

[0035] 2) Selective hydrogenolysis reaction of furfuryl alcohol: the operation is the same as in Example 1, except that 40g of 10wt% furfuryl alcohol in methanol is replaced by 40g of 10wt% furfuryl alcohol in methanol solution. The test results are shown in Table 1.

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Abstract

The present invention discloses a method for producing pentanediol through selective hydrogenolysis of a furan derivative. According to the method, a highly dispersed copper-based composite metal oxide is adopted as a catalyst, methanol, ethanol, isopropanol or dioxane is adopted as a solvent, and a furan derivative is subjected to selective hydrogenolysis in an intermittent stirring reaction kettle or continuous fixed bed reactor at a reaction temperature of 120-180 DEG C under a hydrogen pressure of 1-10 MPa to prepare the pentanediol, wherein a catalyst precursor having a hydrotalcite layered structure is subjected to calcination reduction to obtain the catalyst, mainly a metal ion solution having CuM and an alkaline solution are subjected to a co-precipitation reaction so as to obtain the catalyst precursor, and in the catalyst, Cu is the main active component and has the content is 2-40%, and the content of the M-containing oxide and the spinel carrier is 60-98%. According to the present invention, the catalyst preparation method has characteristics of simpleness, easily available raw materials and low cost, and the prepared catalyst has characteristics of uniform component distribution, small particle size, large specific surface area and stable performance, and provides high reaction reactivity and high selectivity for the pentanediol production through the selective hydrogenolysis of the furan derivative.

Description

technical field [0001] The invention belongs to the field of fine chemicals, and relates to a method for preparing pentanediol by selective hydrogenolysis of furan derivatives. Background technique [0002] Both 1,2-pentanediol and 1,5-pentanediol are organic chemicals with a wide range of uses. 1,2-Pentanediol is a linear diol with a dihydroxyl group at one end and a relatively long alkyl chain at the other end. It has obvious polarity and nonpolarity. It is mainly used as a key raw material for the synthesis of the fungicide propiconazole, and also It is an important raw material for the production of polyester fibers, surfactants, pharmaceuticals and other products. In addition, it is used in various skin care products as an excellent moisturizer, preservative and solvent. 1,5-Pentanediol is a linear diol, which has wide application prospects as a polyester and polyurethane monomer; it is also used as an important organic synthesis intermediate for the manufacture of pl...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C29/132C07C31/20B01J23/72B01J23/83B01J23/80B01J23/78B01J35/10
CPCC07C29/132B01J23/72B01J23/78B01J23/80B01J23/83B01J35/10B01J35/1019B01J35/1061C07C31/20
Inventor 黄志威陈静刘海龙夏春谷赵峰李雪梅
Owner LANZHOU INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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