CN111229204A - Application of bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol - Google Patents
Application of bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 83
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 title claims abstract description 41
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229940043375 1,5-pentanediol Drugs 0.000 title claims abstract description 29
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000032683 aging Effects 0.000 claims abstract description 3
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 4
- 229910003091 WCl6 Inorganic materials 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000004729 solvothermal method Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 229910001510 metal chloride Inorganic materials 0.000 claims 1
- 229910001960 metal nitrate Inorganic materials 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000007327 hydrogenolysis reaction Methods 0.000 abstract description 13
- 238000001354 calcination Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 11
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 9
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000001294 propane Substances 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- 239000010948 rhodium Substances 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- -1 cyclopentenol epoxide Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical class C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 230000001609 comparable effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003247 decreasing effect Effects 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
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical class C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IBMRTYCHDPMBFN-UHFFFAOYSA-N monomethyl glutaric acid Chemical compound COC(=O)CCCC(O)=O IBMRTYCHDPMBFN-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- XNHGKSMNCCTMFO-UHFFFAOYSA-D niobium(5+);oxalate Chemical compound [Nb+5].[Nb+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O XNHGKSMNCCTMFO-UHFFFAOYSA-D 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical class CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Images
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- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
Abstract
The patent relates to the use of a bimetallic catalyst in the preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol, the catalyst consisting of WOxThe carrier is loaded with active components of Pt (or Rh) and Mo (or Au). The preparation method of the catalyst comprises the following steps: a) solvothermal preparation of catalyst support WOx(ii) a b) Impregnating WO with precursor solution of Pt (or Rh)xAfter drying and reduction, M is obtained1/WOx(ii) a c) The prepared Pt/WOxAdding the catalyst into Mo (or Au) precursor solution, aging, drying, calcining and reducing to obtain the final catalyst M2‑M1/WOx. The catalyst prepared by the patent can greatly reduce the hydrogen pressure in the reaction process, so that the tetrahydrofurfurylThe aqueous alcohol solution is subjected to hydrogenolysis at low pressure with high selectivity to produce 1, 5-pentanediol. And the catalyst has excellent stability.
Description
Technical Field
The invention relates to an application of a bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol; in particular to WOxThe support carries the active components Pt (or Rh) and Mo (or Au). The invention relates to a preparation method and application of the catalyst, in particular to a method for preparing WO by adopting a solvothermal methodxThe carrier adopts an impregnation method to carry active components Pt (or Rh) and Mo (or Au), and the activity and the selectivity of the catalyst in the preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol under different preparation and reaction conditions are examined.
Background
The 1, 5-pentanediol is a widely applied chemical product, can be used as a raw material of novel polyester, coating, adhesive, plasticizer and sealant, and can also be directly used as cutting oil, detergent, wetting agent and special solvent. The method for synthesizing the 1, 5-pentanediol mainly comprises the following steps: (1) tetrahydrofurfuryl alcohol is used as a raw material to prepare 1, 5-pentanediol through direct hydrogenation ring opening, the pressure range is 8MPa-42MPa, the temperature is 120-330 ℃, the method has high reaction pressure, large equipment investment and high operation difficulty (chem.Comm.2009); (2) the cyclopentenol epoxide is prepared by the photo-oxidation of cyclopentadiene, and then 1, 5-pentanediol is prepared by hydrogenation at 70-100 ℃ and about 6MPa, but the efficiency of the photo-oxidation preparation of cyclopentadiene is low, so that the economy is not high; (3) firstly, glutaric acid is adopted as a raw material to prepare 1, 5-methyl glutarate, and then 1, 5-pentanediol is prepared by hydrogenation under the action of a copper-zinc-aluminum catalyst at 350 ℃ and 3-5MPa, wherein the conversion rate is more than 95 percent, and the selectivity of the 1, 5-pentanediol is more than 95 percent (Chinese patent CN1565728A), but the process flow is long, and the cost of the glutaric acid is high; (4) substituted vinyl ether and substituted acrolein react to generate substituted 3, 4-dihydropyran, then glutaraldehyde is prepared by catalytic hydrolysis, and then substituted pentanediol is generated by hydrogenation (Chinese patent CN1072168A), wherein the catalyst adopts Raney nickel, modified Raney nickel, and alumina loaded with platinum, palladium or nickel. The method has long technical route and high cost. (5) Ru is adopted as an active component supported catalyst, 1, 5-glutaraldehyde is adopted as a raw material, 1, 5-pentanediol is prepared by hydrogenation under mild reaction conditions at 60-120 ℃ and 2MPa-8MPa, the conversion rate and the selectivity are high, but the cost of the raw material used in the technology is high (Chinese patent CN 101270032A).
In conclusion, the reaction conditions of the existing method for preparing 1, 5-pentanediol are harsh, so that the initial investment cost of the device is high, the operation difficulty is high, and the reaction cost is greatly increased; in addition, the raw materials adopted by the methods have high cost and are all based on fossil energy, and the difficulty that the fossil energy is increasingly exhausted is faced at present.
Disclosure of Invention
The invention provides an application of a bimetallic catalyst in preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol, the bimetallic catalyst can greatly reduce reaction pressure, and the product 1, 5-pentanediol has high selectivity and good catalyst stability.
The catalyst carrier is WO synthesized by a solvothermal methodxThe preparation method comprises the following steps: 1-3g WCl6Dissolving in 100-200mL absolute ethanol until WCl is obtained6After complete dissolution, transferring the solution into a hydrothermal kettle, placing the hydrothermal kettle in an oven at the temperature of 140-x(2.65<x<2.95)。
Sequentially loading Pt (or Rh) and Mo (or Au) as active components on WO (tungsten oxide) by adopting an impregnation methodxOn a carrier;
1) firstly, a Pt (or Rh) precursor solution is impregnated into WOxActive component Pt (or Rh) is loaded on the carrier, after drying for 4-10 hours at 40-100 ℃, the catalyst is reduced for 0.5-5 hours at 100-600 ℃ under the atmosphere of hydrogen, and the prepared catalyst is named as M1/WOx(M1Represents Pt or Rh).
2) Then M is added1/WOxAdding the catalyst into Mo (or Au) precursor solution, aging for 6-24 hours, drying for 2-10 hours, roasting for 0.5-5 hours at 300-600 ℃ air atmosphere, and reducing for 0.5-3 hours at 200-500 ℃ in hydrogen atmosphere to obtain the catalyst named as M2-M1/WOx(M2Represents Mo or Au).
The catalyst is applied to the reaction for preparing 1, 5-pentanediol by hydrogenolysis of tetrahydrofurfuryl alcohol aqueous solution, and the reaction conditions are as follows: the reaction is carried out in an intermittent kettle type reactor, the mass concentration range of the tetrahydrofurfuryl alcohol is 1 to 99.9 percent, the hydrogen pressure is 0.1 to 10MPa, the reaction temperature is 100 ℃ and 300 ℃, the reaction time is 4 to 48 hours, and the dosage of the catalyst is 0.05 to 0.5 g; the mass concentration range of the tetrahydrofurfuryl alcohol is preferably 1-30%, the hydrogen pressure is preferably 0.1-5MPa, the reaction temperature is preferably 120-160 ℃, and the reaction time is preferably 12-24 h.
The invention has the advantages of simple catalyst preparation method, simple and convenient recovery, easy product separation, high reaction activity and selectivity for preparing 1, 5-pentanediol from tetrahydrofurfuryl alcohol, catalyst stability and the like.
The catalyst prepared by the patent can greatly reduce the hydrogen pressure in the reaction process, so that the tetrahydrofurfuryl alcohol aqueous solution is subjected to hydrogenolysis at low pressure with high selectivity to generate the 1, 5-pentanediol. And the catalyst has excellent stability.
Drawings
FIG. 1 vector WOxAnd (6) topography.
FIG. 2 vector WOxPore structure and pore size distribution profile.
FIG. 30.1 Mo/4Pt/WOxCatalyst stability test chart.
Detailed Description
Example 1WOxPreparation of the support
3g of WCl6Dissolving in 100mL of absolute ethyl alcohol until WCl is obtained6After complete dissolution, the solution is quickly transferred into a hydrothermal kettle with a lining, the hydrothermal kettle is placed in a preheated temperature oven for a certain time (T hydrothermal temperature (DEG C) and T hydrothermal time (h) are respectively 120 ℃, 36h, 140 ℃, 36h, 160 ℃, 36h, 180 ℃, 36h, 200 ℃, 36h, 160 ℃, 12h, 160 ℃, 24h, 160 ℃, 48h, 160 ℃ and 72h), then the hydrothermal kettle is naturally cooled to room temperature, washed 3 times by absolute ethyl alcohol and deionized water, and then the hydrothermal kettle is placed in a 50 ℃ vacuum drying oven for drying to obtain the carrier WO with a large needle-shaped specific surfacex-T-t(2.72<x<2.84, T is hydrothermal temperature (DEG C), and T is hydrothermal time (h), the same as below. WOx-160-36 support morphologySee fig. 1, and the pore structure is shown in fig. 2.
EXAMPLE 2 preparation of one-component Metal catalyst
Respectively soaking chloroplatinic acid solution serving as a precursor on the carrier prepared by the alcohol heating method in the embodiment 1 in equal volume, drying the carrier for 6 hours in vacuum at 50 ℃, and reducing the carrier for 1 hour at 300 ℃ in hydrogen atmosphere to obtain the catalyst yPt/WOx-T (y is the mass fraction of supported metal, y is 4%).
As above, various amounts of chloroplatinic acid were supported in WO 1 in example 1 without changing other conditionsx160-36 on a support to obtain catalyst yPt/WOx(y is the mass fraction of the supported metal, and y is 1%, 2%, 6%, 8%, 10%).
As above, while the other conditions were not changed, rhodium chloride, palladium chloride, iridium chloride and ruthenium chloride were supported on WO of example 1 while changing the added active ingredient precursorx160-36 on a support to obtain catalyst yRh/WOx,yPd/WOx,yIr/WOx,yRu/WOx(y is the mass fraction of the supported metal, and y is 4%).
In the same manner as above, respectively, in WO3,CeO2,TiO2,Ta2O5,Nb2O5,SiO2,Al2O3As a carrier, yPt/WO is prepared3,yPt/CeO2,yPt/TiO2,yPt/Ta2O5,yPt/Nb2O5,yPt/SiO2,yPt/Al2O3Catalyst (y is the mass fraction of the supported metal, and y is 4%).
EXAMPLE 3 preparation of bimetallic catalyst
The solution of ammonium molybdate was used as a precursor and dipped in the same volume of 4% Pt/WO solution prepared in example 2xAging on a-T-T catalyst for 16h, drying at 120 ℃ for 12h, roasting at 400 ℃ for 1 h in an air atmosphere, and reducing at 300 ℃ for 1 h in a hydrogen atmosphere to obtain zMo/yPt/WOxT-T, catalyst (z is the atomic ratio of the supported second component metal to the first component metal, z is 0.01,0.05,0.1,0.2,0.5,1.0, 2.0; y is approximately equal to 4%).
As above, othersThe ammonium molybdate solution precursor was loaded on the non-4% Pt/WOx single metal catalyst prepared in example 2 above, with unchanged conditions, to yield zMo/yPt/WOx-T (y ═ 1%, 2%, 6%, 8%, 10%); and zMo/yRh/WOx,zMo/yPd/WOx,zMo/yIr/WOx,zMo/yRu/WOx,zMo/yPt/WO3,zMo/yPt/CeO2,zMo/yPt/TiO2,zMo/yPt/Ta2O5,zMo/yPt/Nb2O5,zMo/yPt/SiO2,zMo/yPt/Al2O3Catalyst (z is the atomic ratio of the supported second component metal to the first component metal, z is 0.1, and y is approximately equal to 4%).
As above, other conditions were not changed, and only the added salts containing the active ingredient were changed to carry chloroauric acid, ferric nitrate, niobium oxalate, ammonium tungstate, and tantalum chloride, respectively, to 4Pt/WO prepared in example 2 abovexOn a catalyst, zAu/yPt/WO is obtainedx,zFe/yPt/WOx,zNb/yPt/WOx,zW/yPt/WOx,zTa/yPt/WOxCatalyst (z is the atomic ratio of the supported second component metal to the first component metal, z is 0.1, and y is approximately equal to 4%).
Example 4 catalyst Performance testing
An intermittent reaction kettle is selected, the mass concentration of the tetrahydrofurfuryl alcohol aqueous solution is 5% (the total solution is 8g), the catalyst amount is 0.3g, the reaction temperature is 140 ℃, the reaction pressure is 1MPa, and the reaction time is 12 h.
Example 5 catalyst stability testing
Selecting a fixed bed reactor, wherein the mass concentration of the tetrahydrofurfuryl alcohol aqueous solution is 5 percent, the catalyst amount is 4.5g, and the gas airspeed is 1000h-1Liquid space velocity of 0.6h-1The reaction temperature was 140 ℃ and the reaction pressure was 2MPa, and the test results are shown in FIG. 3.
Example 6 support WO prepared under different hydrothermal conditionsxThe catalyst activity was contrasted, as shown in Table 1, and the reaction conditions were the same as in example 4.
TABLE 1 Supports WO prepared under different hydrothermal conditionsxInfluence on catalyst Activity
Note: the reaction temperature is 140 ℃, the pressure is 1MPa, the mass concentration of the tetrahydrofurfuryl alcohol is 5%, the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 1, the carrier WO synthesized under the hydrothermal condition of 160 ℃ and 36hxThe prepared catalyst has optimal performance.
Example 7 different active metals have a comparable effect on catalyst activity, as shown in table 2, under the same reaction conditions as in example 4.
TABLE 2 Effect of different active metals on catalyst Activity
Note: the reaction temperature is 140 ℃, the pressure is 1MPa, the mass concentration of the tetrahydrofurfuryl alcohol is 5%, the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 2, 0.1Mo/4Pt/WOxThe catalyst has the highest activity on the hydrogenolysis of tetrahydrofurfuryl alcohol and the best selectivity on 1, 5-pentanediol. While 0.1Mo/4Rh/WOxThe catalyst also has certain activity and selectivity for tetrahydrofurfuryl alcohol hydrogenolysis. And 0.1Mo/4Pd/WOx,0.1Mo/4Ir/WOxAnd 0.1Mo/4Ru/WOxThe catalyst has low activity for hydrogenolysis of tetrahydrofurfuryl alcohol and low selectivity for 1, 5-pentanediol.
Example 8a comparison of the effect of different supports on the catalyst activity is given in table 3, under the same reaction conditions as in example 4.
TABLE 3 Effect of different supports on catalyst Activity
Note: the reaction temperature is 140 ℃, the pressure is 1MPa, the concentration of tetrahydrofurfuryl alcohol is 5%, and the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 3, WOxWhen the catalyst is used as a carrier, the catalyst activity and the selectivity of 1, 5-pentanediol are optimal.
Example 9 the effect of the addition of the second metal on the catalyst activity is compared and is shown in table 4, with the same reaction conditions as in example 4.
TABLE 4 Effect of the addition of the second Metal on the catalyst Activity
Note: the reaction temperature is 140 ℃, the pressure is 1MPa, the concentration of tetrahydrofurfuryl alcohol is 5%, and the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 4, the addition of the second metals Mo, Au and Nb has an effect of promoting the selective hydrogenolysis performance of tetrahydrofurfuryl alcohol, and both the reaction conversion rate and the selectivity can be improved. Among them, Mo has the best promoting effect, and Au has the second order.
Example 10 different Pt loadings were compared to the catalyst activity as shown in table 5 and the reaction conditions were the same as in example 4.
TABLE 5 Effect of different Pt loadings on catalyst Activity
Note: the reaction temperature is 140 ℃, the pressure is 1MPa, the concentration of tetrahydrofurfuryl alcohol is 5%, and the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 5, the yield of 1, 5-pentanediol increased and then decreased as the Pt loading increased. When the loading of Pt is 4%, the catalyst activity and selectivity are optimal.
Example 11 different Mo loadings have a comparable effect on catalyst activity as shown in table 6 and the reaction conditions are the same as in example 4.
TABLE 6 influence of different Mo loadings on catalyst activity
Note: the reaction temperature is 140 ℃, the pressure is 1MPa, the concentration of tetrahydrofurfuryl alcohol is 5%, and the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 6, the yield of 1, 5-pentanediol increased and then decreased as the Mo loading increased. When the atomic ratio of Mo to Pt was increased to 0.1, the catalyst activity and selectivity were optimized.
Example 12 the activity of the catalyst was tested at different tetrahydrofurfuryl alcohol concentrations, as shown in Table 7, and the reaction conditions were the same as in example 4.
TABLE 7 catalyst Activity test at different tetrahydrofurfuryl alcohol concentrations
Note: the catalyst used was 0.1Mo/4Pt/WOxThe reaction temperature is 140 ℃, the pressure is 1MPa, and the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 7, the activity of the catalyst on the hydrogenolysis of tetrahydrofurfuryl alcohol decreases with increasing concentration of the reactant tetrahydrofurfuryl alcohol, but the selectivity to 1, 5-pentanediol remains unchanged.
Example 13 the effect of different hydrogen pressures on tetrahydrofurfuryl alcohol hydrogenolysis activity is shown in table 8, the reaction conditions are the same as in example 4.
TABLE 8 influence of different hydrogen pressures on the tetrahydrofurfuryl alcohol hydrogenolysis activity
Note: the catalyst used was 0.1Mo/4Pt/WOxThe reaction temperature is 140 ℃, and the tetrahydrofurfuryl isThe alcohol concentration is 5%, others include small amounts of methane, ethane, propane, methanol, ethanol, tetrahydropyran, tetrahydrofuran, and overall material conservation.
As can be seen from table 8, the catalyst showed the highest activity for tetrahydrofurfuryl alcohol hydrogenolysis at lower hydrogen pressures (1 MPa).
Example 14 the effect of different reaction temperatures on tetrahydrofurfuryl alcohol hydrogenolysis activity is shown in table 9 with the same reaction conditions as in example 4.
TABLE 9 influence of different reaction temperatures on the hydrogenolysis activity of tetrahydrofurfuryl alcohol
Note: the catalyst used was 0.1Mo/4Pt/WOxThe pressure is 1MPa, the tetrahydrofurfuryl alcohol concentration is 5%, and the others comprise a small amount of methane, ethane, propane, methanol, ethanol, tetrahydropyran and tetrahydrofuran, and the total material is conserved.
As can be seen from Table 9, the conversion of tetrahydrofurfuryl alcohol increases with increasing reaction temperature, but the selectivity to 1, 5-pentanediol decreases. The yield of 1, 5-pentanediol reached a maximum at a temperature of 140 ℃.
Claims (8)
1. The application of the bimetallic catalyst in the preparation of 1, 5-pentanediol from tetrahydrofurfuryl alcohol is characterized in that: the catalyst is prepared by using WOxIs a carrier (2.65)<x<2.95), the active components are Pt (or Rh) and Mo (or Au); preferably, the active components are Pt and Mo;
wherein the Pt (or Rh) content is about 1% to 10%, preferably 2% to 6%, by weight of the catalyst; the atomic ratio of Mo (or Au) to Pt (or Rh) is 0.01 to 2, preferably 0.05 to 0.5.
2. Use according to claim 1, characterized in that: its vector WOxThe preparation method adopts a solvothermal method, and comprises the following specific steps:
1-3g WCl6Dissolving in 100-200mL absolute ethanol until WCl is obtained6After complete dissolution, the solution is transferred into a hydrothermal kettle and is dried in an oven at 140-Standing for 24-48h (preferably 30-40h), cooling to room temperature, vacuum filtering, washing, and drying to obtain carrier WOx(2.65<x<2.95)。
3. Use according to claim 1 or 2, characterized in that: vector WOxThe morphology is a needle-shaped stack (about 290 nm long and 300nm diameter, 4-5nm diameter), and the specific surface area is approximately equal to 120m2G, pore volume is about 0.07m3/g。
4. A use as claimed in any one of claims 1 to 3, wherein: sequentially loading active components Pt or Rh and Mo or Au on WO by adopting an impregnation methodxOn a carrier;
1) firstly, a Pt or Rh precursor solution is impregnated into WOxActive component Pt (or Rh) is loaded on the carrier, after drying for 4-10 hours at 40-100 ℃, the catalyst is reduced for 0.5-5 hours at 100-600 ℃ under the atmosphere of hydrogen, and the prepared catalyst is named as M1/WOx,M1Represents Pt or Rh;
2) then M is added1/WOxAdding the catalyst into Mo or Au precursor solution, aging for 6-24 hours, drying for 2-10 hours, roasting for 0.5-5 hours at 300-600 ℃ air atmosphere, and reducing for 0.5-3 hours at 200-500 ℃ in hydrogen atmosphere, wherein the prepared catalyst is named as M2-M1/WOx,M2Represents Mo or Au.
5. Use according to claim 4, characterized in that: the selected Pt or Rh metal precursor is one or more than two of soluble metal chloride, nitrate and organic complex, and the solution molar concentration is 0.05-5M; the selected Mo or Au soluble metal precursor is one or more than two of chloride, nitrate and organic complex thereof, and the solution molar concentration is 0.001-1M.
6. Use according to any one of claims 1 to 5, characterized in that: the catalyst is used in the reaction of preparing 1, 5-pentanediol from tetrahydrofurfuryl alcohol, the reaction raw material is tetrahydrofurfuryl alcohol aqueous solution, the mass concentration range of the tetrahydrofurfuryl alcohol is 1-99.9%, the hydrogen pressure is 0.1-10MPa, the reaction temperature is 100-300 ℃, and the reaction time is 4-48 h.
7. Use according to claim 6, characterized in that: the mass concentration of the tetrahydrofurfuryl alcohol is preferably 1-30%, the hydrogen pressure is preferably 0.1-5MPa, the reaction temperature is preferably 120-160 ℃, and the reaction time is preferably 12-24 h.
8. Use according to claim 6, characterized in that: the mass ratio of the catalyst dosage to the tetrahydrofurfuryl alcohol is 0.05-0.5.
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