CN101407448B - Method for continuously preparing 1,3-propanediol by one-step glycerol conversion - Google Patents
Method for continuously preparing 1,3-propanediol by one-step glycerol conversion Download PDFInfo
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- CN101407448B CN101407448B CN2008101952181A CN200810195218A CN101407448B CN 101407448 B CN101407448 B CN 101407448B CN 2008101952181 A CN2008101952181 A CN 2008101952181A CN 200810195218 A CN200810195218 A CN 200810195218A CN 101407448 B CN101407448 B CN 101407448B
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 226
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 31
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 title abstract 9
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 title 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 title 1
- 235000011187 glycerol Nutrition 0.000 claims abstract description 97
- 239000001257 hydrogen Substances 0.000 claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 26
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 10
- 239000011973 solid acid Substances 0.000 claims abstract description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000006227 byproduct Substances 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 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 5
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 claims description 71
- 239000002994 raw material Substances 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 12
- 230000009467 reduction Effects 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 19
- 239000007789 gas Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000001588 bifunctional effect Effects 0.000 abstract 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 30
- 239000011541 reaction mixture Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 11
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- AKXKFZDCRYJKTF-UHFFFAOYSA-N 3-Hydroxypropionaldehyde Chemical compound OCCC=O AKXKFZDCRYJKTF-UHFFFAOYSA-N 0.000 description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000000855 fermentation Methods 0.000 description 4
- 230000004151 fermentation Effects 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000007037 hydroformylation reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- XLSMFKSTNGKWQX-UHFFFAOYSA-N hydroxyacetone Chemical compound CC(=O)CO XLSMFKSTNGKWQX-UHFFFAOYSA-N 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- -1 terepthaloyl moietie Chemical compound 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000003190 augmentative effect Effects 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229940106580 ginkgo biloba leaf extract Drugs 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for continuously preparing 1, 3-propylene glycol by glycerin through one step of conversion. With the presence of metal/ solid acid bifunctional catalyst, glycerin water solution and hydrogen are simultaneously and continuously led into a fixed bed reactor and have a catalytic reaction at the temperature of 100-150 DEG C, and a pressure of 2-8MPa, wherein, the volume ratio of hydrogen and glycerin water solution is 600-1200; volume air speed of glycerin water solution is 0.15-1h<-1>; the reaction product is collected and has a gas liquid separation to remove gas hydrogen; the liquid phase is distilled and separated to remove the side product to obtain the 1, 3-propylene glycol product; the metal/ solid acid bifunctional catalyst is functioned by zirconia/tungsten oxide complex oxide with attachment of platinum; and weight ratio of each metallic element in the catalyst is: Pt: W: Zr=1-5:5-20:69-55. The process of the reaction is simple; the production can be continuous; high concentration glycerin can be converted under a relatively moderate reaction condition; content of 1, 3-propylene glycol is high, while content of side product is low; and 1, 3-propylene glycol separation and purification cost is low.
Description
Technical field
The invention provides a kind of one step of biological diesel oil byproduct glycerin catalyzed conversion preparation 1 continuously that utilizes, the method for ammediol belongs to the biomass chemical field,
Background technology
1, (1,3-PDO), molecular formula is HO-CH to ammediol
2-CH
2-CH
2-OH, it is the important source material of field of fine chemical, can be used for solvent, antifreezing agent, protective material, lubricant; Be particularly useful for producing polyester material, it and terephthalic acid generate PTT (PTT), than other glycol (like terepthaloyl moietie, 1; The 4-butyleneglycol) polyester that forms, like polyethyleneterephthalate (being called for short PET), polybutylene terephthalate (being called for short PBT); PTT has unique more character; Like elasticity, dyeability, the pollution resistance of excellence, Ginkgo Biloba Leaf Extract discoloration preferably, and characteristics such as antistatic, favorable biological degradability; Fields such as dress materials in carpet, engineering plastics, film and textile industry are widely used, and PTT has become synthon exploitation focus in the world.
At present, 1, the preparation method of ammediol mainly contains following several kinds:
(1) with the propylene oxide is raw material, through hydroformylation, repeated hydrogenation preparation 1, ammediol.Adopting the promoted cobalt-carbonyl of rhodium carbonyl like US5689016 is hydroformylation catalyst, is hydrogenation catalyst with Ni, Co, Ru, Pt, Pd.The raw material propylene oxide derives from petroleum products, and hydroformylation need under high pressure be carried out, and reacts wayward, and cost is high.
(2) with the propenal be raw material, through hydration, hydrogenation preparing 1, ammediol.EP544120 adopts TiO
2Be the phosphoric acid catalyst of carrier,, acrolein hydration become the 3-hydroxy propanal at 50 ℃～70 ℃, again with the 3-hydroxy propanal with Raney Ni catalyzer, under 60 ℃, 136 bar pressures, make 1, ammediol.Raw material propylene aldehyde valency is high, poisonous, and the concentration that in hydration, hydrogenation two steps reaction, needs strict control 3-hydroxy propanal is in very low level, and not easy to operate, cost is high.
(3) microbe fermentation method is to be raw material with sugar or glycerine, and in the presence of enzyme or cydorge gene bacterium, fermentative prepn 1 under proper condition, ammediol.The advantage of microbe fermentation method is: mild condition, easy and simple to handle, raw material have recyclability, process environment is friendly.But the ubiquitous problem of microbe fermentation method is: in the fermenting process; The glycerine of higher concentration and tunning all can produce restraining effect to the activity of enzyme or cydorge gene bacterium; For keeping microbic activity in the fermented liquid, the general glycerine starting point concentration that adopts very low (maximum concentration can not surpass 17%).So the product 1 in the fermented liquid, ammediol concentration also lower (between 60～80g/L).From rare like this fermented liquid, reclaim 1, ammediol needs the big water gaging of evaporation, and energy consumption is high.Fermenting process also possibly add the nutritive substance as mikrobe such as plurality of inorganic salt in addition, makes and contains various organic acid impurity in the metabolite.It is thus clear that, product 1, ammediol separates the complicacy of purifying, and cost is high, has limited the application widely of microbe fermentation method process.
(4) glycerine transforms through chemical catalysis and synthesizes 1, the ammediol method, and like the homogeneous catalyst that U.S. Pat 4642394 adopts wolframic acids and rhodium complex to form, glycerine and pressure are the synthetic gas (CO/H of 31MPa
2=1/2) in organic amine and amide solution, 200 ℃ were reacted 24 hours down, but 1, the productive rate of ammediol is lower than 20%, and can not use the aqueous glycerin solution reaction.Among the patent CN93114516.3 and US5426249 of the application of Germany Degussa company; Use the aqueous glycerin solution of 10%～40% (weight); The first step generates propenal and pyruvic alcohol through acidic solid catalyst with dehydrating glycerin under 250 ℃～340 ℃ temperature; Second step generated the 3-hydroxy propanal with propenal hydration on an acidic catalyst under 20 ℃～120 ℃ temperature; The two-stage catalytic hydrogenation reaction of the 3rd step through 3-hydroxy propanal and pyruvic alcohol generates 1, ammediol and 1,2-Ucar 35.Reactions step is many, and process is long, and temperature is high.
Summary of the invention
The purpose of this invention is to provide the preparation 1 continuously of a kind of aqueous glycerin solution single stage method, the method for ammediol.This method overcomes the deficiency of prior art, and reaction conditions is gentle, needn't be with an organic solvent, and technology is simple.
The present invention prepares 1; The method of ammediol; With aqueous glycerin solution and hydrogen is raw material, in the presence of metal/solid acid dual-function catalyst, glycerine and hydrogen is fed fixed-bed reactor simultaneously continuously; In temperature is 100～150 ℃, and pressure is to carry out gas-liquid-solid three phase catalytic reaction under 2～8MPa; Wherein, the volume ratio of hydrogen and aqueous glycerin solution is 600～1200, and the volume space velocity of aqueous glycerin solution is 0.15～1h
-1, remove gaseous hydrogen from reactor outlet collecting reaction product and gas-liquid separation, liquid phase is removed by product through fractionation by distillation, gets 1, the ammediol product; Isolated gaseous hydrogen is returned and is utilized; Said metal/solid acid dual-function catalyst is the zirconium white/Tungsten oxide 99.999 composite oxides that are attached with platinum, and the weight ratio of each metallic element is Pt: W: Zr=1～5: 5～20: 69～55 in this catalyzer.
Said aqueous glycerin solution concentration is 20～80%.
Said catalyzed reaction temperature is preferably 120～140 ℃, and reaction pressure is preferably 3～6MPa.
Before said catalyzer uses, reduction activation 1 hour under hydrogen stream and 150 ℃～300 ℃ temperature earlier.
Preferred 180～250 ℃ of catalyst reduction activation temperature.
Said volume space velocity is preferably 0.15～0.5h
-1
The preparation method of said metal/solid acid dual-function catalyst is following: a certain amount of zirconium white impregnated in the ammonium salt solution or heteropoly acid containing tungsten solution of the tungsten that calculates in proportion; Mixture was 110 ℃ of refluxed 24 hours; Then 100～115 ℃ of oven dry down; In 500～800 ℃ of roasting temperatures 2～4 hours, obtain the oxide solid acid of zirconium white load tungsten.The oxide solid acid of obtained zirconium white load tungsten was flooded in containing the solution of precious metals pt 10～12 hours, and oven dry at last 450 ℃ of following roastings 3 hours, obtains being attached with the zirconium white/Tungsten oxide 99.999 composite oxides of platinum.
The present invention adopts tubular fixed-bed reactor, and glycerine solution and hydrogen are passed through solid catalyst continuously, and the air speed size through the control aqueous glycerin solution can make the liquid phase reaction thing form very thin liquid film at catalyst surface, and gas phase hydrogen is then as the continuous flow phase.
Because very thin liquid film is little to the resistance to mass transfer of hydrogen, the katalysis of metal/solid acid dual-function catalyst in addition, thereby can (under 3～6MPa), the gas-liquid-solid three-phase single step reaction obtains higher glycerol conversion yield at relatively low gaseous pressure.In present method gained mixture of reaction products, 1, the concentration of ammediol is high high with productive rate, removes 1, and outside ammediol, water and the unconverted glycerine, by product only has n-propyl alcohol, Virahol and a small amount of 1 on a small quantity, 2-Ucar 35.These sub products only need can remove with simple distillation, and 1, the purifying technique of ammediol is simple easily, cost is lower, and present method is suitable for continuous production.In recent years, along with the development of biodiesel technology, will produce a large amount of sub product glycerine, the by-product glycerol of biological diesel oil of the present invention's double valency capable of using is a raw material production 1, and ammediol further reduces production costs significantly.
In present method, the suitable concentration range of raw material glycerine is wide in range, and weight concentration is that 20～80% aqueous glycerin solution is all applicable.Because water need distill when subsequent purification is handled and remove, and improves the concentration of glycerine in the reaction raw materials as far as possible, reduce water-content, can reduce product 1, the energy consumption of ammediol purification process, better suited concentration is 40～70%.Certainly, the aqueous glycerin solution of low concentration also can be used, but will increase follow-up fractionation by distillation energy consumption.
In sum; Method of the present invention and existing renewable and non-renewable 1; The ammediol production technique is compared, but has the simple continuous production of technology, and reaction conditions is gentle; In the product mixtures water-content low, 1, the content of ammediol is high, other by product is few, separate advantages such as cost for purification is low.
Embodiment
The effect that further specifies embodiment of the present invention and produced through embodiment below, but protection scope of the present invention is not limited to the listed content of embodiment.
Embodiment 1
Adopting length is that 60cm and internal diameter are the 12mm tubular fixed-bed reactor.Catalyzer is the zirconium white/Tungsten oxide 99.999 composite oxides that are attached with platinum, granularity 20～40 orders, and three metallic element weight ratios are: platinum: tungsten: zirconium=2: 10: 64.7.
Above-mentioned catalyzer is logical hydrogen under 250 ℃ earlier, and 2 milliliters of catalyst activated are got in reduction activation 1 hour, in the reactor drum of packing into.
Reaction raw materials is the aqueous glycerin solution and the hydrogen of weight concentration 60%, and hydrogen/glycerine volume ratio is 1200; The glycerine volume space velocity is 0.25h
-1, temperature of reaction is 130 ℃, reaction pressure is 4MPa.
Raw material glycerine and hydrogen are imported from the upper end import of reactor drum continuously, and after the reaction, reaction product is outlet discharge continuously from the reactor drum lower end; Through gas-liquid separation; Gas phase (being excessive hydrogen) Returning reactor, liquid product is purified through rectifying separation, remove anhydrate, n-propyl alcohol, Virahol and 1; 2-Ucar 35 by product and unconverted glycerine, the latter reclaims Returning reactor.
Liquid product whenever at a distance from sampling in 2 hours, carries out gas chromatographic analysis.Except that unconverted glycerine, only have 1 in the reaction mixture, ammediol, 1,2-Ucar 35, n-propyl alcohol, Virahol and water.Be reflected under the stable condition, glycerol conversion yield is 42.6%, contain in the reaction mixture 9.4% (weight) 1,1 of ammediol, 0.8% (weight), the Virahol of the n-propyl alcohol and 1.4% (weight) of 2-Ucar 35,7.2% (weight).With respect to former glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 18.9%.
Embodiment 2
Temperature of reaction is 120 ℃, and other condition is all identical with embodiment 1.
Reaction product gets through stratographic analysis, and glycerol conversion yield is 34.8%, contain in the reaction mixture 7.5% (weight) 1,1 of ammediol, 0.7% (weight), the Virahol of the n-propyl alcohol and 1.2% (weight) of 2-Ucar 35,5.9% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 15.3%.
This example is compared with embodiment 1, shows the reduction temperature of reaction, and glycerol conversion yield is decreased, and in the mixture of reaction back 1, the content of ammediol and 1, the productive rate of ammediol also slightly reduce.
Embodiment 3
Temperature of reaction is 140 ℃, and other condition is all identical with embodiment 1.
It is 60.5% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 10.7% (weight) 1,1 of ammediol, 0.9% (weight), the Virahol of the n-propyl alcohol and 2.1% (weight) of 2-Ucar 35,12.4% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 21.6%.
This example is compared with embodiment 1, shows the raising temperature of reaction, and glycerol conversion yield increases, and has improved in the reaction mixture 1, the weight content of ammediol and 1, and the productive rate of ammediol, but product 1, the selectivity of ammediol decreases.
Embodiment 4
Reaction raw materials employing concentration is 20% aqueous glycerin solution, and other condition is all identical with embodiment 1.
It is 59.0% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 4.9% (weight) 1,1 of ammediol, 0.3% (weight), the Virahol of the n-propyl alcohol and 0.5% (weight) of 2-Ucar 35,3.1% (weight).With respect to former glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 29.4%.
This example is compared with embodiment 1, shows that the glycerine that uses low concentration is reaction raw materials, helps improving glycerol conversion yield and 1, the relative productive rate of ammediol, but in the reaction mixture 1, the weight content of ammediol has reduced.
Embodiment 5
Reaction raw materials employing glycerol content is 80% aqueous glycerin solution, and other condition is all identical with embodiment 1.
It is 20.8% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 5.5% (weight) 1,1 of ammediol, 0.7% (weight), the Virahol of the n-propyl alcohol and 1.0% (weight) of 2-Ucar 35,4.9% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 8.3%.
This example is compared with embodiment 1, shows that the glycerine that uses higher concentration is reaction raw materials, and glycerol conversion yield reduced, 1, and in the productive rate of ammediol and the reaction mixture 1, the weight content of ammediol has also reduced.
Embodiment 6
Adopting the glycerine volume space velocity is 0.5h
-1, hydrogen/glycerine volume ratio is 600, other condition is all with embodiment 1.
It is 22.4% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 4.5% (weight) 1,1 of ammediol, 0.3% (weight), the Virahol of the n-propyl alcohol and 0.7% (weight) of 2-Ucar 35,4.2% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 9%.
This example is compared with embodiment 1, and expression glycerine volume space velocity increases, and hydrogen/glycerine volume ratio reduces, and makes glycerol conversion yield, 1, and in the productive rate of ammediol and the reaction mixture 1, the weight content of ammediol all descends.
Embodiment 7
Reaction pressure adopts 5.0MPa, and other condition is all with embodiment 1.
It is 45.4% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 10.3% (weight) 1,1 of ammediol, 0.9% (weight), the Virahol of the n-propyl alcohol and 1.4% (weight) of 2-Ucar 35,7.5% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 20.8%.
This example is compared with embodiment 1, and expression augmenting response pressure makes in glycerol conversion yield, the reaction mixture 1, and the weight content of ammediol and 1, the productive rate of ammediol all increase to some extent.
Embodiment 8
Reaction pressure adopts 3.0MPa, and instead other condition is all with embodiment 1.
It is 33.8% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 6.3% (weight) 1,1 of ammediol, 1.3% (weight), the Virahol of the n-propyl alcohol and 1.3% (weight) of 2-Ucar 35,6.3% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 12.6%.
This example is compared with embodiment 1, and expression reduces reaction pressure, makes in glycerol conversion yield, the reaction mixture 1, the weight content of ammediol and 1, and the productive rate of ammediol all decreases.
Embodiment 9
Three metallic element weight ratios are platinum in the catalyzer: tungsten: zirconium=2: 5: 69,130 ℃ of temperature of reaction, reaction pressure 4MPa, glycerine volume space velocity 0.25h
-1, hydrogen/glycerine volume ratio 1200, other condition is all with embodiment 1.
It is 27.0% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 6.0% (weight) 1,1 of ammediol, 1.3% (weight), the Virahol of the n-propyl alcohol and 0.8% (weight) of 2-Ucar 35,4.0% (weight).With respect to glycerine (not comprising water) charging capacity, 1, the productive rate of ammediol is 12.0%.
Embodiment 10
Three metallic element weight ratios are platinum in the catalyzer: tungsten: zirconium=3: 10: 64.7.Temperature of reaction (130 ℃), reaction pressure 4MPa, glycerine volume space velocity 0.25h
-1, hydrogen/glycerine volume ratio (1200), other condition is all with embodiment 1.
It is 79.5% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 17.2% (weight) 1,1 of ammediol, 0.6% (weight), the Virahol of the n-propyl alcohol and 1.9% (weight) of 2-Ucar 35,15.2% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 34.7%.
Embodiment 11
Three metallic element weight ratios are platinum in the catalyzer: tungsten: zirconium=3: 10: 64.7.120 ℃ of temperature of reaction, reaction pressure (4MPa), glycerine volume space velocity 0.25h
-1, hydrogen/glycerine volume ratio 1200, other condition is all with embodiment 1.
It is 34.5% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 8.9% (weight) 1,1 of ammediol, 0.3% (weight), the Virahol of the n-propyl alcohol and 0.9% (weight) of 2-Ucar 35,5.3% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 18.0%.
Embodiment 12
Three metallic element weight ratios are platinum in the catalyzer: tungsten: zirconium=2: 15: 60,130 ℃ of temperature of reaction, reaction pressure 4MPa, glycerine volume space velocity 0.25h
-1, hydrogen/glycerine volume ratio 1200, other condition is all with embodiment 1.
It is 29.9% that reaction product gets glycerol conversion yield through stratographic analysis, contain in the reaction mixture 5.3% (weight) 1,1 of ammediol, 1.0% (weight), the Virahol of the n-propyl alcohol and 1.1% (weight) of 2-Ucar 35,5.6% (weight).With respect to glycerine charging capacity (not comprising water), 1, the productive rate of ammediol is 10.7%.
Claims (6)
1. one-step glycerol catalyzed conversion preparation 1 continuously; The method of ammediol; With glycerine is raw material, it is characterized in that in the presence of metal/solid acid dual-function catalyst, and aqueous glycerin solution and hydrogen are fed fixed-bed reactor simultaneously continuously; In temperature is 100～150 ℃, and pressure is to carry out catalyzed reaction under 2～8MPa; Wherein, the volume ratio of hydrogen and aqueous glycerin solution is 600～1200, and the volume space velocity of aqueous glycerin solution is 0.15～1h
-1Remove gaseous hydrogen from reactor outlet collecting reaction product and gas-liquid separation, liquid phase is removed by product through fractionation by distillation, gets 1, the ammediol product; Said metal/solid acid dual-function catalyst is the zirconium white/Tungsten oxide 99.999 composite oxides that are attached with platinum, and the weight ratio of each metallic element is Pt:W:Zr=1～5:5～20:69～55 in this catalyzer.
2. one-step glycerol catalyzed conversion according to claim 1 is preparation 1 continuously, and the method for ammediol is characterized in that said aqueous glycerin solution weight concentration is 20～80%.
3. one-step glycerol catalyzed conversion according to claim 2 is preparation 1 continuously, and the method for ammediol is characterized in that the catalyzed reaction temperature that it is said is 120～140 ℃, and reaction pressure is 3～6MPa.
4. one-step glycerol catalyzed conversion according to claim 3 is preparation 1 continuously, the method for ammediol, and the volume space velocity that it is characterized in that said aqueous glycerin solution is 0.15～0.5h
-1
5. according to the preparation 1 continuously of claim 1 or 2 or 3 or 4 described one-step glycerol catalyzed conversions, the method for ammediol, it is characterized in that said catalyzer uses before, reduction activation 1 hour under hydrogen stream and 150 ℃～300 ℃ temperature earlier.
6. one-step glycerol catalyzed conversion according to claim 5 is preparation 1 continuously, and the method for ammediol is characterized in that the catalyst reduction activation temperature is 180～250 ℃.
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| WO2013024055A1 (en) * | 2011-08-17 | 2013-02-21 | Solvay Sa | Process for the manufacture of propanediol |
| CN102344341B (en) * | 2011-09-30 | 2014-03-12 | 东南大学 | Method for preparing 1,3-propylene glycol by utilizing glycerol one-step hydrogenolysis method |
| JP5886678B2 (en) * | 2012-04-19 | 2016-03-16 | 株式会社ダイセル | Process for producing 1,3-propanediol and catalyst for hydrogenation reaction of glycerin |
| CN102942448A (en) * | 2012-12-10 | 2013-02-27 | 南京工业大学 | Method for continuously preparing 1, 5-pentanediol from tetrahydrofurfuryl alcohol |
| CN103524302A (en) * | 2013-09-30 | 2014-01-22 | 南京工业大学 | Technological method for preparing 1, 3-propylene glycol by adopting glycerin and hydrogen |
| CN103922893B (en) * | 2014-04-19 | 2015-11-25 | 青岛科技大学 | A kind of composite catalyst hydrogenolysis catalysis of glycerin prepares the method for 1,2-PD |
| CN107096564B (en) * | 2017-06-05 | 2019-11-01 | 扬州大学 | A kind of SAPO-34 supporting Pt and the catalyst of WOx and preparation method thereof |
| CN111039756B (en) * | 2018-10-15 | 2023-10-10 | 中国石油化工股份有限公司 | Method and system for preparing 1, 3-propanediol |
| CN112169795B (en) * | 2019-07-02 | 2022-05-06 | 中国科学院大连化学物理研究所 | Optimized polyol hydrogenolysis catalyst activation process |
| CN110746269A (en) * | 2019-11-06 | 2020-02-04 | 山西中医药大学 | Synthesis method of 1, 3-propylene glycol |
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