Catalyst suitable for high-yield production of 1, 5-pentanediol, preparation method of catalyst and production method of 1, 5-pentanediol

Abstract

The invention relates to the field of dihydric alcohol production, in particular to a catalyst suitable for high-yield production of 1, 5-pentanediol, a preparation method of the catalyst and a production method of 1, 5-pentanediol. Under the catalytic action of a nickel-based catalyst with a composite carrier, tetrahydrofurfuryl alcohol is subjected to one-step hydrogenation ring opening to generate 1, 5-pentanediol. According to the method, tetrahydrofurfuryl alcohol is adopted as a raw material and is converted into 1, 5-pentanediol on a hydrogenation-ring-opening bifunctional catalyst in a hydrogenation manner, and byproducts such as 1, 2-pentanediol, 2-methyltetrahydrofuran and n-pentanol are obtained. The composition of the hydrogenation-ring opening bifunctional catalyst is NiO-CoO / La2O3-ZrO2, the hydrogenation component is CuO-CoO and a composite oxide carrier La2O3-ZrO2, and the pressure conditions of the hydro-conversion process are as follows: the H2 pressure is 3.0-4.0 MPa, and the temperature is 165-195 DEG C. The invention also discloses a preparation method of the hydrogenation-ring opening bifunctional catalyst.

Description

Technical Field

[0001] The invention relates to the field of diol production, and in particular to a catalyst and a preparation method suitable for producing 1,5-pentanediol with a high yield, and a method for producing 1,5-pentanediol. Background Art

[0002] 1,5-Pentanediol is a modified linear long-chain diol with an odd number of carbon atoms, which is widely used in the manufacture of polyurethane, polyester, plasticizer, coating and fragrance products. As people's awareness of environmental protection increases, countries around the world are widely using environmentally friendly chemical raw materials such as 1,5-pentanediol.

[0003] At present, the main production route of 1,5-pentanediol in industry is to prepare 1,5-pentanediol by catalytic hydrogenation using glutaric acid or glutaric acid ester as raw materials (EP1048638B1, 2003). Chinese patent CN1565728A reported that 1,5-pentanediol was produced by catalytic hydrogenation of dimethyl 1,5-pentanedioate at a reaction temperature of 150-350°C, 3-5MPa, and copper-zinc-aluminum catalyst. This method requires esterification of 1,5-pentanedioic acid and methanol, separation and purification, and then catalytic hydrogenation to produce 1,5-pentanediol. At present, 1,5-pentanedioic acid is a by-product of the production of 1,6-hexanediol, that is, a mixed acid of 1,5-pentanedioic acid and 1,4-butanediol, which is separated and prepared through a crystallization separation process. The source is short and the price is expensive. In addition, Chinese patents CN101225022A and CN101270032A reported respectively the use of Ni-based and Ru-supported catalysts, 1,5-glutaraldehyde as raw material, reaction temperature 60-120°C, 2-8MPa conditions, catalytic hydrogenation to produce 1,5-pentanediol, the disadvantage of this method is that the raw material resources are not abundant and the price is high. In short, the production of 1,5-pentanediol is overly dependent on fossil resources, and the process route is complex, energy consumption is high, environmental pollution is serious, and production costs are high.

[0004] China is a large agricultural country with many furfural production enterprises, accounting for more than 90% of the world's production capacity. At present, furfural is produced by hydrolysis and refining from agricultural and forestry wastes such as corn cobs and sugarcane bagasse; at the same time, my country has achieved large-scale industrialization in the production of furfuryl alcohol by hydrogenation of furfural. Therefore, the development of high-value-added chemical 1,5-pentanediol from furfuryl alcohol or tetrahydrofurfuryl alcohol hydrogenation is of great significance to the industrial development of biomass furan compounds. Furfuryl alcohol or tetrahydrofurfuryl alcohol has obvious price advantages compared with other raw materials for the production of 1,5-pentanediol.

[0005] At present, there are two main technical routes for producing 1,5-pentanediol by directional hydrogenation and ring-opening using biomass platform compound furfural derivatives as raw materials, namely, tetrahydrofurfuryl alcohol through a multi-step process of dihydropyran and a one-step process of tetrahydrofurfuryl alcohol.

[0006] As early as August 1946, an article (J. Amer. Chem. Soc. 68 (8): 1646-1648) studied the preparation of 1,5-pentanediol by a multi-step process of dihydropyran. Using activated alumina as a catalyst, tetrahydrofurfuryl alcohol was dehydrated to convert into dihydropyran. The hydration reaction of dihydropyran was catalyzed by 0.2N hydrochloric acid to produce a mixture of about 84% γ-hydroxyvaleraldehyde (5-hydroxyvaleraldehyde) and 16% 2-hydroxytetrahydropyran. The acidity of the reaction mixture was then neutralized with 0.4N sodium hydroxide, and the two intermediates in the mixture were separated by vacuum distillation. Finally, 5-hydroxyvaleraldehyde was catalytically hydrogenated to prepare 1,5-pentanediol. Since hydrochloric acid was used for acid hydrolysis and NaOH was used to neutralize the reaction mixture during the reaction, the process was complicated, and the equipment was corroded and polluted seriously.

[0007] In January 2017, the Wisconsin Alumni Research Foundation applied for patent CN 108368015 in China (production of 1,5-pentanediol by upgrading tetrahydrofurfuryl alcohol), using γ-Al2O3 catalyst to dehydrate tetrahydrofurfuryl alcohol into dihydropyran; in the absence of homogeneous acid catalyst and at low temperature of 70-100°C, dihydropyran undergoes hydration reaction to obtain 2-hydroxytetrahydropyran; then 2-hydroxytetrahydropyran catalyzes hydrogenolysis ring-opening reaction to generate 1,5-pentanediol. The improved dihydropyran multi-step process reaction pathway is as follows Figure 1 ;

[0008] Tetrahydrofurfuryl alcohol is produced through a multi-step dihydropyran process, which has a long reaction route, high comprehensive cost (energy consumption and time consumption), low overall yield (total yield is 70-80%), and great environmental pressure (large amounts of three wastes), which is not conducive to the sustainable development of energy resources.

[0009] In addition, as early as 1931, Adkins reported the use of CuCr2O4 (copper chromite) as a catalyst to directly catalyze the hydrogenolysis of furfuryl alcohol to prepare pentanediol at 175°C and 10-15MPa, where the yield of 1,5-pentanediol was about 30%, but the yield of 1,2-pentanediol reached 40% (J.Am.Chem.Soc., 1931, 53(3), 1091-1095). The catalyst contains the poisonous element Cr, which has a great impact on the environment; the reaction pressure is high, and the equipment investment is large.

[0010] At present, the one-step process of tetrahydrofurfuryl alcohol is a research hotspot. The reaction path is simple, and the main reactions are as follows: Figure 2 ;

[0011] Chinese patent CN103071512A reports a method for preparing 1,5-pentanediol by hydrogenolysis of tetrahydrofurfuryl alcohol. In an intermittent reactor, a 2-50% concentration of tetrahydrofurfuryl alcohol aqueous solution, a Raney Ni / MO3 catalyst, 200°C, 6MPa, and 24 hours, the conversion rate of tetrahydrofurfuryl alcohol is about 76%, 1,5-pentanediol is about 66%, n-pentanol is 32%, and 2-pentanol is 2.5%.

[0012] CN102911011 published a method for preparing 1,5-pentanediol by selective hydrogenolysis of tetrahydrofurfuryl alcohol. In a fixed bed reactor, a tetrahydrofurfuryl alcohol aqueous solution concentration of 20%, a 4% I r-Mo / SiO2 catalyst, a reaction temperature of 80-150°C, a pressure of about 6MPa, a tetrahydrofurfuryl alcohol conversion rate of about 75%, 1,5-pentanediol of about 70%, n-pentanol of 24%, 2-methyltetrahydrofuran of 2.5%, and 1,2-pentanediol of about 1%. CN 102942448 studied the continuous preparation of 1,5-pentanediol by tetrahydrofurfuryl alcohol. In a fixed bed reactor, a Pt / WOx-ZrO2 composite oxide catalyst, a 20% tetrahydrofurfuryl alcohol aqueous solution as the raw material, 130°C, a hydrogen pressure of 4MPa, the reaction produced 1,5-pentanediol, a tetrahydrofurfuryl alcohol conversion rate of 92.6%, a 1,5-pentanediol selectivity of 92.3%, and n-pentanol of about 7.4%.

[0013] CN113024350 reported the preparation of 1,5-pentanediol by hydrogenation and ring opening of tetrahydrofurfuryl alcohol. Nickel nitrate, neodymium nitrate and cerium nitrate were dissolved in 100ml of deionized water, stirred for 1 hour, 10% sodium hydroxide was slowly added to pH = 12, stirred for 2 hours, the mixed solution was placed in a hydrothermal kettle, hydrothermal at 150°C for 24 hours, filtered, washed with water, dried, calcined in air at 550°C for 3 hours, and then reduced in hydrogen at 350°C for 3 hours to prepare a composite 30% nickel-30% neodymium / 40% cerium catalyst. In a high-pressure reactor, 1g of the above-prepared catalyst and 30g of tetrahydrofurfuryl alcohol were added, 6MPa, 180°C, and reacted for 20 hours under sufficient stirring to obtain 1,5-pentanediol.

[0014] In summary, in the above patent report, in the process of preparing 1,5-pentanediol by one-step method of tetrahydrofurfuryl alcohol, it is generally necessary to select at least one solvent from methanol, water, benzene, amyl alcohol, isopropanol, ethanol, tetrahydrofuran, butanol, isobutanol, hexanol, and ethyl acetate; and water and ethanol are mainly selected, which has the problems of high energy consumption for 1,5-pentanediol separation, large equipment investment, and waste liquid treatment. Therefore, there are some difficulties in the one-step method of tetrahydrofurfuryl alcohol to prepare 1,5-pentanediol. The reactor generally adopts an intermittent reactor, which leads to high cost of separating powder catalyst from product; in addition, a large amount of methanol, water, isopropanol and other solvents are used, which increases the energy consumption for 1,5-pentanediol separation and investment. The key to solving these difficulties is to develop efficient catalysts and innovative processes.

[0015] On August 29, 2024, with "N iO and CoO and La and ZrO" as the abstract keywords, to avoid the influence of superscripts and subscripts, La2O3 was simplified to La, and the option to allow synonym expansion was checked. A search was conducted in the Chinese Patent Publication Database and a document was found: CN105330282A A method for preparing a high-frequency, low-loss soft ferrite core material. This technology belongs to the field of metallurgy and has nothing to do with this patent.

[0016] On August 29, 2024, an abstract search for "N iO and CoO and La and ZrO" was conducted on CNKI, and six papers were found:

[0017] Chang Xiwang’s doctoral thesis “Research on the laws and optimization design of key materials for solid oxide fuel cells” was published on May 6, 2021;

[0018] AABoryaev's "Brief Review of N2O Decomposition Catalysts for Engineering" published in Journal of Explosives and Pyrotechnics;

[0019] Xu Shipei published on 2015-06-01 "Research on the reaction process of catalytic conversion of synthesis gas to methane"

[0020] Huang Jian published on 2012-11-01 "Study on catalytic reforming of municipal landfill gas to produce synthesis gas"

[0021] Zhang Xiaoling published on 2008-05-01 "Study on Perovskite Buffer Layer in Coated Conductors"

[0022] Li Jinzhou published "Preliminary Study on the Effect of La2O3 Loading on La2O3 / γ-Al2O3 Catalyzed Cinnamaldehyde MPV Reduction Reaction" on 2007-05-01.

[0023] The above patents have nothing to do with this patent.

[0024] On August 29, 2024, a search for "NiO with CoO with La with ZrO" on the USPTO website found oxide-based materials, devices and processes for storing hydrogen US20130004413 A12013-01-03; search URL

[0025] https: / / ppubs.uspto.gov / pubwebapp / .

[0026] On August 29, 2024, a search was conducted on the Korean Patent Office for "NiO and CoO and La2O3 and ZrO2", and no relevant literature was found; the search URL was engpat.ki pr i s.or.kr. Application number (date): 1020160096808 (2016.07.29) Device for energy conversion using liquid; Application number (date): 1020227025217 (2021.01.05) Abrasive and method of use; 1020190081444 (2019.07.05) Hydrophilic fiber-reinforced permeable silicate waterproofing agent with antibacterial activity and waterproofing method using the same; Application number (date): 1020057024143 (2004.01.07)] Substrate for thin film formation, thin film substrate and light-emitting element (substrate for thin film formation, thin film substrate and light-emitting element); Application number (date): 1020057024140 (2004.01.07) Substrate for mounting light-emitting element and light-emitting element , Not related to this patent.

[0027] On August 29, 2024, a search was conducted on WIPO's https: / / patentscope2.wi po.i nt / with "NiO and CoO and La and ZrO"; the following documents were found, which are not related to this patent: 1. EP0960445 New manganese dioxide electrode, its production method and its use;

[0028] 2. WO / 1998 / 034289 Novel manganese dioxide electrode, its production method and use;

[0029] 3. WO / 2018 / 010692Q345 Hot-rolled alloy steel double-sided enamel anti-scaling glaze and functional glaze;

[0030] 4. WO / 2016 / 169385 A soft magnetic MNZN power ferrite;

[0031] 5. WO / 2019 / 093370 Ceramics, probe guide elements, probe cards and package test sockets;

[0032] 6.3927669 Spinel-type ceramic glass materials used to make fashion jewelry and gemstones;

[0033] 7. WO / 2006 / 037917 Glass substrate for viewing display;

[0034] 8. JP 1997030862 Non-magnetic substrate and magnetic head;

[0035] 9. EP1807368 screen glass substrate

[0036] 10. EP0869925 Brown glass that absorbs ultraviolet rays;

[0037] 11. WO / 2003 / 076386 Catalyst and method for producing amines;

[0038] 12. EP1487573 Catalyst and method for producing amines;

[0039] 13. WO / 2011 / 062834 Steel enamel corrosion-resistant glass;

[0040] 14. EP3344731 A method for obtaining liquid biohydrocarbons from oil of natural origin;

[0041] 15. WO / 2017 / 039471 Method for obtaining liquid biohydrocarbons from natural oils;

[0042] 16. WO / 1997 / 023422 Brown glass absorbing ultraviolet light;

[0043] 17. JP2009139362 Nanocrystalline composite oxide thin film, environmental gas sensor having the thin film and manufacturing method thereof;

[0044] 18.MX / A / 2010 / 011010 Sintered products produced from zircon-based charge materials;

[0045] 19. EP3689838 ceramics, probe guide assembly, probe card and package test tank;

[0046] 20. WO / 2009 / 054951 Low creep zircon material containing nano additives and preparation method thereof;

[0047] 21. EP2265559 Sintered products produced from zirconium oxide-based charge;

[0048] 22. WO / 2009 / 138611 Sintered products produced from zircon-based charge materials;

[0049] 23. EP2946685 heat-resistant synthetic jewelry materials;

[0050] 24. EP1879836 Metal appearance enamel paint;

[0051] 25. WO / 2006 / 124415 Enamel with metallic appearance;

[0052] 26. EP0738243 Lead-free crystal glass with a refractive index greater than 1.52;

[0053] 27. WO / 1995 / 013993 Lead-free crystal glass with a refractive index greater than 1.52;

[0054] 28. CN 101316648 Functionalized inorganic membrane for gas separation;

[0055] 29.FR2601354 Light-colored lenses with variable transmittance;

[0056] 30.KR1020040097599 Method for far infrared radiation of natural fibers using composite ceramics;

[0057] 31. JP2009509747 Functional inorganic membrane for gas separation;

[0058] 32. EP1931452 Functionalized inorganic membrane for gas separation;

[0059] 33. US20070265154 Enamel with metallic appearance;

[0060] 34.KR 1020220102708 Light-emitting device and electronic device including the light-emitting device;

[0061] 35. JP1994305816 Conductive ceramics;

[0062] 36. US20070068382 Functionalized inorganic membranes for gas separation;

[0063] 37. EP0700880 Particles and production method of colored ceramic moldings;

[0064] 38.ES2148387 Granulation and procedure for obtaining colored ceramic moldings;

[0065] 39. GB1417791 fiber;

[0066] 40.US20080210087 Carbon dioxide separation membrane.

[0067] On August 29, 2024, a search for "NiO and CoO and La and ZrO" was conducted on the Japan Patent Office website https: / / www.jp l atpat.i np it.go.jp / , and JP2016-5533430A was found as a new adhesion promoter for metallizing the surface of a substrate;

[0068] JP2016-521201A Nanocatalyst filter for removing nitrogen oxides; JP2012-008130A Gas mixture analysis device; JP2013-533188A Lead and tellurium oxide thick film paste and its use in the manufacture of semiconductor devices; JP2013-531863A Lead-tellurium-lithium oxide thick film paste and its use in the manufacture of semiconductor devices; JP2010-139497A Ultra-high sensitivity gas sensor using oxide semiconductor nanofibers and its manufacturing method; JP2009-139362A Nanocrystalline composite oxide thin film, environmental gas sensor with the thin film and method for manufacturing environmental gas sensor; JP2008-166667A High-efficiency heating resistor using oxide, liquid injection head and device, and substrate for liquid injection head;

[0069] JP2005-522696A gas mixture analysis device; JP2004-523731A method and device for analyzing gas mixture; and the concept of this patent are completely different.

[0070] Among them: the defects of these technologies are: all require at least one solvent; high separation energy consumption, large equipment investment and difficulty in waste liquid treatment; high cost of separating powder catalyst from product; high energy consumption and large investment for 1,5-pentanediol separation; and short service life of the catalyst. Summary of the invention

[0071] Purpose of the invention: To provide a better catalyst and preparation method suitable for producing 1,5-pentanediol with high yield, as well as a method for producing 1,5-pentanediol. The specific purpose can be seen in the multiple substantial technical effects in the specific implementation part.

[0072] In order to achieve the above purpose, the present invention adopts the following technical solutions:

[0073] A catalyst suitable for producing 1,5-pentanediol at a high yield, characterized in that the catalyst is NiO-CoO / La2O3-ZrO2.

[0074] A further technical solution of the present invention is that, based on the weight of the catalyst, the contents of the components are: 40-55 parts of NiO, 3-7 parts of CoO, 40-60 parts of La2O3, and 1-5 parts of ZrO2.

[0075] A further technical solution of the present invention is that, based on the weight of the catalyst, the contents of the components are: 43-52 parts of NiO, 4-6 parts of CoO, 41-50 parts of La2O3, and 2-3 parts of ZrO2.

[0076] A further technical solution of the present invention is that, based on the weight of the catalyst, the content of each component is: 52 parts of NiO-4 parts of CoO / 42 parts of La2O3-2 parts of ZrO2 catalyst on the NiO-CoO / La2O3-ZrO2 hydrogenation-ring-opening bifunctional catalyst.

[0077] The method for preparing any one of the above catalysts suitable for high-yield production of 1,5-pentanediol is characterized in that it is prepared by a parallel-current co-precipitation method, firstly, the metal salt solutions of the active components are prepared in the required proportions, and then the metal salt solution and the sodium hydroxide solution are added dropwise to the precipitation kettle at a certain temperature and pH value, stirred for 1 hour, heated to 160°C and hydrothermally heated for 12 hours, filtered, washed, dried, and calcined to obtain the desired hydrogenation-ring-opening bifunctional catalyst.

[0078] A further technical solution of the present invention is that the specific catalyst preparation comprises the following steps:

[0079] (1) preparing 1 mol / L nickel nitrate, cobalt nitrate, lanthanum nitrate and zirconium nitrate solutions, stirring and dissolving them, and mixing them uniformly to obtain a uniformly mixed acidic salt solution;

[0080] (2) preparing 1 mol / L sodium hydroxide solution as a precipitant;

[0081] (3) adding the acid solution and alkali solution prepared in (1) and (2) above to the precipitation kettle in parallel and dropping them to perform co-precipitation, stirring vigorously, and controlling the precipitation temperature to 60-80° C. and the pH value to 13;

[0082] (4) Continue stirring and heat to 160°C for 12 hours;

[0083] (5) Filter and wash to remove residual sodium ions, pH value ~7;

[0084] (6) Dry at 110°C for 12 hours;

[0085] (7) Calcinate at 450°C for 5 hours to obtain the desired catalyst.

[0086] A method for producing 1,5-pentanediol, characterized in that 1,5-pentanediol is selectively produced by hydrogenation ring opening under the catalytic action of any one of the above catalysts suitable for producing 1,5-pentanediol with high yield.

[0087] A further technical solution of the present invention is that the above method adopts a fixed bed reaction to prepare 1,5-pentanediol, specifically: a bimetallic catalyst of a composite carrier is loaded into a fixed bed, firstly subjected to a hydrogen reduction treatment at 350° C. for 30 hours, and pure tetrahydrofurfuryl alcohol is used to react to generate 1,5-pentanediol at a reaction temperature of 160 to 200° C., 3 to 4 MPa, a space velocity of 0.1 h-1, and a hydrogen-to-alcohol molar ratio of 10.

[0088] A further technical solution of the present invention is that under the conditions of a tetrahydrofurfuryl alcohol space velocity of 0.1, a hydrogen / tetrahydrofurfuryl alcohol molar ratio of 10, a reaction temperature in the range of 165-195° C., and a pressure of 3-4 MPa, the tetrahydrofurfuryl alcohol conversion rate and the 1,5-pentanediol selectivity are the highest.

[0089] A further technical solution of the present invention is that, in the above method, tetrahydrofurfuryl alcohol is tetrahydrofurfuryl alcohol without adding solvent; the method adopts a continuous trickle bed reactor or a slurry bed to prepare 1,5-pentanediol.

[0090] The present invention adopting the above technical solution has the following beneficial effects compared with the prior art: the method can be used in a continuous fixed bed reactor to achieve efficient catalytic conversion of tetrahydrofurfuryl alcohol. The catalyst has stable properties, simple separation process, and is valuable for industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0091] In order to further illustrate the present invention, the following is further described in conjunction with the accompanying drawings:

[0092] Figure 1 The multi-step process reaction path of dihydropyran improved by CN108368015;

[0093] Figure 2 It is the main reaction of the one-step process of tetrahydrofurfuryl alcohol;

[0094] Figure 3 Table 1;

[0095] Figure 4 Table 2. DETAILED DESCRIPTION

[0096] The present invention will be further explained below in conjunction with the accompanying drawings and specific embodiments. It should be understood that the following specific embodiments are only used to illustrate the present invention and are not used to limit the scope of the present invention.

[0097] This patent provides a variety of parallel solutions, and the different expressions are improved solutions or parallel solutions based on the basic solution. Each solution has its own unique characteristics.

[0098] Based on the problems existing in the prior art of catalysts, the purpose of the present invention is to provide a method for producing 1,5-pentanediol, which improves the problems of high solvent separation cost and short catalyst service life in the hydrogenolysis ring-opening reaction of tetrahydrofurfuryl alcohol to generate 1,5-pentanediol.

[0099] The objective of the present invention is achieved through the following technical solutions:

[0100] The embodiment of the present invention provides a method for producing 1,5-pentanediol, which is to hydrogenate and ring-open tetrahydrofurfuryl alcohol in one step to generate 1,5-pentanediol under the catalytic action of a nickel-based catalyst on a composite carrier. In order to solve the above technical problems, the present invention provides a hydrogenation-ring-opening bifunctional nickel-based catalyst and a preparation method thereof.

[0101] The hydrogenation-ring-opening bifunctional catalyst suitable for the method of the present invention is: NiO-CoO / La2O3-ZrO2. The hydrogenation component is NiO-CoO and the composite carrier is La2O3-ZrO2. Based on the total weight of the catalyst, the content of each component is: NiO content is 40-55%, CoO content is 3-7%, La2O3 content is 40-60%, and ZrO2 content is 1-5%. The preferred content of each component is: NiO content is 43-52%, CoO content is 4-6%, La2O3 content is 41-50%, and ZrO2 content is 2-3%.

[0102] The nickel-based catalyst for 1,5-pentanediol synthesis provided by the present invention is prepared by a co-current co-precipitation method. First, metal salt solutions of various active components are prepared in the required proportions, such as nitrate solutions; and then precipitants such as sodium hydroxide and sodium carbonate solutions are prepared. Then, at a certain temperature and pH value, the metal salt solution and the sodium hydroxide solution are co-currently added dropwise to the precipitation kettle, stirred for 1 hour, heated to 160°C and hydrothermally heated for 12 hours, filtered, washed, dried, and calcined to obtain the desired hydrogenation-ring-opening bifunctional catalyst. The specific catalyst preparation includes the following steps:

[0103] (1) Prepare 1 mol / L nickel nitrate, cobalt nitrate, lanthanum nitrate and zirconium nitrate solutions, stir and dissolve them, and mix them evenly to obtain a mixed acidic salt solution.

[0104] (2) Prepare a sodium hydroxide solution of about 1 mol / L as a precipitant.

[0105] (3) The acid solution and alkali solution prepared in (1) and (2) are added dropwise to the precipitation kettle in parallel to perform co-precipitation, with strong stirring, and the precipitation temperature is controlled at 60-80°C and the pH value is controlled at 13.

[0106] (4) Continue stirring and heat to 160°C for 12 hours.

[0107] (5) Filter and wash to remove residual sodium ions, pH value ~7.

[0108] (6) Dry at 110°C for 12 hours.

[0109] (7) Calcinate at 450°C for 5 hours to obtain the desired catalyst.

[0110] The embodiment of the present invention provides a method for producing 1,5-pentanediol, which comprises selectively hydrogenating tetrahydrofurfuryl alcohol under the catalytic action of a composite carrier co-precipitated nickel-based catalyst to generate 1,5-pentanediol.

[0111] In the above method, tetrahydrofurfuryl alcohol is tetrahydrofurfuryl alcohol without adding solvent;

[0112] The method adopts a continuous trickle bed reactor to prepare 1,5-pentanediol.

[0113] The above method adopts a fixed bed reaction to prepare 1,5-pentanediol, specifically: a bimetallic catalyst with a composite carrier is loaded into a fixed bed, firstly subjected to a hydrogen reduction treatment at 350°C for 30 hours, and pure tetrahydrofurfuryl alcohol is used to react to generate 1,5-pentanediol at a reaction temperature of 160-200°C, 3-4Mpa, a space velocity of 0.1h-1, and a hydrogen-to-alcohol molar ratio of 10.

[0114] Example 1

[0115] First, prepare 1 mol / L nickel nitrate and lanthanum nitrate solutions, stir and mix them evenly to obtain a mixed metal salt acid solution. Then prepare about 1 mol / L sodium hydroxide solution as alkali solution. Under strong stirring conditions, the above acid solution and alkali solution are added dropwise to the precipitation kettle in parallel to carry out parallel co-precipitation, and the precipitation temperature is controlled at 60-80°C and the pH value is ~13; the temperature is raised to 160°C for hydrothermal treatment for 12 hours, then filtered and washed, dried at 110°C for 12 hours, and calcined at 450°C for about 5 hours to obtain NiO / La2O3 catalyst. Based on the total amount of catalyst: the content of NiO is 41%, and the content of La2O3 is 59%. The catalyst is marked as Cat1. The reaction results are shown in Table 1.

[0116] Example 2

[0117] First, prepare 1 mol / L nickel nitrate, lanthanum nitrate and zirconium nitrate solutions, stir and mix them evenly to obtain a mixed metal salt acid solution. Then prepare about 1 mol / L sodium carbonate solution as alkali solution. Under strong stirring conditions, add the above acid solution and alkali solution to the precipitation kettle in parallel flow, and carry out parallel co-precipitation, control the precipitation temperature at 60-80°C, and the pH value at 13; heat to 160°C for hydrothermal for 12 hours, then filter, wash, dry at 110°C for 12 hours, and roast at 450°C for about 5 hours to obtain NiO / La2O3-ZrO2 catalyst. Based on the total amount of catalyst: NiO content is 45%, La2O3 content is 50%, and ZrO2 content is 5%. The catalyst is marked as Cat2. The reaction results are shown in Table 1.

[0118] Example 3

[0119] (1) First, prepare 1 mol / L nickel nitrate, cobalt nitrate, lanthanum nitrate and zirconium nitrate solutions, stir and mix them evenly to obtain a uniformly mixed metal salt acid solution. Then prepare about 1 mol / L sodium carbonate solution as alkali solution. Under strong stirring conditions, add the above acid solution and alkali solution to the precipitation kettle in parallel flow, and carry out parallel flow co-precipitation. The precipitation temperature is controlled at 60-80°C and the pH value is 13; the temperature is raised to 160°C for hydrothermal treatment for 12 hours, and then filtered, washed, dried at 110°C for 12 hours, and calcined at 450°C for about 5 hours to obtain NiO-CoO / La2O3-ZrO2 catalyst. Based on the total amount of catalyst: NiO content is 50%, CoO content is 5%, La2O3 content is 44%, and ZrO2 content is 1%. The catalyst is marked as Cat3. The reaction results are shown in Table 1.

[0120] Example 4

[0121] (1) First, prepare 1 mol / L nickel nitrate, cobalt nitrate, lanthanum nitrate and zirconium nitrate solutions, stir and mix them evenly to obtain a mixed metal salt acid solution. Then prepare about 1 mol / L sodium carbonate solution as alkali solution. Under strong stirring conditions, add the above acid solution and alkali solution to the precipitation kettle in parallel flow, and carry out parallel co-precipitation. The precipitation temperature is controlled at 60-80°C and the pH value is 13; the temperature is raised to 160°C for hydrothermal treatment for 12 hours, and then filtered, washed, dried at 110°C for 12 hours, and calcined at 450°C for about 5 hours to obtain NiO-CoO / La2O3-ZrO2 catalyst. Based on the total amount of catalyst: NiO content is 52%, CoO content is 4%, La2O3 content is 42%, and ZrO2 content is 2%. The catalyst is marked as Cat4. The reaction results are shown in Table 1.

[0122] Example 5

[0123] (1) First, prepare 1 mol / L nickel nitrate, cobalt nitrate, lanthanum nitrate and zirconium nitrate solutions, stir and mix them evenly to obtain a mixed metal salt acid solution. Then prepare about 1 mol / L sodium carbonate solution as alkali solution. Under strong stirring conditions, add the above acid solution and alkali solution to the precipitation kettle in parallel flow, and carry out parallel flow co-precipitation. The precipitation temperature is controlled at 60-80°C and the pH value is 13; the temperature is raised to 160°C for hydrothermal treatment for 12 hours, and then filtered, washed, dried at 110°C for 12 hours, and calcined at 450°C for about 5 hours to obtain NiO-CoO / La2O3-ZrO2 catalyst. Based on the total amount of catalyst: NiO content is 55%, CoO content is 3%, La2O3 content is 41%, and ZrO2 content is 1%. The catalyst is marked as Cat5. The reaction results are shown in Table 1.

[0124] Reaction conditions: 50g of catalyst was loaded into a fixed bed reactor, and first reduced with hydrogen at 350℃ for 30 hours; reaction pressure 3.9MPa, reaction temperature 180℃, space velocity 0.1, hydrogen / tetrahydrofurfuryl alcohol molar ratio 10 under solvent-free conditions. The conversion of tetrahydrofurfuryl alcohol and selectivity of 1,5-pentanediol are shown in Table 1, and other major by-products are 2-methyltetrahydrofuran, n-pentanol, and 1,2-pentanediol.

[0125] Example 1 Product distribution: 2-methyltetrahydrofuran 3.5%, n-pentanol 7.6%, 1,2-pentanediol 1.4%, 1,5-pentanediol 88.2%.

[0126] Product distribution of Example 4: 2-methyltetrahydrofuran 1.1%, n-pentanol 3.5%, 1,2-pentanediol 0.3%, 1,5-pentanediol 95.1%.

[0127] Table 1. Effects of different catalysts on the hydrogenation of furfuryl alcohol to 1,2-pentanediol

[0128]

[0129] Example 6

[0130] From the results of the reaction of tetrahydrofurfuryl alcohol hydrogenation to 1,5-pentanediol with different catalysts in Table 1, it can be concluded that the catalyst of Example 4 obtains the best 1,5-pentanediol yield. Therefore, 50g of the catalyst of Example 4 was reloaded into the fixed bed reactor, and first reduced at 350°C and hydrogen for 30 hours; then, under the conditions of a space velocity of 0.1, a hydrogen / tetrahydrofurfuryl alcohol molar ratio of 10 and no solvent, the effects of reaction temperature and pressure on the conversion rate of tetrahydrofurfuryl alcohol and the selectivity of 1,5-pentanediol were investigated, as shown in Table 2.

[0131] Table 2. Effects of reaction temperature and pressure on conversion and selectivity of 1,5-pentanediol

[0132]

[0133]

[0134] From the results of the effects of reaction temperature and pressure on tetrahydrofurfuryl alcohol conversion and 1,5-pentanediol selectivity in Table 2, it can be concluded that when the tetrahydrofurfuryl alcohol space velocity is 0.1 and the hydrogen / tetrahydrofurfuryl alcohol molar ratio is 10, the reaction temperature is in the range of 165-195°C and the pressure is in the range of 3-4 MPa, the tetrahydrofurfuryl alcohol conversion and 1,5-pentanediol selectivity are the highest.

[0135] From the above data, it can be seen that on the NiO-CoO / La2O3-ZrO2 hydrogenation-ring-opening bifunctional catalyst, 52% NiO-4% CoO / 42% La2O3-2% ZrO2 catalyst can achieve high selectivity for preparing 1,5-pentanediol from tetrahydrofurfuryl alcohol with a yield of about 95%.

[0136] In summary, the present invention uses a composite carrier nickel-based catalyst to achieve directional catalytic conversion of tetrahydrofurfuryl alcohol under the conditions of H2 pressure of 3.0-4.0 MPa and temperature of 165-195°C. The method can be used in reactors such as continuous fixed beds to achieve efficient catalytic conversion of tetrahydrofurfuryl alcohol. The catalyst has stable properties, simple separation process, and is valuable for industrial production.

[0137] A method for producing 1,5-pentanediol and the like by catalytic ring opening of tetrahydrofurfuryl alcohol, characterized in that: tetrahydrofurfuryl alcohol is used as a raw material, and is converted into 1,5-pentanediol by hydrogenation on a hydrogenation-ring opening bifunctional catalyst, and 1,2-pentanediol, 2-methyltetrahydrofuran, n-pentanol and the like are produced as byproducts. The hydrogenation-ring opening bifunctional catalyst is composed of NiO-CoO / La2O3-ZrO2, the hydrogenation component is CuO-CoO, the composite oxide carrier is La2O3-ZrO2, and the pressure conditions of the hydrogenation conversion process are: H2 pressure is 3.0-4.0MPa, and the temperature is 165-195°C;

[0138] The hydrogenation-ring-opening bifunctional catalyst has the following components, based on the total weight of the catalyst: NiO content is 40-55%, CoO content is 3-7%, La2O3 content is 40-60%, and ZrO2 content is 1-5%, and the above units are wt%.

[0139] The hydrogenation-ring-opening bifunctional catalyst preferably has the following components in the total weight of the catalyst: NiO content is 43-52%, CoO content is 4-6%, La2O3 content is 41-50%, and ZrO2 content is 2-3%, and the above units are wt%.

[0140] The hydrogenation-ring-opening bifunctional catalyst is prepared by a parallel-flow co-precipitation method.

[0141] The hydrogenation reaction is carried out in a continuous fixed bed reactor or a slurry bed.

[0142] The hydrogenation reaction is carried out in a continuous fixed bed reactor, and the fixed bed reactor is a tubular fixed bed reactor;

[0143] The purity of the raw material tetrahydrofurfuryl alcohol in the reaction is 97-100%wt, and the water content is ≤3%;

[0144] The hydrogenation-ring-opening bifunctional catalyst needs to be reduced and activated before use, and the activation steps are as follows: first, 1-15 vol% hydrogen (other components are inert gases, such as nitrogen) is introduced, gradually from room temperature to 250°C for 10 hours, and the temperature is kept constant for 3 hours; this process is at normal pressure, and then gradually switched to pure hydrogen, and the reduction pressure is gradually increased to more than 1.5 MPa (pressure increase rate ≤0.5 Ma / h), and then kept constant at 350°C for more than 30 hours.

[0145] The reaction conditions of the hydrogenation process are: H2 pressure of 3.0-4.0 MPa, temperature of 165-195°C, liquid hourly space velocity of 0.05-0.3 h-1, and molar ratio of hydrogen to tetrahydrofurfuryl alcohol of 5-12.

[0146] Aiming at the defects of the prior art: all of them require at least one solvent; this patent does not use any solvent.

[0147] Aiming at the defects of the prior art: high separation energy consumption, large equipment investment and difficulty in waste liquid treatment; this patent does not need to realize separation, has no excessive by-products, and avoids this part of energy consumption.

[0148] In view of the defects of the prior art: the cost of separating the powdered catalyst from the product is high; this patent does not require separation costs.

[0149] Aiming at the defects of the prior art: high energy consumption and large investment for 1,5-pentanediol separation; short service life of the catalyst, the patent has low investment and long service life of the catalyst.

[0150] It should be noted that the multiple solutions provided by this patent include the basic solution itself, which are independent of each other and do not restrict each other, but they can also be combined with each other without conflict to achieve multiple effects together.

[0151] The basic principle, main features and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the protection required.

Claims

1. A catalyst suitable for producing 1,5-pentanediol in high yield, characterized in that: The catalyst is NiO-CoO / La2O3-ZrO2.

2. The catalyst suitable for producing 1,5-pentanediol in high yield as claimed in claim 1, characterized in that: Calculated by weight of the catalyst, the contents of each component are: NiO content is 40-55 parts, CoO content is 3-7 parts, La2O3 content is 40-60 parts, and ZrO2 content is 1-5 parts.

3. The catalyst suitable for producing 1,5-pentanediol in high yield as claimed in claim 1, characterized in that: Calculated in parts by weight of the catalyst, the contents of the various components are: NiO content is 43-52 parts, CoO content is 4-6 parts, La2O3 content is 41-50 parts, and ZrO2 content is 2-3 parts.

4. The catalyst suitable for producing 1,5-pentanediol in high yield as claimed in claim 1, characterized in that: Calculated in parts by weight of the catalyst, the content of each component is: 52 parts NiO-4 parts CoO / 42 parts La2O3-2 parts ZrO2 catalyst on NiO-CoO / La2O3-ZrO2 hydrogenation-ring opening bifunctional catalyst.

5. A method for preparing a catalyst suitable for producing 1,5-pentanediol in high yield according to any one of claims 1 to 4, characterized in that: The preparation is carried out by the parallel co-precipitation method. First, the metal salt solutions of the active components are prepared in the required proportions. Then, at a certain temperature and pH value, the metal salt solution and the sodium hydroxide solution are added dropwise to the precipitation kettle in parallel, stirred for 1 hour, heated to 160°C and hydrothermally heated for 12 hours. After filtering, washing, drying and calcining, the required hydrogenation-ring-opening bifunctional catalyst is obtained.

6. The method for preparing a catalyst suitable for producing 1,5-pentanediol in high yield according to claim 5, characterized in that: The specific catalyst preparation includes the following steps: (1) preparing 1 mol / L nickel nitrate, cobalt nitrate, lanthanum nitrate and zirconium nitrate solutions, stirring and dissolving them, and mixing them uniformly to obtain a uniformly mixed acidic salt solution; (2) preparing 1 mol / L sodium hydroxide solution as a precipitant; (3) adding the acid solution and alkali solution prepared in (1) and (2) above to the precipitation kettle in parallel and dropping them to perform co-precipitation, stirring vigorously, and controlling the precipitation temperature to 60-80° C. and the pH value to 13; (4) Continue stirring and heat to 160°C for 12 hours; (5) Filter and wash to remove residual sodium ions, pH value ~7; (6) Dry at 110°C for 12 hours; (7) Calcinate at 450°C for 5 hours to obtain the desired catalyst.

7. A method for producing 1,5-pentanediol, characterized in that: 1,5-pentanediol is selectively produced by hydrogenation ring opening under the catalytic action of the catalyst suitable for producing 1,5-pentanediol with high yield as claimed in any one of claims 1 to 4.

8. The method for producing 1,5-pentanediol as claimed in claim 7, characterized in that: The above method adopts a fixed bed reaction to prepare 1,5-pentanediol, specifically: a bimetallic catalyst with a composite carrier is loaded into a fixed bed, firstly subjected to a hydrogen reduction treatment at 350°C for 30 hours, and pure tetrahydrofurfuryl alcohol is used to react to generate 1,5-pentanediol at a reaction temperature of 160-200°C, 3-4Mpa, a space velocity of 0.1h-1, and a hydrogen-to-alcohol molar ratio of 10.

9. The method for producing 1,5-pentanediol as claimed in claim 8, characterized in that: Under the conditions of tetrahydrofurfuryl alcohol space velocity of 0.1, hydrogen / tetrahydrofurfuryl alcohol molar ratio of 10, reaction temperature in the range of 165-195°C and pressure of 3-4MPa, the tetrahydrofurfuryl alcohol conversion rate and 1,5-pentanediol selectivity are the highest.

10. The method for producing 1,5-pentanediol according to claim 9, characterized in that: In the above method, tetrahydrofurfuryl alcohol is tetrahydrofurfuryl alcohol without adding solvent; the method adopts a continuous trickle bed reactor or a slurry bed to prepare 1,5-pentanediol.

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