CN101353291A - Method for preparing 1,2-propanediol by catalysis hydrogenation of biodisel-based crude glycerine - Google Patents
Method for preparing 1,2-propanediol by catalysis hydrogenation of biodisel-based crude glycerine Download PDFInfo
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- CN101353291A CN101353291A CNA2008101207278A CN200810120727A CN101353291A CN 101353291 A CN101353291 A CN 101353291A CN A2008101207278 A CNA2008101207278 A CN A2008101207278A CN 200810120727 A CN200810120727 A CN 200810120727A CN 101353291 A CN101353291 A CN 101353291A
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- propylene glycol
- glycerine
- catalyst
- biodiesel
- reaction
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 213
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 31
- 235000011187 glycerol Nutrition 0.000 title claims description 92
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 9
- 238000006555 catalytic reaction Methods 0.000 title description 4
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 title 1
- 235000013772 propylene glycol Nutrition 0.000 title 1
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000003225 biodiesel Substances 0.000 claims abstract description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000007787 solid Substances 0.000 claims abstract description 17
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- 230000000694 effects Effects 0.000 claims description 12
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 11
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 11
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 11
- 229960001545 hydrotalcite Drugs 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 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 8
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 238000004904 shortening Methods 0.000 claims description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 239000003513 alkali Substances 0.000 abstract description 9
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 2
- 229960004063 propylene glycol Drugs 0.000 abstract 4
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 30
- 230000009466 transformation Effects 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- 239000002551 biofuel Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004702 methyl esters Chemical class 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002674 ointment Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910017767 Cu—Al Inorganic materials 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000003084 food emulsifier Nutrition 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 229910021472 group 8 element Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- -1 propylene glycol fatty acid ester Chemical class 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method for preparing 1, 2-propylene glycol by directly adding hydrogen into glycerol comprises the steps as follows: biodiesel-based crude glycerol is taken as raw material, and intermittent one-step reaction is carried out on the biodiesel-based crude glycerol to prepare the 1, 2-propylene glycol at the temperature of 220 DEG C for 6-20 hours under the action of a solid alkali-metal catalyst. The conversion rate of the glycerol is up to 92%, and the yield of the 1, 2-propylene glycol is up to 87%. Compared with the existing preparation method for 1, 2-propylene glycol, the solid alkali-metal catalyst of the method can effectively avoid the influences of alkali impurities in the biodiesel-based crude glycerol solution; and the method has the advantages of simple process, high yield, low cost, little environmental pollution and simple separation.
Description
Technical field:
The present invention relates to be a kind of be raw material with the biodiesel base crude glycerine, under the metal catalyst effect of solid alkali load, directly the shortening preparation 1, the reaction process of 2-propylene glycol and catalyzer.
Background technology:
1, (1,2-Propylene glycol is called for short 1 to the 2-propylene glycol, 2-PDO), is a kind of colourless, thickness, stable water-absorbent liquid, and the substantially tasteless odorless is inflammable, fusing point-60 ℃.187.3 ℃ of boiling points, relative density 1.036 (25/4 ℃) is with water, ethanol and multiple immiscible organic solvent.In easily oxidation more than 150 ℃.1, the 2-propylene glycol is the important source material of unsaturated polyester, Resins, epoxy, urethane resin, and this unsaturated polyester is used for topcoating and reinforced plastics in a large number.1, the viscosity of 2-propylene glycol and good hygroscopicity, and nontoxic, thereby in food, medicine and cosmetic industry, be widely used as moisture adsorbent, antifreezing agent, lubricant and solvent.In foodstuffs industry, propylene glycol and fatty acid response generate propylene glycol fatty acid ester, mainly as food emulsifier; Propylene glycol is the fine solvent of seasonings and pigment.1, the 2-propylene glycol is commonly used for solvent, tenderizer and the vehicle etc. of making all kinds of ointment, ointment in medicine industry, because propylene glycol has better mutual solubility with all kinds of spices, thereby also is used as the solvent of makeup and tenderizer or the like.Propylene glycol is also as tobacco moistening agent, mould inhibitor, the solvent of food processing plant lubricating oil and food labeling printing ink.The aqueous solution of propylene glycol is effective antifreezing agent.
Present 1, the production method of 2-propylene glycol mainly contains three kinds: (1) propylene oxide direct hydration method is a pressurization non-catalytic hydrolyzing method; Under 150-160 ℃, 0.78-0.98MPa pressure, direct hydration makes by propylene oxide and water, and reaction product is through evaporation, rectifying, finished product.(2) the indirect hydration method of propylene oxide is done the indirect hydration of catalyzer by propylene oxide and water with sulfuric acid and is made.(3) the direct catalytic oxidation of propylene.These methods exist problems such as the serious and cost costliness of environmental pollution, are difficult to scale operation.Simultaneously, because the quick rise of petrochemical material prices such as propylene, the cost of above-mentioned production technique is also more and more higher, so the direct shortening preparation 1 of research and development low cost, efficient, eco-friendly heterogeneous catalysis glycerine, and the method for 2-propylene glycol has great importance.
From glycerine preparation 1, the 2-propylene glycol has had some patent reports, as: German patent DE-PS-541362 has reported glycerine hydrogenation preparation 1 under the nickel-base catalyst effect the earliest, the method of 2-propylene glycol, but reaction needed just can be carried out at (more than 270 degree) under the very high temperature, have a large amount of gaseous products to generate (mainly being methane) simultaneously in the reaction, thereby wastage of material yield serious, the purpose product is not high.European patent EP-A-72629 has described the polyvalent alcohol hydrogenation process (centre also comprises glycerine) under a kind of nickel, platinum, the palladium catalyst effect, in order to obtain corresponding dibasic alcohol, must add mineral alkali in reaction solution.This technology is also adopted by afterwards a lot of research papers (Journal of Catalysis 249 (2007) 328-337 and Catalysis Letters 117 (2007) 62-67), but pollutes big, product separation difficulty.U.S. Pat 4642394 has been described under the homogeneous catalyst effect of tungstenic and group VIII element, and glycerine and synthesis gas reaction prepare the method for propylene glycol, when adopting methyl ethyl diketone rhodium carbonyl and H
2WO
4Acid is solvent, temperature of reaction 200 degree, synthetic gas (CO: H for catalyzer, 1-Methyl-2-Pyrrolidone
2=1: 2) pressure 4600psig, reaction times 24 hours, propylene glycol yield 44%, n-propyl alcohol yield 4%; The product yield of this patent is low, reaction pressure is high, and homogeneous catalyst is difficult to Separation and Recovery and metal rhodium catalyzer and costs an arm and a leg etc. and to make it less economical, does not have competitive power.U.S. Pat 5214219 has been reported a kind of glycerine production 1 that is used for, and the method for 2-propylene glycol, this method are utilized the bimetal loaded catalyst of Cu and Zn.But temperature of reaction is higher than 250 ℃, hydrogen pressure more than 150 normal atmosphere, and catalyst consumption higher (be the 5-15% of glycerol concentration), glycerol concentration low (20-40%) are difficult to the realization industrialization simultaneously.It is the glycerine hydrogenation preparation 1 that catalyzer carries out that U.S. Pat 5276181 provides a kind of Ru/ activated carbon with sulfide and alkali modification, the method of 2-propylene glycol, under the condition of the massfraction 30% of temperature 240 degree, hydrogen pressure 130 normal atmosphere, glycerine, the selectivity of propylene glycol is still very low.U.S. Pat 5616817 and Chinese patent CN1061968C have reported glycerine hydrogenation preparation 1 on the Co-Cu-Mn-Mo catalyzer, the method of 2-propylene glycol, but reaction pressure high especially (250 normal atmosphere), and Preparation of catalysts method complexity, facility investment height, 1, the selectivity of 2-propylene glycol is very low.Chinese invention patent application CN200610105255.X discloses a kind of by glycerine hydrogenation preparation 1, and the method for 2-propylene glycol reaction, this method adopt the CuO-SiO of pure hot method preparation
2Catalyzer carries out but be reflected in the hypertoxic methanol solvate.Chinese invention patent application CN101085719 discloses the directly hydrogenizing glycerol preparation 1 under the effect of a kind of polycomponent compound Co-Cu-Al series catalysts, the technology of 2-propylene glycol, but react that needed temperature is above at 220 degree, reaction pressure more than 100 normal atmosphere, catalyst consumption big (catalyst levels accounts for and reacts feed liquid more than 2%) simultaneously.In recent years, along with the fast development of biofuel industry, glycerine will increase year by year as the output of the main by product in the production of biodiesel process; According to estimates, will be to the output of biodiesel base crude glycerine in 2010 above 1,200,000 tons, superfluous 500,000 tons.Therefore, be that the propylene glycol etc. of raw material production high added value is the important outlet that solves the superfluous problem of glycerine with the biodiesel base crude glycerine, the sound development that promotes biofuel and biomass energy industry is had great importance.
Though above-mentioned serial patent of invention all reported set out by glycerine synthetic 1, the technology of 2-propylene glycol, ubiquitous problem is: temperature of reaction height (generally 220 spend more than), reaction pressure height (generally more than 100 normal atmosphere); Do not take into full account the concrete characteristics of biodiesel base crude glycerine simultaneously, that is: the general content of biodiesel base crude glycerine is glycerine 80-85%, except water, contain the catalyzer of a spot of production biofuel (as alkali (NaOH, Ca (OH) in the raw material toward contact
2And NaH
2PO
4Deng), residual production of biodiesel raw material and component (as: methyl alcohol, glycerine alkyl acid methyl esters), relate in addition in the disclosed in front patent of this part impurity; Wherein mineral alkali has toxic action to the solid acid catalyst that the overwhelming majority has dehydration activity.
Summary of the invention
The objective of the invention is at containing a small amount of alkaline impurities, residual biodiesel fuel component in the biodiesel base crude glycerine, and the temperature of reaction height, the propylene glycol productive rate is low, cost is high and problem such as environmental pollution, it is raw material that a kind of biodiesel base crude glycerine that can directly adopt is provided, under the effect of the metal catalyst of basic supports load, intermittent type single step reaction preparation 1, the method of 2-propylene glycol, have that technology is simple, temperature of reaction is low, productive rate is high, cost is low, low in the pollution of the environment, separate simple advantage.
Solution of the present invention is: adopt solid alkali-metal catalyst to eliminate and break away from the influence of a small amount of alkaline impurities in the biodiesel base crude glycerine, a step is realized the glycerine hydrogenation preparation 1 of different concns, 2-propylene glycol in autoclave.
Biodiesel base crude glycerine shortening of the present invention directly prepares 1, the method of 2-propylene glycol, be being raw material without the biodiesel base crude glycerine of purifying, reductive agent is a high-purity hydrogen, under solid alkali-metal catalyst effect, the catalytic hydrogenolysis biodiesel base crude glycerine obtains 1 of high yield, the 2-propylene glycol, preparation process is as follows:
1. with qualities of glycerin concentration the biodiesel base crude glycerine solution of 15%-90%, join in the stainless steel autoclave that has liner, add a certain amount of catalyzer then in biodiesel base crude glycerine solution, the quality of the metal in the control catalyst is that the ratio of qualities of glycerin is 1/100-1/10000.
2. with after the aforesaid reaction vessel sealing, fall air in the reactor with hydrogen exchange, charge into hydrogen to 30 normal atmosphere then.
3. heat temperature raising makes the temperature in the reactor reach 180-260 ℃, starts agitator simultaneously, reacts 6-20 hour.
4. after reaction finished, with the reactor cool to room temperature, first centrifugation, decompress filter again made reaction product solution and catalyst separating, catalyst recovery.
5. filter to isolate after the catalyzer, reaction solution is carried out constant volume, carry out gas chromatographic analysis.
Solid alkali-metal catalyst of the present invention, carrier comprises: hydrotalcite, magnesium oxide, aluminium sesquioxide, Beta molecular sieve, HZSM5 molecular sieve, zirconium white or cerium oxide; Metal active constituent comprises: platinum, palladium, ruthenium, gold or nickel, the charge capacity of metal is: 1～10wt%.Preferred support of the catalyst is hydrotalcite and magnesium oxide.Preferred reactive metal is platinum and ruthenium.
The preparation process of solid alkali-metal catalyst of the present invention is as follows:
(1) with hydrotalcite, magnesium oxide, aluminium sesquioxide, Beta molecular sieve, HZSM5 molecular sieve, zirconium white or cerium oxide carrier 400-550 ℃ of following pre-treatment 4 hours;
(2) by equi-volume impregnating with metal load to carrier, with pretreated carrier impregnation loaded metal active ingredient, control metal charge capacity 1～10wt%, under the room temperature dipping 12 hours;
(3) carrier of above-mentioned loaded metal is in 110 ℃ of baking ovens dry 12 hours, and roasting 4 hours under 400-550 ℃ of condition then obtains solid alkali-metal catalyst.
Carrier hydrotalcite described in the preparation of solid alkali-metal catalyst of the present invention was 400 ℃ of following pre-treatment 4 hours, and other carrier was 550 ℃ of following pre-treatment 4 hours.
The charge capacity of ruthenium, gold, metallic palladium described in the preparation of solid alkali-metal catalyst of the present invention is 2wt%, and the charge capacity of nickel is 10wt%, and the charge capacity of platinum is 1wt%, 2wt% and 5wt%.
The roasting 4 hours under 400 ℃ of conditions of the metal catalyst of hydrotalcite load described in the preparation of solid alkali-metal catalyst of the present invention; The roasting 4 hours under 550 ℃ of conditions of other carrier loaded metal catalyst.
Before the reaction of solid alkali of the present invention-metal catalyst in the hydrogen stream of certain temperature reductase 12 hour.
Advantage of the present invention:
Biodiesel base crude glycerine shortening of the present invention directly prepares 1, and the method for 2-propylene glycol is being raw material without the biodiesel base crude glycerine of purifying, contain in this raw material a spot of production of biodiesel catalyzer (as alkali: NaOH, Ca (OH)
2, NaH
2PO
4), residual biodiesel fuel component (as: methyl alcohol, glycerine alkyl acid methyl esters, C14-C18 alkyl acid sodium etc.), the consisting of of representational raw glycerine in the embodiments of the invention: glycerine 85.1% (weight percent, as follows), C14-C17 alkanoic acid methyl esters 8.3%, methyl alcohol 3.3%, water 2.8%, C14-C17 alkanoic acid sodium 0.4%, NaOH+Ca (OH)
20.1%.
With existing preparation 1, the method of 2-propylene glycol is compared, solid alkali-metal catalyst of the present invention can effectively overcome the influence of the alkaline impurities in the biodiesel base crude glycerine solution, and this catalyzer not only has very high activity, and low to the purity requirement of raw material.Have that technology is simple, productive rate is high, cost is low, low in the pollution of the environment, separate simple advantage.
Catalyst levels of the present invention is low, and the mass ratio of glycerine/metal is greater than 100 in the reaction system.
Reaction conditions gentleness of the present invention, reaction pressure low (the initial hydrogen atmospheric pressure is lower than 30 normal atmosphere), temperature of reaction are lower than 230 degree.The transformation efficiency of glycerine reaches as high as 92%, 1, and the yield of 2-propylene glycol reaches 87%.Under the effect of Pt/ hydrotalcite catalyst, the transformation efficiency of glycerine is up to 92%, 1, and the yield of 2-propylene glycol reaches 87%; Under the effect of Pt/MgO catalyzer, the transformation efficiency of glycerine reaches 50%, 1, and the yield of 2-propylene glycol reaches 40%.
Technology of the present invention provides a kind of novel suitability for industrialized production 1 that can be used for, the new way of 2-propylene glycol, make carrier with solid alkali, metals such as supporting Pt, Ru, Ni, Au, Pd come hydrogenolysis catalysis of glycerin to produce 1, the 2-propylene glycol, abandoned industrial production 1 in the past, 2-propylene glycol productive rate is low, problems such as cost height and environmental pollution.
Embodiment:
Embodiment 1
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add the Pt/MgO catalyzer (the Pt charge capacity is 2wt%) after 2.0 grams reduce, with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature in the control reactor is 220 ℃, reacts 20 hours.After reaction finishes, reactor cool to room temperature, first centrifugation, decompress filter reaction solution again, make reaction product solution and catalyst separating, reaction solution is carried out gas chromatographic analysis, and the transformation efficiency that calculates glycerine is 50% and 1, and the molar yield of 2-propylene glycol is 40%.
Embodiment 2
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add the Pt/MgO catalyzer (the Pt charge capacity is 2wt%) after 2.0 grams reduce, with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 250 ℃, reacts 20 hours.The transformation efficiency that ultimate analysis obtains glycerine is 92%, 1, and the molar yield of 2-propylene glycol is 67%.
Embodiment 3
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add the Pt/ hydrotalcite catalyst (the Pt charge capacity is 2wt%) after 2.0 grams reduce, with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.The transformation efficiency that ultimate analysis obtains glycerine is 92%, 1, and the molar yield of 2-propylene glycol is 87%.
Embodiment 4
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, add the Pt/Al after the 2.0 gram reduction
2O
3Catalyzer (the Pt charge capacity is 2wt%).With the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.The transformation efficiency of last glycerine is 50%, 1, and the molar yield of 2-propylene glycol is 41%.
Embodiment 5
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, add the Pt/Beta molecular sieve catalysts (the Pt charge capacity is 2wt%) after the 2.0 gram reduction.With the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.The transformation efficiency of last glycerine is 6.9%, 1, and the yield of 2-propylene glycol is 0.61%.
Embodiment 6
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, add the Pt/HZSM5 molecular sieve catalysts (the Pt charge capacity is 2wt%) after the 2.0 gram reduction.With the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.The transformation efficiency of last glycerine is 4.0%, 1, and the yield of 2-propylene glycol is 0.76%.
Embodiment 7
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, add the Ni/MgO catalyzer (the Ni charge capacity is 10wt%) after the 2.0 gram reduction.With the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.Ultimate analysis obtains the transformation efficiency 32%, 1 of glycerine, and the yield of 2-propylene glycol is 25.3%.
Embodiment 8
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, the Au/MgO that add after the 2.0 gram reduction are catalyzer (the Au charge capacity is 2wt%).With the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.Ultimate analysis obtains glycerol conversion yield 3.7%, 1, and the yield of 2-propylene glycol is 2.8%.
Embodiment 9
Accurately measure glycerol content and be 85.1% biodiesel base crude glycerine 20 grams and put in the autoclave, add the Ru/MgO catalyzer (the Ru charge capacity is 2wt%) after the 2.0 gram reduction.With the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.Ultimate analysis obtains the transformation efficiency 61%, 1 of glycerine, and the yield of 2-propylene glycol is 50%.
Embodiment 10
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add the Pt/ hydrotalcite catalyst (the Pt charge capacity is 1wt%) after 2.0 grams reduce, with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.The transformation efficiency that ultimate analysis obtains glycerine is 33%, 1, and the molar yield of 2-propylene glycol reaches 30%.
Embodiment 11
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add the Pt/ hydrotalcite catalyst (the Pt charge capacity is 5wt%) after 2.0 grams reduce, with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 6 hours.The transformation efficiency that ultimate analysis obtains glycerine is 81.7%, 1, and the molar yield of 2-propylene glycol reaches 73.5%.
Embodiment 12
Accurately measuring glycerol content and be 85.1% biodiesel base crude glycerine 20 grams puts in the autoclave, add the Pd/MgO catalyzer (the Pd charge capacity is 2wt%) after 2.0 grams reduce, with the air in the hydrogen exchange reactor, charge into the hydrogen of 3.0MPa then after the sealing.Stirring is started in heating simultaneously, and the temperature of control reaction is 220 ℃, reacts 20 hours.The transformation efficiency that ultimate analysis obtains glycerine is 4%, 1, and the molar yield of 2-propylene glycol reaches 3.6%.
Embodiment 13
Implementation step is consistent with embodiment 3 with catalyzer, and the reaction times changes 12h into, and the last transformation efficiency of glycerine is 87.6%, 1, and the yield of 2-propylene glycol is 82.6%.
Claims (4)
1, a kind of biodiesel base crude glycerine shortening directly prepares 1, and the method for 2-propylene glycol is characterized in that: be raw material with the biodiesel base crude glycerine, under the effect of solid alkali-metal catalyst, intermittent type single step reaction preparation 1, the 2-propylene glycol, preparation process is as follows:
1). with qualities of glycerin concentration is the biodiesel base crude glycerine solution of 15%-90%, join in the stainless steel autoclave that has liner, add solid alkali-metal catalyst then in biodiesel base crude glycerine solution, the quality of the metal in the control catalyst is that the ratio of qualities of glycerin is 1/100-1/10000;
2). with after the aforesaid reaction vessel sealing, fall air in the reactor, charge into hydrogen to 30 normal atmosphere then with hydrogen exchange;
3). heat temperature raising, make the temperature in the reactor reach 180-260 ℃, start agitator simultaneously, reacted 6-20 hour;
4). after reaction finished, with the reactor cool to room temperature, first centrifugation, decompress filter again made reaction product solution and catalyst separating, catalyst recovery.
2, according to the described preparation 1 of claim 1, the method for 2-propylene glycol is characterized in that: the solid alkali-metal catalyst that is adopted, and carrier comprises: hydrotalcite, magnesium oxide, aluminium sesquioxide, Beta molecular sieve, HZSM5 molecular sieve, zirconium white or cerium oxide; Metal active constituent comprises: platinum, palladium, ruthenium, gold or nickel; The charge capacity of metal is: 1～10wt%.
3, according to the direct hydrogenation preparing 1 of the described glycerine warp of claim 2, the method for 2-propylene glycol is characterized in that: support of the catalyst is hydrotalcite or magnesium oxide.
4, glycerine according to claim 2 is through direct hydrogenation preparing 1, and the method for 2-propylene glycol is characterized in that: metal active constituent is platinum or ruthenium.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166525A (en) * | 2011-03-16 | 2011-08-31 | 浙江大学 | Copper-rhodium-magnesium-aluminum four-component catalyst for preparing 1,2-propylene glycol by adding hydrogen directly to biodiesel-based crude glycerine and preparation method of 1,2-propylene glycol |
| CN102198402A (en) * | 2011-03-16 | 2011-09-28 | 浙江大学 | Cu-Pd-Mg-Al four-component catalyst for preparing 1,2-propylene glycol (1,2-PDO) by hydrogenation of biodiesel-based crude glycerin as well as preparation method thereof |
| CN102775949A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Biodiesel byproduct based adhesive, and preparation method and application thereof |
| JP2014152153A (en) * | 2013-02-12 | 2014-08-25 | Daicel Corp | Method for producing 1,2-pentane diol |
| CN104058933A (en) * | 2014-06-23 | 2014-09-24 | 上海康沃生化科技有限公司 | Biodiesel based crude glycerol catalytic hydrogenolysis method for preparation of propylene glycol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100537503C (en) * | 2007-05-31 | 2009-09-09 | 上海华谊丙烯酸有限公司 | Process for preparing n-propanol by hydrogenating glycerol |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102166525A (en) * | 2011-03-16 | 2011-08-31 | 浙江大学 | Copper-rhodium-magnesium-aluminum four-component catalyst for preparing 1,2-propylene glycol by adding hydrogen directly to biodiesel-based crude glycerine and preparation method of 1,2-propylene glycol |
| CN102198402A (en) * | 2011-03-16 | 2011-09-28 | 浙江大学 | Cu-Pd-Mg-Al four-component catalyst for preparing 1,2-propylene glycol (1,2-PDO) by hydrogenation of biodiesel-based crude glycerin as well as preparation method thereof |
| CN102166525B (en) * | 2011-03-16 | 2014-04-30 | 浙江大学 | Copper-rhodium-magnesium-aluminum four-component catalyst for preparing 1,2-propylene glycol by adding hydrogen directly to biodiesel-based crude glycerine and preparation method of 1,2-propylene glycol |
| CN102775949A (en) * | 2012-08-17 | 2012-11-14 | 济南大学 | Biodiesel byproduct based adhesive, and preparation method and application thereof |
| CN102775949B (en) * | 2012-08-17 | 2013-10-30 | 济南大学 | Biodiesel byproduct based adhesive |
| JP2014152153A (en) * | 2013-02-12 | 2014-08-25 | Daicel Corp | Method for producing 1,2-pentane diol |
| CN104058933A (en) * | 2014-06-23 | 2014-09-24 | 上海康沃生化科技有限公司 | Biodiesel based crude glycerol catalytic hydrogenolysis method for preparation of propylene glycol |
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