CN102924233B - Method for preparing propylene glycol by glycerin hydrogenolysis - Google Patents
Method for preparing propylene glycol by glycerin hydrogenolysis Download PDFInfo
- Publication number
- CN102924233B CN102924233B CN201210419541.9A CN201210419541A CN102924233B CN 102924233 B CN102924233 B CN 102924233B CN 201210419541 A CN201210419541 A CN 201210419541A CN 102924233 B CN102924233 B CN 102924233B
- Authority
- CN
- China
- Prior art keywords
- propylene glycol
- glycerin
- hydrogenolysis
- copper
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 88
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 235000011187 glycerol Nutrition 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 229910052684 Cerium Inorganic materials 0.000 claims abstract 2
- 239000010936 titanium Substances 0.000 claims abstract 2
- 229910052719 titanium Inorganic materials 0.000 claims abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 22
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims 2
- 239000000470 constituent Substances 0.000 claims 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 2
- 239000012716 precipitator Substances 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- SMYKVLBUSSNXMV-UHFFFAOYSA-K aluminum;trihydroxide;hydrate Chemical compound O.[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-K 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 5
- 239000010970 precious metal Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000009466 transformation Effects 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- 230000032683 aging Effects 0.000 description 7
- 238000006703 hydration reaction Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000007493 shaping process Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229940017219 methyl propionate Drugs 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- BRARRAHGNDUELT-UHFFFAOYSA-N 3-hydroxypicolinic acid Chemical compound OC(=O)C1=NC=CC=C1O BRARRAHGNDUELT-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- -1 printing and dyeing Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005518 chemical engineering design Methods 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
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- MILWSGRFEGYSGM-UHFFFAOYSA-N propane-1,2-diol;propane-1,2,3-triol Chemical compound CC(O)CO.OCC(O)CO MILWSGRFEGYSGM-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000066 reactive distillation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
The invention discloses a method for preparing propylene glycol by glycerin hydrogenolysis adopting a supported nano-copper-based catalyst. The supported nano-copper-based catalyst utilizes copper as an active component. Titanium or cerium is used as a cocatalyst. Through a coprecipitation method, glycerin undergoes a hydrogenolysis reaction to directly produce propylene glycol in a fixed-bed reactor. In the whole process, the method does not utilize a solvent, and poisonous and harmful metal components. The supported nano-copper-based catalyst is not a precious metal and has a high activity, good stability and a long service life. The method has a high glycerin conversion rate, good propylene glycol selectivity and simple processes, allows mild conditions, realizes continuous production and is environment friendly.
Description
Technical field
The present invention relates to the method for hydrogenolysis of glycerin, specifically about a kind of loaded nano copper-based catalysts that adopts on fixed-bed reactor by the method for glycerin catalytic hydrogenolysis synthesizing propanediol.
Background technology
1,2-PD and 1,3-PD, as important industrial chemicals, because bio-toxicity is low, at solvent, printing and dyeing, wetting Agent for Printing Inks, frostproofer, emulsifying agent etc., are widely used in fields such as medicine, makeup, food and receive much concern.Propylene glycol general method is by the petroleum derivative propylene oxidation of fossil feedstock, then its hydration is obtained.If with the excessive glycerine of the biofuel course of processing for raw material, it is hydrogen synthesis 1 by 1 of glycerine or 2 conversion of hydroxyl, 2-propylene glycol and 1, ammediol, the production not being only propylene glycol provides the synthetic route of a green economy, simultaneously also for the development of biofuel provides the guarantee of economy.
The production method of propylene glycol generally has following several:
Propylene oxide direct hydration method: new Proplene Glycol Process by direct Hydration [J]. chemical engineering design, 1999,9 (3) is raw material with propylene oxide, propylene oxide feeds intake from rectifying tower top through pump, raw materials components mole ratio is water: propylene oxide=1.5 ~ 3: 1, and reactor and distillation column carries out coupling and carries out hydration reaction, and reactive distillation column utilizes steam indirect heating, total reflux operation, control tower pressure on top surface 0.85MPa, temperature 175 DEG C.
3-hydroxy methyl propionate shortening method: (CN101993352A) starting raw material 3-hydroxy methyl propionate, activating solvent and catalyzer are activated under certain condition in autoclave, add reaction solvent and raw material again, 140 ~ 200 DEG C, under 5 ~ 10MPa hydrogen pressure, reaction 3 ~ 30h, 3-hydroxy methyl propionate transformation efficiency can reach 92.31%, and the selectivity of 1,3-PD can reach 85.43%.The active ingredient of catalyzer is the oxide compound of Cu, Mn and Zr, and this inventive method adds reaction solvent and activating solvent, contaminate environment.
Acrolein hydration method: (refining of petroleum and chemical industry, 2001,32,12,21-24), be made up of acrolein hydration, 3-HPA hydrogenation and refining three steps, acrolein hydration adopts fixed-bed reactor, and 3-HPA hydrogenation carries out in intermittent high-pressure reactor.
Microbe fermentation method: glucose and glycerine are that mixing Double bottom thing is cultivated under aerobic condition and transformation of glycerol under anaerobic condition is integrated in same fermentor tank and carries out by (CN1434122A).Complete as the aerobic condition turning anaerobism using glucose consumption, under anaerobic transformation of glycerol is 1,3-PD, and this process generates with coproduct ethanol, acetic acid and lactic acid, and ethanol can produce toxic side effect to fermented liquid.Biological fermentation process enzyme becomes that current is short, cost is high, and how to improve productive rate and the concentration of product 1,3-PD, how product is effectively separated, and the formation how reducing toxic byproduct is all have problem to be solved.
Glycerin catalytic hydrogenolysis method: Low-pressure hydrogenolysis of glycerol to propylene glycol [J] .Applied Catalysis A:Genera1,2005,281 (1-2): 225-231, report adopts Cu-Cr catalyzer, hydrogenolysis of glycerin is divided into two-step reaction, 200 DEG C, under 200psi pressure, under qualities of glycerin mark 80% condition, the first step is that dehydrating glycerin generates hydroxyacetone, second step is that hydroxyacetone hydrogenation obtains propylene glycol, the yield of reaction 1,2-PD reaches 73%, and this catalyzer uses chromium metal contaminate environment.
CN102059116A adopts the composition of catalyzer at least containing Pt, W, refractory oxide or its precursor, and simultaneously containing a kind of carrier.Refractory oxide or its precursor contain ZrO
2or TiO
2or its precursor.Carrier is SiO
2, A1
2o
3, one in HZSM-5 or gac, at 110 ~ 260 DEG C, hydrogen pressure is 0.1 ~ 8.0MPa, reaction 2.5 ~ 50h.Glycerol conversion yield can reach 15.3%, and 1,3-PD selectivity reaches 50.5%.This method use precious metal, price is higher, the transformation efficiency of glycerine and the selectivity of propylene glycol not high.
US4642394 in organic protophobic solvent, 30MPaH
2, under 200 DEG C of conditions, at Rh (CO)
2and HWO (acac)
4homogeneous catalysis, the yield of 1,3-PD is 21%.This severe reaction conditions, and with an organic solvent do not meet green clean requirement.
At present, glycerin catalytic hydrogenolysis method adopts noble metal catalyst mostly, and the transformation efficiency of noble metal catalyst catalyzed reaction glycerine is not high, and process conditional harshness is not easy to operate (see CN102059116A).Its glycerine, in reaction process, is first vaporized by some non-precious metal catalyst, and glycerine boiling point is high, therefore consume energy high (see CN1090568A, CN101747150A).Therefore a kind of non-precious metal catalyst efficiently of exploitation makes glycerine prepare propylene glycol under mild hydrogenation condition, is the problem with realistic meaning and profound influence.
Summary of the invention
The present invention, using copper as main activeconstituents, adds a certain amount of promotor and is prepared into a certain proportion of solid catalyst, uses base metal, low price, and the charging of glycerine normal temperature does not need vaporization, and the gentleer easy handling of condition of reaction, productive rate is advantages of higher comparatively.
The object of this invention is to provide the method that a kind of price is cheap, operational condition is gentle copper-based catalysts is applied to glycerine propylene glycol.
The method of a kind of glycerin catalytic hydrogenolysis propylene glycol provided by the invention, reactor used is fixed-bed reactor, also can be adapted to autoclave reactor, and raw material is glycerine or its aqueous solution.
In the present invention, copper-based catalysts adopts coprecipitation method preparation, the aqueous solution that catalyzer becomes concentration certain according to certain proportional arrangement, the precursor of metal oxide is the concentration of aqueous solution scope of cupric nitrate is 10 ~ 40wt%, precipitation agent adopts aqueous sodium hydroxide solution concentration to be 10 ~ 40wt%, and metal promoter is TiCl
3, TiCl
4, tetrabutyl titanate, Ce (NO
3)
3or its oxide compound, employing carrier is SiO
2, A1
2o
3deng.Precipitation temperature 30 ~ 85 DEG C.Aging temperature is at 45 ~ 120 DEG C, and aging 4 ~ 24h, pH value controls 9 ~ 12.Through washing and filtering, 400 ~ 600 DEG C of roasting 4h ~ 12h beat sheet shaping after load in fixed-bed reactor.
Must activated reduction treatment before catalyzer described in technique scheme uses, catalyzer through temperature programming from 25 ~ 300 DEG C, and according to V (N
2: H
2reduction activation process is carried out in)=170: 30 under pressure 0.5 ~ 4MPa condition.
Through the catalyzer of above-mentioned activation treatment in fixed-bed reactor, regulate reaction pressure 0.5 ~ 5MPa, pass into hydrogen, aqueous glycerin solution advection type volume pump charging, hydrogen alcohol ratio is 30 ~ 100, aqueous glycerin solution concentration (mass ratio 10 ~ 80%), liquid air speed is at 0.3 ~ 0.9h-1, and temperature of reaction is reacted at 180 ~ 240 DEG C.
Catalyzer energy efficient catalytic hydrogenolysis glycerine prepared by the present invention obtains propylene glycol, and not only operational condition is gentle, and does not use solvent and poisonous and hazardous metal component in whole process, free from environmental pollution.Prepared catalyst stability is good, and work-ing life is longer, overcomes and uses the shortcomings such as precious metal catalyst condition is harsh, cost is higher, selectivity is low.
Example
With regard to specific examples, the inventive method is further illustrated below
Example 1
Catalyst preparing: take 10gCu (NO
3)
2.3H
2o adds water the copper nitrate solution be mixed with concentration 20wt%, take 10 grams of sodium hydroxide to add water and be mixed with concentration 16wt% aqueous sodium hydroxide solution, simultaneously by two kinds of solution and drip is added in flask, keep precipitation temperature 45 DEG C, control ph is 10 ~ 11, after dropwising, add the silicon sol of 15 grams of concentration 30wt%, at being warming up to 85 DEG C aging 6 hours, hot wash for several times, through suction filtration, 120 DEG C of dry 12h, 500 DEG C of roasting 6h, pulverize shaping screening 15 ~ 40 order particle stand-by.
Adopt micro fixed-bed reactor, loaded catalyzer, passed into nitrogen and hydrogen V (N
2: H
2)=170: 30, regulation system pressure is under 1.5MPa condition, and 280 DEG C by catalyst reduction 20 hours.
Reduction terminates rear closedown nitrogen, regulation system pressure and temperature of reaction, by the aqueous glycerin solution of 50% steady flow metering pump charging, inlet amount is 0.05sccm, and hydrogen flowing quantity is 225sccm, reacts under 180 ~ 240 DEG C of conditions, sampling analysis after stable reaction, analyzes with gas chromatograph.The selectivity of products therefrom and the transformation efficiency of glycerine as follows.
Example 2
Catalyst preparing: take 10gCu (NO respectively
3)
2.3H
2the TiCl of O and 25 gram 18wt%
3100 ml water obtained aqueous solutions are added after solution mixing, take 15 grams of sodium hydroxide to add water and be mixed with concentration 38wt% aqueous sodium hydroxide solution, simultaneously by two kinds of solution and drip is added in flask, keep precipitation temperature 45 DEG C, control ph is 10 ~ 11, after dropwising, add 5 grams of aluminium hydroxide gels, at being warming up to 85 DEG C aging 6 hours, hot wash for several times, through suction filtration, 120 DEG C of dry 12h, 500 DEG C of roasting 6h, pulverize shaping screening 15 ~ 40 order particle stand-by.
Adopt micro fixed-bed reactor, loaded catalyzer, passed into nitrogen and hydrogen V (N
2: H
2)=170: 30, regulation system pressure is under 1.5MPa condition, and 280 DEG C by catalyst reduction 20 hours.
Reduction terminates rear closedown nitrogen, regulation system pressure and temperature of reaction, by the steady flow metering pump charging of the aqueous glycerin solution of 90wt%, inlet amount is 0.04sccm, and hydrogen flowing quantity is 660sccm, reacts under 180 ~ 240 DEG C of conditions, sampling analysis after stable reaction, analyzes with gas chromatograph.Change reaction temperature be 180 DEG C, 200 DEG C, 220 DEG C, 240 DEG C, the selectivity of products therefrom and the transformation efficiency of glycerine as follows.
Example 3
Catalyst preparing: take 10gCu (NO respectively
3)
2.3H
2the TiCl of O, 2.5 grams of cerous nitrates and 18wt%
3100 ml water obtained aqueous solutions are added after solution 10 grams mixing, take 21 grams of sodium hydroxide to add water and be mixed with concentration 15wt% aqueous sodium hydroxide solution, simultaneously by two kinds of solution and drip is added in flask, keep precipitation temperature 45 DEG C, control ph is 10 ~ 11, after dropwising, add the silicon sol of 17 grams of concentration 30wt%, at being warming up to 85 DEG C aging 6 hours, hot wash for several times, through suction filtration, 120 DEG C of dry 12h, 500 DEG C of roasting 6h, pulverize shaping screening 15 ~ 40 order particle stand-by.
Catalyst loading and reduction is carried out by the method for example 1.By the steady flow metering pump charging of the aqueous glycerin solution of 30wt%, inlet amount is 0.10sccm, and hydrogen flowing quantity is 298sccm, reacts under 160 ~ 220 DEG C of conditions, sampling analysis after stable reaction, the selectivity of products therefrom and the transformation efficiency reaction result of glycerine as follows.
Example 4
Catalyst preparing: take 10gCu (NO respectively
3)
2.3H
2the TiCl of O and 1.2 gram cerous nitrate and 22.5 grams of 18wt%
3100 ml water obtained aqueous solutions are added after solution mixing, take 23 grams of sodium hydroxide to add water and be mixed with concentration 15wt% aqueous sodium hydroxide solution, simultaneously by two kinds of solution and drip is added in flask, keep precipitation temperature 45 DEG C, control ph is 10 ~ 11, after dropwising, add the silicon sol of 8 grams of concentration 30wt%, at being warming up to 85 DEG C aging 6 hours, hot wash for several times, through suction filtration, 120 DEG C of dry 12h, 500 DEG C of roasting 6h, pulverize shaping screening 15 ~ 40 order particle stand-by.
Catalyst loading and reduction and reaction is carried out by the method for example 1.The selectivity of products therefrom and the transformation efficiency reaction result of glycerine as follows
Example 5
Catalyst preparing: take 10gCu (NO respectively
3)
2.3H
2o, adds 100 ml water obtained aqueous solutions after the mixing of 1.2 grams of cerous nitrates, takes 27 grams of sodium hydroxide and adds water and be mixed with concentration 38wt% aqueous sodium hydroxide solution, simultaneously by two kinds of solution and drip is added in flask, keep precipitation temperature 45 DEG C, control ph is 10 ~ 11, after dropwising, add the silicon sol of 17 grams of concentration 30wt%, at being warming up to 85 DEG C aging 6 hours, hot wash for several times, through suction filtration, 120 DEG C of dry 12h, 500 DEG C of roasting 6h, pulverize shaping screening 15 ~ 40 order particle stand-by.
Catalyst loading and reduction and reaction is carried out by the method for example 1.The selectivity of products therefrom and the transformation efficiency reaction result of glycerine as follows.
Claims (4)
1. hydrogenolysis of glycerin prepares a method for propylene glycol, it is characterized in that: on nano-copper base catalyst prepared by the precipitator method, adopt fixed bed that continuous for glycerine hydrogenolysis is prepared propylene glycol; Described nano-copper base catalyst active ingredient is the nano metal Cu of high dispersing, and promotor is the oxide compound of Ti or Ce, and carrier is SiO
2, Al
2o
3; Described nano-copper base catalyst adopts precipitator method preparation.
2. method according to claim 1, is characterized in that: the hydrogenolysis of glycerine carries out in fixed-bed reactor, and reaction pressure is 0.5 ~ 5MPa, and hydrogen alcohol mol ratio is 30 ~ 100, and aqueous glycerin solution concentration is 10 ~ 100wt%, and liquid air speed is at 0.3 ~ 0.9h
-1, temperature of reaction is 180 ~ 240 DEG C.
3. method according to claim 1, is characterized in that: described nano-copper base catalyst is with catalyzer total amount metal active constituent content for 10 ~ 60wt%, and oxide promoter content is less than 20wt%, and all the other are carrier.
4. method according to claim 1, it is characterized in that: the coprecipitation method adopted is carried out in aqueous, the raw material of metal active constituent is nitrate aqueous solution, concentration range is 10 ~ 60wt%, oxide promoter raw material is its nitrate or the hydrochloride aqueous solution, and concentration range is 10 ~ 50wt%, and carrier is silica gel or aluminium hydroxide gel, precipitation agent adopts aqueous sodium hydroxide solution, and concentration is 10 ~ 50wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210419541.9A CN102924233B (en) | 2012-10-20 | 2012-10-20 | Method for preparing propylene glycol by glycerin hydrogenolysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210419541.9A CN102924233B (en) | 2012-10-20 | 2012-10-20 | Method for preparing propylene glycol by glycerin hydrogenolysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102924233A CN102924233A (en) | 2013-02-13 |
| CN102924233B true CN102924233B (en) | 2015-04-15 |
Family
ID=47639196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210419541.9A Active CN102924233B (en) | 2012-10-20 | 2012-10-20 | Method for preparing propylene glycol by glycerin hydrogenolysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102924233B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045546B (en) * | 2014-06-27 | 2017-01-04 | 江苏大学 | A kind of catalyzing glycerol prepares the method for lactic acid |
| CN104045543B (en) * | 2014-06-27 | 2016-08-31 | 江苏大学 | A kind of method that Nanometer Copper catalyzing glycerol prepares lactic acid |
| AR098779A1 (en) * | 2014-12-17 | 2016-06-15 | Univ Nac Del Litoral | A CATALYTIC PROCESS FOR THE PRODUCTION OF PROPYLENGLYCOL FROM GLICEROL, A COPPER AND CERIUS CATALYST, AND A PROCESS TO PREPARE SUCH CATALYST |
| CN105344357A (en) * | 2015-09-30 | 2016-02-24 | 东南大学 | Catalyst for preparing 1,3-propanediol through glycerine hydrogenolysis |
| CN106179366B (en) * | 2016-07-07 | 2019-01-18 | 淮安万邦香料工业有限公司 | A kind of CuO-CeO2-SiO2-Al2O3Catalyst and preparation method thereof prepares the application in 1,2- propylene glycol in glycerine hydrogenation with it |
| CN107774271B (en) * | 2017-10-25 | 2020-07-24 | 宏业生物科技股份有限公司 | High-selectivity catalyst for producing 1, 2-propylene glycol |
| CN111939918B (en) * | 2020-09-08 | 2022-12-23 | 安徽师范大学 | Rare earth oxide/copper oxide-zirconium oxide catalyst, preparation method thereof and method for preparing lactic acid from glycerol |
| CN113429260B (en) * | 2021-05-24 | 2023-04-07 | 中科合成油技术股份有限公司 | Method for preparing propylene glycol by catalytic hydrogenolysis of glycerol |
| CN114247451B (en) * | 2021-12-31 | 2023-12-22 | 厦门欧米克生物科技有限公司 | Glycerol hydrogenation catalyst and preparation method and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4642394A (en) * | 1985-07-16 | 1987-02-10 | Celanese Corporation | Production of propanediols |
| WO2007010299A1 (en) * | 2005-07-15 | 2007-01-25 | Davy Process Technology Ltd | Process |
| CN101195557A (en) * | 2006-12-07 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for producing 1-propylene glycol with glycerol hydrogenation |
| CN101239315A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Catalyst for preparing 1,2-propylene glycol by glycerol hydrogenation and use thereof |
| CN101456791A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for producing 1,2-propanediol by using biological base glycerol |
| CN101898946A (en) * | 2010-06-29 | 2010-12-01 | 江苏大学 | Method for hydrogenolysis catalysis of glycerin |
| CN102225883A (en) * | 2011-03-10 | 2011-10-26 | 江苏大学 | Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst |
-
2012
- 2012-10-20 CN CN201210419541.9A patent/CN102924233B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4642394A (en) * | 1985-07-16 | 1987-02-10 | Celanese Corporation | Production of propanediols |
| WO2007010299A1 (en) * | 2005-07-15 | 2007-01-25 | Davy Process Technology Ltd | Process |
| CN101195557A (en) * | 2006-12-07 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for producing 1-propylene glycol with glycerol hydrogenation |
| CN101456791A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for producing 1,2-propanediol by using biological base glycerol |
| CN101239315A (en) * | 2008-03-10 | 2008-08-13 | 上海华谊丙烯酸有限公司 | Catalyst for preparing 1,2-propylene glycol by glycerol hydrogenation and use thereof |
| CN101898946A (en) * | 2010-06-29 | 2010-12-01 | 江苏大学 | Method for hydrogenolysis catalysis of glycerin |
| CN102225883A (en) * | 2011-03-10 | 2011-10-26 | 江苏大学 | Cu/TiO2 catalyst, preparation method thereof, and method for catalyzing glycerin hydrogenolysis with Cu/TiO2 catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102924233A (en) | 2013-02-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102924233B (en) | Method for preparing propylene glycol by glycerin hydrogenolysis | |
| CN101138730B (en) | Catalyzer for oxalic ester hydrogenation for synthesizing glycolate and method of preparing the same | |
| CN102228831A (en) | Catalyst for gas phase hydrogenation of acetic acid to prepare ethanol | |
| CN102600842A (en) | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof | |
| CN101767006B (en) | Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof | |
| CN105315130B (en) | A kind of method that 1,3 dihydric alcohols are prepared by Prins condensation reactions | |
| CN102728380B (en) | Application of catalyst used for preparing 1,3-propylene glycol through glycerin hydrogenolysis | |
| CN104098439A (en) | Biomass glycol refining method | |
| CN108997274A (en) | A kind of method that liquid phase hydrogen migration catalysis furfural hydrogenation prepares 2- methylfuran | |
| CN102211040A (en) | Mixed oxide supported mesoporous molecular sieve catalyst and application thereof in catalytic preparation of alpha-phenylethanol | |
| CN103664529B (en) | The method of coproduction hexalin and ethanol | |
| CN103145545B (en) | A kind of method preparing hydroxymalonic acid for glycerol catalysis oxidation | |
| CN107159217A (en) | A kind of Cu ZnO/SiO2Aeroge bimetallic catalyst and its production and use | |
| CN101898946B (en) | Method for hydrogenolysis catalysis of glycerin | |
| CN102690170B (en) | Method for preparing ethanol by acetic acid gas phase hydrogenation | |
| CN104923218A (en) | Catalyst for itaconic acid hydrogenation as well as preparation method and use of catalyst, and method for preparing high value-added products from itaconic acid | |
| CN103240095A (en) | Methyl acetate hydrogenation catalyst and preparation method thereof | |
| CN103157490B (en) | Catalyst for producing ethanol by hydrogenation of acetic ester, and preparation method thereof | |
| CN106944050B (en) | A kind of catalyst and its preparation method and application synthesizing 1,3- propylene glycol | |
| CN103664586B (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN103664587A (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN106914247A (en) | The preparation and application of a kind of nickel-base catalyst for carbon dioxide methanation | |
| CN114522738B (en) | Method for preparing 1, 3-propylene glycol by one-step hydrogenation of 3-acetoxy propionaldehyde | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester | |
| CN107793294A (en) | A kind of absolute ethyl alcohol, low-grade ethanol process for refining and purifying |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |