CN102504891A - Preparation method of glyceryl biological fuel additives - Google Patents
Preparation method of glyceryl biological fuel additives Download PDFInfo
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- CN102504891A CN102504891A CN2011103408004A CN201110340800A CN102504891A CN 102504891 A CN102504891 A CN 102504891A CN 2011103408004 A CN2011103408004 A CN 2011103408004A CN 201110340800 A CN201110340800 A CN 201110340800A CN 102504891 A CN102504891 A CN 102504891A
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- glycerine
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- low
- glyceryl
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- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 125000003976 glyceryl group Chemical group [H]C([*])([H])C(O[H])([H])C(O[H])([H])[H] 0.000 title claims abstract description 10
- 239000002816 fuel additive Substances 0.000 title abstract 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 133
- 235000011187 glycerol Nutrition 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000005917 acylation reaction Methods 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000004821 distillation Methods 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- 230000035484 reaction time Effects 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000003377 acid catalyst Substances 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000000376 reactant Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- 239000002551 biofuel Substances 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 claims description 14
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 claims description 8
- 150000002170 ethers Chemical class 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- MQVRLONNONYDJP-UHFFFAOYSA-N propane-1,1,2,3-tetrol Chemical class OCC(O)C(O)O MQVRLONNONYDJP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 239000003456 ion exchange resin Substances 0.000 claims description 3
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 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 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 23
- 238000006266 etherification reaction Methods 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002485 combustion reaction Methods 0.000 abstract description 3
- 150000002314 glycerols Chemical class 0.000 abstract description 2
- HSRJKNPTNIJEKV-UHFFFAOYSA-N Guaifenesin Chemical compound COC1=CC=CC=C1OCC(O)CO HSRJKNPTNIJEKV-UHFFFAOYSA-N 0.000 abstract 2
- 239000002250 absorbent Substances 0.000 abstract 2
- 230000002745 absorbent Effects 0.000 abstract 2
- 125000005456 glyceride group Chemical group 0.000 abstract 2
- 229910001873 dinitrogen Inorganic materials 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 19
- 238000004587 chromatography analysis Methods 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000010025 steaming Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical compound CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000007171 acid catalysis Methods 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003225 biodiesel Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- -1 glycerine deutero-glycerine Chemical compound 0.000 description 2
- 125000005908 glyceryl ester group Chemical group 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229940099204 ritalin Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method for converting glycerol into a glycerol derivative system simultaneously containing glycerin ether and glyceride to be used as a fuel additive. Low-carbon alcohol and glycerol are used as starting materials, the mol ratio of the low-carbon alcohol to the glycerol is 2:1 to 8:1, the dosage of acid catalysts accounts for 0.5 percent to 10 percent of the total mass of reactants, water absorbents account for 1.5 percent to 10 percent of the total mass of the reactants, nitrogen gas is used for replacing air in a kettle, the initial pressure in the kettle is 0 to 4 MPa, the reaction temperature is 30 to 130 DEG C, and the reaction time is 4 to 10 hours; and the reduced pressure distillation is carried out after cooling, then, the acylation reaction is carried out, the reaction temperature is 60 to 150 DEG C, the reaction time is 1 to 4 hours, and glyceryl biological fuel additives are obtained. The fuel combustion performance can be improved through glycerin ether, and simultaneously, the fuel viscocity can be improved through the contained glyceride. The acidylation is carried out after the etherification, and the problem of low glycerol hydroxyl etherification rate is solved, so the additives and the fuel are mixed more uniformly. The catalyst and the water absorbents recovered through filtering and the low-carbon alcohol can be repeatedly utilized.
Description
Technical field
The present invention relates to the fuel technology field, especially relate to the preparation method who improves the fuel combustion performance and reduce the fuel dope of Air, be specifically related to utilize acid catalysis with glycerine elder generation etherificate, back acidylate prepares the method for glyceryl biofuel additive.
Background technology
Along with reducing day by day of world's Nonrenewable energy resources and increasing the weight of day by day of environmental pollution, environmentally friendly and reproducible biofuel has obtained various countries scientific research personnel's extensive concern, and global yield of biodiesel in 2011 is estimated to reach 2,600 ten thousand tons.Glycerine prepares the by product of biofuel as transesterification reaction, and its price constantly descends along with the increase year by year of yield of biodiesel, how efficiently to utilize glycerine, and the preparation high value-added product becomes one of research direction in recent years.Transformation of glycerol for improving the additive of fuel characteristic, is had broad prospects, become the focus of research.
Glycerol molecule contains 3 polar hydroxyls, and it is relatively poor to cause glycerine to mix with biofuel, and insufficient meeting of burning produces obnoxious flavoures such as carbon monoxide, and glycerine viscosity causes motor fault greatly easily simultaneously.Glycerine is developed to the glyceryl fuel dope through approach such as etherificate, esterification or oxidations makes an addition in the fuel gasoline diesel oil, can reduce the discharge of harmful gases amount, improve flash-point, cetane value, reduce cold filter clogging temperature, reduce viscosity and enhanced oxidation property etc.Solve the superfluous problem of glycerine simultaneously, increase the economic benefit of biofuel.
For example, in the prior art: CN101970390A is through using solid acid catalyst, use primary alconol as etherifying agent with the glycerine etherificate, it is lower and be soluble in the glyceryl ether fuel dope of diesel oil, 60～300 ℃ of temperature of reaction, reaction times 5～8h to change into boiling point.
US5476971 and US6174501 are in the presence of strong acid catalyst; Glycerine and iso-butylene or isopentene are reacted with the gas-liquid two-phase form, obtain to reduce the glyceryl ether of biofuel viscosity, though the transformation efficiency of glycerine is high; But the gas-liquid two-phase reacting phase is to the homogeneous reaction complex process; Energy consumption is high, will increase production cost, and the easy polymerization reaction take place of alkene obtains nonflammable throw out simultaneously.
US5308365, US1968033 and US5578090 have explored in the presence of acid catalyst; The method of glycerine and alkene or short chain alcohol prepared in reaction glyceryl ether; Though the glyceryl ether boiling point that obtains is lower than glycerine; But often have one or two hydroxyl on the molecule, be not suitable for the application of fuel dope.
US20100016641 is 150～300 ℃ of temperature of reaction; Reaction pressure 0.1～2.2psia; Under the condition of solid acid catalysis, (C1～C4) reaction has obtained the ether that boiling point is lower than glycerine, and the additive that can be used as fuel improves the combustionproperty of biofuel for glycerine and low-carbon (LC) straight chain alcohol.
Above glyceryl ether is mixed into the cetane value that all can improve fuel in the biofuel; But because steric effect makes the glycerine diether and the glycerine three ether yields that make low; Still have certain hydroxy radical content; Cause additive and biofuel miscible not exclusively, and insufficient possibly the causing of burning contained CO in the products of combustion.
In addition; In the prior art: US7637969B2 has described under Catalyzed by p-Toluenesulfonic Acid; 90 ℃ of temperature of reaction, reaction times 10～36h, vegetables oil and ritalin reaction obtain the mixture fuel of fatty acid methyl ester (biofuel) and glycerol mono acetate bulk; The existence of glycerol mono acetate bulk makes mixture fuel viscosity reduce, and condensation point descends 1～10 ℃.Therefore, the glycerine direct esterification is prepared glycerol mono acetate bulk, can be used as a kind of approach of exploitation fuel dope.
Additive effect in other respects is not obvious but glycerol mono acetate bulk acts as a fuel, and low such as the relative ethers of its cetane value, the relative ethers of density is bigger etc.
Summary of the invention
The technical problem that the present invention will solve is for overcoming the deficiency that above-mentioned prior art exists, and provides transformation of glycerol is the act as a fuel preparation method of additive of the glycerol derivative system that contains glyceryl ether and glyceryl ester simultaneously.
The technical scheme that the present invention is directed to above-mentioned technical problem and propose is: the preparation method of glyceryl biofuel additive; May further comprise the steps: 1) low-carbon alcohol is mixed in autoclave pressure with glycerine; Low-carbon alcohol and glycerine mol ratio 2:1 are to 8:1; The acid catalyst consumption is 0.5%～10% of a reactant total mass, and water-retaining agent or azeotropy dehydrant consumption are 1.5%～10% of reactant total mass; 2) before the reaction beginning, utilize air in the nitrogen replacement still, first pressing is 0～4MPa in the still, and 30～130 ℃ of temperature of reaction are boosted reaction times 4～10h behind the still internal reaction certainly; 3) after reaction finished cooling, the emptying gas reactor with the product underpressure distillation, was collected low-carbon alcohol, if use azeotropy dehydrant then to reclaim; 4) join in the acylation reaction device steaming the ether (mixtures of glycerine one ether, glycerine diether and glycerine three ethers) and a small amount of unreacted glycerine that obtain behind the alcohol in the step 3; Drip diacetyl oxide and carry out acylation reaction; The diacetyl oxide consumption is by not confirmed by the hydroxyl molar weight of etherificate; 60～150 ℃ of temperature of reaction, reaction times 1～4h; 5) after acylation reaction finishes, add the solid alkali neutralization, filtering recovering catalyst, if use water-retaining agent then to reclaim, the underpressure distillation liquid mixture, 140～160 ℃ of distillation temperatures, vacuum tightness 0.01～0.09Mpa, residuum are title product.
Low-carbon alcohol described in the step 1) can be selected for use like methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, isopropylcarbinol, the trimethyl carbinol, primary isoamyl alcohol or their mixture.
Acid catalyst described in the step 1) can be selected acidic ion liquid, organic acid, mineral acid, acidic ion exchange resin, hydrochlorate zeolite molecular sieve, solid-carrying heteropolyacid, solid super-strong acid for use, and various immobilized an acidic catalyst, perhaps their mixture.
Water-retaining agent described in the step 1) can be selected discolour silica gel, gac, water-absorbing resin for use, activated alumina, sal epsom, copper sulfate, NSC 57182 (DCC) or their mixture.Wherein said azeotropy dehydrant is that benzene commonly used, toluene, normal hexane, hexanaphthene etc. are gone up in industry.
Step 2) rare gas element described in is generally selected nitrogen for use.
Glyceryl biofuel additive according to above-mentioned preparation method obtains is glycerine type of deriving material, contains the mixture of glyceryl ether, other no hydroxyl glycerol derivative or glyceryl ether and other no hydroxyl glycerol derivative.Wherein glyceryl ether is by the glycerine that obtains after the low-carbon alcohol etherificate three ethers and isomers.Wherein other no hydroxyl glycerol derivative is the glycerine ether-ether that obtains after the acidylate again of etherificate and isomers, glycerine triacetate, or the mixture of glycerine ether-ether and isomers and glycerine triacetate.
Compared with prior art, adopt technical scheme of the present invention to have following advantage.
1, the glyceryl ether in the additive of this preparing method's acquisition can improve the combustionproperty of fuel, and the glyceryl ester that contains simultaneously also has contribution for improving fuel viscosity and condensation point.
2, etherificate again acidylate solved the low problem of glycerine hydroxyl etherificate rate, make additive and fuel mix more even, burning and exhausting cleans more.
3, adopt low-carbon alcohol and non-pneumatic as the raw material of etherification reaction, technological operation safety, though the water that reaction generates is unfavorable for transformation of glycerol, remaining small amount of moisture has effectively been controlled the polymerization of intermediate product alkene after the water-retaining agent absorption.
4, the low-carbon alcohol of distillation recovery and the catalyzer and the water-retaining agent of filtered and recycled can reuse, and practice thrift cost.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is an etherification procedure reaction formula of the present invention.
Fig. 3 is an acylation process reaction formula of the present invention.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is further specified, embodiment does not receive the restriction of embodiment.
Embodiment 1:Fig. 1 is the preparing method's of glyceryl biofuel additive technical process, and concrete steps are following: step 1 is mixed the 39.5g trimethyl carbinol, 12.6g glycerine, 1.5gD002 ion exchange resin and 1.5g discolour silica gel in autoclave pressure.Step 2 seal-off pressure still before the reaction beginning, feeds air in the nitrogen replacement still, and first pressing is 1MPa in increasing nitrogen pressure to the still, and etherification reaction temperature is controlled at 90 ℃, keeps from boosting reaction times 8h in the still in the reaction process.
Fig. 2 is the etherification procedure reaction formula, and wherein ROH represents low-carbon alcohol, and A, B, C represent glycerine deutero-glycerine one ether, glycerine diether and glycerine three ethers and isomers.
Liquid after the gas chromatographic analysis distillation, the hydroxyl transformation efficiency is 51%.
Fig. 3 is the acylation process reaction formula, and wherein D, E represent glycerine ether-ether and isomers, and F is a glycerine triacetate.
After step 5 acylation reaction finishes, after the adding soda ash light is neutralized to neutrality, filtering recovering catalyst and water-retaining agent, the underpressure distillation liquid mixture obtains title product, 140 ℃ of distillation temperatures, vacuum tightness 0.09MPa.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 98.9%.
Fuel dope of the present invention is the mixing liquid of C, D, E, F, representes with mix.Wherein in etherification reaction, the transformation efficiency of glycerine can reach 99%, so glycerol conversion yield can be estimated as 100% in computation process.So can not used computes described in the present invention's technical scheme by the etherified hydroxy groups molar weight: hydroxyl molar weight=2 * n (A)+n (B), n representes amount of substance, the amount of substance of A, B can be calculated by gas chromatographic analysis.
Fuel dope and the mixed each item index of biofuel B100 that table 1 makes by embodiment 1.
Embodiment 2: Step 1 is mixed 25.6g methyl alcohol, 9.2g glycerine, the activated carbon supported Catalyzed by p-Toluenesulfonic Acid agent of 0.9g and 1.5g activated alumina in autoclave pressure.
After step 5 adding soda ash light is neutralized to neutrality, filtering recovering catalyst and water-retaining agent, the underpressure distillation liquid mixture obtains title product, 150 ℃ of distillation temperatures, vacuum tightness 0.01MPa.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 98.7%.
Embodiment 3: Step 1 is mixed 23.0g ethanol, 9.2g glycerine, 2.6gHZSM-5 zeolite catalyst and 3.2g water-absorbing resin in autoclave pressure.
Step 5 is with embodiment 1 step 5.
WarpGas chromatographic analysis obtains final hydroxyl transformation efficiency 98.2%.
Embodiment 4: Step 1 is mixed 32.9g propyl alcohol, 12.6g glycerine, the activated carbon supported phosphotungstic acid catalyst of 1.4g and 1.5g water-absorbing resin in autoclave pressure.
After step 5 adding soda ash light is neutralized to neutrality, filtering recovering catalyst and water-retaining agent, the underpressure distillation liquid mixture obtains title product, 160 ℃ of distillation temperatures, vacuum tightness 0.05MPa.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 97.2%.
Embodiment 5: Step 1 is mixed 12.0g Virahol, 9.2g glycerine, 1.1g macroporous network type resin GD001 and 1.4g activated alumina in autoclave pressure.
Step 5 is with embodiment 2 steps 5.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 98.9%.
Embodiment 6: Step 1 is mixed 22.2g butanols, 9.2g glycerine, 3.1g phosphorus aluminium silicalite molecular sieve catalyst and 1.6g NSC 57182 (DCC) in autoclave pressure.
Step 5 is with embodiment 1 step 5.
Through gas chromatographic analysis, obtain final hydroxyl transformation efficiency 96.9%.
Embodiment 7: Step 1 is with 40.6g isopropylcarbinol, 12.6g glycerine, 1.5gSO
4 2-/ TiO
2Solid super-strong acid and 0.5g discolour silica gel mix in autoclave pressure.
Step 5 is with embodiment 4 steps 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 99.0%.
Embodiment 8: Step 1 is with 48.3g primary isoamyl alcohol, 12.6g glycerine, 1.2g solid-carrying heteropolyacid salt TiSiW
12O
40/ TiO
2Catalyzer and 1.5g normal hexane azeotropy dehydrant mix in autoclave pressure.
Step 5 is with embodiment 1 step 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 98.9%.
Embodiment 9: Embodiment 1 mixes the 20.6g trimethyl carbinol, 11.2g methyl alcohol, 12.6g glycerine, 1.2g supported on silica-gel sulfuric acid and 1.5g gac water-retaining agent in autoclave pressure.
Step 5 is with embodiment 4 steps 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 98.6%.
Embodiment 10: Step 1 is mixed 14.7g Virahol, 9.8g butanols, 12.6g glycerine, 0.19g sulfuric acid catalyst and 1.5g hexanaphthene azeotropy dehydrant in autoclave pressure.
Step 5 is with embodiment 1 step 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 98.2%.
Embodiment 11: Step 1 is mixed 20.5g butanols, 12.2g isopropylcarbinol, 12.6g glycerine, 1.6g chlorine aluminic acid ionic-liquid catalyst and 1.4g methylbenzene azeotropic dewatering agent in autoclave pressure.
Step 5 is with embodiment 1 step 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 98.3%.
Embodiment 12: Step 1 is with 30.2g primary isoamyl alcohol, 8.7g propyl alcohol, 12.6g glycerine, 1.4g acid-treated clay load ZnCl
2Catalyzer and 1.5g benzene azeotropic dewatering agent mix in autoclave pressure.
Step 5 is with embodiment 1 step 5.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 97.8%.
Embodiment 13: Step 1 is mixed 20.2g butanols, 9.5g ethanol, 8.7g propyl alcohol, 12.6g glycerine, 1.5g Phenylsulfonic acid catalyzer and 1.5g water-absorbing resin in autoclave pressure.
Step 5 is with embodiment 1 step 1.
Through gas chromatographic analysis, obtain hydroxyl transformation efficiency 96.8%.
Claims (9)
1. the preparation method of glyceryl biofuel additive may further comprise the steps:
1) low-carbon alcohol is mixed in autoclave pressure with glycerine, low-carbon alcohol and glycerine mol ratio be 2:1 to 8:1, the acid catalyst consumption is 0.5%～10% of a reactant total mass, water-retaining agent or azeotropy dehydrant consumption are 1.5%～10% of reactant total mass;
2) before the reaction beginning, utilize air in the inert gas replacement still, first pressing is 0～4MPa in the still, and 30～130 ℃ of temperature of reaction are boosted reaction times 4～10h behind the still internal reaction certainly;
3) after reaction finished cooling, the emptying gas reactor with the product underpressure distillation, was collected low-carbon alcohol;
4) mixture and a small amount of unreacted glycerine that steam glycerine one ether, glycerine diether and glycerine three ethers that obtain behind the alcohol in the step 3 are joined in the acylation reaction device; Drip diacetyl oxide and carry out acylation reaction; The diacetyl oxide consumption is by not confirmed by the hydroxyl molar weight of etherificate; 60～150 ℃ of temperature of reaction, reaction times 1～4h;
5) after acylation reaction finishes, add the solid alkali neutralization, filtering recovering catalyst, underpressure distillation obtains title product, 140～160 ℃ of distillation temperatures, vacuum tightness 0.01～0.09MPa.
2. according to the described preparation method of claim 1, it is characterized in that said water-retaining agent can reclaim in step 5); Said azeotropy dehydrant can reclaim in step 3).
3. according to the described preparation method of claim 2, it is characterized in that said rare gas element is a nitrogen.
4. according to the described preparation method of claim 2, it is characterized in that said low-carbon alcohol is methyl alcohol, ethanol, propyl alcohol, butanols, Virahol, isopropylcarbinol, the trimethyl carbinol, primary isoamyl alcohol or their mixture.
5. according to the described preparation method of claim 2; It is characterized in that; Said acid catalyst is acidic ion liquid, organic acid, mineral acid, acidic ion exchange resin, hydrochlorate zeolite molecular sieve, solid-carrying heteropolyacid, solid super-strong acid, and various immobilized an acidic catalyst.
6. according to the described preparation method of claim 2, it is characterized in that said water-retaining agent is discolour silica gel, gac, water-absorbing resin, activated alumina, NSC 57182 (DCC).
7. according to the glyceryl biofuel additive of claim 1 preparation, it is characterized in that said additive is glycerine type of a deriving material, contain the mixture of glyceryl ether, other no hydroxyl glycerol derivative or glyceryl ether and other no hydroxyl glycerol derivative.
8. according to the described additive of claim 7, it is characterized in that said glyceryl ether is by glycerine three ethers that obtain after low-carbon alcohol (ROH) etherificate and isomers (C).
9. according to the described additive of claim 7, it is characterized in that said other no hydroxyl glycerol derivative is the glycerine ether-ether that obtains after the acidylate again of etherificate and isomers (D, E), glycerine triacetate (F), or their mixture.
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| CN103611568A (en) * | 2013-12-02 | 2014-03-05 | 江南大学 | Preparation method of dual-core acidic ionic liquid immobilized SBA-15 molecular sieve catalyst used for synthesizing tert butyl glycidyl ether |
| CN103964988A (en) * | 2014-05-23 | 2014-08-06 | 天津科林泰克科技有限公司 | Application method of compound catalyst in dehydration and condensation reaction |
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| CN104017617A (en) * | 2014-06-20 | 2014-09-03 | 长沙理工大学 | Research on biomass glyceryl-based blended fuel |
| CN107841366A (en) * | 2017-11-23 | 2018-03-27 | 广西银英生物质能源科技开发股份有限公司 | A kind of biomass fuel feed additives |
| CN111057594A (en) * | 2019-12-30 | 2020-04-24 | 李旭 | Preparation method of alcohol-based fuel additive |
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