巴西专利BR112014017585B1 process for the production of hexamethylene diamine from materials containing carbohydrates and inte

专利PDF首页>>巴西专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:
PROCESS FOR THE PRODUCTION OF HEXAMETHYLENE DIAMINE FROM MATERIALS CONTAINING CARBOHYDRATE AND INTERMEDIARIES FOR THE SAME. Processes for converting a carbohydrate source to hexamethylene diamine (HMDA) and to intermediates useful for the production of hexamethylene diamine and other industrial chemicals are disclosed. HMDA is produced by direct reduction of a furfural substrate in 1,6-hexanediol in the presence of hydrogen and a heterogeneous reduction catalyst comprising Pt or by indirect reduction of a furfural substrate in 1,6-hexanediol where 1,2, 6-hexanotriol is produced by reducing the furfural substrate in the presence of hydrogen and a catalyst comprising Pt and 1,2,6-hexanediol is then converted by hydrogenation in the presence of a catalyst comprising Pt into 1,6 hexanediol, each process then proceeding for the production of HMDA by known routes, such as amination of 1.6 hexanediol. Catalysts useful for the direct and indirect production of 1,6-hexanediol are also disclosed.
公开号:BR112014017585B1
申请号:R112014017585-3
申请日:2013-01-11
公开日:2020-11-24
发明作者:Eric L. Dias；James A. W. Shoemaker；Thomas R. Boussie；Vincent J. Murphy
申请人:Archer-Daniels-Midland Company；
IPC主号:

专利说明:

[0001] [0001] This application claims the benefit of provisional application US number 61 / 588,093, filed on January 18, 2012, the disclosure of which is hereby incorporated by reference in its entirety. Field of the Invention
[0002] [0002] The present disclosure relates generally to processes for converting a carbohydrate source to hexamethylene diamine and to useful intermediates for the production of hexamethylene diamine and other industrial chemicals. The present disclosure relates more specifically to chemocatalytic processes for the production of hexamethylene diamine from a furfural substrate derived from a carbohydrate source, the substrate of which is converted into an intermediate comprising 1,6-hexanediol from which hexamethylene diamine can be derived by chemocatalytic amination of the diol. The present invention is also directed to the production of 1,6-hexanediol from a furfural substrate in which at least a portion of the furfural substrate is converted to 1,2,6 hexanotriol, at least a portion of the hexanotriol is then converted to 1,6-hexanediol and 1,6-hexanediol is then converted to hexamethylene diamine, for example, by chemocatalytic amination of the diol. The present disclosure also relates to improved processes for the production of hexanediol from a furfural substrate. Background
[0003] [0003] Hexamethylene diamine (HMDA) is a chemical intermediate mainly used in the production of nylon 6.6 through condensation with adipic acid. HMDA is also used in the production of monomers for polyurethanes. In addition, HMDA is used in the production of epoxy resins. Today, annual HMDA production exceeds 3 billion pounds (avoir).
[0004] [0004] Crude oil is currently the source of most specialty and commodity organic chemicals. Many of these chemicals are used in the manufacture of polymers and other materials. Desired chemicals include, for example, styrene, bisphenol A, terephthalic acid, adipic acid, caprolactam, hexamethylene diamine, adiponitrile, caprolactone, acrylic acid, acrylonitrile, 1,6-hexanediol, 1,3-propanediol and others. Crude oil is first refined, typically by steam cracking, into hydrocarbon intermediates such as ethylene, propylene, butadiene, benzene and cyclohexane. These hydrocarbon intermediates are then typically subjected to one or more catalytic reactions by various processes to produce that desired chemical (s).
[0005] [0005] HMDA is among those chemicals that continue to be produced commercially from oil through a multi-stage process. HMDA is typically produced from butadiene. Butadiene is typically produced from steam cracking from heavier feeds. Steam cracking of such feeds favors the production of butadiene, but it also produces heavier aromatics and olefins. In this way, the butadiene that results from the cracking step is typically extracted in a polar solvent from which it is then extracted by distillation. Butadiene is subjected to a hydrocyanation process in the presence of a nickel catalyst to produce adiponitrile. See, for example, US 6,331,651. HMDA is then typically produced by hydrogenating adiponitrile in the presence of a solid catalyst. See, for example, US 4,064,172 (which discloses a process for the production of HMDA by hydrogenating adiponitrile in the presence of an iron oxide catalyst) and US 5,151,543 (which reveals that HMDA can be prepared by hydrogenating adiponitrile in the presence a Raney nickel catalyst doped with at least one metal element selected from groups 4, 5 and 6 of the periodic table of elements and, more recently, WO-A-93/16034 and WO-A-96/18603 (each one of which reveals processes based on Raney nickel catalyst for the production of HMDA from adiponitrile) and US patent application No. 2003/0144553 (which discloses a process for the production of HMDA from adiponitrile in the presence of a catalyst particularly conditioned Raney nickel).
[0006] [0006] Notably, each of the aforementioned documents aimed at the production of HMDA recognizes the need to improve the efficiency, selectivity and commercial competitiveness of such a process. In reality, the need for improved or alternative commercial processes for the production of HMDA is exacerbated by the evolution of the chemical industry towards the use of lighter feeds which, when subjected to cracking, produce smaller amounts of butadiene and will ultimately lead to increased costs of produce HMDA and increased price volatility.
[0007] [0007] For many years there has been an interest in using bio-renewable materials as a feed material to replace or supplement crude oil. See, for example, Klass, Biomass for Renewable energy, Fuels and Chemicals, Academic Press, 1998, which is incorporated here by way of reference.
[0008] [0008] Recently, HMDA and other chemicals used in the production, among other materials, of polymers such as nylon have been identified as chemicals that can be produced from bio-renewable resources, particularly materials containing carbohydrates from which glucose can be obtained and used as the feed material to manufacture such chemicals. See, for example, US 2010/0317069, which discloses biological pathways that are believed to be useful for producing, among other chemicals, caprolactam and HMDA.
[0009] [0009] To date, there is no commercially viable process for the production of HMDA from food materials containing carbohydrates. Given the shift away from the production of conventional oil-derived starting materials such as butadiene, despite the continued growth in the markets by nylon and polyurethanes, among other materials, derived at least in part from HMDA or derived from them and the benefits attributable to the use of renewable feed materials instead of petroleum-derived feed materials, new industrially scalable methods for the selective and commercially significant production of chemicals from polyhydroxyl containing bio-renewable materials (eg glucose derived from starch, cellulose or sucrose) for important chemical intermediates like HMDA is compelling.
[0010] [00010] 1,6-hexanediol (HDO) was prepared, for example, from adipic acid, caprolactone and hydroxycaproic acid. See, for example, US 5,969,194. Recently, a process for the production of 1,6-hexanediol from glucose-derived furfural was disclosed in WO2011 / 149339. The '399 application provides an overview of at least a two-step catalytic process for the production of HDO from 5-hydroxy methyl furfural (HMF): hydrogenation of HMF in 2,5-bis (hydroxymethyl) tetrahydrofuran (BHMTHF, also mentioned as 2,5-tetrahydrofuran-dimethanol or THFDM) followed by hydrogenation of BHMTHF in 1,2,6-hexanotriol (HTO); and then hydrogenation of 1,2,6-hexanotriol to 1,6-hexanediol. The processes disclosed in the '339 application require at least two different catalyst systems to produce 1,6-hexanediol from HMF. In addition, reported HDO yields from HMF ranging from 4% (directly to HDO) to 22% (using a 3-step process: HMF for THFDM, THFDM for HTO and then HTO for HDO). The low yields reported in the '339 order clearly demonstrate the need to develop alternative, more efficient processes for the production of HDO.
[0011] [00011] SUMMARY
[0012] [00012] Briefly, therefore, the present invention is directed to processes for preparing hexamethylene diamine from a carbohydrate source by converting a carbohydrate source into a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol; and converting at least a portion of the 1,6-hexanediol to hexamethylene diamine. The present invention is also directed to processes for preparing hexamethylene diamine from a carbohydrate source by converting a carbohydrate source to a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce a reaction product comprising 1,2,6-hexanotriol; converting at least a portion of 1,2,6-hexanotriol to 1.6-hexanediol; and converting at least a portion of 1,6-hexanediol to hexamethylene diamine. In some embodiments, the heterogeneous reduction catalyst comprises Pt. In other embodiments, the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W, and Re. In other embodiments, the step of converting at least a portion of 1,2,6-hexanotriol to 1,6-hexanediol is carried out in the presence of hydrogen and a hydrogenation catalyst comprising Pt. In other embodiments, the yield of 1.6 - hexanediol is at least approximately 40%. In other embodiments, the yield of 1,6-hexanediol is at least approximately 50%. In other embodiments, the yield of 1,6-hexanediol is at least approximately 60%. In other embodiments, the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of approximately 60 ° C and approximately 200 ° C and a pressure of hydrogen in the range of approximately 200 psig to approximately 2000 psig. In other embodiments, the furfural substrate is 5-hydroxymethyl furfural. In other embodiments, the carbohydrate source is glucose, fructose or a mixture comprising glucose and fructose. In other embodiments, the catalyst also comprises a support selected from the group consisting of zirconias, silicas and zeolites. In other embodiments, the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of approximately 100 ° C and approximately 180 ° C and a pressure of hydrogen in the range of approximately 200 psig to approximately 2000 psig. In other embodiments, the hydrogenation catalyst comprises Pt and W supported on zirconia. The present invention is also directed to hexamethylene diamine produced by the processes of any of the above modalities.
[0013] [00013] The present invention is also directed to processes for preparing 1,6-hexanediol from a carbohydrate source by converting the carbohydrate source into a furfural substrate; and reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol. The present invention is also directed to processes for preparing 1,6-hexanediol from a carbohydrate source by converting the carbohydrate source into a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst containing Pt to produce a reaction product comprising 1,2,6-hexanotriol; and converting at least a portion of 1,2,6-hexanotriol to 1,6-hexanediol. In some embodiments, the heterogeneous catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W and Re. In other embodiments, the step of converting at least a portion of 1,2,6-hexanotriol to 1,6-hexanediol is conducted in the presence of hydrogen and a hydrogenation catalyst comprising Pt. In other embodiments, the hydrogenation catalyst is a heterogeneous catalyst supported. In other embodiments, the yield of 1,6-hexanediol from the furfural substrate is at least 40%. In other embodiments, the yield of 1,6-hexanediol from the furfural substrate is at least 50%. In other embodiments, the yield of 1,6-hexanediol from the furfural substrate is at least 60%. In other embodiments, the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of approximately 60 ° C and approximately 200 ° C and a pressure of hydrogen in the range of approximately 200 psig to approximately 2000 psig. In other embodiments, the furfural substrate is 5-hydroxy methyl furfural. In other embodiments, the carbohydrate source is glucose, fructose or a mixture comprising glucose and fructose. In other embodiments, the catalyst also comprises a support selected from the group consisting of zirconias, silicas and zeolites. In other embodiments, the reaction of the furfural substrate with hydrogen to produce 1,2,6-hexanotriol is carried out at a temperature in the range of approximately 100 ° C and approximately 140 ° C and a pressure of hydrogen in the range of approximately 200 psig at approximately 1000 psig. In other embodiments, the catalyst comprises Pt and W supported on zirconia. The present invention is also directed to 1,6-hexanediol produced by the processes of any of the above modalities.
[0014] [00014] The present invention is also directed to processes for preparing hexamethylene diamine from a carbohydrate source by: (a) converting a carbohydrate source into a furfural substrate; (b) reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt for a reaction product comprising 1,2,6-hexanotriol; (c) reacting at least a portion of the 1,2,6-hexanotriol with hydrogen in the presence of the heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol and (d) converting at least a portion of the 1,6-hexanediol into hexamethylene diamine, in which steps b) and c) are conducted in a single reactor. The present invention is also directed to processes for preparing 1,6-hexanediol from a carbohydrate source by: (a) converting a carbohydrate source to a furfural substrate; (b) reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt for a reaction product comprising 1,2,6-hexanotriol and (c) reacting at least a portion of 1,2 , 6-hexanotriol with hydrogen in the presence of the heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol, in which steps b) and c) are conducted in a single reactor. In some embodiments, the heterogeneous reduction catalyst further comprises W. In other embodiments, steps (b) and (c) are performed at a temperature in the range of approximately 60 ° C and approximately 200 ° C and a pressure of hydrogen in the range approximately 200 psig to approximately 2000 psig. In other embodiments, the Pt-containing catalysts from steps b) and c) are different and the temperatures and pressures at which steps b) and c) are conducted are substantially the same. In other embodiments, the temperatures and pressures at which steps b) and c) are conducted are different. In other embodiments, step b) is conducted at a temperature in the range of approximately 100 ° C to approximately 140 ° C and a pressure in the range of approximately 200 psig to approximately 1000 psig and step c) is conducted at a temperature in the range from approximately 120 ° C to approximately 180 ° C and a pressure in the range of approximately 200 psig to approximately 2000 psig. In other embodiments, the yield of 1,6-hexanediol from the furfural substrate is at least approximately 40%. In other embodiments, the yield of 1,6-hexanediol from the furfural substrate is at least approximately 50%. In other embodiments, the yield of 1,6-hexanediol from the furfural substrate is at least approximately 60%. In other embodiments, the carbohydrate source is glucose, fructose, or a mixture comprising glucose and fructose. In other modalities, steps (b) and (c) are carried out in a reaction zone. In other embodiments, the catalyst comprises Pt and W supported on zirconia. The present invention is also directed to hexamethylene diamine produced by the processes of any of the above modalities. The present invention is also directed to 1,6-hexanediol prepared by the process of any of the above modalities.
[0015] [00015] The present invention is also directed to processes for preparing a compound of formula II
[0016] [00016] Where each of X2 and X3 is selected from the group of hydrogen and hydroxyl; for converting a carbohydrate source into a furfural substrate; and reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce the compound of formula II. In some embodiments, the catalyst further comprises W. In other embodiments, the catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W and Re.
[0017] [00017] DETAILED DESCRIPTION
[0018] [00018] The following description sets out exemplary methods, parameters and the like. It should be recognized, however, that such a description is not intended to be a limitation on the scope of the present invention.
[0019] [00019] According to the present invention, applicants disclose processes for the chemocatalytic conversion of a furfural substrate, which can be derived from a carbohydrate source (e.g., glucose or fructose) to hexamethylene diamine, and intermediate processes and products along the way. In some modalities, the processes are carried out by converting a carbohydrate source into a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol; and converting at least a portion of 1,6-hexanediol to hexamethylene diamine. In other modalities, the processes are carried out by converting a carbohydrate source into a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce a reaction product comprising 1,2,6-hexanotriol; converting at least a portion of 1,2,6-hexanotriol to 1,6-hexanediol; and converting at least a portion of 1,6-hexanediol to hexamethylene diamine. In some modalities, the processes are carried out by converting the carbohydrate source into a furfural substrate; and reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol. In other modalities, the processes are carried out by converting the carbohydrate source into a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst containing Pt to produce a reaction product comprising 1,2,6-hexanotriol; and converting at least a portion of 1,2,6-hexanotriol to 1,6-hexanediol. In other modalities, the processes are carried out by (a) converting a carbohydrate source into a furfural substrate; (b) reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt for a reaction product comprising 1,2,6-hexanotriol; (c) reacting at least a portion of 1,2,6-hexanotriol with hydrogen in the presence of the heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol; and (d) converting at least a portion of 1,6-hexanediol to hexamethylene diamine, in which steps b) and c) are conducted in a single reactor. In other modalities, the processes are carried out by (a) converting a carbohydrate source into a furfural substrate; (b) reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt for a reaction product comprising 1,2,6-hexanotriol; and (c) reacting at least a portion of 1,2,6-hexanotriol with hydrogen in the presence of the heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol, in which steps b) and c) are conducted in a single reactor . In preferred embodiments, 1,6-hexanediol is converted to hexamethylene diamine by a chemocatalytic amination reaction.
[0020] [00020] In another aspect of the invention, hexamethylene diamine prepared according to the disclosed processes can be converted, according to processes known in the art, into various other industrially significant agents and chemical precursors including, for example, nylon 6,6 and monomers for polyurethanes.
[0021] [00021] Bio-renewable sources such as maize grain (maize), sugar beet, sugar cane as well as energy crops, plant biomass, agricultural refuse, forestry residues, sugar processing residues, household refuse derived from plants, sewage municipal, used paper, switchgrass, miscanthus, cassaya, trees (hardwood and softwood), vegetation, crop residues (eg, bagasse and corn forage) are all rich in hexoses, which can be used to produce furfuraldehyde , such as 5- (hydroxymethyl) furfural. Hexoses can be readily produced from such carbohydrate sources by hydrolysis. It is also generally known that biomass carbohydrates can be enzymatically converted to glucose, fructose and other sugars. Fructose dehydration can easily produce furan derivatives like 5- (hydroxymethyl) furfural. Glucose acid hydrolysis is also known to produce 5- (hydroxymethyl) furfural; see, for example, US patent no. 6,518,440. Several other methods have been developed to produce 5- (hydroxymethyl) furfural including, for example, those described in U.S. Pat. No. 4,533,743 (for Medeiros and others); U.S. Pat. No. 4,912,237 (for Zeitsch); U.S. Pat. No. 4,971,657 (for Avignon and others); Pat. No. 6,743,928 (for Zeitsch); Pat. No. 2,750,394 (for Peniston); Pat. No. 2,917,520 (for Cope); Pat. No. 2,929,823 (for Garber); Pat. No. 3,118,912 (for Smith); Pat. No. 4,339,387 (for Fleche et al.); Pat. No. 4,590,283 (for Gaset et al.); and Pat. No. 4,740,605 (for Rapp). In foreign patent literature, see GB 591,858; GB 600,871; and GB 876,463, all of which were published in English. See also FR 2,663,933; FR 2,664,273; FR 2,669,635; and CA 2,097,812, all of which were published in French. Thus, a variety of carbohydrate sources can be used to produce 5- (hydroxymethyl) furfural by a variety of known techniques.
[0022] [00022] In some preferred embodiments, the carbohydrate source is glucose, and the glucose is converted to fructose using methods known in the art, such as the industrial process for converting glucose into high fructose corn syrup. As described above, a variety of processes have been disclosed directed to the production of a furfural substrate (for example, 5- (hydroxymethyl) furfural), for example, of glucose or other hexoses. I. Furfural substrate and reduction thereof
[0023] [00023] Applicants have found that a compound of formula II, below, can be prepared by chemocatalytically reacting a furfural substrate of formula I with hydrogen in the presence of a heterogeneous catalyst comprising platinum (Pt) according to the following general reaction
[0024] [00024] Where each X2 and X3 are independently hydrogen or hydroxyl. According to various embodiments of the present invention, X2 can be hydrogen or hydroxyl and X3 is preferably hydrogen.
[0025] [00025] In several embodiments, the reaction is conducted in the presence of catalysts containing Pt at temperature (s) in the range of approximately 60 ° C to approximately 200 ° C and pressure (s) in the range of approximately 200 psig to approximately 2000 psig.
[0026] [00026] According to various embodiments of the present invention, a compound of formula IIa can be prepared by converting chemocatalytic 5- (hydroxymethyl) furfural (HMF) into a reaction product comprising the compound of formula IIa by reacting HMF with hydrogen in the presence of catalyst comprising Pt according to the following general reaction:
[0027] [00027] Where X2 is hydroxyl or hydrogen.
[0028] [00028] According to additional embodiments of the present invention, 5- (hydroxymethyl) furfural is initially reacted with hydrogen in the presence of a catalyst comprising Pt under a first set of reaction conditions to convert at least a portion of the 5- (hydroxymethyl) furfural into 1,2,6-hexanotriol, and at least a portion of 1,2,6-hexanotriol is subsequently converted to 1,6-hexanediol in the presence of a catalyst comprising Pt under a second set of reaction conditions according to the following general reaction:
[0029] [00029] In certain embodiments of the invention, the first reduction reaction is to convert 5- (hydroxymethyl) furfural into a reaction product comprising 1,2,6-hexanotriol and the second reduction reaction to convert at least a portion of 1, 2,6-hexanotriol to 1,6-hexanediol can be performed in a single reaction zone where the reaction conditions are modified after a defined period of time to effect the conversion of the triol to diol.
[0030] [00030] In several other embodiments of the present invention, the first reduction reaction and the second reduction reaction are carried out in finite zones of a single reactor, for example, a fixed bed trickle flow reactor, in which in a first a first reduction catalyst operating under reaction conditions to produce a reaction product comprising 1,2,6-hexanotriol and in a second reaction zone a second reduction catalyst operating under reaction conditions to convert at least a portion of the triol in 1.6 hexanediol. In such embodiments, the catalysts can be the same or different and the first set of reaction conditions and the second set of reaction conditions can be the same or different. In some embodiments, the first set of reaction conditions comprises a temperature in the range of approximately 60 ° C to approximately 200 ° C and a pressure in the range of approximately 200 psig to approximately 2000 psig. In some embodiments, the second set of reaction conditions comprises a temperature in the range of approximately 80 ° C to approximately 200 ° C and a pressure in the range of approximately 500 psig to approximately 2000 psig.
[0031] [00031] Catalysts suitable for hydrogenation reactions (reduction catalysts) are specific supported heterogeneous catalysts comprising Pt. In all embodiments of the present invention the catalysts comprise platinum with Pt (O), individually or in combinations with other metals and / or alloys, which is present at least on an external surface of a support (ie, a surface exposed to the reaction constituents). According to certain embodiments of the present invention, the catalysts employed in the processes comprise Pt and at least one metal selected from the group of Mo, La, Sm, Y, W and Re (M2). In various embodiments of the invention one or more other d-block metals, one or more rare earth metals (for example, lanthanides), and / or one or more metals of the main group (for example, Al) may also be present in combination with the combinations of Pt and M2. Typically, the total weight of metal (s) is approximately 0.1% to approximately 10% or 0.2% to 10%, or approximately 0.2% to approximately 8% or approximately 0.2% to approximately 5% of the total weight of the catalyst. In more preferred embodiments the total weight of the metal and the catalyst is less than approximately 4%.
[0032] [00032] The molar ratio of Pt (M1) to (M2) can vary, for example, from approximately 20: 1 to approximately 1:10. In various preferred embodiments, the M1: M2 molar ratio is in the range of approximately 10: 1 to approximately 1: 5. In even more preferred embodiments, the ratio of M1: M2 is in the range of approximately 8: 1 to approximately 1: 2.
[0033] [00033] According to the present invention, the preferred catalyst is a heterogeneous supported catalyst where the catalysts are on the surface of the support. Suitable supports include, for example, acid ion exchange resin, alumina gamma, fluorinated alumina, zirconia promoted by tungstate or sulfate, titania, silica, alumina promoted by silica, aluminum phosphate, tungsten oxide supported on silica-alumina, clay acid, supported mineral acid and zeolites. The support materials can be modified using methods known in the art such as heat treatment, acid treatment or by the introduction of a dopant (for example, metal-doped titanias, metal-doped zirconia (for example, tungstate zirconia), doped by metal, and metal-modified niobiums). Preferred supports include zirconias, silicas and zeolites. When a catalyst support is used, metals can be deposited using procedures known in the art including, but not limited to, incipient moisture, ion exchange, deposit precipitation and vacuum impregnation. When two or more metals are deposited on the same support, they can be deposited sequentially or simultaneously. In various embodiments, after depositing metal, the catalyst is dried at a temperature in the range of approximately 20 ° C to approximately 120 ° C for a period of time ranging from at least approximately 1 hour to approximately 24 hours. In these and other embodiments, the catalyst is dried under conditions of sub-atmospheric pressure. In various embodiments, the catalyst is reduced after drying (for example, by flowing 5% H2 in N2 at a temperature of at least approximately 200 ° C for a period of time, for example, at least approximately 3 hours). In addition, in these and other embodiments, the catalyst is calcined in air at a temperature of at least approximately 200 ° C for a period of time of at least approximately 3 hours.
[0034] [00034] The hydrogenation reaction (s) can also be conducted in the presence of a solvent for the furfural substrate. Solvents suitable for use in combination with the hydrogenation reaction to convert furfural into a reaction product comprising diol or triol may include, for example, water, alcohols, esters, ethers, ketones or mixtures thereof. In several embodiments, the preferred solvent is water.
[0035] [00035] In general, hydrogenation rations can be conducted in a batch, semi-batch or continuous reactor design using fixed bed reactors, drip bed reactors, paste phase reactors, moving bed reactors, or any other design that allows heterogeneous catalytic reactions. Examples of reactors can be seen in Chemical Process Equipment-selection and Design, Couper et al., Elsevier 1990, which is incorporated here by way of reference. It should be understood that the furfural substrate (for example, 5- (hydroxymethyl) furfural), hydrogen, any solvent, and the catalyst can be introduced into an appropriate reactor separately or in various combinations.
[0036] [00036] The chemocatalytic conversion of a furfural substrate to 1,6-hexanediol, as two separate chemocatalytic reduction steps or as a combined chemocatalytic reduction step, can provide a mixture of products. For example, when the furfural substrate is 5- (hydroxymethyl) furfural, the reaction product mixture may include not only 1,6-hexanediol and / or 1,2,6-hexanotriol, but also amounts less than 1.5 -hexanediol; 1,2,5-hexanotriol; 1,2,5,6-hexanequatrol; 1-hexanol and 2-hexanol. The production of 1,6-hexanediol from the furfural substrate (for example, 5- (hydroxymethyl) furfural) is unexpectedly quite easy. In various embodiments, at least 50%, at least 60% or at least 70% of the product mixture is 1,2,6-hexanotriol. In various embodiments, HDO production is at least approximately 40%, at least approximately 50% or at least approximately 60%.
[0037] [00037] The product mixture can be separated into one or more products by any appropriate methods known in the art. In some embodiments, the product mixture can be separated by fractional distillation under subatmospheric pressures. For example, in some embodiments, 1,6-hexanediol can be separated from the product mixture at a temperature between approximately 90 ° C and approximately 110 ° C; 1,2,6-hexanotriol can be separated from the product mixture at a temperature between approximately 150 ° C and 175 ° C; 1,2-hexanediol and hexanol can be separated from the product mixture at a temperature between approximately 100 ° C and 125 ° C. In certain embodiments, 1,2,6-hexanotriol can be isolated from the product mixture, and recycled in an additional reduction reaction to produce additional 1,6-hexanediol. 1,6-hexanediol can be recovered from any remaining products of the reaction mixture by one or more conventional methods known in the art including, for example, solvent extraction, crystallization or evaporative processes.
[0038] [00038] According to the present invention the production of HDO from the substrate of formula I can be carried out at reaction temperatures in the range of approximately 60 ° C to approximately 200 ° C, more typically in the range of approximately 80 ° C to approximately 200 ° C. In various preferred embodiments, the step of converting furfuraldehyde to 1,2,6-hexanotriol is conducted at reaction temperatures in the range of approximately 100 ° C to approximately 140 ° C and the conversion of 1,2,6-hexanotriol to 1 , 6-hexanediol is carried out at reaction temperatures in the range of approximately 120 ° C to approximately 180 ° C. According to the present invention the production of HDO from the substrate of formula I can be conducted at hydrogen pressures in the range of approximately 200 psig to approximately 2000 psig. In various preferred embodiments, the step of converting furfuraldehyde to 1,2,6-hexanotriol is conducted at hydrogen pressure in the range of approximately 200 psig to approximately 1000 psig and the conversion of 1,2,6-hexanotriol to 1,6 -hexanotriol is conducted under hydrogen pressure in the range of approximately 200 psig to approximately 2000 psig. II. Preparation of hexamethylene diamine from 1,6-hexanediol
[0039] [00039] The preparation of hexamethylene diamine from 1,6-hexanediol can be carried out using procedures known in the art. See, for example, the processes disclosed in US patents nos. 2,754,330; 3,215,742; 3,268,588 and 3,270,059.
[0040] [00040] When introducing elements of the present invention in the preferred embodiment (s) of the same, the articles "one", "one" are intended to be in the singular unless the context allows otherwise and "o" and "referenced" are intended to mean that there is one or more of the elements. The terms "comprising", "including" and "having" are not intended to be inclusive and use such terms as they may be additional elements other than those listed.
[0041] [00041] In view of the above, it will be seen that the various objectives of the invention are obtained and other advantageous results obtained.
[0042] [00042] As several changes could be made to the above compositions and processes without departing from the scope of the invention, it is intended that all matter contained in the description above be interpreted as illustrative and not in a limiting sense.
[0043] [00043] Having described the invention in detail, it will be evident that modifications and variations are possible without departing from the scope of the invention defined in the appended claims. EXAMPLES
[0044] [00044] The following non-limiting examples are provided to further illustrate the present invention.
[0045] [00045] Reactions were carried out in 1 ml glass flasks in a pressurized container according to the procedures described in the examples below. Conversion, product yields and selectivity were determined using ion chromatography with electrochemical detection. Example 1: conversion of furfural hydroxymethyl to 1,6-hexanediol
[0046] [00046] Cariact Q-10 silica support samples (Fuji Silysia) were dried at 60 ° C. Properly concentrated aqueous solutions of (NH4) 6Mo7024 were added to ~ 10 mg of solids and stirred to impregnate the supports. The solids were calcined at 600 ° C in air for 3 hours. Subsequently, properly concentrated aqueous solutions of Pt (NO3) 2 were added to ~ 10 mg solids and stirred to impregnate the supports. The samples were dried in an oven at 60 ° C overnight under a dry air purge. Then reduced to 350 ° C under a formation gas atmosphere (5% H2 and 95% N2) for 3 hours at a temperature rise rate of 5 ° C / min. The final catalysts were composed of 3.9 wt% Pt & 1.3 wt% Mo.
[0047] [00047] These catalysts have been tested for reduction of furfural hydroxymethyl using the following catalyst test protocol. Catalyst (about 8 mg) was weighed in a glass vial insert followed by the addition of an aqueous hydroxymethyl furfural solution (200 μ1 of 0.1 Μ). The glass bottle insert was loaded into a reactor and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 ° C and kept at the respective temperature for 300 minutes while the flasks were shaken. After 300 minutes, stirring was stopped and the reactor was cooled to 40 ° C. Pressure in the reactor was then slowly released. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with flame ionization detection. The results are reported in Table 1.
[0048] [00048] The alumina support samples were dried at 120 ° C. Properly concentrated aqueous solutions of Pt (NO3) 2 were added to ~ 8 mg solids and stirred to impregnate the supports. The solids were dried at 120 ° C in air for 16 hours. Subsequently, properly concentrated aqueous solutions of (NH4) 6Mo7O24 or La (NO3) 3 or Sm (NO3) 2 were added to ~ 8mg solids and stirred to impregnate the supports. The samples were dried in an oven at 120 ° C overnight under air. Then calcined at 500 ° C in air for 3 hours with a temperature rise rate of 30 ° C / min. The final catalysts were composed of about 4 wt% Pt and several M2 loads (see table 2).
[0049] [00049] These catalysts have been tested for reduction of furfural hydroxymethyl using the following catalyst test protocol. The catalyst (about 8 mg) was weighed in a glass vial insert followed by the addition of an aqueous hydroxymethyl furfural solution (250 μ1 0.4 M). the glass bottle insert was loaded into a reactor and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized at 200 psig at room temperature. The reactor was heated to 120 ° C and maintained at the respective temperature for 300 minutes while the flasks were shaken. After 300 minutes, stirring was stopped and the reactor was cooled to 40 ° C. The pressure in the reactor was then slowly released. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with flame ionization detection. The results are reported in table 2.
[0050] [00050] Zirconia support samples SZ 61143 (Saint-Gobain Norpro) were calcined at 750 - 800 ° C in air for 0.5 - 2 hours. Properly concentrated aqueous solutions of Pt (NO3) 2 were added to ~ 10 mg of solids and stirred to impregnate the supports. The samples were dried in an oven at 60 ° C overnight under a dry air purge. Then reduced to 350 ° C under a formation gas atmosphere (5% H2 and 95% N2) for 3 hours at a temperature rise rate of 5 ° C / min. The final catalysts were composed of about 3.9% by weight of Pt.
[0051] [00051] These catalysts have been tested for 1,2,6-hexanotriol ratio reduction using the following catalyst test protocol. The catalyst (about 10 mg) was weighed in a glass vial insert followed by the addition of an aqueous 1,2,6-hexanotriol solution (200 μ1 of 0.2 Μ). The glass bottle insert was loaded into a reactor and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 ° C and kept at the respective temperature for 150 minutes while the flasks were shaken. After 150 minutes, stirring was stopped and the reactor was cooled to 40 ° C. The pressure in the reactor was then slowly released. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with flame ionization detection. The results are reported in table 3.
[0052] [00052] Example 4: conversion of 1,2,6-hexanotriol to 1,6-hexanediol
[0053] [00053] Cariact Q-10 silica support samples (Fuji Silysia) were dried at 60 ° C. Properly concentrated aqueous solutions of (NH4) 6Μο7O24 or (NH4) 10W12O41 were added to ~ 10 mg of solids and stirred to impregnate the supports. The solids were calcined at 600 ° C in air for 3 hours. Subsequently, properly concentrated aqueous solutions of Pt (NO3) 2 were added to ~ 10 mg solids and stirred to impregnate the supports. The samples were dried in an oven at 60 ° C overnight under a dry air purge. Then reduced to 350 ° C under a formation gas atmosphere (5% H2 and 95% N2) for 3 hours at a temperature rise rate of 5 ° C / min. The final catalysts were composed of 3.9 wt% Pt & 0.8 wt% Mo or 3.9 wt% Pt & 1.3 wt% W.
[0054] [00054] These catalysts have been tested for 1,2,6-hexanotriol reduction using the following catalyst test protocol. Catalyst (about 10 mg) was weighed in a glass vial insert followed by the addition of an aqueous 1,2-hexanotriol solution (200 μ1 of 0.2 M). The glass bottle insert was loaded into a reactor and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 ° C and kept at the respective temperature for 150 minutes while the flasks were shaken. After 150 minutes, stirring was stopped and the reactor was cooled to 40 ° C. Pressure in the reactor was then slowly released. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with flame ionization detection. The results are reported in the table
[0055] [00055] Properly concentrated aqueous solutions of Pt (NO3) 2 and (NH4) 6Mo7O24 were individually added to approximately 10 mg of solids and stirred to impregnate the supports. The sample was dried in an oven at 60 ° C overnight under a dry air purge. The dry sample was then reduced to 500 ° C or 350 ° C under a formation gas atmosphere (5% H2 and 95% N2) for 3 hours with a temperature rise rate of 5 ° C / min. The final catalyst was composed of approximately 3.9 wt% PT and 0.2 wt% Mo.
[0056] [00056] The catalyst was tested for 1,2,6-hexanotriol reduction under the following catalyst test: catalyst (about 10 mg) was weighed in a glass vial insert followed by adding a solution of 1 , 2,6-aqueous hexanotriol (200 μ1 of 0.2 M). The glass bottle insert was loaded into a reactor and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized at 830 or 670 psig at room temperature. The reactor was heated to 160 ° C. The temperature was maintained for 5 hours while the flask was shaken. After 5 hours, the stirring stopped and the reactor was cooled to 40 ° C. Pressure in the reactor was then slowly released. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with deionized water, and analyzed by ion chromatography with electrochemical detection. The results are summarized in Table 5 below.
[0057] [00057] The samples of zeolite supports (Zeolyst) were dried at 60 ° C. Properly concentrated aqueous solutions of (NH4) 10W12O41 were added to ~ 10 mg of solids and stirred to impregnate the supports. The solids were calcined at 500 ° C in air for 3 hours. Subsequently, properly concentrated aqueous solutions of Pt (NO3) 2 were added to ~ 10 mg solids and stirred to impregnate the supports. The samples were dried in an oven at 60 ° C overnight under a dry air purge. Then reduced to 350 ° C under a formation gas atmosphere (5% H2 and 95% N2) for 3 hours with a temperature rise rate of 5 ° C / min.
[0058] [00058] These catalysts have been tested for 1,2,6-hexanotriol reduction using the following catalyst test protocol. Catalyst (about 10 mg) was weighed in a glass vial insert followed by the addition of an aqueous 1,2,6-hexanotriol solution (200 μ1 of 0.2 M). The glass bottle insert was loaded into a reactor and the reactor was closed. The atmosphere in the reactor was replaced with hydrogen and pressurized to 670 psig at room temperature. The reactor was heated to 160 ° C and kept at the respective temperature for 150 minutes while the flasks were shaken. After 150 minutes, stirring was stopped and the reactor was cooled to 40 ° C. the pressure in the reactor was then slowly released. The glass bottle insert was removed from the reactor and centrifuged. The clear solution was diluted with methanol and analyzed by gas chromatography with flame ionization detection. The results are summarized in table 6 below.

权利要求:
Claims (30)
[0001]
Process for preparing hexamethylene diamine from a carbohydrate source, the process being characterized by the fact that it comprises: converting a carbohydrate source into a furfural substrate; reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst to produce 1,6-hexanediol; and converting at least a portion of the 1,6-hexanediol to hexamethylene diamine.
[0002]
Process for preparing hexamethylene diamine from a carbohydrate source, the process being characterized by the fact that it comprises: converting the carbohydrate source into a furfural substrate; and reacting at least a portion of the furfural substrate with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt to produce 1,6-hexanediol.
[0003]
Process according to claim 1, characterized by the fact that the heterogeneous reduction catalyst comprises Pt.
[0004]
Process according to claim 2 or 3, characterized by the fact that the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W and Re.
[0005]
Process according to claim 4, characterized by the fact that the molar ratio of Pt to at least one metal selected from the group consisting of Mo, La, Sm, Y, W and Re is 20: 1 to 1: 10.
[0006]
Process according to any of claims 1 to 5, characterized in that the yield of 1,6-hexanediol is at least approximately 40%.
[0007]
Process according to any of claims 1 to 6, characterized in that the yield of 1,6-hexanediol is at least approximately 50%.
[0008]
Process according to any of claims 1 to 7, characterized in that the yield of 1,6-hexanediol is at least approximately 60%.
[0009]
Process according to any of claims 1 to 8, characterized by the fact that the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of approximately 60 ° C to approximately 200 ° C and a pressure of hydrogen in the range of approximately 200 psig to approximately 2000 psig.
[0010]
Process according to any of claims 1-9, characterized by the fact that the furfural substrate is 5-hydroxymethyl furfural.
[0011]
Process according to any of claims 1-10, characterized in that the carbohydrate source is glucose, fructose or a mixture comprising glucose and fructose.
[0012]
Process according to any of claims 1-11, characterized by the fact that the heterogeneous reduction catalyst further comprises a support selected from the group consisting of zirconias, silicas and zeolites.
[0013]
Process according to any of claims 1-12, characterized in that the reaction of the furfural substrate with hydrogen is carried out at a temperature in the range of approximately 100 ° C to approximately 180 ° C and a pressure of hydrogen in the range of approximately 200 psig to approximately 2000 psig.
[0014]
Process according to any of claims 1 to 13, characterized by the fact that the hydrogenation catalyst comprises Pt and W supported on zirconia.
[0015]
Process for preparing a compound of formula II
[0016]
Process according to claim 15, characterized by the fact that the heterogeneous reduction catalyst further comprises W.
[0017]
Process according to claim 15, characterized by the fact that the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W and Re.
[0018]
Process for preparing 1,6-hexanediol characterized by the fact that it comprises reacting 1,2,6-hexanetriol with hydrogen in the presence of a heterogeneous reduction catalyst comprising Pt.
[0019]
Process according to claim 18, characterized by the fact that the heterogeneous reduction catalyst further comprises at least one metal selected from the group consisting of Mo, La, Sm, Y, W and Re.
[0020]
Process according to claim 19, characterized by the fact that the molar ratio of Pt to at least one metal selected from the group consisting of Mo, La, Sm, Y, W and Re is 20: 1 to 1: 10.
[0021]
Process according to any one of claims 18 to 20, characterized in that the heterogeneous reduction catalyst is a supported heterogeneous catalyst.
[0022]
Process according to claim 21, characterized by the fact that the supported heterogeneous reduction catalyst comprises a support of zirconia, silica or zeolite.
[0023]
Process according to any one of claims 18 to 22, characterized in that 1,2,6-hexanotriol reacts with hydrogen in the presence of the heterogeneous reduction catalyst at a temperature in the range of approximately 80 ° C to approximately 200 ° C and at a hydrogen pressure in the range of approximately 200 psig to approximately 2000 psig.
[0024]
Process according to any one of claims 18 to 23, characterized in that the process further comprises obtaining 1,2,6-hexanotriol by means of a reduction process of a furfural substrate, in which the furfural substrate reacts with hydrogen in the presence of the heterogeneous reduction catalyst comprising Pt, and where the heterogeneous reduction catalyst used to reduce the furfural substrate is the same or a different heterogeneous reduction catalyst from that used for the 1,2,6-hexanotriol reaction with hydrogen.
[0025]
Process according to claim 24, characterized by the fact that the furfural substrate is 5- (hydroxymethyl) furfural.
[0026]
Process according to claim 25, characterized by the fact that 5- (hydroxymethyl) furfural reacts with hydrogen in the presence of a heterogeneous reduction catalyst different from that used in the reaction of 1,2,6-hexanotriol with hydrogen.
[0027]
Process according to any one of claims 2 to 2 6, characterized by the fact that the furfural substrate reacts with hydrogen in the presence of the heterogeneous reduction catalyst at a temperature in the range of approximately 60 ° C to approximately 200 ° C and at a pressure in the range of approximately 200 psig to approximately 2000 psig.
[0028]
Process according to any one of claims 1 to 27, characterized by the fact that the process is carried out in the presence of a solvent selected from the group consisting of water, alcohols, esters, ethers, ketones and mixtures thereof.
[0029]
Process according to claim 28, characterized by the fact that the solvent is water.
[0030]
Process for preparing hexamethylene diamine characterized by the fact that it comprises: preparing 1,6-hexanediol from the process as defined in claims 18 to 27; and convert 1,6-hexanediol to hexamethylene diamine.

类似技术:

公开号 | 公开日 | 专利标题

BR112014017585B1|2020-11-24|process for the production of hexamethylene diamine from materials containing carbohydrates and intermediates for them

TWI735409B|2021-08-11|Selective conversion of a saccharide containing feedstock to ethylene glycol

US20190127304A1|2019-05-02|Production of Monomers from Lignin During Depolymerization of Lignocellulose-Containing Composition

JP2013522281A|2013-06-13|Depolymerization of lignocellulosic biomass

Jiang et al.2018|“One-pot” conversions of carbohydrates to 5-hydroxymethylfurfural using Sn-ceramic powder and hydrochloric acid

US10087160B2|2018-10-02|Process for the manufacture of furural and furfural derivatives

US9790140B2|2017-10-17|Method for producing butadiene

CN105814063A|2016-07-27|Control of color-body formation in isohexide esterification

CN108129250A|2018-06-08|A kind of method for preparing alpha-olefin with positive configuration carbonic ester cracking

EP3263578B1|2021-08-18|Method for preparing xylulose from biomass containing xylose using butanol, and method for separating the same

CN106316735A|2017-01-11|Method for producing aromatic hydrocarbons

CN106316741A|2017-01-11|Method for preparing aromatic hydrocarbons through aromizing

CN106316764A|2017-01-11|Method for preparing aromatic hydrocarbon through aromatization

同族专利:

公开号 | 公开日

EP2804848A1|2014-11-26|

AR089707A1|2014-09-10|

CN104066710B|2016-06-29|

AU2013210005A1|2014-07-31|

US20130184495A1|2013-07-18|

CA2860886A1|2013-07-25|

US20160068469A1|2016-03-10|

US20140343323A1|2014-11-20|

EA201491289A1|2014-12-30|

SG11201404098XA|2014-10-30|

US9518005B2|2016-12-13|

MX336933B|2016-02-08|

WO2013109477A1|2013-07-25|

EP2804848B1|2018-10-03|

ZA201405258B|2016-08-31|

HK1204318A1|2015-11-13|

MX2014008638A|2014-12-08|

SG10201700153WA|2017-03-30|

SA115360430B1|2015-09-03|

MY165219A|2018-03-09|

US20170144962A1|2017-05-25|

EP3466919A1|2019-04-10|

US9783473B2|2017-10-10|

CN106008163B|2019-10-08|

US20170050906A1|2017-02-23|

US20180170844A1|2018-06-21|

CN104066710A|2014-09-24|

JP2015506943A|2015-03-05|

EP3466919B1|2021-10-06|

SA113340200B1|2015-07-09|

ZA201505891B|2016-12-21|

SG10201913670TA|2020-03-30|

JP6253203B2|2017-12-27|

EA025555B1|2017-01-30|

BR112014017585A8|2017-07-04|

IN2014DN06596A|2015-05-22|

AU2017208286A1|2017-08-10|

US9035109B2|2015-05-19|

CN106008163A|2016-10-12|

KR20140113706A|2014-09-24|

AU2013210005B2|2017-04-27|

US20160068470A1|2016-03-10|

US8853458B2|2014-10-07|

BR112014017585A2|2017-06-13|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

GB600871A|1945-10-17|1948-04-21|Walter Norman Haworth|Improvements relating to the manufacture of 5-hydroxymethyl 2-furfural|

GB591858A|1944-05-30|1947-09-01|Walter Norman Haworth|Improvements relating to the manufacture of 5-hydroxy-methyl furfural or levulinic acid|

US2082025A|1933-04-13|1937-06-01|Quaker Oats Co|Method for the reduction of furfural and furan derivatives|

US2750394A|1952-05-22|1956-06-12|Food Chemical And Res Lab Inc|Manufacture of 5-hydroxymethyl 2-furfural|

US2754330A|1952-12-12|1956-07-10|Du Pont|Manufacture of aliphatic diamines|

US2929823A|1956-11-26|1960-03-22|Merck & Co Inc|Production of 5-hydroxymethylfurfural|

US2917520A|1957-09-11|1959-12-15|Arthur C Cope|Production and recovery of furans|

US3070633A|1958-09-10|1962-12-25|Merck & Co Inc|Process for producing 1, 6-hexanediol|

US3083236A|1958-09-10|1963-03-26|Merck & Co Inc|Hydrogenation of 5-hydroxy-methyl furfural|

GB876463A|1959-02-25|1961-09-06|Atlas Powder Co|Process for preparing hydroxymethyl furfural|

US3215742A|1960-02-02|1965-11-02|Celanese Corp|Process for the preparation of alkylene diamines|

US3118912A|1960-04-18|1964-01-21|Rayonier Inc|Preparation of hydroxymethylfurfural|

US3040062A|1960-11-14|1962-06-19|Atlas Chem Ind|Process for preparing 2, 5-bis hydroxymethyl tetrahydrofuran|

DE1172268B|1962-02-21|1964-06-18|Basf Ag|Process for the production of diamines|

US3268588A|1962-11-16|1966-08-23|Celanese Corp|Process for producing hexamethylenediamine from 1-6-hexanediol|

US4064172A|1973-09-12|1977-12-20|Imperial Chemical Industries Limited|Hexamethylene diamine by hydrogenation of adiponitrile in presence of an activated iron oxide catalyst|

US3985814A|1975-02-28|1976-10-12|Celanese Corporation|Production of alcohols from carboxylic acids|

FR2464260B1|1979-09-05|1983-01-21|Roquette Freres|

US4400468A|1981-10-05|1983-08-23|Hydrocarbon Research Inc.|Process for producing adipic acid from biomass|

FR2551754B1|1983-09-14|1988-04-08|Roquette Freres|PROCESS FOR THE MANUFACTURE OF 5-HYDROXYMETHYLFURFURAL|

US4533743A|1983-12-16|1985-08-06|Atlantic Richfield Company|Furfural process|

DE3601281C2|1986-01-17|1988-08-04|Sueddeutsche Zucker Ag, 6800 Mannheim, De|

AT387247B|1987-05-12|1988-12-27|Voest Alpine Ind Anlagen|COMBINED PROCESS FOR THE THERMAL AND CHEMICAL TREATMENT OF BIOMASS CONTAINING LIGNOCELLULOSE AND FOR THE EXTRACTION OF FURFURAL|

DE3842825C2|1988-01-08|1991-01-24|Fried. Krupp Gmbh, 4300 Essen, De|

FR2663933B1|1990-06-27|1994-06-17|Beghin Say Sa|NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES.|

FR2664273B1|1990-06-27|1994-04-29|Beghin Say Sa|NEW PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL FROM SACCHARIDES.|

FR2669635B1|1990-11-22|1994-06-10|Furchim|PROCESS FOR THE MANUFACTURE OF HIGH PURITY HYDROXYMETHYLFURFURAL .|

FR2670209B1|1990-12-07|1995-04-28|Commissariat Energie Atomique|PROCESS FOR THE PREPARATION OF FURFURAL HYDROXYMETHYL-5 BY HETEROGENEOUS CATALYSIS.|

US5151543A|1991-05-31|1992-09-29|E. I. Du Pont De Nemours And Company|Selective low pressure hydrogenation of a dinitrile to an aminonitrile|

US5296628A|1992-02-13|1994-03-22|E. I. Du Pont De Nemours And Company|Preparation of 6-aminocapronitrile|

FR2728259B1|1994-12-14|1997-03-14|Rhone Poulenc Chimie|PROCESS FOR HEMIHYDROGENATION OF DINITRILES IN AMINONITRILES|

TW500716B|1997-03-04|2002-09-01|Mitsubishi Chem Corp|A method for producing 1,6-hexanediol|

DE19750532A1|1997-11-14|1999-05-20|Basf Ag|Process for production of1,6-hexanediol and 6-hydroxycaproic acid|

DE19905655A1|1999-02-11|2000-08-17|Karl Zeitsch|Process for the production of furfural by delayed relaxation|

KR100546986B1|1999-11-05|2006-01-26|아사히 가세이가부시키가이샤|Process for the preparation of diol mixtures|

FR2806081B1|2000-03-08|2003-03-14|Rhodia Polyamide Intermediates|PROCESS FOR HYDROGENATION OF NITRILE FUNCTIONS TO AMINE FUNCTIONS|

US6331651B1|2000-09-18|2001-12-18|E. I. Du Pont De Nemours And Company|Process for making hexamethylene diamine using ozone-treated adiponitrile that contains phosphorous compounds|

US6518440B2|2001-03-05|2003-02-11|Gene E. Lightner|Hydroxymethylfurfural derived from cellulose contained in lignocellulose solids|

DE10258316A1|2002-12-13|2004-06-24|Basf Ag|High purity 1,6-hexanediol production involves dimerizing an acrylic acid ester then hydrogenating the product with a chromium-free copper catalyst|

DE102004033557A1|2004-07-09|2006-02-16|Basf Ag|Process for the preparation of 1,6-hexanediol in a purity of more than 99.5%|

DE102004054047A1|2004-11-05|2006-05-11|Basf Ag|Process for the preparation of 1,6-hexanediol|

US7393963B2|2004-12-10|2008-07-01|Archer-Daniels-Midland Company|Conversion of 2,5-furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor|

WO2007129560A1|2006-05-09|2007-11-15|Kao Corporation|Process for producing product of hydrogenolysis of polyhydric alcohol|

US7994347B2|2006-06-09|2011-08-09|Battelle Memorial Institute|Hydroxymethylfurfural reduction methods and methods of producing furandimethanol|

JP5035790B2|2006-12-06|2012-09-26|独立行政法人産業技術総合研究所|Propanediol production method|

JP5336714B2|2007-08-20|2013-11-06|株式会社日本触媒|Ring opening method of cyclic ether|

JP5549594B2|2008-10-20|2014-07-16|宇部興産株式会社|High purity 1,6-hexanediol and process for producing the same|

AU2010245687A1|2009-05-07|2011-11-24|Genomatica, Inc.|Microorganisms and methods for the biosynthesis of adipate, hexamethylenediamine and 6-aminocaproic acid|

EP2390247A1|2010-05-26|2011-11-30|Netherlands Organisation for Scientific Research |Preparation of caprolactone, caprolactam, 2,5-tetrahydrofuran dimethanol, 1,6-hexanediol or 1,2,6-hexanetriol from 5-hydroxymethyl-2-furfuraldehyde|

US8940946B2|2011-11-18|2015-01-27|Ube Industries, Ltd.|Method for producing high-purity 1,5-pentanediol|

US8884035B2|2011-12-30|2014-11-11|E I Du Pont De Nemours And Company|Production of tetrahydrofuran-2, 5-dimethanol from isosorbide|

CN104024197A|2011-12-30|2014-09-03|纳幕尔杜邦公司|Process for the production of hexanediols|

US8884036B2|2011-12-30|2014-11-11|E I Du Pont De Nemours And Company|Production of hydroxymethylfurfural from levoglucosenone|

WO2013101980A1|2011-12-30|2013-07-04|E. I. Du Pont De Nemours And Company|Process for preparing 1, 6-hexanediol|

US8889912B2|2011-12-30|2014-11-18|E I Du Pont De Nemours And Company|Process for preparing 1,6-hexanediol|

JP6253203B2|2012-01-18|2017-12-27|レノヴィアインコーポレイテッド|Method for producing hexamethylenediamine from 5-hydroxymethylfurfural|

US9018423B2|2012-04-27|2015-04-28|E I Du Pont De Nemours And Company|Production of alpha, omega-diols|

US8846984B2|2012-04-27|2014-09-30|E I Du Pont De Nemours And Company|Production of α,ω-diols|

US8859826B2|2012-04-27|2014-10-14|E I Du Pont De Nemours And Company|Production of alpha, omega-diols|

EA201492252A1|2012-06-11|2015-05-29|Ренновиа, Инк.|METHOD FOR OBTAINING ADIPIC ACID FROM 1,6-HEXANDIOL|

EP2867405B1|2012-06-28|2019-08-14|Shell International Research Maatschappij B.V.|Methods for hydrothermal digestion of cellulosic biomass solids in the presence of a distributed slurry catalyst|

US8946458B2|2012-08-15|2015-02-03|Virent, Inc.|Catalysts for hydrodeoxygenation of oxygenated hydrocarbons|

WO2014152366A1|2013-03-14|2014-09-25|Pronghorn Renewables Llc|Method and catalyst for the production of alcohols, diols, cyclic ethers and other products from pentose and hexose sugars|

US20140275638A1|2013-03-15|2014-09-18|Wisconsin Alumni Research Foundation|Method for preparing triols and diols from biomass-derived reactants|AU2010245687A1|2009-05-07|2011-11-24|Genomatica, Inc.|Microorganisms and methods for the biosynthesis of adipate, hexamethylenediamine and 6-aminocaproic acid|

US8865940B2|2011-12-30|2014-10-21|E I Du Pont De Nemours And Company|Process for preparing 1,6-hexanediol|