JP5238147B2 - Tall fatty acid ester, method for producing the same, and use thereof - Google Patents
Tall fatty acid ester, method for producing the same, and use thereof Download PDFInfo
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- JP5238147B2 JP5238147B2 JP2006208803A JP2006208803A JP5238147B2 JP 5238147 B2 JP5238147 B2 JP 5238147B2 JP 2006208803 A JP2006208803 A JP 2006208803A JP 2006208803 A JP2006208803 A JP 2006208803A JP 5238147 B2 JP5238147 B2 JP 5238147B2
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- 235000014113 dietary fatty acids Nutrition 0.000 title claims description 115
- 239000000194 fatty acid Substances 0.000 title claims description 115
- 229930195729 fatty acid Natural products 0.000 title claims description 115
- -1 fatty acid ester Chemical class 0.000 title claims description 68
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 150000004665 fatty acids Chemical class 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 239000003463 adsorbent Substances 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 24
- 239000011593 sulfur Substances 0.000 claims description 24
- 238000005886 esterification reaction Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- 238000001179 sorption measurement Methods 0.000 claims description 19
- 239000012295 chemical reaction liquid Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000010828 elution Methods 0.000 claims description 11
- 239000000741 silica gel Substances 0.000 claims description 11
- 229910002027 silica gel Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 10
- 239000004927 clay 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
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 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
- 239000010457 zeolite Substances 0.000 claims description 3
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 21
- 239000000126 substance Substances 0.000 description 21
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 20
- 239000003225 biodiesel Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 239000003480 eluent Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 239000003784 tall oil Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000003925 fat Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 235000019197 fats Nutrition 0.000 description 6
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 5
- 239000007809 chemical reaction catalyst Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 239000012454 non-polar solvent Substances 0.000 description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- NPPQSCRMBWNHMW-UHFFFAOYSA-N Meprobamate Chemical compound NC(=O)OCC(C)(CCC)COC(N)=O NPPQSCRMBWNHMW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 235000021588 free fatty acids Nutrition 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 239000004367 Lipase Substances 0.000 description 2
- 102000004882 Lipase Human genes 0.000 description 2
- 108090001060 Lipase Proteins 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 125000002843 carboxylic acid group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 235000019421 lipase Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002898 organic sulfur compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 150000004141 diterpene derivatives Chemical class 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 229940013317 fish oils Drugs 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical class CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- ASUAYTHWZCLXAN-UHFFFAOYSA-N prenol Chemical compound CC(C)=CCO ASUAYTHWZCLXAN-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003648 triterpenes Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Fats And Perfumes (AREA)
Description
本発明は、バイオディーゼル燃料等に利用しうるトール脂肪酸エステルとその製造方法に関し、さらに該トール脂肪酸エステルを用いたバイオディーゼル燃料に関する。 The present invention relates to a tall fatty acid ester that can be used for biodiesel fuel and the like and a method for producing the same, and further relates to a biodiesel fuel using the tall fatty acid ester.
近年、地球環境保全に関する意識が高まるなか、特に地球温暖化を防止する対策の実行が求められている。具体的には、１９９７年に開催された地球温暖化防止京都会議において我国は温室効果の高い二酸化炭素の排出量を１９９０年実績比で６％削減することを国際公約しており、この目標を達成するために、省エネルギーの一層の推進および新エネルギーの開発利用を促進する法律が成立している。 In recent years, as awareness of global environmental conservation has increased, it is particularly necessary to implement measures to prevent global warming. Specifically, at the Kyoto Conference on Global Warming Prevention held in 1997, Japan has made an international commitment to reduce high-carbon dioxide emissions by 6% compared to the 1990 level. To achieve this, legislation has been enacted to further promote energy conservation and promote the development and use of new energy.
植物由来のバイオマスは、カーボンニュートラルの考え方を基礎として新エネルギー法により規定されたエネルギー資源であり、植物油脂類から製造される脂肪酸メチルエステルがバイオディーゼル燃料として実用化されつつある。例えば、資源の有効利用を主目的として、脂肪酸グリセリンエステルを主成分とする油脂類とメタノールとを触媒の存在下で反応させて得られる脂肪酸メチルエステルをバイオディーゼル燃料に利用することが検討されている。バイオディーゼル燃料を燃料油とした場合、利点として、炭酸ガス排出削減効果、パティキュレート（ＰＭ）・黒煙の減少効果、硫黄酸化物の削減効果などが期待される。 Plant-derived biomass is an energy resource defined by the New Energy Law based on the concept of carbon neutral, and fatty acid methyl esters produced from vegetable oils and fats are being put into practical use as biodiesel fuel. For example, for the effective use of resources, the use of fatty acid methyl esters obtained by reacting fats and oils mainly composed of fatty acid glycerin esters with methanol in the presence of a catalyst has been studied. Yes. When biodiesel fuel is used as the fuel oil, the carbon dioxide emission reduction effect, the particulate (PM) / black smoke reduction effect, the sulfur oxide reduction effect, etc. are expected as advantages.
従来から、脂肪酸エステルは、遊離脂肪酸と低級アルコールとの直接エステル化反応により得られることが知られている（非特許文献１参照）。このようなエステル化反応は、生成する水による加水分解が起こるために可逆反応となり、化学平衡を生成系側に移行させるためには、原料として用いるアルコールの量を過剰にすることや、生成水を効率よく反応系外に取り出すことなどの工夫が必要になる。また、遊離脂肪酸と低級アルコールとのエステル化反応には、反応触媒として、一般に酸やアルカリが使用されるが、反応後の分離工程を簡略化するためには、イオン交換樹脂やヘテロポリ酸担持シリカゲルなどの固体酸触媒あるいは酵素（リパーゼ）等も使用されることがある。 Conventionally, it is known that a fatty acid ester is obtained by a direct esterification reaction between a free fatty acid and a lower alcohol (see Non-Patent Document 1). Such esterification reaction is a reversible reaction due to hydrolysis by the water produced, and in order to shift the chemical equilibrium to the production system side, the amount of alcohol used as a raw material is excessive, It is necessary to devise such as efficiently removing the product from the reaction system. In the esterification reaction between a free fatty acid and a lower alcohol, an acid or an alkali is generally used as a reaction catalyst. In order to simplify the separation step after the reaction, an ion exchange resin or a heteropolyacid-supported silica gel is used. A solid acid catalyst such as, or an enzyme (lipase) may also be used.
しかしながら、遊離脂肪酸と低級アルコールとから脂肪酸エステルを生成する場合、一般的な条件ではエステル化反応を１００％完結させることは困難である。例えば、前述したような反応触媒を用い、かつ生成水を反応系外に排出させる操作を行っても、反応を１００％完結させるには多大な反応時間を要することになる。さらに、生じたエステルの精製方法として、アルカリ水溶液で水洗することにより未反応の脂肪酸を除去する方法が知られているが、この場合にはアルカリ廃水が発生し、しかもその精製処理には多大な労力がかかるという問題があった。また、反応触媒は反応液中で均一状態となる場合が多く、分離するための煩雑な工程が必要になるという問題もある。これらの問題はいずれも、脂肪酸エステルのコストの高騰を招く要因となる。バイオディーゼル燃料の実用化には、品質確保は勿論のこと、汎用化を目指すには低コストを実現することが必要不可欠である。 However, when producing a fatty acid ester from a free fatty acid and a lower alcohol, it is difficult to complete the esterification reaction 100% under general conditions. For example, even if the reaction catalyst as described above is used and the generated water is discharged from the reaction system, a long reaction time is required to complete the reaction 100%. Furthermore, as a method for purifying the resulting ester, a method of removing unreacted fatty acids by washing with an aqueous alkaline solution is known, but in this case, alkaline waste water is generated, and the purification process requires a large amount. There was a problem that labor was required. In addition, the reaction catalyst is often in a uniform state in the reaction solution, and there is a problem that a complicated process for separation is required. All of these problems cause a rise in the cost of fatty acid esters. For practical use of biodiesel fuel, it is indispensable to realize low cost in order to ensure general quality as well as to ensure quality.
ところで、クラフト法パルプ化工程において発生する粗トール油には、木材の油脂がパルプ蒸解工程で加水分解されて生成した脂肪酸や、木材中に遊離酸の形で存在するロジン酸および多種類の中性物質が含まれている。これらトール油成分は連続精留操作によりそれぞれ分離され、ロジン（松脂）およびトール脂肪酸が製造されることとなる。したがって、トール脂肪酸は、天然油脂（植物油脂、動物油脂、魚油など）の加水分解により得られる一般的な脂肪酸に比べて安価であり、バイオディーゼル燃料に用いる脂肪酸エステルの原料として有用であると言える。 By the way, crude tall oil generated in the kraft pulping process includes fatty acids produced by hydrolyzing wood fats and oils in the pulp cooking process, rosin acid present in the form of free acid in wood, and various types of oils. Contains sexual substances. These tall oil components are separated by continuous rectification operation, and rosin (pine resin) and tall fatty acid are produced. Therefore, tall fatty acids are cheaper than general fatty acids obtained by hydrolysis of natural fats and oils (vegetable fats, animal fats, fish oils, etc.) and can be said to be useful as raw materials for fatty acid esters used in biodiesel fuels. .
しかしながら、クラフト法パルプ化工程では蒸解時に硫化ナトリウムを使用するため、植物成分とイオウが反応して有機性イオウ化合物を生じる。この有機性イオウ化合物は粗トール油の精留によっては完全に分離されず、結果としてトール脂肪酸には、通常、イオウ分が数百ｐｐｍ程度残留する。このようなイオウ分濃度でイオウ化合物を含んだままバイオディーゼル燃料に供すると、燃焼によって硫黄酸化物（ＳＯX）を発生することになる。したがって、これまで、バイオディーゼル燃料に用いる脂肪酸エステルの原料としてトール脂肪酸を利用することは困難であった。 However, since kraft process pulping uses sodium sulfide during cooking, plant components and sulfur react to produce organic sulfur compounds. This organic sulfur compound is not completely separated by rectification of crude tall oil, and as a result, the sulfur content usually remains in the order of several hundred ppm in tall fatty acids. When subjected to such a sulfur concentration in biodiesel fuels still contains sulfur compounds, will generate sulfur oxides (SO X) by combustion. Therefore, it has been difficult to use tall fatty acids as raw materials for fatty acid esters used in biodiesel fuels.
また、トール脂肪酸は、通常、その組成中にロジン酸を１〜５質量％程度含有している。このロジン酸のカルボン酸基は２級の構造であるので、反応性が低く、トール脂肪酸と低級アルコールとをエステル化する際に大部分が未反応のまま残存し、生成するエステルの酸価を一層高める原因となっている。酸価が高いまま（すなわち、カルボン酸基が多く残留したまま）燃料に供すると、燃焼機器類の腐食など好ましくない現象を引き起こすことになるので、この点でもやはり、トール脂肪酸をバイオディーゼル燃料に用いる脂肪酸エステルの原料とすることには無理があった。なお、トール脂肪酸は、通常、ロジン酸のほかにもステロイド、ジテルペン、トリテルペン、ワックスアルコール、プレノール、ポリフェノール、スチルベンなどの中性物質を１〜１０質量％程度含有している。 Further, tall fatty acids usually contain about 1 to 5% by mass of rosin acid in the composition. Since the carboxylic acid group of this rosin acid has a secondary structure, the reactivity is low, and when esterifying a tall fatty acid and a lower alcohol, most of them remain unreacted, and the acid value of the resulting ester is reduced. This is the cause of further increase. If it is used for fuel with a high acid value (ie, with many carboxylic acid groups remaining), it will cause undesirable phenomena such as corrosion of combustion equipment. It was impossible to use as a raw material for the fatty acid ester used. In addition, tall fatty acids usually contain about 1 to 10% by mass of a neutral substance such as steroid, diterpene, triterpene, wax alcohol, prenol, polyphenol, stilbene in addition to rosin acid.
なお、一般に、油脂や脂肪酸エステルの精製方法として、油脂を白土で精製する方法（非特許文献２参照）、脂肪酸エステルを白土、アルミナ、シリカゲル、活性炭などで吸着精製する方法（特許文献１、２参照）等が知られている。しかしながら、これらの精製方法をトール酸エステルに適用した例はこれまで報告されていない。
本発明の課題は、低酸価でイオウ分が少ないというバイオディーゼル燃料に適した特性を有するとともに安価でもあるトール脂肪酸エステルと、該トール脂肪酸エステルを特別な装置を使用せずに簡単な操作で製造する製造方法と、該トール脂肪酸エステルを用いたバイオディーゼル燃料とを提供することである。 An object of the present invention is to provide a tall fatty acid ester that has characteristics suitable for biodiesel fuel with a low acid value and low sulfur content and is inexpensive, and the tall fatty acid ester can be easily operated without using a special apparatus. The manufacturing method to manufacture and the biodiesel fuel using this tall fatty acid ester are provided.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、比較的安価なトール脂肪酸と低級アルコールとを脂肪酸エステルの原料として用いれば、バイオディーゼル燃料として汎用される可能性を有する程度の低コストを達成できるのではないかと考えた。ただし、トール脂肪酸を原料としたトール脂肪酸エステルは、バイオディーゼル燃料としては品質（具体的には、酸価およびイオウ分）が不充分であったので、コストを高騰させることなくこれを改善する方法を検討した。そして、トール脂肪酸と低級アルコールとのエステル化で得られた反応生成物から未反応のトール脂肪酸やロジン酸、低級アルコールおよび中性物質等からなる不純物（特に酸価を上げるロジン酸およびイオウ分）等をコストをかけずに効率良く取り除くには、トール脂肪酸エステルと前述した不純物等との極性の違いを利用し、これら不純物等を無機系吸着剤に吸着させて分離する方法が、種々ある精製方法の中でも最も有効であることを見出し、本発明を完成した。 As a result of intensive studies to solve the above problems, the present inventors have a possibility of being widely used as a biodiesel fuel if relatively inexpensive tall fatty acids and lower alcohols are used as raw materials for fatty acid esters. I thought that I could achieve the low cost. However, since the tall fatty acid ester made from tall fatty acid has insufficient quality (specifically, acid value and sulfur content) as a biodiesel fuel, a method for improving this without increasing the cost. It was investigated. Impurities consisting of unreacted tall fatty acids, rosin acids, lower alcohols, neutral substances, etc. (especially rosin acids and sulfur components that increase the acid value) from the reaction products obtained by esterification of tall fatty acids and lower alcohols In order to efficiently remove the impurities, etc. without cost, there are various purification methods utilizing the difference in polarity between the tall fatty acid ester and the impurities described above, and adsorbing these impurities etc. on an inorganic adsorbent. The present invention was completed by finding the most effective method.
すなわち、本発明は以下の構成からなる。
（１）トール脂肪酸と低級アルコールとを原料として得られるトール脂肪酸エステルであって、酸価が０．５ｍｇＫＯＨ／ｇ未満、イオウ分が５０質量ｐｐｍ以下である、ことを特徴とするトール脂肪酸エステル。
（２）トール脂肪酸と低級アルコールとを原料としエステル化反応によりトール脂肪酸エステル反応液を得、この反応液を無機系吸着剤が充填された吸着カラムに通液させる、ことを特徴とするトール脂肪酸エステルの製造方法。
（３）前記トール脂肪酸エステル反応液を、無機系吸着剤１００質量部に対して１００質量部以下の割合で、かつ０．０１〜１．００ｍＬ／ｃｍ2・分の溶出速度で通液させる前記（２）記載のトール脂肪酸エステルの製造方法。
（４）トール脂肪酸と低級アルコールとを原料としエステル化反応によりトール脂肪酸エステル反応液を得、この反応液に無機系吸着剤を加えて攪拌する、ことを特徴とするトール脂肪酸エステルの製造方法。
（５）前記トール脂肪酸エステル反応液が無機系吸着剤１００質量部に対して１００質量部以下となる割合で、無機系吸着剤を加える前記（４）記載のトール脂肪酸エステルの製造方法。
（６）原料とする前記トール油脂肪酸は、１〜５質量％のロジン酸を含むものである前記（２）〜（５）のいずれかに記載のトール脂肪酸エステルの製造方法。
（７）原料とする前記低級アルコールは、炭素数１〜４のアルキルアルコールである前記（２）〜（６）のいずれかに記載のトール脂肪酸エステルの製造方法。
（８）前記無機系吸着剤は、活性炭、ゼオライト、活性アルミナ、活性白土およびシリカゲルからなる群より選ばれる少なくとも１種である前記（２）〜（７）のいずれかに記載のトール脂肪酸エステルの製造方法。
（９）前記（１）記載のトール脂肪酸エステルを含む、ことを特徴とするバイオディーゼル燃料。
That is, the present invention has the following configuration.
(1) A tall fatty acid ester obtained from tall fatty acid and a lower alcohol as raw materials, having an acid value of less than 0.5 mg KOH / g and a sulfur content of 50 ppm by mass or less.
(2) A tall fatty acid ester reaction solution is obtained by esterification using tall fatty acid and lower alcohol as raw materials, and the reaction solution is passed through an adsorption column filled with an inorganic adsorbent. Ester production method.
(3) The said tall fatty acid ester reaction liquid is made to flow at a rate of 100 parts by mass or less with respect to 100 parts by mass of the inorganic adsorbent and at an elution rate of 0.01 to 1.00 mL / cm 2 · min. (2) The manufacturing method of the tall fatty acid ester as described.
(4) A method for producing a tall fatty acid ester, comprising using a tall fatty acid and a lower alcohol as raw materials to obtain a tall fatty acid ester reaction liquid by an esterification reaction, adding an inorganic adsorbent to the reaction liquid and stirring the reaction liquid.
(5) The method for producing tall fatty acid ester according to (4), wherein the inorganic adsorbent is added at a ratio such that the tall fatty acid ester reaction solution is 100 parts by mass or less with respect to 100 parts by mass of the inorganic adsorbent.
(6) The said tall oil fatty acid used as a raw material is a manufacturing method of the tall fatty acid ester in any one of said (2)-(5) which contains 1-5 mass% rosin acid.
(7) The method for producing a tall fatty acid ester according to any one of (2) to (6), wherein the lower alcohol used as a raw material is an alkyl alcohol having 1 to 4 carbon atoms.
(8) The inorganic fatty adsorbent according to any one of (2) to (7), wherein the inorganic adsorbent is at least one selected from the group consisting of activated carbon, zeolite, activated alumina, activated clay, and silica gel. Production method.
(9) A biodiesel fuel comprising the tall fatty acid ester according to (1).
本発明によれば、低酸価でイオウ分が少ないというバイオディーゼル燃料に適した特性を有するとともに安価でもあるトール脂肪酸エステルを、特別な装置を使用せずに簡単な操作で製造することができる、という効果がある。また、本発明のバイオディーゼル燃料は、汎用される可能性を有する程度の低コストを達成できるものであり、しかも低酸価でイオウ分が少ないというバイオディーゼル燃料に適した特性を有する。 According to the present invention, a tall fatty acid ester having characteristics suitable for biodiesel fuel having a low acid value and low sulfur content and being inexpensive can be produced by a simple operation without using a special apparatus. There is an effect that. In addition, the biodiesel fuel of the present invention can achieve low cost to the extent that it can be widely used, and has characteristics suitable for biodiesel fuel with low acid value and low sulfur content.
以下、本発明にかかるトール脂肪酸エステル、トール脂肪酸エステルの製造方法およびバイオディーゼル燃料の一実施形態について詳細に説明する。
本発明のトール脂肪酸エステルは、トール脂肪酸と低級アルコールとを原料として得られるものであり、具体的には、後述する本発明のトール脂肪酸エステルの製造方法によって得ることができる。ただし、本発明のトール脂肪酸エステルは、後述する本発明の製造方法で得られたものに限定されるわけではない。
Hereinafter, an embodiment of a tall fatty acid ester, a method for producing a tall fatty acid ester, and a biodiesel fuel according to the present invention will be described in detail.
The tall fatty acid ester of the present invention is obtained using a tall fatty acid and a lower alcohol as raw materials. Specifically, it can be obtained by the method for producing the tall fatty acid ester of the present invention described later. However, the tall fatty acid ester of the present invention is not limited to those obtained by the production method of the present invention described later.
本発明のトール脂肪酸エステルは、酸価が０．５ｍｇＫＯＨ／ｇ未満であり、イオウ分が５０質量ｐｐｍ以下である。イオウ分は、４０質量ｐｐｍ以下であるのが好ましく、１０質量ｐｐｍ以下であるのがより好ましい。酸価が０．５ｍｇＫＯＨ／ｇ以上であると、長期間の使用において燃焼機器類の腐食原因となる。他方、イオウ分が５０質量ｐｐｍを超えると、軽油のＪＩＳ規格値を超えることとなる。なお、本発明における酸価およびイオウ分は、実施例で後述する方法により測定されるものである。 The tall fatty acid ester of the present invention has an acid value of less than 0.5 mg KOH / g and a sulfur content of 50 mass ppm or less. The sulfur content is preferably 40 ppm by mass or less, and more preferably 10 ppm by mass or less. If the acid value is 0.5 mgKOH / g or more, it will cause corrosion of combustion equipment over a long period of use. On the other hand, if the sulfur content exceeds 50 mass ppm, the JIS standard value of light oil will be exceeded. In addition, the acid value and sulfur content in this invention are measured by the method mentioned later in an Example.
本発明におけるトール脂肪酸は、粗トール油を精留に付した際の留分として得られるものである。トール脂肪酸は、通常、酸価(中和価)が１８０〜１９５ｍｇＫＯＨ／ｇであり、組成としては、脂肪族カルボン酸（オレイン酸、リノール酸など）を主成分とし、若干のロジン酸および中性成分が含まれる。特に、本発明においては、１〜５質量％のロジン酸を含むトール脂肪酸を原料とするのが好ましい。なぜなら、この場合、通常は酸価が上がるところ、本発明においては前記範囲の低い酸価を維持できる、という効果が有意になるからである。トール脂肪酸は１種のみであってもよいし、２種以上であってもよい。なお、粗トール油に含まれる脂肪酸およびロジン酸を真空蒸留により分離し各々を工業原料に利用する分野はネーバルストアーズと呼ばれる。 The tall fatty acid in the present invention is obtained as a fraction when crude tall oil is subjected to rectification. Tall fatty acids usually have an acid value (neutralization value) of 180 to 195 mg KOH / g, and the composition is mainly composed of aliphatic carboxylic acids (oleic acid, linoleic acid, etc.), and some rosin acids and neutrals. Ingredients included. In particular, in the present invention, it is preferable to use a tall fatty acid containing 1 to 5% by mass of rosin acid as a raw material. This is because, in this case, the acid value usually increases, but in the present invention, the effect that the acid value within the above range can be maintained becomes significant. Only one type of tall fatty acid may be used, or two or more types may be used. In addition, the field | area which isolate | separates the fatty acid and rosin acid contained in crude tall oil by vacuum distillation, and utilizes each as an industrial raw material is called naval store.
本発明における低級アルコールとしては、特に制限はないが、例えば、メタノール、エタノール、プロパノール、ブタノール等の炭素数１〜４のアルキルアルコールが、得られるトール脂肪酸エステルの燃料特性の点で好ましく挙げられる。低級アルコールは１種のみであってもよいし、２種以上であってもよい。
特に、低級アルコールの炭素数が１〜３のアルコールは水と広い割合で混合するために反応生成水の分離が困難となり、しかも沸点が低いので反応温度も低くなり、反応速度が不十分となる。炭素数が大きくなると生成水の分離や反応速度の面では有利であるが、それ自体の価格も高くなる。これらの理由により、常圧での回分式反応においてエステル化反応を行う際には低級アルコールの炭素数は４（ブタノール）が好ましい。
Although there is no restriction | limiting in particular as a lower alcohol in this invention, For example, C1-C4 alkyl alcohols, such as methanol, ethanol, propanol, butanol, are mentioned preferably at the point of the fuel characteristic of the obtained tall fatty acid ester. Only one type of lower alcohol may be used, or two or more types may be used.
In particular, the alcohol having 1 to 3 carbon atoms of the lower alcohol is mixed with water in a wide proportion, so that it is difficult to separate the reaction product water, and since the boiling point is low, the reaction temperature becomes low and the reaction rate becomes insufficient. . Increasing the number of carbon atoms is advantageous in terms of separation of produced water and reaction rate, but also increases the price of itself. For these reasons, the carbon number of the lower alcohol is preferably 4 (butanol) when performing the esterification reaction in a batch reaction at normal pressure.
本発明において原料として用いるトール脂肪酸と低級アルコールとの使用割合は、特に限定されないが、低級アルコールが過剰となるようにするのが望ましく、具体的には、トール脂肪酸：低級アルコール＝１：１〜５（モル比）の範囲が好ましい。低級アルコールの割合が前記範囲よりも低い場合、反応の達成率が不充分となるおそれがあり、一方、低級アルコールの割合が前記範囲よりも高い場合、反応中のアルコール留出量が大きくなり、その結果、アルコールを回収再利用するにしても経済的に不利となり、トール脂肪酸を原料とすることにより低コストを実現できるという本発明の効果が損なわれる傾向がある。 The proportion of tall fatty acid and lower alcohol used as raw materials in the present invention is not particularly limited, but it is desirable that the lower alcohol be excessive. Specifically, tall fatty acid: lower alcohol = 1: 1 to 1. A range of 5 (molar ratio) is preferred. When the proportion of the lower alcohol is lower than the above range, the achievement rate of the reaction may be insufficient. On the other hand, when the proportion of the lower alcohol is higher than the above range, the amount of alcohol distilling during the reaction increases. As a result, even if alcohol is recovered and reused, it is economically disadvantageous, and the effect of the present invention that low costs can be realized by using tall fatty acid as a raw material tends to be impaired.
本発明のトール脂肪酸エステルの製造方法においては、トール脂肪酸と低級アルコールとを原料としエステル化反応によりトール脂肪酸エステル反応液を得る。
本発明の製造方法において用いられるトール脂肪酸および低級アルコールについては、前述した通りである。また、トール脂肪酸と低級アルコールの使用割合についても前述した通りである。
In the method for producing a tall fatty acid ester of the present invention, a tall fatty acid ester reaction solution is obtained by an esterification reaction using tall fatty acids and lower alcohols as raw materials.
The tall fatty acid and lower alcohol used in the production method of the present invention are as described above. Further, the use ratio of tall fatty acid and lower alcohol is as described above.
前記エステル化反応は、まず、トール脂肪酸と低級アルコールと、必要に応じて溶剤（例えば、トルエン、キシレン等）を所定の割合で混合し、適当な反応触媒を加えて加熱することにより行なう。 The esterification reaction is carried out by first mixing tall fatty acid, lower alcohol and, if necessary, a solvent (for example, toluene, xylene, etc.) at a predetermined ratio, adding an appropriate reaction catalyst and heating.
エステル化反応で用いられる触媒については、特に制限はなく、例えば、酸およびアルカリ、さらには固体触媒や酵素（リパーゼ）など公知の触媒から適宜選択すればよい。本発明においては、特に、反応活性及び反応後の分離が容易であるなどの点から、エステル化反応を後述する回分式で行なう場合にはパラトルエンスルホン酸が好ましく、エステル化反応を後述する連続式で行なう場合には硫酸化ジルコニアが好ましい。 The catalyst used in the esterification reaction is not particularly limited, and may be appropriately selected from known catalysts such as acids and alkalis, and further solid catalysts and enzymes (lipases). In the present invention, paratoluenesulfonic acid is preferred when the esterification reaction is carried out in a batch system described later, particularly from the viewpoint of easy reaction activity and separation after the reaction. When carried out by the formula, sulfated zirconia is preferred.
前記エステル化反応の反応装置の形式としては、回分式（バッチ式）または流通式反応器を用いた連続式が採用できる。エステル化反応を回分式で行なう場合、反応温度は高いほど反応速度が速くなり好ましいが、常圧での回分操作では還流する低級アルコールまたは溶剤の沸点により反応温度が制約される。他方、連続式のエステル化反応については、バイオディーゼル燃料として公知の脂肪酸メチルエステルを製造する際に、通常、加圧下での連続式反応が選択されている。この場合には効率的に生成水を反応系外に排出するために特殊な脱水装置が必要となるので、設備費用負担面では不利となる。しかし、本発明においては、固体触媒を充填した連続式反応器を使用して２段階反応を行うことで、トール脂肪酸エステルの残存酸価を次工程での精製可能な範囲にすることができる。 As a type of the reaction apparatus for the esterification reaction, a batch type (batch type) or a continuous type using a flow type reactor can be adopted. When the esterification reaction is carried out batchwise, the higher the reaction temperature, the faster the reaction rate and the better. However, in the batch operation at normal pressure, the reaction temperature is limited by the boiling point of the refluxing lower alcohol or solvent. On the other hand, for the continuous esterification reaction, a continuous reaction under pressure is usually selected when producing a known fatty acid methyl ester as a biodiesel fuel. In this case, a special dehydrator is required to efficiently discharge the produced water out of the reaction system, which is disadvantageous in terms of equipment cost burden. However, in the present invention, by performing a two-stage reaction using a continuous reactor filled with a solid catalyst, the residual acid value of the tall fatty acid ester can be within a purifiable range in the next step.
本発明のトール脂肪酸エステルの製造方法においては、前記エステル化反応で得られたトール脂肪酸エステル反応液に対して、（Ｉ）無機系吸着剤が充填された吸着カラムに通液させる処理を施すか、もしくは、（ＩＩ）無機系吸着剤を加えて攪拌する処理を施す、ものである。この（Ｉ）または（ＩＩ）により、トール脂肪酸エステル反応液に含まれる極性物質（未反応の脂肪酸・樹脂酸、中性成分および反応触媒）を無機系吸着剤に吸着させて除去するのである。（Ｉ）、（ＩＩ）のいずれにしても、トール脂肪酸エステルと極性物質との極性の違いを利用するものであるので、特別な装置を使用せずに、簡単な操作でトール脂肪酸エステルを製造することができる。
前記（Ｉ）または（ＩＩ）を行う際には、あらかじめエステル反応に続いて、蒸留操作などにより残存する低級アルコールを除去させておくことが好ましい。低級アルコールが残存していると、エステル反応液中の極性物質が無機系吸着剤に吸着されることを妨害するからである。
In the method for producing a tall fatty acid ester of the present invention, the tall fatty acid ester reaction solution obtained by the esterification reaction is subjected to (I) a treatment for passing through an adsorption column filled with an inorganic adsorbent. Or (II) An inorganic adsorbent is added and stirred. By this (I) or (II), polar substances (unreacted fatty acid / resin acid, neutral component and reaction catalyst) contained in the tall fatty acid ester reaction liquid are adsorbed and removed by the inorganic adsorbent. Regardless of (I) or (II), since the difference in polarity between the tall fatty acid ester and the polar substance is utilized, the tall fatty acid ester is produced by a simple operation without using a special apparatus. can do.
When performing (I) or (II), it is preferable to remove the remaining lower alcohol by distillation operation or the like in advance after the ester reaction. This is because if the lower alcohol remains, the polar substance in the ester reaction solution is prevented from being adsorbed by the inorganic adsorbent.
前記無機系吸着剤は、極性物質を吸着することができる無機系吸着剤であれば、特に制限されるものではないが、活性炭、ゼオライト、活性アルミナ、活性白土およびシリカゲルからなる群より選ばれる少なくとも１種であるのが、極性物質に対する吸着性の点で好ましい。これらの中でも、極性物質に対する分離性能および収率の点で、多孔質シリカゲルが特に好ましい。好ましく用いられるシリカゲルの物性は、例えば、細孔径は５〜１０ｎｍ、細孔容積は０．１〜２．０ｍＬ／ｇ、比表面積は３００〜６００ｍ２／ｇ、粒度は４５〜７５μｍが６５〜８５％以上、７５μｍ残分が１〜１０％以下程度である。このような物性を有する多孔質シリカゲルの具体例として、例えば、和光純薬工業社製の商品名「ワコーゲルＣ３００」等が挙げられる。 The inorganic adsorbent is not particularly limited as long as it is an inorganic adsorbent capable of adsorbing a polar substance, but at least selected from the group consisting of activated carbon, zeolite, activated alumina, activated clay and silica gel. One type is preferable in terms of adsorptivity to polar substances. Among these, porous silica gel is particularly preferable in terms of separation performance and yield with respect to polar substances. The physical properties of the silica gel preferably used include, for example, a pore diameter of 5 to 10 nm, a pore volume of 0.1 to 2.0 mL / g, a specific surface area of 300 to 600 m <2> / g, and a particle size of 45 to 75 [mu] m of 65 to 85%. As described above, the 75 μm residue is about 1 to 10% or less. As a specific example of the porous silica gel having such physical properties, for example, trade name “Wakogel C300” manufactured by Wako Pure Chemical Industries, Ltd. may be mentioned.
前記（Ｉ）においては、前記トール脂肪酸エステル反応液を、無機系吸着剤１００質量部に対して１００質量部以下の割合で、かつ０．０１〜１．００ｍＬ／ｃｍ2・分の溶出速度で通液させることが好ましい。これにより、トール脂肪酸エステル反応液に含まれる極性物質を効率よく無機系吸着剤に吸着させることができる。トール脂肪酸エステル反応液の量が無機系吸着剤１００質量部に対して１００質量部を超えると、極性物質の全量が無機系吸着剤に吸着されないおそれがある。また、溶出速度が０．０１ｍＬ／ｃｍ2・分よりも遅いと、作業効率が低下し、一方、１．００ｍＬ／ｃｍ2・分より速いと、極性物質が無機系吸着剤に吸着されにくくなるので好ましくない。 In the above (I), the tall fatty acid ester reaction liquid is added at a rate of 100 parts by mass or less with respect to 100 parts by mass of the inorganic adsorbent and at an elution rate of 0.01 to 1.00 mL / cm 2 · min. It is preferable to let the liquid pass. Thereby, the polar substance contained in the tall fatty acid ester reaction liquid can be efficiently adsorbed to the inorganic adsorbent. When the amount of the tall fatty acid ester reaction solution exceeds 100 parts by mass with respect to 100 parts by mass of the inorganic adsorbent, the total amount of the polar substance may not be adsorbed by the inorganic adsorbent. In addition, when the elution rate is slower than 0.01 mL / cm 2 · min, the working efficiency is lowered. On the other hand, when the elution rate is faster than 1.00 mL / cm 2 · min, the polar substance is hardly absorbed by the inorganic adsorbent. Therefore, it is not preferable.
前記（Ｉ）においては、必要に応じて、トール脂肪酸エステル反応液に非極性溶剤（例えば、ヘキサン、ヘプタンなどの飽和炭化水素系溶剤）を混合し、混合溶液として通液させることもできる。これにより、極性物質の分離除去を促進するという効果が期待できる。 In the above (I), if necessary, a non-polar solvent (for example, a saturated hydrocarbon solvent such as hexane or heptane) may be mixed with the tall fatty acid ester reaction solution and passed as a mixed solution. Thereby, the effect of promoting the separation and removal of polar substances can be expected.
また、前記（Ｉ）においては、無機系吸着剤が充填された吸着カラムにトール脂肪酸エステル反応液を通液させた後、さらに所定量の非極性溶剤（例えば、前述と同様）を通液するのが好ましい。これにより、吸着カラム内に残存しているトール脂肪酸エステルを、吸着カラムから溶出させることができる。通液させる非極性溶剤の量は、残存しているトール脂肪酸エステルを溶出させることができる量であればよく、特に限定されるものではない。 In (I) above, after a tall fatty acid ester reaction solution is passed through an adsorption column filled with an inorganic adsorbent, a predetermined amount of a nonpolar solvent (for example, the same as described above) is further passed. Is preferred. Thereby, the tall fatty acid ester remaining in the adsorption column can be eluted from the adsorption column. The amount of the nonpolar solvent to be passed is not particularly limited as long as it is an amount capable of eluting the remaining tall fatty acid ester.
前記（ＩＩ）を行なう場合、具体的には、反応器に、無機系吸着剤、トール脂肪酸エステル反応液、および必要に応じて非極性溶剤（例えば、前述と同様）を入れて攪拌すればよい。非極性溶剤を加えることにより、極性物質の分離除去を促進するという効果が期待できる。 When performing the above (II), specifically, an inorganic adsorbent, a tall fatty acid ester reaction liquid, and, if necessary, a nonpolar solvent (for example, the same as described above) may be added to the reactor and stirred. . By adding a nonpolar solvent, the effect of promoting the separation and removal of polar substances can be expected.
前記（ＩＩ）においては、前記トール脂肪酸エステル反応液を、無機系吸着剤１００質量部に対して１００質量部以下となる割合で、無機系吸着剤を加えることが好ましい。これにより、トール脂肪酸エステル反応液に含まれる極性物質を効率よく無機系吸着剤に吸着させることができる。トール脂肪酸エステル反応液の量が無機系吸着剤１００質量部に対して１００質量部を超えると、極性物質の全量が無機系吸着剤に吸着されないおそれがある。 In said (II), it is preferable to add an inorganic adsorbent to the said tall fatty acid ester reaction liquid in the ratio used as 100 mass parts or less with respect to 100 mass parts of inorganic adsorbents. Thereby, the polar substance contained in the tall fatty acid ester reaction liquid can be efficiently adsorbed to the inorganic adsorbent. When the amount of the tall fatty acid ester reaction solution exceeds 100 parts by mass with respect to 100 parts by mass of the inorganic adsorbent, the total amount of the polar substance may not be adsorbed by the inorganic adsorbent.
以下、実施例を挙げて本発明を詳細に説明するが、本発明は以下の実施例に限定されるものではない。
なお、以下の実施例における酸価およびイオウ分の測定方法は、下記の通りである。
＜酸価＞ ＪＩＳ−Ｋ００７０に準じ、電位差滴定法にて測定した。
＜イオウ分＞ ＪＩＳ−Ｋ２５４１−２に準じ、微量電量滴定式酸化法にて測定した。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to a following example.
In addition, the acid value and the measuring method of a sulfur content in the following Examples are as follows.
<Acid value> It measured by the potentiometric titration method according to JIS-K0070.
<Sulfur content> Measured by a microcoulometric titration method according to JIS-K2541-2.
（実施例１）
攪拌装置、温度計、窒素ガス導入管、リービッヒ冷却器および水抜き管を備えたガラス製４つ口フラスコに、トール脂肪酸（ハリマ化成株式会社製「ハートールＦＨ」；実機のトール油精留プラントより生産されたトール脂肪酸であり、酸価：１９０ｍｇＫＯＨ／ｇ、イオウ分：５２０質量ｐｐｍ）３００．０ｇと、ブタノール１１５.８ｇと、パラトルエンスルホン酸（試薬特級）１.５ｇと、キシレン５０．０ｇとを仕込み、キシレン／ブタノール還流下１００〜１４０℃で２時間攪拌し、生成水を水抜き管で排出しつつエステル化反応を行った後、ブタノールおよびキシレンを留去して、トール脂肪酸ブチルエステル反応液３８０.１ｇを得た。このトール脂肪酸ブチルエステル反応液の酸価は３.７ｍｇＫＯＨ／ｇであった。
Example 1
In a glass four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, Liebig condenser and drain tube, tall fatty acid ("Hartol FH" manufactured by Harima Kasei Co., Ltd .; from the actual tall oil rectification plant Tall fatty acid produced, acid value: 190 mgKOH / g, sulfur content: 520 mass ppm) 300.0 g, butanol 115.8 g, paratoluenesulfonic acid (reagent special grade) 1.5 g, and xylene 50.0 g And stirred at 100-140 ° C. for 2 hours under reflux of xylene / butanol, and after performing esterification reaction while discharging the generated water through a drain pipe, butanol and xylene were distilled off to give tall fatty acid butyl ester 380.1 g of a reaction solution was obtained. The acid value of this tall fatty acid butyl ester reaction solution was 3.7 mg KOH / g.
ついで、直径５０ｍｍのガラス製の吸着カラムにシリカゲル（和光純薬工業社製「ワコーゲルＣ３００」；細孔径：７ｎｍ、細孔容積：０．８ｍＬ／ｇ、比表面積：４５０ｍ2／ｇ、粒度：４５〜７５μｍが７５％以上であり、７５μｍ残分が５％以下）３００.０ｇをヘキサン湿式充填法により充填した。この吸着カラムに、上記で得たトール脂肪酸ブチルエステル反応液３００．０ｇを０．２５ｍＬ／ｃｍ2・分の溶出速度で通液して、吸着カラム底部より溶出する溶離液を回収した。さらに、ヘキサン９００．０ｇを前記と同様の溶出速度で通液し、吸着カラム底部より溶出する溶離液を回収して、先に回収した溶離液と混合した。この混合した溶離液からヘキサンを蒸留操作により留去して、トール脂肪酸ブチルエステル２８２.３ｇを得た。得られたトール脂肪酸ブチルエステルの酸価は０.４ｍｇＫＯＨ／ｇであり、イオウ分は３７質量ｐｐｍであった。 Next, silica gel (“Wakogel C300” manufactured by Wako Pure Chemical Industries, Ltd .; pore diameter: 7 nm, pore volume: 0.8 mL / g, specific surface area: 450 m 2 / g, particle size: 45) is placed on a glass adsorption column having a diameter of 50 mm. ˜75 μm is 75% or more and 75 μm residue is 5% or less) 30.0 g was filled by a hexane wet filling method. Through this adsorption column, 300.0 g of the tall fatty acid butyl ester reaction solution obtained above was passed at an elution rate of 0.25 mL / cm 2 · min, and the eluate eluted from the bottom of the adsorption column was recovered. Further, 900.0 g of hexane was passed through at the same elution rate as described above, and the eluent eluted from the bottom of the adsorption column was recovered and mixed with the previously recovered eluent. From this mixed eluent, hexane was distilled off by distillation to obtain 282.3 g of tall fatty acid butyl ester. The acid value of the obtained tall fatty acid butyl ester was 0.4 mgKOH / g, and the sulfur content was 37 mass ppm.
（実施例２）
攪拌装置、温度計、窒素ガス導入管、リービッヒ冷却器および水抜き管を備えたガラス製４つ口フラスコに、トール脂肪酸（ハリマ化成株式会社製「ハートールＦＨ」；実機のトール油精留プラントより生産されたトール脂肪酸であり、酸価：１９０ｍｇＫＯＨ／ｇ、イオウ分：５２０質量ｐｐｍ）１０００.０ｇと、メタノール５４１.９ｇと、パラトルエンスルホン酸５.０ｇとを仕込み、メタノール還流下６５〜７０℃で１６時間攪拌し、エステル化反応を行った後、メタノールおよび生成水を留去して、トール脂肪酸メチルエステル反応液１０５０.９ｇを得た。このトール脂肪酸メチルエステル反応液の酸価は８.４ｍｇＫＯＨ／ｇであった。
(Example 2)
In a glass four-necked flask equipped with a stirrer, thermometer, nitrogen gas inlet tube, Liebig condenser and drain tube, tall fatty acid ("Hartol FH" manufactured by Harima Kasei Co., Ltd .; from the actual tall oil rectification plant The produced tall fatty acid was charged with 100.0 g of acid value: 190 mg KOH / g, sulfur content: 520 mass ppm), 541.9 g of methanol, and 5.0 g of paratoluenesulfonic acid, and 65-70 under methanol reflux. After stirring for 16 hours at 0 ° C. and carrying out an esterification reaction, methanol and product water were distilled off to obtain 1050.9 g of a tall fatty acid methyl ester reaction solution. The acid value of this tall fatty acid methyl ester reaction solution was 8.4 mgKOH / g.
ついで、直径５０ｍｍのガラス製の吸着カラムにシリカゲル（和光純薬工業社製「ワコーゲルＣ３００」；細孔径：７ｎｍ、細孔容積：０．８ｍＬ／ｇ、比表面積：４５０ｍ2／ｇ、粒度：４５〜７５μｍが７５％以上であり、７５μｍ残分が５％以下）３００.０ｇをヘキサン湿式充填法により充填した。この吸着カラムに、上記で得たトール脂肪酸メチルエステル反応液１００．０ｇを０．２５ｍＬ／ｃｍ2・分の溶出速度で通液して、吸着カラム底部より溶出する溶離液を回収した。さらに、ヘキサン６００．０ｇを前記と同様の溶出速度で通液し、吸着カラム底部より溶出する溶離液を回収して、先に回収した溶離液と混合した。この混合した溶離液からヘキサンを蒸留操作により留去して、トール脂肪酸メチルエステル９０．５ｇを得た。得られたトール脂肪酸メチルエステルの酸価は０.２ｍｇＫＯＨ／ｇであり、イオウ分は３９質量ｐｐｍであった。 Next, silica gel (“Wakogel C300” manufactured by Wako Pure Chemical Industries, Ltd .; pore diameter: 7 nm, pore volume: 0.8 mL / g, specific surface area: 450 m 2 / g, particle size: 45) is placed on a glass adsorption column having a diameter of 50 mm. ˜75 μm is 75% or more and 75 μm residue is 5% or less) 30.0 g was filled by a hexane wet filling method. Through this adsorption column, 100.0 g of the tall fatty acid methyl ester reaction solution obtained above was passed at an elution rate of 0.25 mL / cm 2 · min, and the eluate eluted from the bottom of the adsorption column was recovered. Further, 600.0 g of hexane was passed at the same elution rate as described above, and the eluent eluted from the bottom of the adsorption column was recovered and mixed with the previously recovered eluent. From this mixed eluent, hexane was distilled off by distillation to obtain 90.5 g of tall fatty acid methyl ester. The acid value of the obtained tall fatty acid methyl ester was 0.2 mgKOH / g, and the sulfur content was 39 mass ppm.
（実施例３）
内径１５ｍｍ、長さ２５０ｍｍのステンレス製円筒管に硫酸化ジルコニア（ペレット状試薬）１００.０ｇ充填して流通式反応器とした。この反応器の両端に原料供給および反応液流出用のステンレスチューブ（外径１.５８ｍｍ、内径１.０ｍｍ）を装着し、１８０℃に設定した恒温油槽に円筒管全体を浸した。他方、トール脂肪酸（ハリマ化成株式会社製「ハートールＦＡ−１」；実機のトール油精留プラントより生産されたトール脂肪酸であり、酸価１９４ｍｇＫＯＨ／ｇ、イオウ分１００質量ｐｐｍ）５５２.０ｇとメタノール３０５.６ｇとを混合した溶液を調製し、これを定量プランジャーポンプにより１ｍＬ／分の流量にて前記流通式反応管へ送液した。送液開始２時間後から流通式反応器より流出する反応液を採取し、この反応液からメタノールおよび反応生成水を留去して、トール脂肪酸メチルエステル４４５.０ｇを得た（ここまでを第１段反応とし、ここで得られたトール脂肪酸メチルエステルを「第１段反応後トール脂肪酸メチルエステル」と称す）。この第１段反応後トール脂肪酸メチルエステルの酸価は４２.４ｍｇＫＯＨ／ｇであった。
(Example 3)
A stainless steel cylindrical tube having an inner diameter of 15 mm and a length of 250 mm was charged with 100.0 g of sulfated zirconia (pellet-like reagent) to obtain a flow reactor. Stainless steel tubes (outer diameter: 1.58 mm, inner diameter: 1.0 mm) for supplying raw materials and flowing out the reaction solution were attached to both ends of the reactor, and the entire cylindrical tube was immersed in a constant temperature oil tank set at 180 ° C. On the other hand, tall fatty acid ("Hartol FA-1" manufactured by Harima Chemicals Co., Ltd .; tall fatty acid produced from an actual tall oil rectification plant, acid value 194 mg KOH / g, sulfur content 100 mass ppm) 552.0 g and methanol A solution in which 305.6 g was mixed was prepared, and this was sent to the flow-through reaction tube at a flow rate of 1 mL / min by a quantitative plunger pump. The reaction liquid flowing out from the flow reactor was collected 2 hours after the start of liquid feeding, and methanol and reaction product water were distilled off from this reaction liquid to obtain 445.0 g of tall fatty acid methyl ester. A one-stage reaction is performed, and the tall fatty acid methyl ester obtained here is referred to as “the first fatty acid methyl ester after the first stage reaction”). After this first stage reaction, the acid value of the tall fatty acid methyl ester was 42.4 mgKOH / g.
次に、上記で得た第１段反応後トール脂肪酸メチルエステル４４０.０ｇとメタノール２４４.０ｇとを混合した溶液を調製し、これを前記第１段反応と同様に定量プランジャーポンプにより１ｍＬ／分の流量にて前記流通式反応管へ送液した。送液開始２時間後から流通式反応器より流出する反応液を採取し、この反応液からメタノールおよび反応生成水を留去して、トール脂肪酸メチルエステル３３６.５ｇを得た（ここで得られたトール脂肪酸メチルエステルを「第２段反応後トール脂肪酸メチルエステル」と称す）。この第２段反応後トール脂肪酸メチルエステルの酸価は２４.６ｍｇＫＯＨ／ｇであった。 Next, a solution in which 440.0 g of tall fatty acid methyl ester obtained after the first-stage reaction and 244.0 g of methanol were mixed was prepared, and this was added to the 1 mL / mL by a quantitative plunger pump as in the first-stage reaction. The solution was fed to the flow reaction tube at a flow rate of minutes. The reaction liquid flowing out from the flow reactor was collected 2 hours after the start of liquid feeding, and methanol and reaction product water were distilled off from this reaction liquid to obtain 336.5 g of tall fatty acid methyl ester (obtained here). The tall fatty acid methyl ester is referred to as “after the second stage reaction, the tall fatty acid methyl ester”). After this second stage reaction, the acid value of tall fatty acid methyl ester was 24.6 mgKOH / g.
ついで、直径５０ｍｍのガラス製の吸着カラムにシリカゲル（和光純薬工業社製「ワコーゲルＣ３００」；細孔径：７ｎｍ、細孔容積：０．８ｍＬ／ｇ、比表面積：４５０ｍ2／ｇ、粒度：４５〜７５μｍが７５％以上であり、７５μｍ残分が５％以下）３００.０ｇをヘキサン湿式充填法により充填した。この吸着カラムに、上記で得た第２段反応後トール脂肪酸メチルエステル６０．０ｇを０．１２５ｍＬ／ｃｍ2・分の溶出速度で通液して、吸着カラム底部より溶出する溶離液を回収した。さらに、ヘキサン４００．０ｇを前記と同様の溶出速度で通液し、吸着カラム底部より溶出する溶離液を回収して、先に回収した溶離液と混合した。この混合した溶離液からヘキサンを蒸留操作により留去して、トール脂肪酸メチルエステル５１.５ｇを得た。得られたトール脂肪酸メチルエステルの酸価は０.１ｍｇＫＯＨ／ｇであり、イオウ分は９質量ｐｐｍであった。 Next, silica gel (“Wakogel C300” manufactured by Wako Pure Chemical Industries, Ltd .; pore diameter: 7 nm, pore volume: 0.8 mL / g, specific surface area: 450 m 2 / g, particle size: 45) is placed on a glass adsorption column having a diameter of 50 mm. ˜75 μm is 75% or more and 75 μm residue is 5% or less) 30.0 g was filled by a hexane wet filling method. Through this adsorption column, 60.0 g of tall fatty acid methyl ester after the second stage reaction obtained above was passed at an elution rate of 0.125 mL / cm 2 · min, and the eluate eluted from the bottom of the adsorption column was recovered. . Furthermore, 400.0 g of hexane was passed through at the same elution rate as described above, and the eluent eluted from the bottom of the adsorption column was recovered and mixed with the previously recovered eluent. From this mixed eluent, hexane was distilled off by distillation to obtain 51.5 g of tall fatty acid methyl ester. The acid value of the resulting tall fatty acid methyl ester was 0.1 mgKOH / g, and the sulfur content was 9 mass ppm.
以上の結果から、比較的安価なトール脂肪酸を原料としてエステル化反応を行い、トール脂肪酸エステルとその他不純物との極性の違いを利用すると、特別な装置を使用せずに、吸着カラムを使用するなどの簡単な操作で、高品質のトール脂肪酸エステルが得られることがわかる。
さらに、上記実施例１〜３で得られた高品質のトール脂肪酸エステルをそれぞれバイオディーゼル燃料に用いたところ、軽油の消費に関わる環境負荷を軽減することができた。
Based on the above results, esterification reaction is performed using relatively inexpensive tall fatty acid as a raw material, and if the difference in polarity between tall fatty acid ester and other impurities is used, an adsorption column is used without using a special device. It can be seen that high-quality tall fatty acid esters can be obtained by a simple operation.
Furthermore, when the high-quality tall fatty acid esters obtained in Examples 1 to 3 were respectively used for biodiesel fuel, the environmental load related to the consumption of light oil could be reduced.
Claims (4)
前記トール脂肪酸エステル反応液を、前記無機系吸着剤１００質量部に対して１００質量部以下の割合で、かつ０．０１〜１．００ｍＬ／ｃｍ 2 ・分の溶出速度で通液させる、ことを特徴とするトール脂肪酸エステルの製造方法。 A tall fatty acid ester reaction liquid is obtained by an esterification reaction using tall fatty acid containing 1 to 5% by mass of rosin acid and lower alcohol as raw materials, and this reaction liquid is passed through an adsorption column packed with an inorganic adsorbent. A method for producing a tall fatty acid ester having an acid value of less than 0.5 mg KOH / g and a sulfur content of 50 ppm by mass or less ,
Allowing the tall fatty acid ester reaction solution to flow at a rate of 100 parts by mass or less with respect to 100 parts by mass of the inorganic adsorbent and at an elution rate of 0.01 to 1.00 mL / cm 2 · min. A method for producing a tall fatty acid ester.
前記無機系吸着剤１００質量部に対して、前記トール脂肪酸エステル反応液が１００質量部以下となる割合で、前記無機系吸着剤を加える、ことを特徴とするトール脂肪酸エステルの製造方法。 A tall fatty acid ester reaction liquid is obtained by an esterification reaction using 1 to 5% by mass of rosin acid containing rosin acid and lower alcohol as raw materials, and an inorganic adsorbent is added to the reaction liquid and stirred to give an acid value of 0. A method for producing a tall fatty acid ester having a sulfur content of less than 5 mg KOH / g and a sulfur content of 50 mass ppm or less ,
A method for producing a tall fatty acid ester , wherein the inorganic adsorbent is added at a ratio of 100 parts by mass or less with respect to 100 parts by mass of the inorganic adsorbent .
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