JP2010254486A - Compounded oil for purifying titanium tetrachloride - Google Patents
Compounded oil for purifying titanium tetrachloride Download PDFInfo
- Publication number
- JP2010254486A JP2010254486A JP2009103081A JP2009103081A JP2010254486A JP 2010254486 A JP2010254486 A JP 2010254486A JP 2009103081 A JP2009103081 A JP 2009103081A JP 2009103081 A JP2009103081 A JP 2009103081A JP 2010254486 A JP2010254486 A JP 2010254486A
- Authority
- JP
- Japan
- Prior art keywords
- oil
- titanium tetrachloride
- mass
- sulfur
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 39
- 239000003921 oil Substances 0.000 claims abstract description 38
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002199 base oil Substances 0.000 claims abstract description 21
- 239000002480 mineral oil Substances 0.000 claims abstract description 21
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000010446 mineral oil Nutrition 0.000 claims abstract description 20
- 239000000654 additive Substances 0.000 claims abstract description 15
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 239000005077 polysulfide Substances 0.000 claims abstract description 10
- 229920001021 polysulfide Polymers 0.000 claims abstract description 10
- 150000008117 polysulfides Polymers 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 5
- 238000007670 refining Methods 0.000 claims description 11
- 239000003925 fat Substances 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000013256 coordination polymer Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 15
- -1 polycyclic aromatic compound Chemical class 0.000 abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 abstract description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract 1
- 235000019198 oils Nutrition 0.000 description 31
- 238000000034 method Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- ONJROLGQWMBXAP-UHFFFAOYSA-N 2-methyl-1-(2-methylpropyldisulfanyl)propane Chemical compound CC(C)CSSCC(C)C ONJROLGQWMBXAP-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000014593 oils and fats Nutrition 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010698 whale oil Substances 0.000 description 1
Landscapes
- Lubricants (AREA)
Abstract
Description
本発明は、ルチルなどのチタン鉱石を塩素化して得られた粗製四塩化チタンを精製する際に配合する四塩化チタン精製用配合油に関する。 The present invention relates to a compounded oil for purifying titanium tetrachloride, which is blended when purifying crude titanium tetrachloride obtained by chlorinating titanium ore such as rutile.
金属チタニウムや顔料などに用いられる酸化チタニウムの原料となる四塩化チタンは、ルチル鉱石、イルメナイト鉱石などのチタン鉱石を、コークスなどの炭素質物質の存在下に塩素化して得られた粗製四塩化チタンを蒸留精製することにより製造されている。しかし、バナジウムや珪素などの塩化物は、沸点が四塩化チタンと同程度であるため、蒸留によっては除去が困難である。このため、石油系オイル、例えば鉱油、ワックス、水素化ナフテン系オイル、潤滑油、重質残渣油など、あるいは脂肪酸、脂肪族アルコール、石鹸、トール油、動物油脂、植物油、ろう、ポリエチレン、ポリプロピレンなどの有機物質を添加して四塩化チタンを蒸留することでバナジウムなどを除去する方法が知られている（特許文献１〜２）。 Titanium tetrachloride, the raw material for titanium oxide used in metallic titanium and pigments, is crude titanium tetrachloride obtained by chlorinating titanium ores such as rutile or ilmenite ore in the presence of carbonaceous materials such as coke. Is produced by distillation purification. However, chlorides such as vanadium and silicon have a boiling point similar to that of titanium tetrachloride and are difficult to remove by distillation. For this reason, petroleum oils such as mineral oils, waxes, hydrogenated naphthenic oils, lubricating oils, heavy residual oils, or fatty acids, aliphatic alcohols, soaps, tall oils, animal fats, vegetable oils, waxes, polyethylene, polypropylene, etc. There is known a method for removing vanadium and the like by adding the organic substance and distilling titanium tetrachloride (Patent Documents 1 and 2).
ところで、どのような有機物質を配合すれば不純物除去に有効であるかは、良く知られておらず、しかも、鉱油には多環芳香族化合物（ＰＣＡ）が多く含まれる油が多々あり、近年、健康への影響が心配され、このような油の使用を規制する動きがある。したがって、鉱油を用いる場合は多環芳香族化合物（ＰＣＡ）が少ない、具体的にはジメチルスルホキシド（ＤＭＳＯ）抽出分の低い鉱油の使用が推奨されている。しかし、このような鉱油のみを用いた場合、不純物が十分に除去されないという問題があった。 By the way, it is not well known what kind of organic substance is effective in removing impurities, and there are many oils containing a large amount of polycyclic aromatic compounds (PCA) in mineral oil. There are concerns about health effects and there are moves to regulate the use of such oils. Therefore, when mineral oil is used, it is recommended to use mineral oil with a low polycyclic aromatic compound (PCA), specifically, a low dimethyl sulfoxide (DMSO) extract. However, when only such mineral oil is used, there is a problem that impurities are not sufficiently removed.
本発明は、粗製四塩化チタンを蒸留精製する際に用いる四塩化チタン精製用配合油として、人の健康に対する影響が小さい多環芳香族化合物（ＰＣＡ）の含有量が少ない鉱油を用い、バナジウムなどの不純物除去に優れたものを提供することにある。 The present invention uses a mineral oil with a low content of polycyclic aromatic compounds (PCA) having a small influence on human health as a blended oil for purifying titanium tetrachloride used for refining crude titanium tetrachloride by distillation, vanadium, etc. It is to provide an excellent material for removing impurities.
本発明者は、多環芳香族化合物（ＰＣＡ）の少ない鉱油に何らかの添加物を配合することにより、さらに不純物濃度を低下させることが可能であるはずとの着想に基づき、様々な添加剤との組み合わせについて調査、研究した結果、特定の鉱油系基油に、特定の硫黄系添加剤を所定量添加することで、不純物濃度を低下させることができることを見出し、本発明を完成した。 Based on the idea that it is possible to further reduce the impurity concentration by adding some additive to mineral oil with a low polycyclic aromatic compound (PCA), the present inventor As a result of investigating and researching the combination, the inventors have found that the impurity concentration can be reduced by adding a predetermined amount of a specific sulfur-based additive to a specific mineral base oil, and the present invention has been completed.
すなわち、本発明は次のとおりの四塩化チタン精製用配合油である。
（１）ＤＭＳＯ抽出分が３質量％未満、％ＣＡが１０〜２５、クロマトによる芳香族分が５０質量％以上である鉱油系基油に、硫化油脂、硫化オレフィン、硫化エステル、ポリスルフィドの少なくとも１種類からなる硫黄系添加剤を硫黄分として２〜８質量％含有する四塩化チタン精製用配合油。
（２）１００℃における動粘度が１８〜４０mm２/s、引火点が２００℃以上、１６３℃で３時間後の蒸発量が０.５質量％以下である上記（１）に記載の四塩化チタン精製用配合油。
（３）鉱油系基油が、１００℃における動粘度２５〜５０mm２/s、％ＣＮ１０〜２５、％ＣＰ５０〜８０、硫黄分４％以下である上記（１）に記載の四塩化チタン精製用配合油。
（４）硫黄系添加剤の硫黄含有量が１５〜４５質量％である上記（１）に記載の四塩化チタン精製用配合油。
That is, the present invention is the following compounding oil for purifying titanium tetrachloride.
(1) Mineral oil base oil having a DMSO extract of less than 3% by mass,% CA of 10 to 25, and aromatic content by chromatography of 50% by mass or more is added to at least one of sulfurized fats, sulfurized olefins, sulfurized esters and polysulfides. Formulated oil for refining titanium tetrachloride containing 2 to 8% by mass of a sulfur-based additive of various types as a sulfur content.
(2) The tetrachloride according to (1), wherein the kinematic viscosity at 100 ° C. is 18 to 40 mm 2 / s, the flash point is 200 ° C. or more, and the evaporation amount after 3 hours at 163 ° C. is 0.5% by mass or less. Formulated oil for titanium purification.
(3) Mineral oil-based base oil has a kinematic viscosity at 100 ° C. of 25 to 50 mm 2 / s,% CN of 10 to 25,% CP of 50 to 80, and a sulfur content of 4% or less, for purification of titanium tetrachloride as described in (1) above Formulated oil.
(4) The blended oil for purifying titanium tetrachloride according to (1) above, wherein the sulfur content of the sulfur-based additive is 15 to 45% by mass.
本発明の四塩化チタン精製用配合油は、多環芳香族化合物による人への健康被害の心配が少なく、しかも粗製四塩化チタンからバナジウムなどの不純物濃度を大幅に低下できるという効果を有する。 The blended oil for refining titanium tetrachloride of the present invention has the effect that there is little concern about human health damage due to polycyclic aromatic compounds, and that the concentration of impurities such as vanadium from crude titanium tetrachloride can be greatly reduced.
〔鉱油系基油〕
本発明に用いる鉱油系基油としては、人の健康への影響が少ないＤＭＳＯ抽出分が３質量％未満のものである。このＤＭＳＯ抽出分は、イギリス石油協会がＩＰ３４６として規定する方法で測定されるもので、特には２.５質量％未満とすることが好ましい。
また、この鉱油系基油は、バナジウムなどの不純物を効率よく除去するために、％ＣＡは１０〜２５のもので、特には、１５〜２０が好ましく、さらに、より不純物を効率的に除去するため、％ＣＮが１０〜２５、特には、１５〜２０のものが、％ＣＰが５０〜８０、特には、６０〜７０のものが、好ましい。この％ＣＡ、％ＣＮ、％ＣＰは、ＡＳＴＭ Ｄ３２３８に規定されるｎ-ｄ-Ｍ環分析の方法で測定されるものである。
さらに、この鉱油系基油は、不純物を効率よく除去するために、クロマトによる芳香族分が５０質量％以上である。このクロマトによる芳香族分は、ＡＳＴＭ Ｄ２００７に規定される方法で測定されるもので、特には５５質量％以上、８０質量％以下が好ましい。
[Mineral oil base oil]
The mineral base oil used in the present invention has a DMSO extract of less than 3% by mass with little impact on human health. This DMSO extract is measured by the method defined by the British Petroleum Institute as IP346, and is particularly preferably less than 2.5% by mass.
In addition, in order to efficiently remove impurities such as vanadium, this mineral oil-based base oil has a% CA of 10 to 25, particularly preferably 15 to 20, and more efficiently removes impurities. Therefore, those having% CN of 10 to 25, particularly 15 to 20 and% CP of 50 to 80, particularly 60 to 70 are preferable. The% CA,% CN, and% CP are measured by the ndM ring analysis method defined in ASTM D3238.
Further, this mineral oil base oil has an aromatic content of 50% by mass or more by chromatography in order to efficiently remove impurities. The aromatic content by this chromatography is measured by the method prescribed in ASTM D2007, and is particularly preferably 55% by mass or more and 80% by mass or less.
なお、鉱油系基油は、ハンドリングが容易であり、かつ、この基油が精製された四塩化チタンへの混合をできるだけ少なくするために、１００℃における動粘度として２５〜５０mm２/sのものが好ましく、バナジウムなどの不純物を効率的に除去し、かつＤＭＳＯ抽出分の３質量％未満とするために、硫黄分が４％以下、特には１〜３％がのものが好ましく、安全上の観点から引火点が３００℃以上のものが好ましく、精製後の四塩化チタンに混入する量をできるだけ少なくするために蒸発量が０.１質量％未満であることが好ましい。前記動粘度はＪＩＳ Ｋ２２８３に規定する方法で１００℃で測定されるもの、硫黄分はＪＩＳ Ｋ ２５４１−５に規定する方法で測定されるもの、引火点はＪＩＳ Ｋ２２６５−４に規定する方法で測定されるもの、蒸発量はＪＩＳ Ｋ ２２０７に規定する方法で３時間で測定されるものである。 Mineral oil base oil is easy to handle and has a kinematic viscosity of 25 to 50 mm 2 / s at 100 ° C. in order to minimize the mixing of the base oil with the refined titanium tetrachloride. In order to efficiently remove impurities such as vanadium and make the DMSO extract less than 3% by mass, it is preferable that the sulfur content is 4% or less, particularly 1 to 3%. From the viewpoint, the one having a flash point of 300 ° C. or higher is preferable, and the amount of evaporation is preferably less than 0.1% by mass in order to minimize the amount mixed into the purified titanium tetrachloride. The kinematic viscosity is measured at 100 ° C. by the method specified in JIS K2283, the sulfur content is measured by the method specified in JIS K2541-5, and the flash point is measured by the method specified in JIS K2265-4. The evaporation amount is measured in 3 hours by the method defined in JIS K 2207.
本発明の鉱油系基油としては、原油を常圧蒸留して、さらには減圧蒸留して得られた潤滑油留分を、溶剤脱れき、溶剤抽出、水素化分解、溶剤脱蝋、水素化脱蝋、水素化精製、硫酸洗浄、白土処理等の潤滑油精製手段を適宜組み合わせて処理して得られた精製潤滑油留分が好適に用いられる。なお、この場合、各種の原料と各種の精製手段の組み合わせから得られた性状の異なる精製潤滑油留分を単独で用いてもよいし、２種以上を組み合わせて用いることもできる。このように石油の比較的高沸点な留分より作られる鉱油系の潤滑油基油は一般的に安価なこともあり、様々な潤滑油やグリースなどに広く用いられているので、本発明においては、これらのうち上記要件を具備するものを適宜選択して用いることができる。 As the mineral oil base oil of the present invention, the crude oil fraction obtained by atmospheric distillation and further vacuum distillation is subjected to solvent removal, solvent extraction, hydrocracking, solvent dewaxing, hydrogenation. A refined lubricating oil fraction obtained by treatment by appropriately combining lubricating oil refining means such as dewaxing, hydrorefining, sulfuric acid washing and clay treatment is suitably used. In this case, refined lubricating oil fractions having different properties obtained from combinations of various raw materials and various purification means may be used alone, or two or more kinds may be used in combination. As described above, mineral oil base oils made from a relatively high boiling fraction of petroleum are generally inexpensive and widely used in various lubricating oils and greases. Can be used by appropriately selecting those having the above requirements.
〔硫黄系添加剤〕
硫黄系添加剤としては、硫化油脂、硫化オレフィン、硫化エステル、ポリスルフィドを単独で、又は複数種、混合して用いてもよい。硫黄系添加剤の添加量は、硫黄分として２〜８質量％であり、特には、２.５〜６質量％が好ましい。添加量が、硫黄分として２質量％未満であると、粗製四塩化チタン中の不純物を十分に除去できず、また、８質量％を超えると、精製後の四塩化チタン中に硫黄系添加剤由来の軽質分が増加するという問題が生じる。この硫黄系添加剤は硫黄含有量が５〜４５質量％のものが好ましく、特には１５〜２５質量％がより好ましい。硫黄含有量が５質量%よりも低いと、バナジウムなどの不純物の除去が十分でなく、さらに多量の添加が必要性となり、好ましくない。また、４５質量％よりも高いと精製中に硫黄が析出する可能性が高く、好ましくない。
[Sulfur additives]
As the sulfur-based additive, sulfurized fats and oils, sulfurized olefins, sulfurized esters, and polysulfides may be used singly or in combination. The addition amount of the sulfur-based additive is 2 to 8% by mass, particularly 2.5 to 6% by mass as the sulfur content. If the addition amount is less than 2% by mass as the sulfur content, impurities in the crude titanium tetrachloride cannot be sufficiently removed, and if it exceeds 8% by mass, the sulfur-based additive is added to the purified titanium tetrachloride. There arises a problem that light components derived from the source increase. This sulfur-based additive preferably has a sulfur content of 5 to 45% by mass, more preferably 15 to 25% by mass. If the sulfur content is lower than 5% by mass, removal of impurities such as vanadium is not sufficient, and a larger amount of addition becomes necessary, which is not preferable. Moreover, when higher than 45 mass%, possibility that sulfur will precipitate during refinement | purification is high, and it is not preferable.
硫化油脂は、油脂の不飽和結合を硫黄で架橋してなる化合物であり、例えば、硫黄と、菜種油、ひまし油、大豆油等の植物油や、牛脂、豚脂、鯨油等の動物油とを反応させて得られ、潤滑油用の硫黄系極圧剤として市販されているものを利用することができる。また、硫化オレフィンは、オレフィン類の不飽和結合を硫黄で架橋してなる化合物であり、ポリサルファイドは、オレフィン類以外の炭化水素原料をを硫化して得られるもので、さらに、硫化エステルは、動植物油脂と各種アルコールとの反応により得られる脂肪酸エステルを硫化することにより得られるもので、硫化油脂と硫化エステルは、化学構造そのものは明確でない。ポリサルファイドの具体的なものとしては、ジイソブチルジサルファイド、ジオクチルポリサルファイド、ジ‐tert‐ブチルポリサルファイド、ジ‐tertーベンジルポリサルファイドなどが挙げられる。これらはいずれも潤滑油用の硫黄系極圧剤として市販されているものを利用することができる。
これら硫化油脂、硫化オレフィン、ポリサルファイドあるいは硫化エステルは、それぞれに一種単独で使用してもよく、二種以上を組み合わせて使用してもよい。
Sulfurized fats and oils are compounds formed by crosslinking unsaturated bonds of fats and oils with sulfur, for example, by reacting sulfur with vegetable oils such as rapeseed oil, castor oil and soybean oil, and animal oils such as beef fat, pork fat and whale oil. What is obtained and can be utilized what is marketed as a sulfur type extreme pressure agent for lubricating oil. Sulfurized olefins are compounds obtained by crosslinking unsaturated bonds of olefins with sulfur. Polysulfides are obtained by sulfiding hydrocarbon raw materials other than olefins. Furthermore, sulfurized esters are used for animals and plants. It is obtained by sulfiding fatty acid esters obtained by reaction of fats and oils with various alcohols, and the chemical structure itself of the sulfurized fats and sulfurized esters is not clear. Specific examples of polysulfide include diisobutyl disulfide, dioctyl polysulfide, di-tert-butyl polysulfide, and di-tert-benzyl polysulfide. Any of these commercially available sulfur-based extreme pressure agents for lubricating oils can be used.
These sulfurized oils and fats, sulfurized olefins, polysulfides or sulfurized esters may be used alone or in combination of two or more.
〔四塩化チタン精製用配合油〕
本発明の四塩化チタン精製用配合油は、１００℃における動粘度が１８〜４０mm２/sが好ましく、より好ましくは２０〜３０mm２/sであり、この範囲ではハンドリングが容易であり、かつ、配合油が精製後の四塩化チタンにほとんど混合しない。また、同様に、精製後の四塩化チタンへの混合を抑制するために、蒸発量が０.５質量％以下、特には０.３質量％以下とすることが好ましい。なお、この１００℃における動粘度及び蒸発量は、上記鉱油系基油で示した方法と同じ方法で測定するものである。
[Formulated oil for titanium tetrachloride purification]
The compounded oil for refining titanium tetrachloride of the present invention preferably has a kinematic viscosity at 100 ° C. of 18 to 40 mm 2 / s, more preferably 20 to 30 mm 2 / s, and is easy to handle in this range, and The blended oil hardly mixes with the refined titanium tetrachloride. Similarly, the amount of evaporation is preferably 0.5% by mass or less, particularly 0.3% by mass or less, in order to suppress mixing into the purified titanium tetrachloride. The kinematic viscosity and the evaporation amount at 100 ° C. are measured by the same method as the method shown for the mineral oil base oil.
本発明の四塩化チタン精製用配合油は、粗製四塩化チタン液に添加して蒸留精製する方法でも、あるいは蒸留工程の途中のガス状態の粗製四塩化チタンと接触させる方法でも用いることができる。 The blended oil for purifying titanium tetrachloride of the present invention can be used either by adding to a crude titanium tetrachloride solution and purifying by distillation, or by contacting with crude titanium tetrachloride in a gas state during the distillation step.
以下、実施例および比較例に基づいてより本発明をより詳細に説明するが、本発明はかかる実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example and a comparative example, this invention is not limited to this Example.
〔四塩化チタン精製用配合油の調製〕
表１に示す基油１、２を用いて、表２に示す配合により供試油を調整した。
基油１は、減圧蒸留残渣油の脱瀝油を溶剤抽出して得られたＤＭＳＯ抽出分が３質量％未満のエキストラクトに、減圧蒸留留分を溶剤精製して得られたラフィネートを水素化精製及び脱ロウ処理することにより得られた鉱油系基油を混合することにより製造した。
基油２は、減圧蒸留残渣油の脱瀝油を溶剤精製して得られたラフィネートを水素化精製及び脱ロウ処理することにより製造した。
硫黄系添加剤として、硫黄分として２０質量％の硫黄を含有する硫化オレフィンを用いた。
[Preparation of oil for titanium tetrachloride purification]
Using the base oils 1 and 2 shown in Table 1, the test oil was adjusted according to the formulation shown in Table 2.
Base oil 1 is a hydrogenated raffinate obtained by solvent-refining a vacuum distillation fraction to an extract having a DMSO extract of less than 3% by mass obtained by solvent extraction of degassed oil obtained by distillation under reduced pressure. It was produced by mixing mineral oil base oil obtained by refining and dewaxing treatment.
Base oil 2 was produced by hydrorefining and dewaxing a raffinate obtained by solvent refining of the dewaxed oil of vacuum distillation residue oil.
As the sulfur-based additive, a sulfurized olefin containing 20% by mass of sulfur as a sulfur content was used.
〔四塩化チタン精製用配合油の評価〕
表２に供試油の評価結果を示す。評価は、バナジウムの含有量が３２０ppmである粗製四塩化チタン３００mlに、供試油１.０g添加し、撹拌子で撹拌しながら、１４０℃まで加熱し、時間あたり１４０mlの留出速度で単蒸留する方法で行った。留出液は初留（５０ml）と第２留分（１５０ml）に分け、第２留分のバナジウム量（ＩＣＰ金属分析）と炭化水素含有量（ガスクロマトグラフィー）の測定を行った。バナジウム量、炭化水素量ともに１ppm未満であった場合を合格とし、どちらか一方でも１pm以上検出された場合を不合格とした。
[Evaluation of oil blended with titanium tetrachloride]
Table 2 shows the evaluation results of the test oil. Evaluation was made by adding 1.0 g of test oil to 300 ml of crude titanium tetrachloride having a vanadium content of 320 ppm, heating to 140 ° C. while stirring with a stirrer, and performing simple distillation at a distillation rate of 140 ml per hour. It was done by the method. The distillate was divided into an initial fraction (50 ml) and a second fraction (150 ml), and the amount of vanadium (ICP metal analysis) and hydrocarbon content (gas chromatography) of the second fraction were measured. The case where both the amount of vanadium and the amount of hydrocarbons were less than 1 ppm was accepted, and the case where either one was detected at 1 pm or more was regarded as unacceptable.
供試油１、２では、不純物濃度を十分に下げることができたが、同じ基油を用いた場合であっても硫黄系添加剤の配合量が少ない場合や、多すぎる場合には不純物濃度を十分に下げることはできない。また、％ＣＡや芳香族分が少ない基油の場合には、同様に硫黄系添加剤を配合しても十分な特性は得られなかった。 In the sample oils 1 and 2, the impurity concentration could be lowered sufficiently, but even when the same base oil was used, the impurity concentration was too small when the amount of the sulfur-based additive was small or too large. Cannot be lowered sufficiently. Further, in the case of a base oil having a low% CA and aromatic content, sufficient characteristics could not be obtained even when a sulfur-based additive was blended.
本発明の四塩化チタン精製用配合油は、金属チタンなどの原料となる四塩化チタンの精製に用いることにより、高純度の四塩化チタンの製造が可能となる。 The blended oil for refining titanium tetrachloride of the present invention can be used to purify titanium tetrachloride as a raw material such as titanium metal, whereby high-purity titanium tetrachloride can be produced.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009103081A JP5208044B2 (en) | 2009-04-21 | 2009-04-21 | Formulated oil for titanium tetrachloride purification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009103081A JP5208044B2 (en) | 2009-04-21 | 2009-04-21 | Formulated oil for titanium tetrachloride purification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010254486A true JP2010254486A (en) | 2010-11-11 |
| JP5208044B2 JP5208044B2 (en) | 2013-06-12 |
Family
ID=43315873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009103081A Active JP5208044B2 (en) | 2009-04-21 | 2009-04-21 | Formulated oil for titanium tetrachloride purification |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5208044B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109956498A (en) * | 2019-04-29 | 2019-07-02 | 渤海大学 | A kind of crude titanic chloride efficiently removes vanadium compounding organic matter and preparation method thereof |
| CN111087017A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Method for removing vanadium from crude titanium tetrachloride |
| CN113603136A (en) * | 2021-08-25 | 2021-11-05 | 云南国钛金属股份有限公司 | Method for removing vanadium from titanium tetrachloride by using waste lubricating oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5021992A (en) * | 1973-06-07 | 1975-03-08 | ||
| JPH09286618A (en) * | 1996-04-23 | 1997-11-04 | Ishihara Sangyo Kaisha Ltd | Method for purifying titanium tetrachloride |
| JP2006515264A (en) * | 2003-01-09 | 2006-05-25 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Purification of titanium tetrachloride |
-
2009
- 2009-04-21 JP JP2009103081A patent/JP5208044B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5021992A (en) * | 1973-06-07 | 1975-03-08 | ||
| JPH09286618A (en) * | 1996-04-23 | 1997-11-04 | Ishihara Sangyo Kaisha Ltd | Method for purifying titanium tetrachloride |
| JP2006515264A (en) * | 2003-01-09 | 2006-05-25 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Purification of titanium tetrachloride |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087017A (en) * | 2018-10-24 | 2020-05-01 | 中国石油化工股份有限公司 | Method for removing vanadium from crude titanium tetrachloride |
| CN109956498A (en) * | 2019-04-29 | 2019-07-02 | 渤海大学 | A kind of crude titanic chloride efficiently removes vanadium compounding organic matter and preparation method thereof |
| CN109956498B (en) * | 2019-04-29 | 2021-08-03 | 渤海大学 | Compound organic matter for efficiently removing vanadium from crude titanium tetrachloride and preparation method thereof |
| CN113603136A (en) * | 2021-08-25 | 2021-11-05 | 云南国钛金属股份有限公司 | Method for removing vanadium from titanium tetrachloride by using waste lubricating oil |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5208044B2 (en) | 2013-06-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI464252B (en) | Method for preparing naphthenic process oil by hydrogenation | |
| JP2009013421A (en) | Process oil and process for its production | |
| CA2874826C (en) | Process for producing ketones from fatty acids | |
| JP5208044B2 (en) | Formulated oil for titanium tetrachloride purification | |
| JP2010047682A (en) | Manufacturing method of rubber process oil | |
| JP2019501274A5 (en) | ||
| JP5410807B2 (en) | Rubber compounding oil and method for producing the same | |
| JP2005213447A (en) | Lubricant composition | |
| EP2829586A1 (en) | Highly aromatic base oil and method for producing highly aromatic base oil | |
| US20200087595A1 (en) | Method for processing used oils | |
| JP4036374B2 (en) | Recycle additive composition for asphalt pavement waste | |
| JPH09505326A (en) | Method for producing base oil for lubricating oil by low-severity hydrorefining of used industrial circulating oil | |
| JP6152356B2 (en) | Compressor oil, compressor oil production method, hydrogen compression method, power generation method, and hydrogen supply method | |
| JP5171317B2 (en) | Lubricating oil composition for plastic working | |
| US20220041526A1 (en) | Base oil synthesis via ionic catalyst oligomerization and waterless separation of the oligomerization catalyst | |
| JP5390233B2 (en) | Rubber compounding oil and method for producing the same | |
| Thi et al. | Green chemistry for the preparation of bio-based oil from catfish fat using a cavitation system | |
| WO2024105947A1 (en) | Method for producing recovered oil composition and method for producing recovered industrial oil composition | |
| JP6574390B2 (en) | Lubricating oil composition | |
| KR101804663B1 (en) | Method of Preparing Hydroprocessing Catalysts from in Waste Oil and Method of Converting Heavy oil using the same | |
| JP2020059835A (en) | Environmentally friendly, low viscosity, highly flammable, non-water soluble processing oil | |
| JP4257186B2 (en) | Recycle additive composition for asphalt pavement waste | |
| JP6017130B2 (en) | Process oil production method | |
| JP2011162723A (en) | Additive composition for lubricating oil | |
| WO2021009295A1 (en) | Low pour point derivatives of dimer fatty acids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20100921 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20111122 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121203 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20121212 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121227 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130129 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130219 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160301 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5208044 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |