CN108607553A - A kind of hydrogenolysis of glycerin prepares catalyst and preparation and the application of 1,3- propylene glycol - Google Patents
A kind of hydrogenolysis of glycerin prepares catalyst and preparation and the application of 1,3- propylene glycol Download PDFInfo
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- CN108607553A CN108607553A CN201611127797.7A CN201611127797A CN108607553A CN 108607553 A CN108607553 A CN 108607553A CN 201611127797 A CN201611127797 A CN 201611127797A CN 108607553 A CN108607553 A CN 108607553A
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- hydrogenolysis
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 26
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000001052 transient effect Effects 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 3
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract 2
- 239000002243 precursor Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000010955 niobium Substances 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000001802 infusion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- 239000012752 auxiliary agent Substances 0.000 claims 2
- 229910052723 transition metal Inorganic materials 0.000 claims 2
- 150000003624 transition metals Chemical group 0.000 claims 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 238000005342 ion exchange Methods 0.000 claims 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims 1
- -1 catalyst carrier Nb Chemical class 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 abstract 1
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 4
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003225 biodiesel Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910019804 NbCl5 Inorganic materials 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229910003091 WCl6 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- BSABBBMNWQWLLU-UHFFFAOYSA-N lactaldehyde Chemical compound CC(O)C=O BSABBBMNWQWLLU-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000002503 metabolic effect Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CMDGQTVYVAKDNA-UHFFFAOYSA-N propane-1,2,3-triol;hydrate Chemical compound O.OCC(O)CO CMDGQTVYVAKDNA-UHFFFAOYSA-N 0.000 description 1
- 229960004063 propylene glycol Drugs 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The patent is related to a kind of catalyst and preparation method thereof of 1,3 propylene glycol of hydrogenolysis of glycerin preparation, and catalyst is made of the carrier loaded active component Pt of the transient metal doped tungsten oxide such as Nb, Ta, Pd or promoter metal.The preparation method of catalyst includes：A) hydro-thermal method or solvent-thermal method prepare the transient metal doped tungsten oxides such as catalyst carrier Nb, Ta；B) Pt, the precursor solution impregnated catalyst support of Pd or promoter metal is used simultaneously to dry reduction, obtain Pt, Pd or promoter metal/transient metal doped type tungsten oxide catalyst.Catalyst obtained by the patent, can making glycerine water solution, hydrogenolysis generates 1,3 propylene glycol with high selectivity within the scope of larger Hydrogen Vapor Pressure range and larger temperature.
Description
The present invention relates to the catalyst that a kind of hydrogenolysis of glycerin prepares 1,3- propylene glycol；Specially use hydro-thermal or solvent heat side
Method prepares transient metal doped tungsten oxide carrier, and active noble metal constituent is supported using infusion process, obtains your gold of high dispersive
Belong to catalyst-loaded.
Technical background
With the rapid development of biodiesel, the by-product glycerin produced in biodiesel process is excessive, and conversion is sweet
Oil, which prepares high value chemicals, becomes the effective means for promoting Biodiesel economy.Glycerine can be given birth to by hydrogenolysis
At 1,3-PD, 1,2-PD etc., wherein 1,3-PD is the important of production polypropylene terephthalate (PTT)
Monomer.PTT is a kind of new type polyester fiber with biodegradability, it overcomes polyethylene terephthalate
(PET) too hard and too soft polybutylene terephthalate (PBT) (PBT) disadvantage, while there is excellent resilience, chromatophilia is raw
Object degradability etc. has huge development potentiality in industries such as carpet, Textile Engineering plastics.
At present the industrial process of 1,3- propylene glycol have Shell companies oxirane carbonyl hydrogenation method and
The acrolein hydration hydrogenation method of Degussa and Dupont companies.Oxirane carbonyl hydrogenation method (Chinese patent
CN1201407A) use ethylene oxide under cobalt-base catalyst with synthesis gas generate 3-HPA, then by 3-HPA with
The method that hydrogen is hydrogenated to 1,3- propylene glycol under hydrogenation catalyst effect.Acrolein hydration method (Chinese patent
CN93114516.3 it) is dehydrated under solid acid catalyst using gaseous state glycerine hydrate and generates methacrylaldehyde, the methacrylaldehyde of generation exists
Hydration generates 3-HPA under acidic catalyst effect, and the 3-HPA of the generation Hydrogenation under conventional hydrogenation catalyst is standby
1,3-PD, while by-product 1,2-PD.Above-mentioned industrial manufacture process is complicated, and environmental pollution is serious, gained 1,3- the third two
Alcohol contains impurity, needs further purified treatment.
Document (Appl.Microbiol.Biotechnol.1992,36,592-597) reports a kind of use
The method that Clostridiurn strain bio conversions prepare 1,3-PD can turn the glycerite of 110g/L after 29h
Change obtains the 1,3-PD of 56g/L, and this method is influenced by biological metabolic activities, low production efficiency, and due to
Production concentration is low, and the energy consumption needed for purifies and separates 1,3-PD is also very high.Document (Catal.Commun.2008,9,1360-
1363) a kind of in the case where 1,3-Dimethyl-2-imidazolidinone is solvent, the method that hydrogenolysis of glycerin prepares 1,3-PD is reported,
The yield of the method 1,3- propylene glycol is 24%.Organic solvent is used in above-mentioned reaction as reaction medium, and is used
Adding liquid acid method, do not meet the requirement of Green Chemistry.
The direct hydrogenolysis of glycerine prepares 1,3-PD and has obtained very big concern in recent years, because it is simple for process, raw material is honest and clean
Valence.But the reaction cascade reaction that 1,3-PD is prepared by the direct hydrogenolysis of glycerine is reacted and is deposited with parallel connection, 1,3-PD is made
For intermediate product, its generation takes off hydroxyl by glycerine first and generates carbonium ion, and slough carbon that intermediate hydroxyl generates just from
Son wants more stable, is that dynamics is preferential, and the hydroxy propanal generated thereafter is thermodynamically unstable, phase between the two
Mutually competition is also the key for generating 1,3.The formation mechanism of 1,3- propylene glycol makes the efficient preparation presence of 1,3- propylene glycol very big
Challenge.
Invention content
The present invention provides a kind of direct hydrogenolysis of glycerine and prepares catalyst of 1,3-PD and preparation method thereof, with existing skill
Art is compared, and the inventive technique is under very wide reaction condition window, the selectivity with good 1,3-PD, effectively
Reduce the generation of 1,2- propylene glycol.
Patent of the present invention provides the catalyst that a kind of hydrogenolysis of glycerin prepares 1,3-PD, and catalyst carrier is hydro-thermal or molten
The tungsten oxide of Nb or/and the Ta doping of the hot method synthesis of agent, doping metals mass content is the 0.01%-30% of W weight；Activearm
It is divided into platinum group metal Pt or/and Pd, the mass content of active component is the 0.01%-10% of catalyst weight.
The preparation method of the tungsten oxide of the carrier Nb or/and Ta doping of catalyst of the present invention is：
By the presoma of tungsten and niobium or/and tantalum in proportion (1:0.0001~0.3) it is dissolved in solvent, after it is completely dissolved
Solution is transferred in the water heating kettle with liner, this water heating kettle is placed 6h-1 weeks in 40-200 DEG C of preheated baking oven,
Then cooled to room temperature, after suction filtration for several times with absolute ethyl alcohol and deionized water successively washing, then conventional drying, freezing are dry
Dry or vacuum drying carrier Nb or/and Ta doping tungsten oxide.
Using preparation catalyst.With chloroplatinic acid or/and the tungsten oxide of chlorine palladium acid solution dipping Nb or/and Ta doping
Supported carrier active component Pt or/and Pd, after conventional drying, freeze-drying or vacuum drying, the H at 100-600 DEG C2Reduction,
Catalyst is made.
Catalyst is prepared applied to glycerine water solution hydrogenolysis in 1,3-PD reaction, and reaction condition is as follows：Reaction be
It is carried out in intermittent tank reactor, glycerine water solution mass concentration is 1-99.9%, and reaction temperature is 100-300 DEG C, preferably
It it is 110-200 DEG C, glycerine is 0.5-50 hours, preferably 6-24 hours with the catalyst reaction time.
Compared with prior art, the present invention the selectivity that hydrogenolysis of glycerin prepares 1,3-PD can be improved, glycerine is improved
Conversion ratio, effectively inhibits the generation of 1,2-PD, and widens reaction pressure window, improves stability.
Description of the drawings
The pattern of Fig. 1 carrier Nb- tungsten oxides：A, c are 0.1%Nb- tungsten oxide carrier patterns；B, d are 2%Nb- tungsten oxides
Carrier pattern.
Specific implementation mode
The preparation of embodiment 1-Nb- tungsten oxide carriers
Nb- tungsten oxides (Nb is prepared using solvent-thermal method：W=0.1%, 2%, 5%) carrier, specific preparation process are：It will
WCl6And NbCl5(1:0.001~0.1) it is dissolved in absolute ethyl alcohol, waits for WCl6And NbCl5By yellow transparent solution after being completely dissolved
It is transferred in the water heating kettle with liner rapidly, it (is herein 24 that this water heating kettle places 6-36h in 160 DEG C of preheated baking ovens
Hour), then cooled to room temperature is then placed in 50 DEG C of vacuum drying with absolute ethyl alcohol and deionized water successively washing 3 times
Case it is dry carrier Nb- tungsten oxides.Its pattern is shown in attached drawing 1.
The preparation of embodiment 2- catalyst
By on platinum acid chloride solution incipient impregnation to Nb- tungsten oxide carriers, room temperature is dried in the shade, and the loading of Pt is 2%, 50 DEG C
After baking oven is dried in vacuo 6h, Hydrogen activation, activation condition is 300 DEG C, hydrogen flowing quantity 60ml/min, soak time 1h, system
Obtain 2%Pt/Nb- tungsten oxide catalysts.
Embodiment 3- catalyst performances are tested
It is 5% (the total 12g of solution) to select batch reactor, glycerine water solution mass concentration, and catalytic amount is that 0.3g (is urged
Agent is 1 with qualities of glycerin ratio:2), reaction temperature is 160 DEG C, reaction pressure 1MPa, reaction time 12h.Test result
It is shown in Table 1.
Embodiment 4- catalyst performances are tested
It is 5% (the total 12g of solution) to select batch reactor, glycerine water solution mass concentration, and catalytic amount is that 0.3g (is urged
Agent is 1 with qualities of glycerin ratio:2), reaction temperature is 160 DEG C, reaction pressure 5MPa, reaction time 12h.Test result
It is shown in Table 1.
1 hydrogenolysis of glycerin of table prepares the catalytic performance of 1,3- propylene glycol
* other include a small amount of methane, ethane, propane, methanol, ethyl alcohol, ethylene glycol, acetone, hydroxypropanone-, and overall material is kept
It is permanent.
Claims (9)
1. a kind of hydrogenolysis of glycerin prepares the catalyst of 1,3-PD, it is characterised in that：The catalyst carrier is transition metal
The tungsten oxide material of doping, active component are platinum group metal or platinum group metal and its auxiliary agent；
Transient metal doped amount is the 0.01%-30% of W weight, and platinum group metal is Pt or/and Pd, and the content of platinum group metal is
The 0.01%-10% of catalyst weight.
2. catalyst according to claim 1, it is characterised in that：Auxiliary agent is one kind or two kinds in Mo, Au, Fe, La, Al
More than, weight is the 0.01%-0.5% of platinum group metal weight.
3. catalyst according to claim 1, it is characterised in that：The transition metal of doping is Nb or/and Ta.
4. catalyst according to claim 2, it is characterised in that：Transient metal doped tungsten oxide uses hydro-thermal method or molten
The hot method of agent prepares；
It is dissolved in solvent by tungsten, with the presoma of niobium or/and tantalum, solution is transferred to the kettle with liner after it is completely dissolved
In, this kettle is placed 6h-1 weeks in 40-200 DEG C of preheated baking oven, then cooled to room temperature, with anhydrous second after suction filtration
Successively washing 2-8 time of alcohol and deionized water, the tungsten oxide that then dry carrier Nb or/and Ta are adulterated.
Selected solvent is the one or two or more kinds in water, ethyl alcohol, normal propyl alcohol, isopropanol or acetone.
5. catalyst according to claim 4, it is characterised in that：Drying mode is conventional drying, freeze-drying or vacuum
It is dry.
6. the preparation method of catalyst described in a kind of claim 1-5, it is characterised in that：The side of supporting of catalyst activity noble metal
Method is equi-volume impregnating, excessive infusion process, vacuum impregnation technology or ion-exchange.
7. the preparation method of catalyst according to claim 6, it is characterised in that：The reduction temperature of catalyst is 100-600
℃；Selected platinum group metal is Pt or/and Pd.Noble metal precursor is the solution such as chloroplatinic acid, chlorine palladium acid, solution molar concentration 0.05-
5M。
8. the application of catalyst described in a kind of claim 1-5, it is characterised in that：The catalyst prepares 1 for hydrogenolysis of glycerin,
In 3-propanediol reaction, reaction raw materials are glycerine water solution, mass concentration ranging from 1-99.9%.
9. the application of catalyst according to claim 8, it is characterised in that：Hydrogen Vapor Pressure is 0.1-10MPa, and reaction temperature is
100-300℃。
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611127797.7A CN108607553B (en) | 2016-12-09 | 2016-12-09 | Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenolysis, preparation and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611127797.7A CN108607553B (en) | 2016-12-09 | 2016-12-09 | Catalyst for preparing 1, 3-propylene glycol by glycerol hydrogenolysis, preparation and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036203A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Niobium-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102728380A (en) * | 2012-05-08 | 2012-10-17 | 中国科学院大连化学物理研究所 | Catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis, preparation method thereof, and application thereof |
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| CN111036203A (en) * | 2018-10-15 | 2020-04-21 | 中国石油化工股份有限公司 | Niobium-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method |
| CN111036203B (en) * | 2018-10-15 | 2023-04-11 | 中国石油化工股份有限公司 | Niobium-containing catalyst, preparation method and application thereof, and glycerol hydrogenolysis method |
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