WO2014171398A1 - Method for producing alkyl-benzene composition and alkyl benzene sulfonate - Google Patents
Method for producing alkyl-benzene composition and alkyl benzene sulfonate Download PDFInfo
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- WO2014171398A1 WO2014171398A1 PCT/JP2014/060438 JP2014060438W WO2014171398A1 WO 2014171398 A1 WO2014171398 A1 WO 2014171398A1 JP 2014060438 W JP2014060438 W JP 2014060438W WO 2014171398 A1 WO2014171398 A1 WO 2014171398A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C15/00—Cyclic hydrocarbons containing only six-membered aromatic rings as cyclic parts
- C07C15/02—Monocyclic hydrocarbons
- C07C15/107—Monocyclic hydrocarbons having saturated side-chain containing at least six carbon atoms, e.g. detergent alkylates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- the present invention relates to an alkylbenzene composition for producing an alkylbenzene sulfonated product, and relates to an alkylbenzene composition capable of improving the hue of the alkylbenzene sulfonated product produced using the alkylbenzene composition, and a method for producing an alkylbenze sulfonated product.
- linear alkylbenzenes in the detergent range (C15 to C20) are produced on a commercial scale by a process that includes a step in which benzene is alkylated with linear monoolefins in the presence of an acid catalyst.
- this alkylbenzene is further sulfonated and used as a useful surfactant in various applications.
- Examples of the method for producing the alkylbenzene sulfonated product include a method in which fuming sulfuric acid or excess concentrated sulfuric acid (about 4 times mole) is added to alkylbenzene in a batch reaction method, and trioxide obtained by diluting alkylbenzene with an inert gas. There is a method of sulfonating with sulfur to obtain alkylbenzenesulfonic acid.
- Patent Document 2 describes an alkylaryl sulfonic acid containing at least 1% by weight of an olefin having improved thermal stability and color stability and reduced sludge and sulfuric acid content.
- the alkylaryl sulfonic acid described in Patent Document 2 suppresses the deterioration of hue in long-term storage.
- it contains propylene and butene oligomers, such as propylene trimer and tetramer olefins for storage after storage. In this case, it is necessary to remove olefins, which not only complicates the process but also requires storage facilities.
- Patent Document 3 describes sulfonic acid treatment using an unsaturated hydrocarbon having a number average molecular weight of about 600 to 3000.
- patent document 3 reports that the hue in alkylaryl sulfonic acid refinement
- purification can be improved, it does not report about the hue improvement effect by contact with an unsaturated hydrocarbon structure.
- Patent Document 3 it is necessary to remove unsaturated hydrocarbons from the alkylaryl sulfonic acid.
- Patent Document 4 discloses a method of treating a small amount of organic fluoride impurities in alkylbenzene produced by an alkylation method using HF (hydrogen fluoride) as a catalyst with basic alumina.
- organic fluoride impurities can be removed by basic alumina, the increase in bromine value can be suppressed by the treatment, and the hue of the sulfonated product when sulfonating the alkylbenzene produced by the method is improved. It has been reported.
- the bromine number level of Patent Document 4 is a very high value exceeding 0.01 according to the Br value increase value in the examples, and the sulfonated clets are also very high.
- Patent Documents 5 and 6 report that various clays and zeolites can remove colored substance precursors of alkylbenzene in the detergent range before sulfonation.
- Patent Documents 5 and 6 focus on a colored substance precursor that absorbs light with a wavelength of 368 nm, and it is said that the colored substance precursor can be adsorbed and removed by various clays and zeolites. There is no description or suggestion of the substance to be absorbed.
- An object of the present invention is to provide an alkylbenzene composition capable of improving the hue of a linear alkylbenzene sulfonated product particularly for detergent use and a method for producing an alkylbenze sulfonated product.
- an alkylbenzene composition having a specific range of properties improves the hue of the alkylbenzene sulfonated product, and has completed the present invention. It is.
- the alkylbenzene composition of the present invention is an alkylbenzene composition for producing an alkylbenzene sulfonate, and the wavelength measured when the alkylbenzene composition is stored in a quartz sample holder having a path length of 1 cm and subjected to spectroscopic analysis.
- the UV absorbance at 314 nm is 2.98 or less.
- the alkylbenzene composition of the present invention is characterized in that, in the above invention, the UV absorbance at a wavelength of 314 nm is below 2.69.
- the alkylbenzene composition of the present invention is characterized in that, in the above invention, the UV absorbance at a wavelength of 314 nm is 2.40 or less.
- alkylbenzene composition of the present invention is characterized in that, in the above-mentioned invention, 95 mass% or more of C16-C19 alkylbenzene is contained.
- alkylbenzene composition of the present invention is characterized in that, in the above invention, the bromine number is 0.01 or less.
- the alkylbenzene composition of the present invention is characterized in that, in the above invention, the fluorine content is 0.5 ppm or less.
- the method for producing an alkylbenze sulfonated product of the present invention is characterized in that the alkylbenzene composition described above is sulfonated by a sulfate group.
- an alkylbenzene sulfonic acid having an improved hue can be produced by sulfonated an alkylbenzene composition having a UV absorbance at a specific wavelength that is not more than a specific value. It has the characteristics. For a small amount of hue, a method of measuring by UV absorbance may be taken, but by suppressing the UV absorbance at a wavelength of 314 nm of alkylbenzene before sulfonation to a specific value or less, the hue after sulfonation is suppressed. The discovery of this is technological.
- FIG. 1 is a graph showing the relationship between UV absorbance at 314 nm of an alkylbenzene composition and a klet of alkylbenzene sulfonate.
- the alkylbenzene composition of the present invention improves the hue of the alkylbenzene sulfonated product.
- the alkylbenzene composition of the present invention facilitates the production of an alkylbenzene sulfonate having less color.
- These improvements are obtained by selecting an alkylbenzene composition that contains low levels of impurities responsible for UV-Vis absorption at a wavelength of 314 nm. More specifically, when the alkylbenzene composition is analyzed using a UV-Vis spectrometer, the absorbance at this wavelength is 2.98 or less, more preferably 2.69 or less, and most preferably 2.40 or less.
- the wavelength of 314 nm was selected to analyze a raw sample of the alkylbenzene composition in the “1 cm path length” cell. Some wavelengths of about 314 nm may be useful when using cells with a path length of 1 centimeter or more.
- the absorbance at the wavelength (314 nm) discussed herein is the absorbance at the specified wavelength and need not be the absorbance with the maximum peak. Any analysis that measures UV-Vis absorption can be used in the present invention.
- the path length of the sample holder can vary depending on the analysis method and apparatus used. However, the path length of the sample holder must be long enough to ensure that the impurity of interest in the alkylbenzene composition is detectable.
- a UV-Vis spectrometer that can operate in the near ultraviolet region, typically 200 nm to 380 nm, may be used.
- alkylbenzene refers to a mixture of C15-C20 alkylbenzenes.
- Commercial products of alkylbenzenes that are the raw materials for alkylbenzene sulfonates for detergent applications typically have a purity of 95 mass% or higher in the C16 to C19 carbon range. Therefore, the alkylbenzene composition of the present invention preferably contains 95 mass% or more of alkylbenzene having a carbon range of C16 to C19.
- the alkylbenzene composition is produced from a monoolefin produced by dehydrogenating a C9 to C14 normal paraffin with a platinum catalyst and benzene, using a catalyst.
- a catalyst As the catalyst, HF, zeolite, silica alumina, or the like is used.
- the method for producing alkylbenzene using HF as a catalyst is called a Detergent Alkylation process, in which benzene and linear monoolefin are alkylated in the presence of liquid hydrofluoric acid (HF).
- HF liquid hydrofluoric acid
- a method for producing alkylbenzene using a zeolite as a catalyst is called a “Detal process” in which benzene and a linear monoolefin are alkylated in the presence of zeolite as a solid catalyst.
- a “Detal process” in which benzene and a linear monoolefin are alkylated in the presence of zeolite as a solid catalyst.
- fluorine contained in a trace amount in the alkylbenzene deteriorates the quality of the alkylbenzene, so that it is treated with a solid alumina adsorbent at a later stage and becomes at least 0.5 ppm or less.
- the solid alumina adsorbent include activated alumina used for organic substance adsorption. These may be molded using an appropriate binder. As long as it can adsorb fluorine, it can be modified by suitably impregnating alumina with alkali metal, alkaline earth metal or other metal in an oxide, hydroxide or other form or by appropriately supporting it by other methods. Can also be used. However, usually, such loading / modification is not particularly necessary, and alumina having an alkali metal or alkaline earth metal content such as sodium of 0.5% by weight or less is used.
- alkylbenzene since a reaction is carried out with monoolefin and benzene, a trace amount of olefin component is mixed in alkylbenzene. Since these deteriorate the quality of alkylbenzene, they are usually treated and reduced by an adsorbent such as activated clay in the subsequent stage. The mixing amount of these impurities can be grasped by measuring the bromine number.
- the bromine number is preferably 0.01 or less, more preferably 0.005 or less, and still more preferably 0.001 or less.
- alkylbenzene sulfonated product refers to a C15 to C20 alkylbenzene composition sulfonated with sulfate radicals.
- raw sample of alkylbenzene is formed from chemical synthesis of alkylbenzene and subsequent purification (s) of the synthesized alkylbenzene, and chemical synthesis and / or purification (s).
- chemical product alkylbenzene
- impurity refers to one or more compounds that are not chemically equivalent to alkylbenzenes when referring to UV-Vis absorption spectra, but have UV absorption at a wavelength of 314 nm. .
- the inventors have found that these impurities can be purified by contact with an inorganic compound or removed by distillation.
- the purified alkylbenzene composition according to the present invention is a product obtained by thermally distilling the alkylbenzene composition containing the above-mentioned trace amount of impurities under an arbitrary pressure and purifying the UV absorbance at 314 nm to 2.98 or less. May be.
- distillation Any type of distillation can be used, such as batch or continuous.
- the purified alkylbenzene composition according to the present invention may have been purified to have a UV absorbance at 314 nm of 2.98 or less by an adsorbent contact treatment in which the alkylbenzene containing the trace amount of impurities and the adsorbent are brought into contact with each other. Good.
- the adsorbent contact treatment is performed, for example, by bringing the alkylbenzene composition containing the above-mentioned trace amount of impurities into contact with an adsorbent such as alumina (Al 2 O 3 ), activated clay, silica, or zeolite.
- an adsorbent such as alumina (Al 2 O 3 ), activated clay, silica, or zeolite.
- alumina and activated clay used for removing one or more compounds having UV absorption at a wavelength of 314 nm alumina and activated clay for removing HF and olefin can be used.
- the particle size of the adsorbent used here is usually in the range of 1 to 10 mm, preferably 2 to 4 mm, and the specific surface area is usually in the range of 50 to 500 m 2 / g, preferably 200 to 500 m 2 / g. .
- the alkylbenzene composition and the adsorbent are separated by a method such as filtration or sedimentation of the adsorbent and collecting the supernatant. Can do.
- the alkylbenzene composition purified to have a UV absorbance at a wavelength of 314 nm of 2.98 or less obtained by performing the distillation treatment and / or the adsorbent contact treatment is used as a raw material for the alkylbenzene sulfonated product, Compared to using commercially available alkylbenzene as it is, it is less colored and excellent in quality. This is presumably because impurities contained in commercially available alkylbenzene that affect the coloration during sulfonation can be removed.
- the bromine number in the present invention was measured by an electro titration method based on JIS K2605 (petroleum product-bromine number test method-electro titration method).
- the fluorine content in the present invention was measured using ion chromatography.
- Alkylbenzene was produced using C9-C14 normal paraffin mixture and benzene as raw materials and liquid HF as a catalyst, and then treated with alumina (PSG-A25 manufactured by Axense) and white clay (activated white clay: galeonite 251 manufactured by Mizusawa Chemical, treatment temperature) 70 ° C.), 5 samples of alkylbenzene subjected to distillation purification and having a C16-C19 of 95 mass% or more, an average molecular weight of 240 to 244, a bromine number of 0.01 or less, and an F content of 0.5 ppm or less ( Examples 1-3 and Comparative Examples 1-2).
- Example 2 Samples were collected as in Experiment 1 and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (comparative example 3).
- Example 3 The sample of Experiment 2 was distilled again to obtain a sample from which light and heavy components were removed by 3%. About this sample, the light absorbency of 314 nm was measured with the UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (Example 4).
- Example 4 A sample was collected in the same manner as in Experiment 1 without performing the clay treatment, and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of the alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (comparative example 4).
- Example 5 The sample of Experiment 2 was repeatedly treated with activated clay to obtain a sample, and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (Example 5).
- UV-Vis analysis Raw alkylbenzene samples were placed in a quartz cuvette with a 1 cm path length and then analyzed by a UV-Vis spectrometer. An air blank was used instead of a cell. UV-Vis spectra were collected on a SHIMADZU UV-2550 UV-VIS SPECTROTOPOMETER. The spectrometer recorded a UV-Vis absorption spectrum from about 200 nm to about 800 nm and produced a numerical output reporting the absorbance at 314 nm. The absorption at 314 nm is typically in the shoulder of a significantly higher intensity peak. The absorption at 314 nm is the absorption measured at the specified wavelength and need not be the absorption with the peak maximum.
- FIG. 1 shows the relationship between the absorbance of all alkylbenzene samples and the alkylbenzene sulfonated material.
- the alkylbenzene composition of the present invention that is, the UV-Vis absorption
- the alkylbenzene sulfonated product obtained from the alkylbenzene composition having a UV absorbance at 314 nm of 2.98 or less has a low hue. I understand. Further, it was confirmed from FIG. 1 that there was a high correlation between the absorbance at 314 nm and the hue.
- Alkylbenzene sulfonated products for detergent use can be used in the market if the klet is 40 or less, more preferably 30 or less, and most preferably 20 or less.
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Abstract
Provided is a method for producing an alkyl-benzene composition and an alkyl benzene sulfonate which makes it possible to improve the hue of a linear alkyl benzene sulfonate to be used as a cleaning agent. This alkyl-benzene composition is an alkyl-benzene composition to be used in the production of an alkyl benzene sulfonate, the alkyl-benzene composition being characterized in that upon placing the composition in a quartz sample holder having a path length of 1 cm and performing a spectroscopic analysis thereon, the measured 314nm UV absorbance is 2.98 or less.
Description
本発明は、アルキルベンゼンスルホン化物製造用のアルキルベンゼン組成物であって、該アルキルベンゼン組成物を用いて製造されたアルキルベンゼンスルホン化物の色相を改善しうるアルキルベンゼン組成物およびアルキルベンゼスルホン化物の製造方法に関する。
The present invention relates to an alkylbenzene composition for producing an alkylbenzene sulfonated product, and relates to an alkylbenzene composition capable of improving the hue of the alkylbenzene sulfonated product produced using the alkylbenzene composition, and a method for producing an alkylbenze sulfonated product.
洗剤範囲（Ｃ１５～Ｃ２０）の線状アルキルベンゼンは、ベンゼンが線状モノオレフィンにより酸触媒の存在下でアルキル化される工程を含む方法により商業的規模で製造することは知られている。一般に、このアルキルベンゼンはさらにスルホン化され、有用な界面活性剤として各種用途に使用されている。
It is known that linear alkylbenzenes in the detergent range (C15 to C20) are produced on a commercial scale by a process that includes a step in which benzene is alkylated with linear monoolefins in the presence of an acid catalyst. In general, this alkylbenzene is further sulfonated and used as a useful surfactant in various applications.
アルキルベンゼンスルホン化物の製造方法としては、例えば、アルキルベンゼンに発煙硫酸或いは過剰の濃硫酸（約４倍モル）を添加してバッチ反応方式で製造する方法や、アルキルベンゼンを、不活性ガスで希釈した三酸化硫黄によりスルホン化し、アルキルベンゼンスルホン酸を得る方法がある。また、アルキルベンゼンとアルキルベンゼンスルホン酸の共存下に、アルキルベンゼンと三酸化硫黄を等モル比で連続スルホン化し、スルホン生成等の抑制をしてアルキルベンゼンスルホン酸を得る方法も知られている（例えば、特許文献１参照）。
Examples of the method for producing the alkylbenzene sulfonated product include a method in which fuming sulfuric acid or excess concentrated sulfuric acid (about 4 times mole) is added to alkylbenzene in a batch reaction method, and trioxide obtained by diluting alkylbenzene with an inert gas. There is a method of sulfonating with sulfur to obtain alkylbenzenesulfonic acid. Also known is a method of obtaining alkylbenzene sulfonic acid by continuously sulfonating alkylbenzene and sulfur trioxide at an equimolar ratio in the presence of alkylbenzene and alkylbenzene sulfonic acid to suppress sulfone formation and the like (for example, Patent Documents). 1).
アルキルベンゼンスルホン化物の色相の改善は、従来からの課題であった。これまでにスルホン酸化物の色相を改良する方法がいくつか提案されている。特許文献２には、熱安定性及び色彩安定性が改善され、かつスラッジ及び硫酸含量が低減された、少なくとも１重量％のオレフィンを含むアルキルアリールスルホン酸が記載されている。特許文献２に記載のアルキルアリールスルホン酸は、長期保管における色相の悪化を抑制するものであるが、プロピレン及びブテンオリゴマー、例えばプロピレンのトリマーやテトラマー等のオレフィンを含有させて保管した後の出荷の際、オレフィン類を除去する必要があり、工程が複雑になるばかりか、保管設備も課題となる。
Improvement of the hue of alkylbenzene sulfonated products has been a conventional problem. Several methods for improving the hue of sulfonic oxide have been proposed so far. Patent Document 2 describes an alkylaryl sulfonic acid containing at least 1% by weight of an olefin having improved thermal stability and color stability and reduced sludge and sulfuric acid content. The alkylaryl sulfonic acid described in Patent Document 2 suppresses the deterioration of hue in long-term storage. However, it contains propylene and butene oligomers, such as propylene trimer and tetramer olefins for storage after storage. In this case, it is necessary to remove olefins, which not only complicates the process but also requires storage facilities.
また、特許文献３には、約６００～３０００の数平均分子量を有する不飽和炭化水素を用いたスルホン酸処理が記載されている。しかしながら、特許文献３は、アルキルアリールスルホン酸精製における色相を改善しうると報告するが、不飽和炭化水素構造体との接触による色相改善効果についての報告をしていない。更に、特許文献３では、アルキルアリールスルホン酸から不飽和炭化水素を除去する必要がある。
Patent Document 3 describes sulfonic acid treatment using an unsaturated hydrocarbon having a number average molecular weight of about 600 to 3000. However, although patent document 3 reports that the hue in alkylaryl sulfonic acid refinement | purification can be improved, it does not report about the hue improvement effect by contact with an unsaturated hydrocarbon structure. Furthermore, in Patent Document 3, it is necessary to remove unsaturated hydrocarbons from the alkylaryl sulfonic acid.
さらに、特許文献４には、ＨＦ（フッ化水素）を触媒としたアルキル化法により製造されたアルキルベンゼン中の微量の有機フッ化物不純物を塩基性アルミナで処理する方法が開示されている。特許文献４では、塩基性アルミナにより有機フッ化物不純物が除去できるとともに、該処理により臭素価値の上昇が抑制できること、ならびに該方法より製造されたアルキルベンゼンをスルホン化した際のスルホン化物の色相が改善されることが報告されている。しかしながら、特許文献４の臭素価レベルは、実施例内のＢｒ価上昇値によれば０．０１を超えるような非常に高い値であるとともに、スルホン化物のクレットも非常に高いものであった。
Furthermore, Patent Document 4 discloses a method of treating a small amount of organic fluoride impurities in alkylbenzene produced by an alkylation method using HF (hydrogen fluoride) as a catalyst with basic alumina. In Patent Document 4, organic fluoride impurities can be removed by basic alumina, the increase in bromine value can be suppressed by the treatment, and the hue of the sulfonated product when sulfonating the alkylbenzene produced by the method is improved. It has been reported. However, the bromine number level of Patent Document 4 is a very high value exceeding 0.01 according to the Br value increase value in the examples, and the sulfonated clets are also very high.
さらにまた、特許文献５および６では、種々の粘土及びゼオライトにより、スルホン化前の洗剤範囲のアルキルベンゼンの着色物質前駆体が除去できることが報告されている。しかしながら、特許文献５および６では、波長３６８ｎｍの光を吸収する着色物質前駆体に注目し、該着色物質前駆体が種々の粘土及びゼオライトで吸着除去できるとされているが、波長３１４ｎｍの光を吸収する物質については記載も示唆もされていない。
Furthermore, Patent Documents 5 and 6 report that various clays and zeolites can remove colored substance precursors of alkylbenzene in the detergent range before sulfonation. However, Patent Documents 5 and 6 focus on a colored substance precursor that absorbs light with a wavelength of 368 nm, and it is said that the colored substance precursor can be adsorbed and removed by various clays and zeolites. There is no description or suggestion of the substance to be absorbed.
近年、洗剤範囲（Ｃ１５～Ｃ２０）の線状アルキルベンゼンは、臭素価が０．０１以下であることは主流であり、その中でさらに色相を良化することが強く求められている。しかしながら、上記特許文献では、臭素価が０．０１以下であるアルキルベンゼンをスルホン化した際、色相に影響しうる不純物について、何ら報告されていない。
In recent years, linear alkylbenzenes in the detergent range (C15 to C20) have a bromine number of 0.01 or less, and among them, there is a strong demand for further improving the hue. However, in the above-mentioned patent document, there is no report on impurities that can affect the hue when alkylbenzene having a bromine number of 0.01 or less is sulfonated.
本発明は、特に洗剤用途の線状アルキルベンゼンスルホン化物の色相を改善できるアルキルベンゼン組成物およびアルキルベンゼスルホン化物の製造方法を提供することを目的とする。
An object of the present invention is to provide an alkylbenzene composition capable of improving the hue of a linear alkylbenzene sulfonated product particularly for detergent use and a method for producing an alkylbenze sulfonated product.
そこで、本発明者らは上記課題を解決するために、鋭意研究を行った結果、特定範囲の性状を有するアルキルベンゼン組成物がアルキルベンゼンスルホン化物の色相を改善することを見出し、本発明を完成したものである。
Accordingly, as a result of intensive studies to solve the above problems, the present inventors have found that an alkylbenzene composition having a specific range of properties improves the hue of the alkylbenzene sulfonated product, and has completed the present invention. It is.
すなわち、本発明のアルキルベンゼン組成物は、アルキルベンゼンスルホン化物製造用のアルキルベンゼン組成物であって、前記アルキルベンゼン組成物は、経路長１ｃｍの石英サンプルホルダに収容して分光分析を行なう際、測定される波長３１４ｎｍのＵＶ吸光度が２．９８以下であることを特徴とする。
That is, the alkylbenzene composition of the present invention is an alkylbenzene composition for producing an alkylbenzene sulfonate, and the wavelength measured when the alkylbenzene composition is stored in a quartz sample holder having a path length of 1 cm and subjected to spectroscopic analysis. The UV absorbance at 314 nm is 2.98 or less.
また、本発明のアルキルベンゼン組成物は、上記発明において、波長３１４ｎｍのＵＶ吸光度が２．６９下であることを特徴とする。
The alkylbenzene composition of the present invention is characterized in that, in the above invention, the UV absorbance at a wavelength of 314 nm is below 2.69.
また、本発明のアルキルベンゼン組成物は、上記発明において、波長３１４ｎｍのＵＶ吸光度が２．４０以下であることを特徴とする。
The alkylbenzene composition of the present invention is characterized in that, in the above invention, the UV absorbance at a wavelength of 314 nm is 2.40 or less.
また、本発明のアルキルベンゼン組成物は、上記発明において、Ｃ１６－Ｃ１９のアルキルベンゼンを９５ｍａｓｓ％以上含むことを特徴とする。
Further, the alkylbenzene composition of the present invention is characterized in that, in the above-mentioned invention, 95 mass% or more of C16-C19 alkylbenzene is contained.
また、本発明のアルキルベンゼン組成物は、上記発明において、臭素価が０．０１以下であることを特徴とする。
Further, the alkylbenzene composition of the present invention is characterized in that, in the above invention, the bromine number is 0.01 or less.
また、本発明のアルキルベンゼン組成物は、上記発明において、フッ素分が０．５ｐｐｍ以下であることを特徴とする。
The alkylbenzene composition of the present invention is characterized in that, in the above invention, the fluorine content is 0.5 ppm or less.
また、本発明のアルキルベンゼスルホン化物の製造方法は、上記のいずれかに記載のアルキルベンゼン組成物を硫酸根によってスルホン化することを特徴とする。
The method for producing an alkylbenze sulfonated product of the present invention is characterized in that the alkylbenzene composition described above is sulfonated by a sulfate group.
本発明のアルキルベンゼン組成物およびアルキルベンゼスルホン化物の製造方法は、特定波長のＵＶ吸光度が特定値以下であるアルキルベンゼン組成物をスルホン化することにより、色相を改善したアルキルベンゼンスルホン酸を製造することができるという特徴を有する。微量の色相については、ＵＶ吸光度で測定する手法が取られることがあるが、スルホン化前のアルキルベンゼンの波長３１４ｎｍのＵＶ吸光度を特定の値以下にすることによって、スルホン化後の色相を抑制するということを見出したことは画期的なことである。
According to the method for producing an alkylbenzene composition and an alkylbenze sulfonated product of the present invention, an alkylbenzene sulfonic acid having an improved hue can be produced by sulfonated an alkylbenzene composition having a UV absorbance at a specific wavelength that is not more than a specific value. It has the characteristics. For a small amount of hue, a method of measuring by UV absorbance may be taken, but by suppressing the UV absorbance at a wavelength of 314 nm of alkylbenzene before sulfonation to a specific value or less, the hue after sulfonation is suppressed. The discovery of this is groundbreaking.
以下に本発明について詳細に説明する。
Hereinafter, the present invention will be described in detail.
本発明のアルキルベンゼン組成物は、アルキルベンゼンスルホン化物の色相の改善をもたらす。また、本発明のアルキルベンゼン組成物は、着色の少ないアルキルベンゼンスルホン化物の製造を容易にする。これらの改善は、波長３１４ｎｍのＵＶ－Ｖｉｓ吸収の原因である低レベルの不純物を含むアルキルベンゼン組成物を選択することによって得られる。より具体的には、アルキルベンゼン組成物をＵＶ－Ｖｉｓ分光計を用いて分析するとき、この波長の吸光度が２．９８以下、より好ましくは２．６９以下、最も好ましくは２．４０以下である。
The alkylbenzene composition of the present invention improves the hue of the alkylbenzene sulfonated product. In addition, the alkylbenzene composition of the present invention facilitates the production of an alkylbenzene sulfonate having less color. These improvements are obtained by selecting an alkylbenzene composition that contains low levels of impurities responsible for UV-Vis absorption at a wavelength of 314 nm. More specifically, when the alkylbenzene composition is analyzed using a UV-Vis spectrometer, the absorbance at this wavelength is 2.98 or less, more preferably 2.69 or less, and most preferably 2.40 or less.
３１４ｎｍの波長は「１ｃｍ経路長」セル中のアルキルベンゼン組成物の生サンプルを分析するために選択した。約３１４ｎｍの幾つかの波長が、１センチメートルまたはそれ以上の経路長のセルを用いるとき、有用であり得る。本明細書で論じられる波長（３１４ｎｍ）の吸光度は指定された波長の吸光度であり、最大ピークを伴う吸光度である必要はない。ＵＶ－Ｖｉｓ吸収を測定するあらゆる分析を本発明において用いることができる。
The wavelength of 314 nm was selected to analyze a raw sample of the alkylbenzene composition in the “1 cm path length” cell. Some wavelengths of about 314 nm may be useful when using cells with a path length of 1 centimeter or more. The absorbance at the wavelength (314 nm) discussed herein is the absorbance at the specified wavelength and need not be the absorbance with the maximum peak. Any analysis that measures UV-Vis absorption can be used in the present invention.
本発明において、サンプルホルダの経路長は、用いられる分析法、装置に依存して変化し得る。しかしながら、サンプルホルダの経路長は、アルキルベンゼン組成物中の注目される不純物が検出可能であることを保証するのに十分な長さでなければならない。ＵＶ－Ｖｉｓ分光計は近紫外領域、典型的には、２００ｎｍから３８０ｎｍで作動可能なものを使用すればよい。
In the present invention, the path length of the sample holder can vary depending on the analysis method and apparatus used. However, the path length of the sample holder must be long enough to ensure that the impurity of interest in the alkylbenzene composition is detectable. A UV-Vis spectrometer that can operate in the near ultraviolet region, typically 200 nm to 380 nm, may be used.
「アルキルベンゼン」という用語は、本明細書で用いられる場合、Ｃ１５～Ｃ２０のアルキルベンゼンの混合物を指す。洗剤用途のアルキルベンゼンスルホン化物の原料となるアルキルベンゼンの商業製品は、典型的には、Ｃ１６～Ｃ１９の炭素範囲で９５ｍａｓｓ％以上の純度を有する。したがって、本発明のアルキルベンゼン組成物は、Ｃ１６～Ｃ１９の炭素範囲のアルキルベンゼンを９５ｍａｓｓ％以上含むことが好ましい。
The term “alkylbenzene” as used herein refers to a mixture of C15-C20 alkylbenzenes. Commercial products of alkylbenzenes that are the raw materials for alkylbenzene sulfonates for detergent applications typically have a purity of 95 mass% or higher in the C16 to C19 carbon range. Therefore, the alkylbenzene composition of the present invention preferably contains 95 mass% or more of alkylbenzene having a carbon range of C16 to C19.
本発明において、アルキルベンゼン組成物は、Ｃ９～Ｃ１４のノルマルパラフィンを白金触媒によって脱水素して製造されたモノオレフィンとベンゼンから、触媒を用いて製造される。触媒には、ＨＦやゼオライト、シリカアルミナなどが使用される。ＨＦを触媒としたアルキルベンゼンの製造方法は、Ｄｅｔｅｒｇｅｎｔ Ａｌｋｙｌａｔｉｏｎプロセスと呼ばれ、ベンゼンと線状モノオレフィンとを液体フッ化水素酸（ＨＦ）の存在下でアルキル化するものである。他方、ゼオライトを触媒としたアルキルベンゼンの製造方法は、Ｄｅｔａｌプロセスと呼ばれ、ベンゼンと線状モノオレフィンとを固体触媒であるゼオライトの存在下でアルキル化するものである。アルキルベンゼンの製造方法は種々の方法があるが、本発明においてアルキルベンゼン組成物の製造方法はそれらに限定されるものではない。
In the present invention, the alkylbenzene composition is produced from a monoolefin produced by dehydrogenating a C9 to C14 normal paraffin with a platinum catalyst and benzene, using a catalyst. As the catalyst, HF, zeolite, silica alumina, or the like is used. The method for producing alkylbenzene using HF as a catalyst is called a Detergent Alkylation process, in which benzene and linear monoolefin are alkylated in the presence of liquid hydrofluoric acid (HF). On the other hand, a method for producing alkylbenzene using a zeolite as a catalyst is called a “Detal process” in which benzene and a linear monoolefin are alkylated in the presence of zeolite as a solid catalyst. There are various methods for producing alkylbenzene, but the method for producing an alkylbenzene composition in the present invention is not limited thereto.
通常、ＨＦを触媒としたアルキルベンゼンの製造においては、アルキルベンゼン中に微量に混入するフッ素分はアルキルベンゼンの品質を悪化させることから、後段で固体アルミナ吸着剤によって処理され、少なくとも０．５ｐｐｍ以下となる。
固体アルミナ吸着剤としては、有機物の吸着用に使用される活性アルミナなどを例示することができる。これらは適宜のバインダーを用いて成型したものでもよい。フッ素分を吸着できるものであれば、アルミナに適宜アルカリ金属、アルカリ土類金属またはその他の金属を、酸化物、水酸化物あるいはその他の形態で含浸あるいはその他の方法により適宜担持させて変性したものを用いることもできる。しかしながら、通常は、特にこのような担持・変性は必要なく、ナトリウム等のアルカリ金属またはアルカリ土類金属の含有量が０．５重量％以下のアルミナが用いられる。 Usually, in the production of alkylbenzene using HF as a catalyst, fluorine contained in a trace amount in the alkylbenzene deteriorates the quality of the alkylbenzene, so that it is treated with a solid alumina adsorbent at a later stage and becomes at least 0.5 ppm or less.
Examples of the solid alumina adsorbent include activated alumina used for organic substance adsorption. These may be molded using an appropriate binder. As long as it can adsorb fluorine, it can be modified by suitably impregnating alumina with alkali metal, alkaline earth metal or other metal in an oxide, hydroxide or other form or by appropriately supporting it by other methods. Can also be used. However, usually, such loading / modification is not particularly necessary, and alumina having an alkali metal or alkaline earth metal content such as sodium of 0.5% by weight or less is used.
固体アルミナ吸着剤としては、有機物の吸着用に使用される活性アルミナなどを例示することができる。これらは適宜のバインダーを用いて成型したものでもよい。フッ素分を吸着できるものであれば、アルミナに適宜アルカリ金属、アルカリ土類金属またはその他の金属を、酸化物、水酸化物あるいはその他の形態で含浸あるいはその他の方法により適宜担持させて変性したものを用いることもできる。しかしながら、通常は、特にこのような担持・変性は必要なく、ナトリウム等のアルカリ金属またはアルカリ土類金属の含有量が０．５重量％以下のアルミナが用いられる。 Usually, in the production of alkylbenzene using HF as a catalyst, fluorine contained in a trace amount in the alkylbenzene deteriorates the quality of the alkylbenzene, so that it is treated with a solid alumina adsorbent at a later stage and becomes at least 0.5 ppm or less.
Examples of the solid alumina adsorbent include activated alumina used for organic substance adsorption. These may be molded using an appropriate binder. As long as it can adsorb fluorine, it can be modified by suitably impregnating alumina with alkali metal, alkaline earth metal or other metal in an oxide, hydroxide or other form or by appropriately supporting it by other methods. Can also be used. However, usually, such loading / modification is not particularly necessary, and alumina having an alkali metal or alkaline earth metal content such as sodium of 0.5% by weight or less is used.
また、アルキルベンゼンの製法では、モノオレフィンとベンゼンにより反応を行うため、アルキルベンゼン中に微量のオレフィン成分が混入する。これらはアルキルベンゼンの品質を悪化させるため、通常は後段で活性白土などの吸着剤によって処理され、低減される。これらの不純物の混入量は臭素価を測定することで把握することができる。臭素価は０．０１以下が好ましく、さらには０．００５以下が好ましく、より好ましくは０．００１以下である。
Also, in the process for producing alkylbenzene, since a reaction is carried out with monoolefin and benzene, a trace amount of olefin component is mixed in alkylbenzene. Since these deteriorate the quality of alkylbenzene, they are usually treated and reduced by an adsorbent such as activated clay in the subsequent stage. The mixing amount of these impurities can be grasped by measuring the bromine number. The bromine number is preferably 0.01 or less, more preferably 0.005 or less, and still more preferably 0.001 or less.
「アルキルベンゼンスルホン化物」という用語は、本明細書で用いられる場合、Ｃ１５～Ｃ２０のアルキルベンゼン組成物を硫酸根によってスルホン化したものを指す。
The term “alkylbenzene sulfonated product” as used herein refers to a C15 to C20 alkylbenzene composition sulfonated with sulfate radicals.
「アルキルベンゼンの生サンプル」という用語は、本明細書で用いられる場合、アルキルベンゼンの化学合成、および合成されたアルキルベンゼンの引き続く精製（単数または複数）から形成され、化学合成および／または精製（単数または複数）から生じたものではない、いかなる追加人工化学物質（単数または複数）も含まない、化学製品（アルキルベンゼン）を指す。
The term “raw sample of alkylbenzene” as used herein is formed from chemical synthesis of alkylbenzene and subsequent purification (s) of the synthesized alkylbenzene, and chemical synthesis and / or purification (s). ) Refers to a chemical product (alkylbenzene) that does not contain any additional artificial chemical (s) that are not derived from.
「不純物」という用語は、本明細書で用いられる場合、ＵＶ－Ｖｉｓ吸収スペクトルを参照する際、アルキルベンゼンと化学的に等価ではないが、波長３１４ｎｍにＵＶ吸収を有する１またはそれ以上の化合物を指す。本発明者らは、これらの不純物が、無機化合物と接触させて精製するか、蒸留により除去することができることを見出した。
The term “impurity” as used herein refers to one or more compounds that are not chemically equivalent to alkylbenzenes when referring to UV-Vis absorption spectra, but have UV absorption at a wavelength of 314 nm. . The inventors have found that these impurities can be purified by contact with an inorganic compound or removed by distillation.
（蒸留）
本発明に係る精製されたアルキルベンゼン組成物は、上記微量の不純物を含むアルキルベンゼン組成物を任意の圧力下で、熱的に蒸留し、３１４ｎｍのＵＶ吸光度が２．９８以下まで精製されたものであってもよい。 (distillation)
The purified alkylbenzene composition according to the present invention is a product obtained by thermally distilling the alkylbenzene composition containing the above-mentioned trace amount of impurities under an arbitrary pressure and purifying the UV absorbance at 314 nm to 2.98 or less. May be.
本発明に係る精製されたアルキルベンゼン組成物は、上記微量の不純物を含むアルキルベンゼン組成物を任意の圧力下で、熱的に蒸留し、３１４ｎｍのＵＶ吸光度が２．９８以下まで精製されたものであってもよい。 (distillation)
The purified alkylbenzene composition according to the present invention is a product obtained by thermally distilling the alkylbenzene composition containing the above-mentioned trace amount of impurities under an arbitrary pressure and purifying the UV absorbance at 314 nm to 2.98 or less. May be.
蒸留の形式は、バッチ式や連続式などいかなる形態も利用できる。
Any type of distillation can be used, such as batch or continuous.
（吸着剤接触処理）
本発明に係る精製されたアルキルベンゼン組成物は、上記微量の不純物を含むアルキルベンゼンと吸着剤とを接触させる吸着剤接触処理により、３１４ｎｍのＵＶ吸光度が２．９８以下まで精製されたものであってもよい。 (Adsorbent contact treatment)
The purified alkylbenzene composition according to the present invention may have been purified to have a UV absorbance at 314 nm of 2.98 or less by an adsorbent contact treatment in which the alkylbenzene containing the trace amount of impurities and the adsorbent are brought into contact with each other. Good.
本発明に係る精製されたアルキルベンゼン組成物は、上記微量の不純物を含むアルキルベンゼンと吸着剤とを接触させる吸着剤接触処理により、３１４ｎｍのＵＶ吸光度が２．９８以下まで精製されたものであってもよい。 (Adsorbent contact treatment)
The purified alkylbenzene composition according to the present invention may have been purified to have a UV absorbance at 314 nm of 2.98 or less by an adsorbent contact treatment in which the alkylbenzene containing the trace amount of impurities and the adsorbent are brought into contact with each other. Good.
吸着剤接触処理は、例えば上記微量の不純物を含むアルキルベンゼン組成物と、アルミナ（Ａｌ２Ｏ３）、活性白土、シリカ、ゼオライト等の吸着剤とを接触させることにより行われる。波長３１４ｎｍにＵＶ吸収を有する１またはそれ以上の化合物の除去に使用するアルミナおよび活性白土は、ＨＦおよびオレフィン除去用のアルミナおよび活性白土を使用することができる。
The adsorbent contact treatment is performed, for example, by bringing the alkylbenzene composition containing the above-mentioned trace amount of impurities into contact with an adsorbent such as alumina (Al 2 O 3 ), activated clay, silica, or zeolite. As the alumina and activated clay used for removing one or more compounds having UV absorption at a wavelength of 314 nm, alumina and activated clay for removing HF and olefin can be used.
ここで用いられる吸着剤の粒径は、通常１～１０ｍｍ、好ましくは２～４ｍｍの範囲にあり、比表面積は、通常５０～５００ｍ２／ｇ、好ましくは２００～５００ｍ２／ｇの範囲にある。
The particle size of the adsorbent used here is usually in the range of 1 to 10 mm, preferably 2 to 4 mm, and the specific surface area is usually in the range of 50 to 500 m 2 / g, preferably 200 to 500 m 2 / g. .
上記微量の不純物を含むアルキルベンゼン組成物と吸着剤とを接触させた後は、例えば濾過する、または吸着剤を沈降させ上澄みを採取する、などの方法によりアルキルベンゼン組成物と吸着剤とを分離することができる。
After contacting the adsorbent with the alkylbenzene composition containing the above-mentioned trace amount of impurities, the alkylbenzene composition and the adsorbent are separated by a method such as filtration or sedimentation of the adsorbent and collecting the supernatant. Can do.
上記蒸留処理、および／または上記吸着剤接触処理を行って得られた、波長３１４ｎｍのＵＶ吸光度が２．９８以下まで精製されたアルキルベンゼン組成物は、これをアルキルベンゼンスルホン化物用の原料として用いると、市販のアルキルベンゼンをそのまま用いるよりも着色が少なく品質に優れる。これは、市販のアルキルベンゼンに含まれる、スルホン化時の着色に影響を与える不純物を除去できるためであると考えられる。
When the alkylbenzene composition purified to have a UV absorbance at a wavelength of 314 nm of 2.98 or less obtained by performing the distillation treatment and / or the adsorbent contact treatment is used as a raw material for the alkylbenzene sulfonated product, Compared to using commercially available alkylbenzene as it is, it is less colored and excellent in quality. This is presumably because impurities contained in commercially available alkylbenzene that affect the coloration during sulfonation can be removed.
（臭素価の測定）
本発明における臭素価は、ＪＩＳ Ｋ２６０５（石油製品－臭素価試験方法－電気滴定法）に基づいた電気滴定法により測定した。 (Measurement of bromine number)
The bromine number in the present invention was measured by an electro titration method based on JIS K2605 (petroleum product-bromine number test method-electro titration method).
本発明における臭素価は、ＪＩＳ Ｋ２６０５（石油製品－臭素価試験方法－電気滴定法）に基づいた電気滴定法により測定した。 (Measurement of bromine number)
The bromine number in the present invention was measured by an electro titration method based on JIS K2605 (petroleum product-bromine number test method-electro titration method).
（フッ素分の測定）
本発明におけるフッ素分は、イオンクロマトグラフィーを用いて測定した。 (Measurement of fluorine content)
The fluorine content in the present invention was measured using ion chromatography.
本発明におけるフッ素分は、イオンクロマトグラフィーを用いて測定した。 (Measurement of fluorine content)
The fluorine content in the present invention was measured using ion chromatography.
以下実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
（実験１）
Ｃ９～Ｃ１４のノルマルパラフィン混合物とベンゼンを原料とし、触媒に液体ＨＦを用いてアルキルベンゼンを製造した後、アルミナ（アクセンス社製ＰＳＧ－Ａ２５）および白土処理（活性白土：水澤化学製ガレオナイト２５１、処理温度７０℃）、蒸留精製を施した、Ｃ１６－Ｃ１９が９５ｍａｓｓ％以上で、平均分子量が２４０～２４４でかつ臭素価が０．０１以下、Ｆ分が０．５ｐｐｍ以下のアルキルベンゼンを５サンプル収集した（実施例１～３、比較例１～２）。このサンプルについて、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼン組成物についてスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した。結果を表１に示す。 (Experiment 1)
Alkylbenzene was produced using C9-C14 normal paraffin mixture and benzene as raw materials and liquid HF as a catalyst, and then treated with alumina (PSG-A25 manufactured by Axense) and white clay (activated white clay: galeonite 251 manufactured by Mizusawa Chemical, treatment temperature) 70 ° C.), 5 samples of alkylbenzene subjected to distillation purification and having a C16-C19 of 95 mass% or more, an average molecular weight of 240 to 244, a bromine number of 0.01 or less, and an F content of 0.5 ppm or less ( Examples 1-3 and Comparative Examples 1-2). About this sample, the light absorbency of 314 nm was measured with the UV-Vis spectrometer. Moreover, sulfonation was implemented about these alkylbenzene compositions, and the klet was measured about the obtained alkylbenzene sulfonated material. The results are shown in Table 1.
Ｃ９～Ｃ１４のノルマルパラフィン混合物とベンゼンを原料とし、触媒に液体ＨＦを用いてアルキルベンゼンを製造した後、アルミナ（アクセンス社製ＰＳＧ－Ａ２５）および白土処理（活性白土：水澤化学製ガレオナイト２５１、処理温度７０℃）、蒸留精製を施した、Ｃ１６－Ｃ１９が９５ｍａｓｓ％以上で、平均分子量が２４０～２４４でかつ臭素価が０．０１以下、Ｆ分が０．５ｐｐｍ以下のアルキルベンゼンを５サンプル収集した（実施例１～３、比較例１～２）。このサンプルについて、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼン組成物についてスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した。結果を表１に示す。 (Experiment 1)
Alkylbenzene was produced using C9-C14 normal paraffin mixture and benzene as raw materials and liquid HF as a catalyst, and then treated with alumina (PSG-A25 manufactured by Axense) and white clay (activated white clay: galeonite 251 manufactured by Mizusawa Chemical, treatment temperature) 70 ° C.), 5 samples of alkylbenzene subjected to distillation purification and having a C16-C19 of 95 mass% or more, an average molecular weight of 240 to 244, a bromine number of 0.01 or less, and an F content of 0.5 ppm or less ( Examples 1-3 and Comparative Examples 1-2). About this sample, the light absorbency of 314 nm was measured with the UV-Vis spectrometer. Moreover, sulfonation was implemented about these alkylbenzene compositions, and the klet was measured about the obtained alkylbenzene sulfonated material. The results are shown in Table 1.
（実験２）
実験１と同様にサンプルを収集し、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（比較例３）。 (Experiment 2)
Samples were collected as in Experiment 1 and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (comparative example 3).
実験１と同様にサンプルを収集し、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（比較例３）。 (Experiment 2)
Samples were collected as in Experiment 1 and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (comparative example 3).
（実験３）
実験２のサンプルを再度蒸留し、軽質分および重質分を３％ずつ除去したサンプルを得た。このサンプルについて、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（実施例４）。 (Experiment 3)
The sample of Experiment 2 was distilled again to obtain a sample from which light and heavy components were removed by 3%. About this sample, the light absorbency of 314 nm was measured with the UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (Example 4).
実験２のサンプルを再度蒸留し、軽質分および重質分を３％ずつ除去したサンプルを得た。このサンプルについて、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（実施例４）。 (Experiment 3)
The sample of Experiment 2 was distilled again to obtain a sample from which light and heavy components were removed by 3%. About this sample, the light absorbency of 314 nm was measured with the UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (Example 4).
（実験４）
白土処理を実施せずに実験１と同様にサンプルを収集し、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（比較例４）。 (Experiment 4)
A sample was collected in the same manner as in Experiment 1 without performing the clay treatment, and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of the alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (comparative example 4).
白土処理を実施せずに実験１と同様にサンプルを収集し、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（比較例４）。 (Experiment 4)
A sample was collected in the same manner as in Experiment 1 without performing the clay treatment, and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of the alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (comparative example 4).
（実験５）
実験２のサンプルを繰り返し活性白土で処理を施しサンプルを得た後、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（実施例５）。 (Experiment 5)
The sample of Experiment 2 was repeatedly treated with activated clay to obtain a sample, and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (Example 5).
実験２のサンプルを繰り返し活性白土で処理を施しサンプルを得た後、ＵＶ－Ｖｉｓ分光計で３１４ｎｍの吸光度を測定した。また、これらのアルキルベンゼンについてアルキルベンゼンのスルホン化を実施し、得られたアルキルベンゼンスルホン化物について、クレットを測定した（実施例５）。 (Experiment 5)
The sample of Experiment 2 was repeatedly treated with activated clay to obtain a sample, and the absorbance at 314 nm was measured with a UV-Vis spectrometer. Moreover, sulfonation of alkylbenzene was implemented about these alkylbenzenes, and the klet was measured about the obtained alkylbenzene sulfonation thing (Example 5).
（ＵＶ－Ｖｉｓ分析）
生アルキルベンゼンサンプルを経路長１ｃｍの石英キュベットに入れた後、ＵＶ－Ｖｉｓ分光計によって分析した。ブランクにはセルを入れず、エアーブランクとした。ＵＶ－ＶｉｓスペクトルはＳＨＩＭＡＤＺＵ ＵＶ－２５５０ ＵＶ－ＶＩＳ ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＲで収集した。分光計は約２００ｎｍから約８００ｎｍまでのＵＶ－Ｖｉｓ吸収スペクトルを記録し、３１４ｎｍの吸光度を報告する数値出力が生成された。３１４ｎｍの吸収は、典型的には、有意に高い強度のピークのショルダーに存在する。３１４ｎｍの吸収は指定された波長で測定される吸収であり、ピーク最大を伴う吸収である必要はない。 (UV-Vis analysis)
Raw alkylbenzene samples were placed in a quartz cuvette with a 1 cm path length and then analyzed by a UV-Vis spectrometer. An air blank was used instead of a cell. UV-Vis spectra were collected on a SHIMADZU UV-2550 UV-VIS SPECTROTOPOMETER. The spectrometer recorded a UV-Vis absorption spectrum from about 200 nm to about 800 nm and produced a numerical output reporting the absorbance at 314 nm. The absorption at 314 nm is typically in the shoulder of a significantly higher intensity peak. The absorption at 314 nm is the absorption measured at the specified wavelength and need not be the absorption with the peak maximum.
生アルキルベンゼンサンプルを経路長１ｃｍの石英キュベットに入れた後、ＵＶ－Ｖｉｓ分光計によって分析した。ブランクにはセルを入れず、エアーブランクとした。ＵＶ－ＶｉｓスペクトルはＳＨＩＭＡＤＺＵ ＵＶ－２５５０ ＵＶ－ＶＩＳ ＳＰＥＣＴＲＯＰＨＯＴＯＭＥＴＥＲで収集した。分光計は約２００ｎｍから約８００ｎｍまでのＵＶ－Ｖｉｓ吸収スペクトルを記録し、３１４ｎｍの吸光度を報告する数値出力が生成された。３１４ｎｍの吸収は、典型的には、有意に高い強度のピークのショルダーに存在する。３１４ｎｍの吸収は指定された波長で測定される吸収であり、ピーク最大を伴う吸収である必要はない。 (UV-Vis analysis)
Raw alkylbenzene samples were placed in a quartz cuvette with a 1 cm path length and then analyzed by a UV-Vis spectrometer. An air blank was used instead of a cell. UV-Vis spectra were collected on a SHIMADZU UV-2550 UV-VIS SPECTROTOPOMETER. The spectrometer recorded a UV-Vis absorption spectrum from about 200 nm to about 800 nm and produced a numerical output reporting the absorbance at 314 nm. The absorption at 314 nm is typically in the shoulder of a significantly higher intensity peak. The absorption at 314 nm is the absorption measured at the specified wavelength and need not be the absorption with the peak maximum.
（アルキルベンゼンのスルホン化およびクレットの測定）
特開２００８－９４９４１号公報の実施例１に記載の方法を参考にして、アルキルベンゼンスルホン化物を合成した。得られたアルキルベンゼンスルホン化物の１０％エタノール溶液を調製し、分光光度計にてエタノールを対照に波長４２０ｎｍ、試料セル１０ｍｍで吸光度を測定し、その値に係数１０００を乗じた値（クレット）とした。
すべてのアルキルベンゼンサンプルの吸光度とアルキルベンゼンスルホン化物のクレットとの関係を図１に示す。 (Sulphonation of alkylbenzene and measurement of klett)
An alkylbenzene sulfonate was synthesized with reference to the method described in Example 1 of JP2008-94941A. A 10% ethanol solution of the resulting alkylbenzene sulfonate was prepared, and the absorbance was measured with a spectrophotometer at a wavelength of 420 nm and a sample cell of 10 mm using ethanol as a control, and the value was multiplied by a coefficient of 1000 (clet). .
FIG. 1 shows the relationship between the absorbance of all alkylbenzene samples and the alkylbenzene sulfonated material.
特開２００８－９４９４１号公報の実施例１に記載の方法を参考にして、アルキルベンゼンスルホン化物を合成した。得られたアルキルベンゼンスルホン化物の１０％エタノール溶液を調製し、分光光度計にてエタノールを対照に波長４２０ｎｍ、試料セル１０ｍｍで吸光度を測定し、その値に係数１０００を乗じた値（クレット）とした。
すべてのアルキルベンゼンサンプルの吸光度とアルキルベンゼンスルホン化物のクレットとの関係を図１に示す。 (Sulphonation of alkylbenzene and measurement of klett)
An alkylbenzene sulfonate was synthesized with reference to the method described in Example 1 of JP2008-94941A. A 10% ethanol solution of the resulting alkylbenzene sulfonate was prepared, and the absorbance was measured with a spectrophotometer at a wavelength of 420 nm and a sample cell of 10 mm using ethanol as a control, and the value was multiplied by a coefficient of 1000 (clet). .
FIG. 1 shows the relationship between the absorbance of all alkylbenzene samples and the alkylbenzene sulfonated material.
表１から明らかなように、本発明のアルキルベンゼン組成物、すなわちＵＶ－Ｖｉｓ吸収において、３１４ｎｍのＵＶ吸光度が２．９８以下であるアルキルベンゼン組成物を原料としたアルキルベンゼンスルホン化物は色相が低くなることが分かる。また、図1より３１４ｎｍの吸光度と色相に高い相関があることが確認された。洗剤用途のアルキルベンゼンスルホン化物は、市場ではクレットが４０以下であれば使用可能であるが、３０以下がより好ましく、２０以下が最も望ましい。
As can be seen from Table 1, the alkylbenzene composition of the present invention, that is, the UV-Vis absorption, the alkylbenzene sulfonated product obtained from the alkylbenzene composition having a UV absorbance at 314 nm of 2.98 or less has a low hue. I understand. Further, it was confirmed from FIG. 1 that there was a high correlation between the absorbance at 314 nm and the hue. Alkylbenzene sulfonated products for detergent use can be used in the market if the klet is 40 or less, more preferably 30 or less, and most preferably 20 or less.
As can be seen from Table 1, the alkylbenzene composition of the present invention, that is, the UV-Vis absorption, the alkylbenzene sulfonated product obtained from the alkylbenzene composition having a UV absorbance at 314 nm of 2.98 or less has a low hue. I understand. Further, it was confirmed from FIG. 1 that there was a high correlation between the absorbance at 314 nm and the hue. Alkylbenzene sulfonated products for detergent use can be used in the market if the klet is 40 or less, more preferably 30 or less, and most preferably 20 or less.
Claims (7)
- アルキルベンゼンスルホン化物製造用のアルキルベンゼン組成物であって、
前記アルキルベンゼン組成物は、経路長１ｃｍの石英サンプルホルダに収容して分光分析を行なう際、測定される波長３１４ｎｍのＵＶ吸光度が２．９８以下であることを特徴とするアルキルベンゼン組成物。 An alkylbenzene composition for producing an alkylbenzene sulfonate,
When the alkylbenzene composition is stored in a quartz sample holder having a path length of 1 cm and subjected to spectroscopic analysis, the measured UV absorbance at a wavelength of 314 nm is 2.98 or less. - 波長３１４ｎｍの吸光度が２．６９以下であることを特徴とする、請求項１に記載のアルキルベンゼン組成物。 The alkylbenzene composition according to claim 1, wherein the absorbance at a wavelength of 314 nm is 2.69 or less.
- 波長３１４ｎｍの吸光度が２．４０以下であることを特徴とする、請求項２に記載のアルキルベンゼン組成物。 The alkylbenzene composition according to claim 2, wherein the absorbance at a wavelength of 314 nm is 2.40 or less.
- Ｃ１６－Ｃ１９のアルキルベンゼンを９５ｍａｓｓ％以上含むことを特徴とする、請求項１～３のいずれか一つに記載のアルキルベンゼン組成物。 The alkylbenzene composition according to any one of claims 1 to 3, comprising 95 mass% or more of C16-C19 alkylbenzene.
- 臭素価が０．０１以下であることを特徴とする、請求項１～４のいずれか一つに記載のアルキルベンゼン組成物。 The alkylbenzene composition according to any one of claims 1 to 4, wherein the bromine number is 0.01 or less.
- フッ素分が０．５ｐｐｍ以下であることを特徴とする、請求項１～５のいずれか一つに記載のアルキルベンゼン組成物。 6. The alkylbenzene composition according to any one of claims 1 to 5, wherein the fluorine content is 0.5 ppm or less.
- 請求項１～６のいずれかに記載のアルキルベンゼン組成物を硫酸根によってスルホン化することを特徴とするアルキルベンゼスルホン化物の製造方法。 7. A process for producing an alkylbenze sulfonated product, wherein the alkylbenzene composition according to claim 1 is sulfonated by sulfate radicals.
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| JP2015512464A JP6283662B2 (en) | 2013-04-19 | 2014-04-10 | Method for producing alkylbenzene composition for producing alkylbenzene sulfonated product, method for producing alkylbenzene sulfonated product, and method for determining quality of alkylbenzene composition for producing alkylbenzene sulfonated product |
| CN201480022351.0A CN105283430A (en) | 2013-04-19 | 2014-04-10 | Alkylbenzene composition and process for producing alkylbenzene sulfonate |
| KR1020157030732A KR20150144761A (en) | 2013-04-19 | 2014-04-10 | Method for producing alkyl-benzene composition and alkyl benzene sulfonate |
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