CN103524302A - Technological method for preparing 1, 3-propylene glycol by adopting glycerin and hydrogen - Google Patents
Technological method for preparing 1, 3-propylene glycol by adopting glycerin and hydrogen Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 13
- 239000001257 hydrogen Substances 0.000 title claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 12
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000006227 byproduct Substances 0.000 claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 9
- 239000000047 product Substances 0.000 claims abstract description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 18
- 238000003672 processing method Methods 0.000 claims description 14
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000001994 activation Methods 0.000 claims description 6
- OJYBUGUSFDKJEX-UHFFFAOYSA-N tungsten zirconium Chemical compound [Zr].[W].[W] OJYBUGUSFDKJEX-UHFFFAOYSA-N 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 239000012263 liquid product Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000008016 vaporization Effects 0.000 claims description 3
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 5
- 229910052796 boron Inorganic materials 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 1
- 238000005373 pervaporation Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- -1 terephthalic acid propylene diester Chemical class 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 239000011968 lewis acid catalyst Substances 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 230000004992 fission Effects 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 150000007517 lewis acids Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 229920004935 Trevira® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000001020 rhythmical effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- HAIMOVORXAUUQK-UHFFFAOYSA-J zirconium(iv) hydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[Zr+4] HAIMOVORXAUUQK-UHFFFAOYSA-J 0.000 description 1
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- 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
-
- 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
Abstract
The invention relates to a technological method for preparing 1, 3-propylene glycol by adopting glycerin and hydrogen. A catalyst is Pt/B2O3-WO3-ZrO2, and the mass ratio of elements of Pt, B, W and Zr is (1-4): (0.1-2): 10: (58-65); and glycerin and hydrogen are fed into a fixed bed reactor simultaneously and react at the temperature ranging from 100 DEG C to 150 DEG C under the pressure ranging from 2 MPa to 5 MPa, the resultants of reaction are subjected to gas-liquid separation, water in a liquid-phase product is separated and removed by a pervaporation membrane, a rectifying tower is used for separation, 1,3-propylene glycol, by-products containing 1,2-propylene glycol, normal propyl alcohol and isopropyl alcohol and non-converted glycerin are obtained, glycerin and a part of the by-products are circularly returned to the reactor, and the mass ratio of the circulation volume of the by-products to feeding glycerin is 0.25-1.5. According to the technological method, the reaction condition is temperate, the producing speed of 1, 3-propylene glycol is high, and 1, 3-propylene glycol can be prepared stably.
Description
Technical field
The present invention relates to a kind ofly take glycerine as the processing method of raw material Hydrogenation for 1,3-PD.
Background technology
1, ammediol is a kind of important industrial chemicals, mainly can be used as the macromolecular material of the synthetic excellent performance of polymer monomer, with 1, ammediol is the synthetic trevira terephthalic acid propylene diester (PTT) of monomer, than thering is better characteristic with polyethylene terephthalate ester (PET) and polybutylene terephthalate (PBT), have the high-performance of PET and the workability of PBT concurrently, therefore 1,3-PD has broad application prospects in producing the fields such as softening agent, washing composition, sanitas, emulsifying agent.
At present, the preparation method of 1,3-PD mainly contains: epoxyethane method, acrolein hydration method, microbe fermentation method and glycerin catalytic conversion method.Epoxyethane method and acrolein hydration method all need two-step reaction to prepare 1,3-PD, and reaction process is loaded down with trivial details, and equipment requirements is high, and operational condition is harsh.Microbe fermentation method production concentration is low, and separation needs lot of energy, and the required biological enzyme life-span is short, strict to ingredient requirement; Opposite face speech, the glycerin catalytic conversion method technique that the glycerine of take is raw material is simple.
In recent years, along with being gradually improved of biomass-making diesel oil technique, the glycerine output that the biodiesel of take is raw material sharply increases, make glycerin catalytic conversion method produce 1, the cost of ammediol, it is the active path of the chemical utilization of glycerine that catforming is produced 1,3-PD.The method that glycerine hydrogenation is prepared 1,3-PD mainly contains:
Chinese patent 200810195218.1 provides a kind of one-step glycerol catalyzed conversion to prepare the method for 1,3-PD, and the method is that aqueous glycerin solution and hydrogen are passed into fixed-bed reactor continuously, at 100 ~ 150 ℃, under 2 ~ 8MPa, reacts.This process using Pt/WO
3/ ZrO
2catalyzer, water is as reaction solvent.Generating rate very low [convert in embodiment 1,3-PD generating rate be up to 1.62(mol
1,3-PDO/ mol
pth
-1) left and right].
Document Catalysis Communications 9 (2008) 1360 – 1363 adopt intermittently tank reactor, at Pt/WO
3/ ZrO
2under catalyst action, glycerine hydrogenation is prepared 1,3-PD.The method is with 1,3-dimethyl 2-imidazolone (DMI) for reaction solvent, and the generating rate of 1,3-PD is lower [to convert to such an extent that its generating rate is 3.93(mol
1,3-PDO/ mol
pth
-1)].
Chinese patent CN200810186614.8 be take glycerin vapor as raw material, with after diluted in hydrogen glycerin vapor, adopts continuous fixed bed reactor to carry out catalyzed reaction and prepares 1,3-PD, and temperature of reaction and pressure are 190 ~ 240 ℃, 0.1 ~ 0.54MPa.The method is used copper-based catalysts, and glycerine needs vaporization, and energy consumption is larger, and glycerine feed air speed is low, and 1,3-PD yield is lower.
Various glycerin catalytic Hydrogenations are for the method for 1,3-PD above, or temperature of reaction is higher; Or employing rhythmic reaction technique; Or use glycerin vapor charging, and energy consumption is large, and reaction stability is poor.
Summary of the invention
summary of the invention
The object of the invention is to provide the processing method that a kind of glycerine hydrogenation is prepared 1,3-PD, and its reaction conditions is gentle, stable reaction, and the generating rate of 1,3-PD is high.
The inventive method, at catalyst Pt/B
2o
3-WO
3-ZrO
2under existence, glycerine and hydrogen are passed into fixed-bed reactor simultaneously, under 100 ~ 150 ℃, 2 ~ 5MPa, react, resultant of reaction is through gas-liquid separation, gained liquid product is removed water through infiltration evaporation membrane sepn, then by rectifying separation, obtain 1,3-PD product and take the glycerine not being converted in by product that 1,2-PD, n-propyl alcohol and Virahol be main component and reaction; By the glycerine not being converted and part by product circulation Returning reactor, described by product internal circulating load is 0.25 ~ 1.5 with reactor feed qualities of glycerin ratio; In described catalyzer, the mass ratio of each element is Pt ﹕ B ﹕ W ﹕ Zr=1 ~ 4 ﹕ 0.1 ~ 2 ﹕ 10 ﹕ 58 ~ 65.
Described by product internal circulating load and glycerin fed mass ratio are preferably 0.6 ~ 1.5.
In described reactor, glycerin fed mass space velocity is 0.1 ~ 1h
-1.
Described glycerine feed mass space velocity is preferably 0.5 ~ 0.7h
-1.
Described infiltrating and vaporizing membrane is selected from a kind of in NaA type molecular screen membrane, type T molecular sieve film, X-type molecular screen membrane.
Described rectifying separation is completed by two rectifying tower, and the first rectifying tower is controlled 190 ~ 200 ℃ of tower top temperatures, and tower top obtains by product, bottoms input Second distillation column, controls 220 ~ 240 ℃ of tower top temperatures, and tower top obtains 1, ammediol product, the glycerine for not being converted at the bottom of tower.
Described reactor reaction temperature is preferably 130 ~ 150 ℃,
Before described catalyzer is used, in hydrogen stream, 160 ~ 300 ℃ of reduction activations 1 hour.
The preferred temperature of described catalyst reduction activation is 180 ~ 240 ℃.
Described catalyst Pt/B
2o
3-WO
3-ZrO
2by following methods, made:
By a certain percentage, zirconium hydroxide is poured in the water that is dissolved with ammonium metawolframate and mixed well, keep 20 hours at 90 ~ 100 ℃, 110 ℃ are dried to appropriate degree, extrusion moulding, and 110 ℃ of oven dry, 700 ℃ of roastings 2 ~ 4 hours, obtain tungsten zirconium mixed oxide.Get appropriate tungsten zirconium mixed oxide and impregnated in boric acid and Platinic chloride mixing solutions 8 ~ 10 hours, dry, roasting is 2 ~ 4 hours at 400 ~ 500 ℃, makes catalyzer.
The present invention adopts platinum/composite oxides solid Lewis acid catalyst Pt/B
2o
3-WO
3-ZrO
2, hydrogen heterolytic fission activation on platinum/composite oxides solid Lewis acid catalyst is proton (H
+) and hydride ion (H
-).Utilize the secondary carbonium ion principle more stable compared with primary carbon positive ion, make glycerine hydrogenation reaction more be conducive to the generation of 1,3-PD.Reaction principle following formula:
Glycerine hydrogenation reaction, except generating 1,3-PD, also has a certain amount of by product n-propyl alcohol, Virahol, 1,2-PD and water to generate.Because the water that reaction generates is easily combined the Lewis acid position on catalyzer, thereby cause the catalytic performance of catalyzer to reduce.The present invention proposes to adopt the method for partial reaction by product circulation Returning reacting system can be stoped to the combination of water and Lewis acid position, and the catalytic performance that maintains catalyzer is stable.Adopt by product circulation can also promote the H of heterolytic fission activation on platinum/composite oxides lewis acid catalyst
+and H
-ion migration, improves 1,3-PD generating rate.
In sum, the present invention prepares the method product Pt/B of 1,3-PD
2o
3-WO
3-ZrO
2as catalyzer and part by product, loop back the technique of reactive system, prepare 1,3-PD technique with existing shortening and compare, reaction conditions is gentle, Energy Intensity Reduction, and catalyzer is stable, time and the 1,3-PD generating rate of system in stable reaction all increased substantially.
Accompanying drawing explanation
In figure, 1-liquid mixer, 2-reactor, 3-gas-liquid separator, 4-infiltration evaporation device, the 5-the first rectifying tower, 6-Second distillation column.
Embodiment
Below by embodiment and comparative example, the present invention will be further described, but protection scope of the present invention is not limited to the listed content of embodiment.
One. the preparation of catalyzer and processing
100.0 grams of zirconium hydroxides are poured in 50 ml waters that are dissolved with 2.4 grams of ammonium metawolframates and mixed well, keep 20 hours at 90 ~ 100 ℃, 110 ℃ are dried to appropriate degree, extrusion moulding, and 110 ℃ of oven dry, 700 ℃ of roastings 3 hours, obtain tungsten zirconium mixed oxide.Get 5.0 grams of tungsten zirconium mixed oxides impregnated in 3.18ml containing the boric acid aqueous solution of 8.0mg boron/milliliter and 1.45ml containing in the mixing solutions of the chloroplatinic acid aqueous solution of 70.0mg platinum/milliliter 8 ~ 10 hours, oven dry, roasting is 2 ~ 4 hours at 450 ℃, makes catalyzer.In this catalyzer, the mass ratio of each element is Pt ﹕ B ﹕ W ﹕ Zr=2 ﹕ 0.5 ﹕ 10 ﹕ 61.2.
Adopting length is that 60 cm, internal diameter are 10 mm tubular fixed-bed reactors.Pack 4.4 grams of above-mentioned catalyzer into, granularity 20 ~ 40 orders.Catalyzer is before use first in hydrogen stream, and 200 ℃ are reduced 1 hour.
Two .1, the preparation of ammediol
By reference to the accompanying drawings 1, first, glycerine mixes as feeding liquid with by product, in liquid mixer 1, is mixed in proportion, and mixed solution is inputted in fixed-bed reactor 2 simultaneously and reacted with hydrogen.
Reaction conditions is:
150℃、4MPa，
Glycerine feed mass space velocity 0.5h
-1,
By product internal circulating load and glycerin fed mass ratio 2/3.
The gas-liquid mixture of discharging from reactor 2 outlet is cooled to room temperature, through gas-liquid separator 3 separation give vent to anger, liquid two phase materials, a part of circulation Returning reactor 2 recyclings of gas gas-phase objects (being mainly wherein hydrogen), all the other speed to put; Liquid phase thing first through infiltration evaporation device 4 except anhydrating, then isolate light constituent (being by product) in product and return in liquid mixer 1 with certain proportion (in this example be glycerin fed quality 2/3) circulation through the first rectifier unit 5; All the other components are isolated product 1,3-PD through the second rectifier unit 6, and recycling liquid mixer 1 is exported and looped back to unconverted glycerine at the bottom of the tower of the second rectifier unit 6.
Experiment at interval of sampling analysis in 5 hours once, adopts the generating rate evaluation response performance (generating rate refers in the unit time, the mole number of the 1,3-PD that in catalyzer, every mole of pt atom generates) of 1,3-PD.Table 1 represents, when glycerine feed air speed is 0.5h
-1, successive reaction 100 hours, in process at interval of within 25 hours, recording 1,3-PD generating rate.
Table 1
Continue embodiment 1 reaction, after 100 hours, the glycerine feed mass space velocity of this reactor 2 is adjusted into 0.7h
-1, other condition is identical with embodiment 1, continues reaction 100 hours, in process, at interval of 25 hours, records 1,3-PD generating rate in Table 2.
Table 2
Embodiment 3
Table 3
Table 1 ~ table 3 represents, raw catalyst is interior through embodiment 1, embodiment 2 and embodiment 3 successive reactions totally 300 hours at this reactor 2, and wherein every reaction changes glycerine feed mass space velocity for 100 hours, from each table data, can find out, in successive reaction 300 hours, under different air speeds, it is stable that the generating rate of 1,3-PD keeps, illustrate that changing air speed does not affect 1, the generating rate stability of ammediol, represents that catalyzer does not have inactivation in the successive reaction of being investigated in 300 hours, active good.
Embodiment 3 generating rates may be because embodiment 3 glycerine feed mass space velocities are lower lower than embodiment 1 and embodiment 2, make part 1,3-PD be further converted to the cause of n-propyl alcohol, visible glycerine feed mass space velocity 0.5 ~ 0.7h
-1better.
Reaction conditions is: 150 ℃, 4MPa,
Glycerine feed mass space velocity 0.5h
-1,
By product internal circulating load and glycerin fed mass ratio 1.5,
Catalyst Pt/B
2o
3-WO
3-ZrO
2in, Pt ﹕ B ﹕ W ﹕ Zr=2 ﹕ 0.5 ﹕ 10 ﹕ 61.2.
Table 4 represents, successive reaction is 100 hours in the above conditions, in process at interval of the generating rate that records 1,3-PD for 25 hours.
Table 4
Table 5
Reaction conditions is: 140 ℃, 4MPa,
Glycerine feed mass space velocity 0.5h
-1,
By product internal circulating load and glycerin fed mass ratio 1.5,
Catalyst Pt/B
2o
3-WO
3-ZrO
2in, Pt ﹕ B ﹕ W ﹕ Zr=2 ﹕ 0.5 ﹕ 10 ﹕ 61.2.
Table 6 represents, successive reaction is 100 hours in the above conditions, in process at interval of the generating rate that records 1,3-PD for 25 hours.
Table 6
Embodiment 7
Table 7
Comparative example 1
Glycerine is as feeding liquid, and by product internal circulating load is zero, and other reaction conditions is identical with embodiment 1.In process at interval of the generating rate that records 1,3-PD for 25 hours in Table 8.
Table 8
Comparative example 2
130 ℃ of temperature of reaction, glycerine feed liquid, by product internal circulating load is zero, other reaction conditions is identical with embodiment 1.At interval of the generating rate that records 1,3-PD for 25 hours in Table 9.
Table 9
Comparative example 1 is compared with embodiment 1,4,5, and comparative example 2 is compared and shown with embodiment 7, adopts Pt/B of the present invention
2o
3-WO
3-ZrO
2catalyzer and by product circulation technology carry out glycerine hydrogenation, can stablize and prepare 1,3-PD, and 1,3-PD generating rate is higher; And the 1,3-PD generating rate of no coupling product circulation technology is relatively low, and be downtrending gradually.
Comparative example 3
Adopt Pt/ WO
3/ ZrO
2catalyzer, other reaction conditions is identical with embodiment 1.In process at interval of the generating rate that records 1,3-PD for 25 hours in Table 10.
Table 10
Comparative example 3 is compared and is shown with embodiment 1, adopts by product circulation technology, uses Pt/B
2o
3-WO
3-ZrO
2catalyzer, the generating rate of 1,3-PD is continually and steadily at higher numerical value, and use Pt/ WO
3/ ZrO
2catalyzer, the lower continuous decrease of the generating rate of 1,3-PD, cannot stablize and prepare 1,3-PD.
By embodiment, compare with comparative example visible, Pt/B
2o
3-WO
3-ZrO
2catalyzer can reach the stable object of preparing 1,3-PD under by product circulation technology, and does not adopt by product circulation technology or do not adopt Pt/B
2o
3-WO
3-ZrO
2catalyzer all possibly cannot be stablized and prepare 1,3-PD.
Claims (10)
1. glycerine hydrogenation is prepared a processing method for 1,3-PD, it is characterized in that, at catalyst Pt/B
2o
3-WO
3-ZrO
2under existence, glycerine and hydrogen are passed into fixed-bed reactor simultaneously, under 100 ~ 150 ℃, 2 ~ 5MPa, react, resultant of reaction is through gas-liquid separation, gained liquid product is removed water through infiltration evaporation membrane sepn, then by rectifying separation, obtain 1,3-PD product and take the glycerine not being converted in by product that 1,2-PD, n-propyl alcohol and Virahol be main component and reaction; By the glycerine not being converted and part by product circulation Returning reactor, described by product internal circulating load is 0.25 ~ 1.5 with reactor feed qualities of glycerin ratio; In described catalyzer, the mass ratio of each element is Pt ﹕ B ﹕ W ﹕ Zr=1 ~ 4 ﹕ 0.1 ~ 2 ﹕ 10 ﹕ 58 ~ 65.
2. glycerine hydrogenation is prepared the processing method of 1,3-PD according to claim 1, it is characterized in that, described by product internal circulating load and glycerin fed mass ratio are 0.6 ~ 1.5.
3. glycerine hydrogenation is prepared the processing method of 1,3-PD according to claim 1, it is characterized in that, in described reactor, glycerin fed mass space velocity is 0.1 ~ 1h
-1.
4. glycerine hydrogenation is prepared the processing method of 1,3-PD according to claim 3, it is characterized in that, it is characterized in that, described glycerine feed mass space velocity is 0.5 ~ 0.7h
-1.
5. glycerine hydrogenation is prepared the processing method of 1,3-PD according to claim 1, it is characterized in that, described infiltrating and vaporizing membrane is selected from a kind of in NaA type molecular screen membrane, type T molecular sieve film, X-type molecular screen membrane.
6. glycerine hydrogenation prepares 1 according to claim 1, the processing method of ammediol, is characterized in that, it is characterized in that, described rectifying separation is completed by two rectifying tower, the first rectifying tower is controlled 190 ~ 200 ℃ of tower top temperatures, and tower top obtains by product, bottoms input Second distillation column, control 220 ~ 240 ℃ of tower top temperatures, tower top obtains 1,3-PD product, the glycerine for not being converted at the bottom of tower.
7. according to glycerine hydrogenation described in claim or 2 or 3 or 4 or 5 or 6, prepare the processing method of 1,3-PD, it is characterized in that, the temperature of reaction of described fixed-bed reactor is 130 ~ 150 ℃.
8. glycerine hydrogenation is prepared the processing method of 1,3-PD according to claim 7, it is characterized in that, before described catalyzer is used, and in hydrogen stream, 160 ~ 300 ℃ of reduction activations 1 hour.
9. glycerine hydrogenation is prepared the processing method of 1,3-PD according to claim 8, it is characterized in that, described catalyst reduction activation temperature is 180 ~ 240 ℃.
10. glycerine hydrogenation is prepared the processing method of 1,3-PD according to claim 9, it is characterized in that described catalyst Pt/B
2o
3-WO
3-ZrO
2make by the following method:
By a certain percentage, zirconium hydroxide is poured in the water that is dissolved with ammonium metawolframate and mixed well, keep 20 hours at 90 ~ 100 ℃, 110 ℃ are dried to appropriate degree, extrusion moulding, and 110 ℃ of oven dry, 700 ℃ of roastings 2 ~ 4 hours, obtain tungsten zirconium mixed oxide; Get appropriate tungsten zirconium mixed oxide and impregnated in boric acid and Platinic chloride mixing solutions 8 ~ 10 hours, dry, roasting is 2 ~ 4 hours at 400 ~ 500 ℃, makes catalyzer.
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| CN107159300A (en) * | 2017-06-27 | 2017-09-15 | 太原理工大学 | A kind of support type mesoporous molecular sieve catalyst and its preparation method and application |
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| CN109593025A (en) * | 2017-09-30 | 2019-04-09 | 张家港美景荣化学工业有限公司 | Method for preparing 1, 3-propylene glycol and reaction system thereof |
| WO2021000523A1 (en) * | 2019-07-02 | 2021-01-07 | 中国科学院大连化学物理研究所 | Optimized activation method for polyol hydrogenolysis catalyst |
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| CN115636727A (en) * | 2022-10-09 | 2023-01-24 | 山东京博石油化工有限公司 | Method for preparing 1, 3-propylene glycol by glycerol hydrogenation |
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| CN108636404A (en) * | 2018-04-16 | 2018-10-12 | 江苏七洲绿色化工股份有限公司 | A kind of glycerine water solution Hydrogenation is for the regular catalyst of 1,3- propylene glycol and the preparation method of 1,3- propylene glycol |
| WO2021000523A1 (en) * | 2019-07-02 | 2021-01-07 | 中国科学院大连化学物理研究所 | Optimized activation method for polyol hydrogenolysis catalyst |
| CN114230440A (en) * | 2022-01-06 | 2022-03-25 | 江苏扬农化工集团有限公司 | Method for continuously dehydrating and removing aldehyde by using dihydric alcohol aqueous solution |
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