CN113549034B - Method for preparing tetrahydrofurfuryl alcohol by adopting two-section fully-mixed flow series kettle type reactor in one step - Google Patents
Method for preparing tetrahydrofurfuryl alcohol by adopting two-section fully-mixed flow series kettle type reactor in one step Download PDFInfo
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- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 title claims abstract description 42
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 22
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 100
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 102000002322 Egg Proteins Human genes 0.000 claims abstract description 17
- 108010000912 Egg Proteins Proteins 0.000 claims abstract description 17
- 210000003278 egg shell Anatomy 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004005 microsphere Substances 0.000 claims description 33
- 239000000047 product Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000006227 byproduct Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
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- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- LBPYPRXFFYUUSI-UHFFFAOYSA-N furan-2-carbaldehyde;hydrate Chemical compound O.O=CC1=CC=CO1 LBPYPRXFFYUUSI-UHFFFAOYSA-N 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 26
- 239000007864 aqueous solution Substances 0.000 abstract description 11
- 238000002360 preparation method Methods 0.000 abstract description 8
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- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 15
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- 239000012298 atmosphere Substances 0.000 description 4
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- 239000007789 gas Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
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- 238000011161 development Methods 0.000 description 3
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
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- 239000008346 aqueous phase Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229940043375 1,5-pentanediol Drugs 0.000 description 1
- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
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- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
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- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/12—Radicals substituted by oxygen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/397—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a method for preparing tetrahydrofurfuryl alcohol by adopting a two-section complete mixed flow series kettle type reactor in one step, belonging to the field of fine chemical engineering. The method is characterized in that a furfural aqueous solution is used as a raw material, a two-stage fully-mixed flow series kettle type reactor is adopted, an eggshell type nickel-based alloy catalyst is subjected to one-step hydrogenation at a reaction temperature of 80-160 ℃ and a hydrogen pressure of 0.5-7MPa to generate tetrahydrofurfuryl alcohol, and the yield is over 96 percent. The method adopts a two-stage fully-mixed flow series kettle type reaction process to realize the continuous production of the tetrahydrofurfuryl alcohol; water is used as a solvent, so that the green chemical concept is met, and the reaction cost and the separation difficulty are reduced; the catalyst has simple preparation process, low cost, high activity, high selectivity and high stability, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a method for preparing tetrahydrofurfuryl alcohol by adopting a two-section fully-mixed flow series kettle type reactor in one step.
Background
The tetrahydrofurfuryl alcohol is used as a fine chemical product with high added value, is widely used for coatings, resins, grease, industrial and electronic cleaning agents and the like, and can be used as a solvent for grease, wax, resin, dye, cellulose acetate, cellulose nitrate, ethyl cellulose and the like. Furthermore, tetrahydrofurfuryl alcohol is also used for preparing dihydrofuran, lysine, polyamide plastics, plasticizers, etc., and also can be used as a gelatin solution stabilizer, a wetting agent and a dispersing agent in the printing and dyeing industry, a decoloring and deodorizing agent of certain medicines, etc. At present, tetrahydrofurfuryl alcohol is mainly realized by furfural selective hydrogenation, however, the catalytic hydrogenation process of furfural is relatively complex, and a large number of byproducts exist, such as: furfuryl alcohol, 2-methylfuran, 2-methyltetrahydrofuran, cyclopentanone, 1, 5-pentanediol, and the like. Therefore, the preparation of the tetrahydrofurfuryl alcohol by furfural selective hydrogenation with high efficiency and high selectivity puts high requirements on the catalyst and the process engineering.
The traditional preparation method of tetrahydrofurfuryl alcohol takes furfural as an initial substrate and prepares the tetrahydrofurfuryl alcohol by a two-step method,in the process, furfuryl alcohol is used as an intermediate product, furfural is firstly catalyzed by a Cu-Cr catalyst to be hydrogenated and converted into furfuryl alcohol, and the furfuryl alcohol is further catalyzed by a noble metal catalyst to be hydrogenated to generate tetrahydrofurfuryl alcohol. However, the reaction process is harsh and environmentally unfriendly, which limits its large-scale development to some extent. Therefore, the method for preparing the tetrahydrofurfuryl alcohol by hydrogenating the furfural is researched, and the process is expected to be realized in one step under mild conditions, so that the aims of greenization and economy are fulfilled. The method for preparing tetrahydrofurfuryl alcohol by furfural one-step hydrogenation is mainly realized by constructing a catalyst and optimizing a process in a fixed bed reactor and a stirred tank reactor at present. Chinese patent CN105693659 discloses that high yield (98%) of tetrahydrofurfuryl alcohol is achieved in aqueous phase at 140 ℃ and 4MPa under the action of nickel-based catalyst supported on alumina modified with one or more of alkaline earth metals Mg, Ca, Sr, Ba in a stirred tank reactor. However, the reaction process is a batch type, the operation is complex, the product stability is poor, and the catalyst has poor aqueous phase stability, so that large-scale application is difficult to realize. Chinese patent CN106967018 discloses a process for preparing tetrahydrofurfuryl alcohol by hydrogenation of furfural using apatite supported metal as catalyst in a stirred tank reactor. Although the reaction system can realize high yield of tetrahydrofurfuryl alcohol, and the apatite as the carrier has certain hydrothermal stability, the acting force between the metal and the carrier is poor, and the loss of active centers is easily caused in long-time circulation experiments. In addition, intermittent operation easily brings about some potential safety hazards. Chinese patent CN109529946 discloses an immobilized Cu-Ni bimetallic catalyst and a method for preparing tetrahydrofurfuryl alcohol by catalyzing furfural and completely hydrogenating the furfural. In the method, under a fixed bed reactor, a microsphere silica gel loaded CuNi bimetallic catalyst modified by amino-terminated groups is adopted, and the reaction is carried out at 80 ℃ and 0.3MPa for 0.2h-1The conversion rate of furfural is 80%, and the selectivity of tetrahydrofurfuryl alcohol is 100%. Although the reaction system can realize continuous production, the conversion rate of furfural is low, so that the subsequent separation cost is increased. Therefore, a catalyst and a process which can efficiently and continuously convert furfural and realize high selectivity on tetrahydrofurfuryl alcohol are sought, and the refinement of the tetrahydrofurfuryl alcohol with high additional value is realized by one-step hydrogenation of furfuralThe study of the chemical products has become a hotspot and a difficulty of the current research.
Disclosure of Invention
Due to the adoption of different hydrogenation operation processes and catalyst systems, furfural can be hydrogenated to obtain a complex downstream product, and C-O double bond hydrogenation, furan ring C-C double bond hydrogenation, furan ring opening and rearrangement are involved, so that important high-value-added chemicals in petrochemical industries such as furfuryl alcohol, tetrahydrofurfuryl alcohol, gamma-valerolactone, cyclopentanone and the like can be generated. Currently, the more systematic catalyst for high-activity furfural hydrogenation mainly comprises noble metals such as Ir, Pt and Pd and a supported alloy catalyst of the noble metals and transition metals. However, in view of the limitation of economical efficiency and industrial scale-up, research on selective hydrogenation of furfural has recently been shifted to the development and application of transition metal (e.g., Cu, Co, Ni, etc.) based catalysts. Because the furfural hydrogenation reaction network is complex and the products are various, how to design a high-efficiency and high-selectivity transition metal catalyst and realize the one-step selective hydrogenation of furfural to prepare tetrahydrofurfuryl alcohol under certain process conditions; the structure-activity relationship and the reaction mechanism of the catalyst and the performance thereof are deeply analyzed, the controllable optimization of the catalyst is realized, and the method is a key scientific problem in a furfural hydrogenation industrial chain.
Aiming at the technical bottleneck and scientific problems in the furfural selective hydrogenation catalytic system, the invention provides a method for preparing tetrahydrofurfuryl alcohol by one step by adopting a two-section fully mixed flow series kettle type reactor. According to the technology, the eggshell type nickel-based alloy catalyst is developed, and one-step selective hydrogenation of furfural is selected under mild conditions to obtain high-end fine chemicals of tetrahydrofurfuryl alcohol with high added values, so that the problem that the traditional noble metal catalyst is expensive is effectively solved, and the bottlenecks of poor selectivity of the transition metal catalyst and impurity distribution of products are broken through. By optimizing the chemical process and adopting the two-section fully-mixed flow series kettle type reactor, the problem of poor intermittent operation stability is solved compared with the kettle type reactor, and meanwhile, the investment cost is obviously reduced compared with the fixed bed reactor. In addition, the technology takes a bio-based renewable resource-furfural as a raw material, actively extends the industry chain of downstream products, realizes diversification of product schemes, improves the value chain of the products, and makes the product leap to the middle and high end, thereby realizing green sustainable development.
The technical scheme of the invention is as follows:
a method for preparing tetrahydrofurfuryl alcohol by adopting a two-section fully mixed flow series kettle type reactor in one step comprises the following steps:
taking 5-30 wt.% furfural aqueous solution as a raw material, adopting a two-stage fully-mixed flow series kettle type reactor, using an eggshell type nickel-based alloy catalyst, performing atmospheric distillation on the reaction solution in a desolventizing tower at the reaction temperature of 80-180 ℃ and the hydrogen pressure of 0.5-7MPa for 2-5h, circulating the aqueous solution distilled from the top of the tower to re-dilute furfural after the reaction, and feeding the product at the bottom of the tower into a rectifying tower to remove heavy byproducts, thereby obtaining the high-purity tetrahydrofurfuryl alcohol.
The nickel-based alloy of the eggshell type nickel-based alloy catalyst is NiM, and M is one or more than two of Cu, Fe, Co and Zn.
The molar ratio of Ni to M is 3:1, the mass content of Ni is 5-30 wt.%, and the carrier is carbon microsphere and TiO2Microspheres, Al2O3One of the microspheres.
The invention has the beneficial effects that: the continuous production of the tetrahydrofurfuryl alcohol is realized by adopting a two-section fully-mixed flow series kettle type reaction process; water is used as a solvent, so that the green chemical concept is met, and the reaction cost and the separation difficulty are reduced; the catalyst has simple preparation process, low cost, high activity, high selectivity and high stability, and is suitable for industrial production.
Drawings
FIG. 1 is a flow chart of a process for preparing tetrahydrofurfuryl alcohol by one-step selective hydrogenation of furfural in a two-stage fully mixed flow series kettle type reactor.
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1 Eggshell-type carbon microsphere loaded with Ni3Preparation of Cu catalyst
1486.5g of nickel nitrate and 319.58g of copper nitrate were weighed out to prepare 2L of an aqueous solution as a metal precursor, wherein the ratio of Ni: the Cu molar ratio is 3:1, 1000g of carbon microspheres are taken as a carrier, a rotary coating machine is adopted, and the rotating speed of the coating machine is controlled to be 20Carrying a metal precursor to deposit on the surface of the carbon microsphere at the speed of 0rpm, the temperature of 80 ℃ and the gas flow rate of 500mL/min, drying the solid at 120 ℃ overnight after spraying, and reducing the solid at 400 ℃ for 3 hours in a hydrogen atmosphere to obtain the eggshell type carbon microsphere Ni-loaded with 30 wt.% of Ni3A Cu catalyst.
EXAMPLE 2 Eggshell TiO2Microsphere loaded Ni3Preparation of Zn catalyst
1486.5g of nickel nitrate and 322.7g of zinc nitrate were weighed to prepare 2L of an aqueous solution as a metal precursor, wherein the ratio of Ni: zn molar ratio of 3:1, 1000g TiO2The microspheres are taken as a carrier, a rotary coating machine is adopted, the rotating speed of the coating machine is controlled to be 200rpm, the temperature is 90 ℃, the gas flow rate is 800mL/min, and metal precursors are carried to be deposited on TiO2After the spraying on the surface of the microsphere is finished, drying the solid at 120 ℃ overnight, and then reducing the dried solid at 400 ℃ for 3 hours in a hydrogen atmosphere to obtain the eggshell type TiO with the Ni content of 30 wt%2Microsphere loaded Ni3A Zn catalyst.
Example 3 Eggshell type Al2O3Microsphere loaded Ni3Preparation of Fe catalyst
247.8g of nickel nitrate and 68.7g of ferric nitrate were weighed out to prepare 1L of an aqueous solution as a metal precursor, wherein the ratio of Ni: fe molar ratio of 3:1, 1000gAl2O3The microspheres are taken as a carrier, a rotary coating machine is adopted, the rotating speed of the coating machine is controlled to be 200rpm, the temperature is 80 ℃, the gas flow rate is 800mL/min, and metal precursors are carried to be deposited on Al2O3After the spraying on the surface of the microsphere is finished, the solid is dried at 120 ℃ overnight, and then is reduced for 4 hours at 450 ℃ in a hydrogen atmosphere to prepare eggshell type Al with the Ni content of 5 wt%2O3Microsphere loaded Ni3And (3) Fe catalyst.
Example 4 Eggshell-type carbon microsphere loaded with Ni3Preparation of Co catalyst
1486.5g of nickel nitrate and 311.7g of cobalt nitrate are weighed to prepare 2L of aqueous solution as a metal precursor, wherein the ratio of Ni: the molar ratio of Co is 3:1, 1000g of carbon microspheres are taken as a carrier, a rotary coating machine is adopted, the rotating speed of the coating machine is controlled to be 200rpm, the temperature is 80 ℃, the gas flow rate is 500mL/min, metal precursors are carried to be deposited on the surfaces of the carbon microspheres,after spraying, the solid is dried at 120 ℃ overnight, and then reduced at 400 ℃ for 3h in hydrogen atmosphere to prepare the eggshell type carbon microsphere Ni-loaded with 30 wt.% Ni3A Co catalyst.
Example 5 Eggshell-type carbon microspheres loaded with Ni in a two-stage fully mixed flow series tank reactor3Cu-catalyzed furfural selective hydrogenation is carried out on prepared eggshell-type carbon microspheres in a two-section 1L fully-mixed flow series kettle type reactor3The Cu catalyst was subjected to furfural selective hydrogenation activity test as shown in fig. 1. Respectively weighing 10g of catalyst, placing the catalyst in two kettle type reactors, continuously stirring and reacting furfural aqueous solution with the mass fraction of 30% at 180 ℃ and the hydrogen pressure of 6.0MPa for 2h, sampling on line, analyzing by a chromatograph-mass spectrometer, and obtaining the furfural conversion rate>99% selectivity to tetrahydrofurfuryl alcohol>93 percent. The reaction solution passes through a desolventizing tower, is distilled at normal pressure, the hydrosolvent distilled from the tower top is recycled to re-dilute the furfural, the product at the tower bottom enters a rectifying tower to remove heavy byproducts, and the high-purity tetrahydrofurfuryl alcohol is obtained>99.3％。
EXAMPLE 6 Eggshell type TiO in two stage fully mixed flow in series tank reactor2Microsphere loaded Ni3Selectively hydrogenating furfural by Zn catalysis in a two-section 1L fully-mixed flow series kettle type reactor to prepare eggshell type TiO2Microsphere loaded Ni3And (3) carrying out furfural selective hydrogenation activity test on the Zn catalyst. Respectively weighing 10g of catalyst, placing the catalyst in two kettle type reactors, continuously stirring and reacting furfural aqueous solution with the mass fraction of 20% at the temperature of 80 ℃ and the hydrogen pressure of 7.0MPa for 5h, sampling on line, analyzing by a chromatograph-mass spectrometer, and obtaining the furfural conversion rate>99% selectivity to tetrahydrofurfuryl alcohol>95 percent. The reaction solution passes through a desolventizing tower, is distilled at normal pressure, the hydrosolvent distilled from the tower top is recycled to re-dilute the furfural, the product at the tower bottom enters a rectifying tower to remove heavy byproducts, and the high-purity tetrahydrofurfuryl alcohol is obtained>99.6％。
EXAMPLE 7 Eggshell type Al in two-stage fully mixed flow series tank reactor2O3Microsphere loaded Ni3Fe-catalyzed furfural selective hydrogenation is carried out on the prepared eggshell type Al in a two-section 1L fully mixed flow series kettle type reactor2O3Microsphere loaded Ni3And (4) carrying out furfural selective hydrogenation activity test on the Fe catalyst. Respectively weighing 10g of catalyst, placing the catalyst in two kettle type reactors, continuously stirring and reacting a furfural aqueous solution with the mass fraction of 5% at the temperature of 120 ℃ and the hydrogen pressure of 0.5MPa for 5h, sampling on line, analyzing by a chromatograph-mass spectrometer, and obtaining the furfural conversion rate>99% selectivity to tetrahydrofurfuryl alcohol>96 percent. The reaction solution passes through a desolventizing tower, is distilled at normal pressure, the hydrosolvent distilled from the tower top is recycled to re-dilute the furfural, the product at the tower bottom enters a rectifying tower to remove heavy byproducts, and the high-purity tetrahydrofurfuryl alcohol is obtained>99.9％。
Example 8 Eggshell-type carbon microspheres loaded with Ni in a two-stage fully mixed flow series tank reactor3Co-catalyzed furfural selective hydrogenation is carried out on prepared eggshell type carbon microspheres in a two-section 1L fully-mixed flow series kettle type reactor3And (3) performing furfural selective hydrogenation activity test on the Co catalyst. Respectively weighing 10g of catalyst, placing the catalyst in two kettle type reactors, continuously stirring and reacting furfural aqueous solution with the mass fraction of 30% at 180 ℃ and the hydrogen pressure of 4.0MPa for 2h, sampling on line, analyzing by a chromatograph-mass spectrometer, and obtaining the furfural conversion rate>99% selectivity to tetrahydrofurfuryl alcohol>92 percent. The reaction solution passes through a desolventizing tower, is distilled at normal pressure, the hydrosolvent distilled from the tower top is circulated to re-dilute the furfural, the product at the tower bottom enters a rectifying tower to remove heavy byproducts, and the high-purity tetrahydrofurfuryl alcohol is obtained, wherein the purity of the tetrahydrofurfuryl alcohol is>99.5％。
Example 9 Eggshell-type carbon microspheres loaded with Ni in a two-stage fully mixed flow series tank reactor3Cu-catalyzed furfural selective hydrogenation stability test result loads Ni on prepared eggshell-type carbon microspheres in two-stage 1L fully-mixed flow series kettle type reactor3And (3) carrying out a furfural selective hydrogenation stability test on the Cu catalyst. On the basis of example 5, the reaction conditions were: continuously stirring and reacting at 180 ℃ under the hydrogen pressure of 4.0MPa for 2h, wherein the furfural concentration is 20 wt.%, performing a stability test for 1000h, and analyzing by an online sampling chromatograph-mass spectrometer, wherein the results are shown in the following table 1. The reaction solution passes through a desolventizing tower, is distilled at normal pressure, the hydrosolvent distilled from the tower top is recycled to re-dilute the furfural, and the product at the tower bottom entersThe heavy by-product is removed by a rectifying tower to obtain the high-purity tetrahydrofurfuryl alcohol with the purity>99.8％。
Claims (1)
1. A method for preparing tetrahydrofurfuryl alcohol by adopting a two-section fully mixed flow series kettle type reactor in one step is characterized by comprising the following steps:
takes 5-30 wt.% furfural water solution as raw material, adopts two-section fully mixed flow series kettle type reactor, takes eggshell type nickel base alloy catalyst, and has the reaction temperature of 80-180 DEGoC, hydrogen pressure is 0.5-7MPa, after the reaction lasts for 2-5h, the reaction solution is distilled under normal pressure through a desolventizing tower, the water solvent distilled from the top of the tower is circulated to re-dilute the furfural, the product at the bottom of the tower enters a rectifying tower, heavy byproducts are removed, and high-purity tetrahydrofurfuryl alcohol is obtained;
the eggshell type nickel-based alloy catalyst is characterized in that the nickel-based alloy is NiM, and M is one or more than two of Cu, Fe, Co and Zn;
the molar ratio of Ni to M is 3:1, the mass content of Ni is 5-30 wt.%, and the carrier is carbon microsphere and TiO2Microspheres, Al2O3One of the microspheres.
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