JP2008094941A - Method for manufacturing alkylbenzenesulfonic acid salt composition - Google Patents
Method for manufacturing alkylbenzenesulfonic acid salt composition Download PDFInfo
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- neutralized product
- alkylbenzene sulfonate
- alkylbenzene
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- alkylbenzenesulfonic acid
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 239000002253 acid Substances 0.000 title claims abstract description 17
- 150000003839 salts Chemical class 0.000 title abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 14
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 7
- -1 alkylbenzene sulfonate Chemical class 0.000 claims description 44
- 239000000126 substance Substances 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 239000003513 alkali Substances 0.000 abstract description 3
- 239000003518 caustics Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000003756 stirring Methods 0.000 description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 13
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000008051 alkyl sulfates Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UZILCZKGXMQEQR-UHFFFAOYSA-N decyl-Benzene Chemical compound CCCCCCCCCCC1=CC=CC=C1 UZILCZKGXMQEQR-UHFFFAOYSA-N 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JIRNEODMTPGRGV-UHFFFAOYSA-N pentadecylbenzene Chemical compound CCCCCCCCCCCCCCCC1=CC=CC=C1 JIRNEODMTPGRGV-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- MCVUKOYZUCWLQQ-UHFFFAOYSA-N tridecylbenzene Chemical compound CCCCCCCCCCCCCC1=CC=CC=C1 MCVUKOYZUCWLQQ-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- DEQLTFPCJRGSHW-UHFFFAOYSA-N hexadecylbenzene Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1 DEQLTFPCJRGSHW-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSVDSBZMYJJMSB-UHFFFAOYSA-N octadecylbenzene Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1 WSVDSBZMYJJMSB-UHFFFAOYSA-N 0.000 description 1
- VXNSQGRKHCZUSU-UHFFFAOYSA-N octylbenzene Chemical compound [CH2]CCCCCCCC1=CC=CC=C1 VXNSQGRKHCZUSU-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000006254 rheological additive Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- JZALLXAUNPOCEU-UHFFFAOYSA-N tetradecylbenzene Chemical compound CCCCCCCCCCCCCCC1=CC=CC=C1 JZALLXAUNPOCEU-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明はアルキルベンゼンスルホン酸塩組成物の製造方法に関し、詳しくは、高濃度でありながら低粘性であるアルキルベンゼンスルホン酸塩組成物の製造方法に関する。 The present invention relates to a method for producing an alkylbenzene sulfonate composition, and more particularly, to a method for producing an alkylbenzene sulfonate composition having high concentration and low viscosity.
アルキルベンゼンスルホン酸塩は、アルキルベンゼンのスルホン化物を適当なアルカリ性物質で中和することにより得られ、良好な起泡性や浸透性、及び高い乳化力を持つことから、家庭用洗剤、例えば衣料用、食器用、住居用洗剤の界面活性剤として広く使用されている。また、工業用途では、乳化重合用乳化剤、各種洗浄剤、農薬用乳化剤、潤滑油添加剤等の非常に多くの分野で利用されている。 Alkyl benzene sulfonate is obtained by neutralizing a sulfonated product of alkyl benzene with a suitable alkaline substance, and has good foaming property and permeability and high emulsifying power. Widely used as a surfactant for tableware and residential detergents. In industrial applications, they are used in many fields such as emulsifiers for emulsion polymerization, various cleaning agents, emulsifiers for agricultural chemicals, and lubricating oil additives.
一般に、アルキルベンゼンスルホン酸塩は液状組成物又は水を含有するペーストとして製造されるが、多大な使用量を誇る衣料用洗剤としては粉末の形態で使用される。このため、粉末化に要するエネルギーや輸送コストの低減の観点から、アルキルベンゼンスルホン塩の液状組成物及びペーストはできるだけ高濃度であることが望ましい。しかしながら、アルキルベンゼンスルホン酸塩は、有効分濃度の上昇と共に著しく増粘し、製造設備に大きな負荷をかけ、例えば撹拌モーターの破損や配管の閉塞というトラブルが生じている。
従って、アルキルベンゼンスルホン酸塩の濃度を低下させることなく、これを高濃度で含む組成物の粘性を改善できれば、設備負荷の軽減と共に、生産効率の上昇、省エネルギー化、輸送コストの減少が達成でき、工業的に極めて有利である。
In general, alkylbenzene sulfonate is manufactured as a liquid composition or a paste containing water, but is used in the form of a powder as a detergent for clothing having a great amount of use. For this reason, from the viewpoint of reducing energy required for pulverization and transportation cost, it is desirable that the alkylbenzenesulfone salt liquid composition and paste have as high a concentration as possible. However, the alkylbenzene sulfonate salt increases markedly with an increase in the effective component concentration and places a heavy load on the production equipment, causing problems such as breakage of the stirring motor and blockage of the piping.
Therefore, if the viscosity of the composition containing this at a high concentration can be improved without reducing the concentration of the alkylbenzene sulfonate, an increase in production efficiency, energy saving, and a reduction in transportation cost can be achieved along with a reduction in equipment load. It is extremely advantageous industrially.
一方、原料となるアルキルベンゼンの製造法としては、モノクロパラフィン法（ＭＣＰ法）と内部オレフィン法（ＵＯＰ法）の２つが代表的である。ＭＣＰ法由来のアルキルベンゼンは２−フェニル体含有量が多く、それを用いたアルキルベンゼンスルホン酸塩は高濃度においてもある程度の流動性を有している。それに対し、ＵＯＰ法由来のアルキルベンゼンは２−フェニル体の含有量が少なく、そのスルホン化物の中和においての増粘がＭＣＰ法のものに比べ著しい。ところが、近年、アルキルベンゼンの製造法の殆どがＵＯＰ法へ移行しており、高濃度アルキルベンゼンスルホン酸塩の効率的な製造方法が望まれている。 On the other hand, as a method for producing alkylbenzene as a raw material, two methods, a monochrome paraffin method (MCP method) and an internal olefin method (UOP method), are representative. Alkylbenzene derived from the MCP method has a high 2-phenyl content, and an alkylbenzene sulfonate using the alkylbenzene has a certain degree of fluidity even at high concentrations. On the other hand, the alkylbenzene derived from the UOP method has a low 2-phenyl content, and the viscosity increase in neutralization of the sulfonated product is remarkable compared to the MCP method. In recent years, however, most of the alkylbenzene production methods have shifted to the UOP method, and an efficient production method for high-concentration alkylbenzene sulfonates is desired.
高濃度界面活性剤組成物を製造する方法としては、例えば、アルキルベンゼンスルホン酸の中和反応を、高剪断ニーダーを用いて設備的に解決する方法（特許文献１）が知られている。また、アルキルサルフェート（ＡＳ）又はアルキルエーテルサルフェート（ＡＥＳ）の粗中和物に対し、該サルフェートと苛性アルカリを添加して中和することにより濃度を上げる方法（特許文献２）が知られている。しかしながら、ＡＳやＡＥＳはアルキルベンゼンスルホン酸塩（ＬＡＳ）とは異なり、高濃度（例えば６０〜７５質量％）では減粘するため、粘性を低下させる工夫の必要がない技術分野である。
一方、高濃度アルキルベンゼンスルホン酸塩の粘性を低下させる方法としては、例えば高濃度アルキルベンゼンスルホン酸塩にレオロジー改質剤として、アルキルジアリルアルカン等のスルホン酸塩誘導体を添加する方法（特許文献３）、アルキルエーテルサルフェート（ＡＥＳ）等を添加する方法（特許文献４）、芳香族系添加物を添加したアルキルベンゼンをスルホン化し、中和する方法（特許文献５）等が知られている。しかしながら、特許文献３〜５の方法は、最終中和物に添加物を加えて粘性を低下させる方法であり、製造技術のみで粘性を低下させる方法ではない。
As a method for producing a high-concentration surfactant composition, for example, a method (Patent Document 1) is known in which the neutralization reaction of an alkylbenzene sulfonic acid is solved in terms of equipment using a high shear kneader. In addition, a method for increasing the concentration of a crude neutralized product of alkyl sulfate (AS) or alkyl ether sulfate (AES) by adding the sulfate and caustic alkali to neutralize is known (Patent Document 2). . However, AS and AES, unlike alkylbenzene sulfonate (LAS), are a technical field that does not require any device to reduce the viscosity because the viscosity decreases at a high concentration (for example, 60 to 75% by mass).
On the other hand, as a method for reducing the viscosity of the high concentration alkylbenzene sulfonate, for example, a method of adding a sulfonate derivative such as alkyl diallyl alkane as a rheology modifier to the high concentration alkylbenzene sulfonate (Patent Document 3), A method of adding alkyl ether sulfate (AES) or the like (Patent Document 4), a method of sulfonating and neutralizing alkylbenzene added with an aromatic additive (Patent Document 5), and the like are known. However, the methods of Patent Documents 3 to 5 are methods of adding an additive to the final neutralized product to reduce the viscosity, and are not a method of reducing the viscosity only by the production technique.
本発明者らの検討によると、アルキルベンゼンスルホン酸塩の粘性は有効分が６０質量％程度までは、容易に撹拌可能な流動性を有しているが、６０質量％を超える高濃度領域においては著しい増粘が生じ、撹拌が難しくなることが判明している。このため、高濃度対応ではない設備において、有効分が６０質量％以上の高濃度品を得るには、設備上製造が可能な領域にまで製造規模を縮小せざるを得なかった。
本発明は、高濃度でありながら低粘性のアルキルベンゼンスルホン酸塩組成物及びその製造方法を提供することを課題とする。
According to the study by the present inventors, the viscosity of the alkylbenzene sulfonate has fluidity that can be easily stirred up to an effective content of about 60% by mass, but in a high concentration region exceeding 60% by mass. It has been found that significant thickening occurs and stirring becomes difficult. For this reason, in order to obtain a high-concentration product having an effective content of 60% by mass or more in equipment that is not compatible with high concentration, the production scale has to be reduced to an area that can be manufactured on equipment.
An object of the present invention is to provide an alkylbenzene sulfonate composition having a high viscosity and a low viscosity, and a method for producing the same.
本発明者らは、アルキルベンゼンスルホン酸塩の製造工程において、アルキルベンゼンスルホン酸塩の撹拌性が良好な濃度領域において、あらかじめ粗中和物を作っておき、そこへアルキルベンゼンスルホン酸を添加して、ｐＨが酸性である領域を経由するようにして中和を行うことにより、最終中和物の粘性を従来法で得られたものよりも大幅に低下させることができることを見出した。
すなわち、本発明は次の（１）〜（３）を提供する。
（１）下記の（ａ）、（ｂ）及び（ｃ）工程を含むアルキルベンゼンスルホン酸塩組成物の製造方法。
（ａ）下記式（１）で表されるアルキルベンゼンスルホン酸をアルカリ性物質にて中和し、粗中和物を得る工程
Ｒ−Ｃ6Ｈ4ＳＯ3Ｈ （１）
（式中、Ｒは炭素数６〜２０のアルキル基を示す。）
（ｂ）粗中和物に前記アルキルベンゼンスルホン酸を添加し、酸性混合物を得る工程
（ｃ）酸性混合物にアルカリ性物質を添加し、中和する工程
（２）前記（１）の製造方法によって得られたアルキルベンゼンスルホン酸塩組成物。
In the production process of the alkylbenzene sulfonate, the present inventors made a crude neutralized product in advance in a concentration range where the stirrability of the alkylbenzene sulfonate is good, and then added the alkylbenzene sulfonic acid to the pH, It was found that the viscosity of the final neutralized product can be greatly reduced as compared with that obtained by the conventional method by carrying out the neutralization so as to pass through the acidic region.
That is, the present invention provides the following (1) to (3).
(1) A method for producing an alkylbenzene sulfonate composition comprising the following steps (a), (b) and (c):
(A) Step of neutralizing alkylbenzenesulfonic acid represented by the following formula (1) with an alkaline substance to obtain a crude neutralized product R—C 6 H 4 SO 3 H (1)
(In the formula, R represents an alkyl group having 6 to 20 carbon atoms.)
(B) Step of adding the alkylbenzenesulfonic acid to the crude neutralized product to obtain an acidic mixture (c) Step of adding an alkaline substance to the acidic mixture for neutralization (2) Obtained by the production method of (1) Alkylbenzene sulfonate composition.
本発明方法によれば、高濃度でありながら低粘性のアルキルベンゼンスルホン酸塩組成物を効率よく製造することができる。また、高濃度においても設備への負担が軽微であるため、高粘度対応ではない製造設備においても、生産性よく高濃度アルキルベンゼンスルホン酸塩組成物を製造することができる。 According to the method of the present invention, it is possible to efficiently produce a low-viscosity alkylbenzene sulfonate composition with a high concentration. In addition, since the burden on the facility is light even at high concentrations, a high concentration alkylbenzene sulfonate composition can be produced with high productivity even in production facilities that do not support high viscosity.
本発明のアルキルベンゼンスルホン酸塩組成物の製造方法は、（ａ）下記式（１）で表されるアルキルベンゼンスルホン酸をアルカリ性物質にて中和し、粗中和物を得る工程
Ｒ−Ｃ6Ｈ4ＳＯ3Ｈ （１）
（式中、Ｒは炭素数６〜２０のアルキル基を示す。）
（ｂ）粗中和物に前記アルキルベンゼンスルホン酸を添加し、酸性混合物を得る工程、及び（ｃ）酸性混合物にアルカリ性物質を添加し、中和する工程を含むことを特徴とする。
In the method for producing an alkylbenzene sulfonate composition of the present invention, (a) a step of neutralizing an alkylbenzene sulfonic acid represented by the following formula (1) with an alkaline substance to obtain a crude neutralized product RC 6 H 4 SO 3 H (1)
(In the formula, R represents an alkyl group having 6 to 20 carbon atoms.)
(B) adding the alkylbenzenesulfonic acid to the crude neutralized product to obtain an acidic mixture, and (c) adding an alkaline substance to the acidic mixture to neutralize.
（ａ）工程
（ａ）工程で用いられるアルキルベンゼンスルホン酸は、好ましくは炭素数８〜１８、より好ましくは炭素数１０〜１６のアルキル基を有するアルキルベンゼンを、公知の方法によりスルホン化して得られるものである。
用いることのできる原料アルキルベンゼンとしては、オクチルベンゼン、デシルベンゼン、ドデシルベンゼン、トリデシルベンゼン、テトラデシルベンゼン、ペンタデシルベンゼン、ヘキサデシルベンゼン、オクタデシルベンゼン、あるいはこれらの混合物が挙げられる。
Step (a) The alkylbenzene sulfonic acid used in step (a) is preferably obtained by sulfonating an alkylbenzene having an alkyl group having 8 to 18 carbon atoms, more preferably 10 to 16 carbon atoms by a known method. It is.
Examples of the raw material alkylbenzene that can be used include octylbenzene, decylbenzene, dodecylbenzene, tridecylbenzene, tetradecylbenzene, pentadecylbenzene, hexadecylbenzene, octadecylbenzene, and mixtures thereof.
スルホン化剤としては、例えば、三酸化硫黄（液体又は気体）、三酸化硫黄含有ガス、発煙硫酸、クロルスルホン酸等を用いることができるが、特に、廃硫酸及び廃塩酸等の発生を防止する観点から、三酸化硫黄をアルキルベンゼンと同時にガス状又は液状で連続的に供給する方法が好ましい。三酸化硫黄を用いる場合は、スルホン化後に微量に残る酸無水物を加水分解することによりアルキルベンゼンスルホン酸を得ることが好ましい。
スルホン化剤の使用量は、芒硝、硫酸、未反応アルキルベンゼンを低減する等の観点から、アルキルベンゼンに対し、好ましくは０．８〜１．２倍モル、より好ましくは０．９〜１．１倍モルである。
上記の方法により得られるアルキルベンゼンスルホン酸は、通常、純度が９２〜９７質量％、遊離硫酸０．５〜４質量％、水０．２〜１．０質量％、油分０．５〜４質量％を含有する組成を有している。
As the sulfonating agent, for example, sulfur trioxide (liquid or gas), sulfur trioxide-containing gas, fuming sulfuric acid, chlorosulfonic acid and the like can be used. In particular, generation of waste sulfuric acid and waste hydrochloric acid is prevented. From the viewpoint, a method of continuously supplying sulfur trioxide in a gaseous or liquid state simultaneously with the alkylbenzene is preferable. When sulfur trioxide is used, it is preferable to obtain alkylbenzenesulfonic acid by hydrolyzing the acid anhydride remaining in a trace amount after sulfonation.
The amount of the sulfonating agent is preferably 0.8 to 1.2 times mol, more preferably 0.9 to 1.1 times the amount of alkylbenzene, from the viewpoint of reducing sodium sulfate, sulfuric acid, and unreacted alkylbenzene. Is a mole.
The alkylbenzenesulfonic acid obtained by the above method usually has a purity of 92 to 97% by mass, free sulfuric acid 0.5 to 4% by mass, water 0.2 to 1.0% by mass, and oil content 0.5 to 4% by mass. It has the composition containing.
（ａ）工程においては、上記方法により得られたアルキルベンゼンスルホン酸を、アルカリ性物質にて中和し、粗中和物を得る。ここで言う粗中和物とは、有効成分であるアルキルベンゼンスルホン酸塩濃度が目的濃度（最終中和物の濃度）にまで達していない中和物を意味するものである。
用いることのできるアルカリ性物質としては、水酸化ナトリウム、水酸化カリウム、水酸化リチウム、水酸化アンモニウム、トリエタノールアミン等があげられるが、それらの中でも水酸化ナトリウムが特に好ましい。
（ａ）工程における中和は、アルキルベンゼンスルホン酸当量のアルカリ性物質を用いて、例えば撹拌翼付きの反応槽内で撹拌しつつ行い、撹拌を容易にする観点から、アルキルベンゼンスルホン酸塩の有効分濃度を好ましくは５５〜６２質量％、より好ましくは５７〜６２質量％に調整した粗中和物を得る。このときの温度条件としては特に制限はないが、粗中和物の粘性調整、撹拌負荷低減の観点から、好ましくは５５℃以下、より好ましくは４０〜５５℃に制御することが望ましい。
In step (a), the alkylbenzenesulfonic acid obtained by the above method is neutralized with an alkaline substance to obtain a crude neutralized product. The crude neutralized product as used herein means a neutralized product in which the concentration of the alkylbenzene sulfonate, which is an active ingredient, does not reach the target concentration (final neutralized product concentration).
Examples of the alkaline substance that can be used include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, etc. Among them, sodium hydroxide is particularly preferable.
The neutralization in the step (a) is performed using an alkaline substance equivalent to an alkylbenzene sulfonic acid, for example, while stirring in a reaction vessel equipped with a stirring blade. From the viewpoint of facilitating stirring, the effective concentration of the alkylbenzene sulfonate Is preferably 55 to 62% by mass, and more preferably 57 to 62% by mass. Although there is no restriction | limiting in particular as temperature conditions at this time, It is desirable to control to 55 degrees C or less, More preferably, 40-55 degreeC from a viewpoint of viscosity adjustment of a rough neutralized material, and stirring load reduction.
（ｂ）工程
（ｂ）工程においては、（ａ）工程で得られた粗中和物に前記アルキルベンゼンスルホン酸を添加し、〔アルキルベンゼンスルホン酸／アルキルベンゼンスルホン酸塩粗中和物〕の酸性混合物を得る。添加するアルキルベンゼンスルホン酸の量は、最終中和物におけるアルキルベンゼンスルホン酸塩の有効分濃度が、好ましくは６２〜７５質量％、より好ましくは６３〜７０質量％となる量とする。
この混合物は、例えば撹拌翼付きの反応槽内にて適当な時間撹拌しながら酸性に保持される。酸性保持時間（撹拌時間）は特に制限はないが、通常、最終中和物の粘度を低下させる観点から、好ましくは１時間以上、より好ましくは２時間以上、更に好ましくは３時間以上、特に好ましくは４時間以上である。しかし４時間以上撹拌することによる更なる粘度低下は期待できず、酸性保持時間が長いほど本発明の効果が増大するわけではない。
撹拌中の混合物のｐＨは常に酸性である必要はないが、酸性の時間をできるだけ長くすることが好ましく、ｐＨ値としては、好ましくはｐＨ４以下、より好ましくはｐＨ３以下、特に好ましくはｐＨ１〜２となるように制御する。
本発明の効果を損なわない範囲であれば、前記混合物のｐＨが一時的にアルカリ性となってもよい。
(B) Step (b) In step (b), the alkylbenzene sulfonic acid is added to the crude neutralized product obtained in step (a), and an acidic mixture of [alkylbenzene sulfonic acid / alkylbenzene sulfonate crude neutralized product] is added. obtain. The amount of the alkylbenzenesulfonic acid to be added is such that the effective concentration of the alkylbenzenesulfonate in the final neutralized product is preferably 62 to 75% by mass, more preferably 63 to 70% by mass.
This mixture is kept acidic with stirring for an appropriate time in a reaction vessel equipped with a stirring blade, for example. The acidic retention time (stirring time) is not particularly limited, but usually from the viewpoint of reducing the viscosity of the final neutralized product, it is preferably 1 hour or longer, more preferably 2 hours or longer, still more preferably 3 hours or longer, particularly preferably. Is 4 hours or more. However, further reduction in viscosity due to stirring for 4 hours or more cannot be expected, and the effect of the present invention does not increase as the acidic retention time increases.
The pH of the mixture during stirring does not always need to be acidic, but it is preferable to make the acidic time as long as possible, and the pH value is preferably pH 4 or less, more preferably pH 3 or less, and particularly preferably pH 1-2. Control to be.
As long as the effects of the present invention are not impaired, the pH of the mixture may be temporarily alkaline.
（ｃ）工程
（ｃ）工程においては、（ｂ）工程で得られた酸性混合物に対して、中和当量のアルカリ性物質を添加し、該酸性混合物を中和し、最終中和物を得る。用いることのできるアルカリ性物質は前記と同じであり、このときの温度条件も前記（ａ）工程で記載した条件と同様である。
本発明においては、前記（ａ）工程、（ｂ）工程、及び（ｃ）工程を含んでいればよく、前記（ｂ）工程と（ｃ）工程は、目標とする最終中和物の有効分濃度が目標値に到達するまで何回でも繰り返し行うことができる。
Step (c) In step (c), a neutralizing equivalent of an alkaline substance is added to the acidic mixture obtained in step (b) to neutralize the acidic mixture to obtain a final neutralized product. The alkaline substance that can be used is the same as described above, and the temperature condition at this time is the same as the condition described in the step (a).
In the present invention, the step (a), the step (b), and the step (c) may be included, and the step (b) and the step (c) are effective components of the target final neutralized product. This can be repeated any number of times until the density reaches the target value.
前記（ａ）〜（ｃ）工程で使用する装置に特に制限はないが、温度制御用ジャケット、循環ライン、及びｐＨメーターを備えた撹拌翼付きの中和反応槽を用いることで中和操作を効率的に行うことが出来、このとき攪拌翼は、攪拌性能の観点からスパイラル型であることが望ましい。 Although there is no restriction | limiting in particular in the apparatus used at the said (a)-(c) process, Neutralization operation is performed by using the neutralization reaction tank with the stirring blade provided with the jacket for temperature control, the circulation line, and the pH meter. In this case, the stirring blade is preferably a spiral type from the viewpoint of stirring performance.
本発明方法により得られるアルキルベンゼンスルホン酸塩（最終中和物）は、低粘性であり、その降伏応力は、好ましくは１４００Ｐａ以下、より好ましくは１３００Ｐａ以下、特に好ましくは１２００Ｐａ以下である。ここで、降伏応力は、ジャスコインタナショナル株式会社製レオメーター「ＶＡＲ-５０ビスコアナライザー」を用い、温度５０℃、剪断速度１ｓｅｃ-1で７０秒間プレシェアを行った後、５０℃にて０．００１〜２０００Ｐａまで２４０秒間で徐々に剪断をかけていき、剪断速度が１００ｓｅｃ-1になったときに生じる応力を測定した値をいう。
また、得られるアルキルベンゼンスルホン酸塩組成物は、その有効分濃度が、好ましくは６２〜７５質量％、より好ましくは６３〜７０質量％という高濃度である。このため、ペースト状スラリーのまま、噴霧乾燥法によらずに、真空薄膜乾燥法、真空撹拌乾燥法等の公知の簡便な乾燥方法を採用して粉末化することができるので、乾燥に要するエネルギーを大幅に削減することができる。
The alkylbenzene sulfonate (final neutralized product) obtained by the method of the present invention has a low viscosity, and its yield stress is preferably 1400 Pa or less, more preferably 1300 Pa or less, and particularly preferably 1200 Pa or less. Here, the yield stress was 0.001 at 50 ° C. after preshearing for 70 seconds at a temperature of 50 ° C. and a shear rate of 1 sec −1 using a rheometer “VAR-50 Visco Analyzer” manufactured by Jusco International Co., Ltd. It is a value obtained by measuring stress generated when shearing is gradually applied up to ˜2000 Pa in 240 seconds and the shear rate becomes 100 sec −1 .
Moreover, the alkylbenzene sulfonate composition obtained has an effective component concentration of preferably 62 to 75% by mass, more preferably 63 to 70% by mass. For this reason, since it can be pulverized by using a known simple drying method such as a vacuum thin film drying method, a vacuum stirring drying method, etc. without using a spray drying method, the paste-like slurry can be pulverized. Can be greatly reduced.
実施例１
（ａ）アルキルベンゼン（新日本石油株式会社製、商品名：アルケンＬ）にＳＯ3ガスを接触させ、〔ＳＯ3／アルキルベンゼン〕の反応モル比＝１．０３０の条件でスルホン化して、アルキルベンゼンスルホン酸を得た。
得られたアルキルベンゼンスルホン酸１６３６ｋｇを２７質量％の水酸化ナトリウム水溶液７６３．２ｋｇに添加し、撹拌翼付きの反応槽にて、槽内温度を４５〜５５℃の範囲で制御するよう撹拌しながら中和を行った。中和後のｐＨは７で、有効分が６０質量％のアルキルベンゼンスルホン酸塩の粗中和物を得た。
（ｂ）得られた粗中和物に対し、イオン交換水を１２８ｋｇ、前記アルキルベンゼンスルホン酸を５７６．２ｋｇ添加し、混合物のｐＨを１〜２に維持しながら４時間撹拌した。
（ｃ）得られた混合物に３２質量％水酸化ナトリウム水溶液２２３．５ｋｇを添加して中和を行い、有効分６３質量％のアルキルベンゼンスルホン酸塩を得た。
（ｂ’）得られた中和物に対し、イオン交換水１２８ｋｇと前記アルキルベンゼンスルホン酸３５６．２ｋｇを添加し、ｐＨを１〜２に維持しながら１時間撹拌した。
（ｃ’）得られた混合物に３２質量％水酸化ナトリウム水溶液１４８．１ｋｇを添加して中和を行い、有効分６５質量％でｐＨが７〜８であるアルキルベンゼンスルホン酸塩を得た。
得られた中和物に無水硫酸ナトリウム（分離抑制剤）を３６ｋｇ加えて撹拌し、最終中和物とした。
Example 1
(A) An alkylbenzene (manufactured by Nippon Oil Corporation, trade name: Alkene L) is contacted with SO 3 gas, and sulfonated under the condition of a reaction molar ratio of [SO 3 /alkylbenzene]=1.030 to obtain an alkylbenzenesulfonic acid Got.
While adding 1636 kg of the obtained alkylbenzene sulfonic acid to 763.2 kg of a 27 mass% sodium hydroxide aqueous solution, in a reaction tank equipped with a stirring blade, stirring while controlling the temperature in the tank within a range of 45 to 55 ° C. The sum was done. The pH after neutralization was 7, and a crude neutralized product of alkylbenzene sulfonate having an effective content of 60% by mass was obtained.
(B) 128 kg of ion-exchanged water and 576.2 kg of the alkylbenzenesulfonic acid were added to the resulting crude neutralized product, and the mixture was stirred for 4 hours while maintaining the pH of the mixture at 1-2.
(C) The obtained mixture was neutralized by adding 223.5 kg of a 32% by mass aqueous sodium hydroxide solution to obtain an alkylbenzene sulfonate having an effective content of 63% by mass.
(B ′) To the obtained neutralized product, 128 kg of ion-exchanged water and 356.2 kg of the alkylbenzene sulfonic acid were added and stirred for 1 hour while maintaining the pH at 1-2.
(C ′) The resulting mixture was neutralized by adding 148.1 kg of a 32% by mass aqueous sodium hydroxide solution to obtain an alkylbenzene sulfonate having an effective content of 65% by mass and a pH of 7-8.
To the obtained neutralized product, 36 kg of anhydrous sodium sulfate (separation inhibitor) was added and stirred to obtain a final neutralized product.
得られた最終中和物の粘性を充填圧力及び降伏応力で評価した。充填圧力としては、容器充填時のポンプ圧を測定し、降伏応力としては、ジャスコインタナショナル株式会社製レオメーター「ＶＡＲ-５０ビスコアナライザー」を用いて、温度５０℃、剪断速度１ｓｅｃ-1で７０秒間プレシェアを行った後、５０℃にて０．００１〜２０００Ｐａまで２４０秒間で徐々に剪断をかけていき、剪断速度が１００ｓｅｃ-1になったときに生じる応力を測定した。
その結果、得られた最終中和物の充填圧力は０．５〜１．０ＭＰａ、降伏応力は１１０６Ｐａであった。なお、充填圧力１．０ＭＰａで容器への充填を開始したが、流動性が良好なことから充填圧力を０．５ＭＰａまで低下させても充填できた。アルキルベンゼンスルホン酸塩の最終中和物は、比較例１及び２で得られた最終中和物に比べて軟らかであった。
The viscosity of the final neutralized product obtained was evaluated by filling pressure and yield stress. As the filling pressure, the pump pressure at the time of filling the container was measured. As the yield stress, a rheometer “VAR-50 Visco Analyzer” manufactured by Jusco International Co., Ltd. was used, and the yield was 70 at a temperature of 50 ° C. and a shear rate of 1 sec −1 . After pre-shearing for 2 seconds, shear was gradually applied from 0.001 to 2000 Pa at 50 ° C. over 240 seconds, and the stress generated when the shear rate reached 100 sec −1 was measured.
As a result, the filling pressure of the obtained final neutralized product was 0.5 to 1.0 MPa, and the yield stress was 1106 Pa. In addition, although the filling to the container was started at a filling pressure of 1.0 MPa, it was able to be filled even if the filling pressure was reduced to 0.5 MPa because of good fluidity. The final neutralized product of alkylbenzene sulfonate was softer than the final neutralized product obtained in Comparative Examples 1 and 2.
比較例１
２２質量％水酸化ナトリウム１４５５．３ｋｇに、実施例１で得られたアルキルベンゼンスルホン酸を２５０８．７ｋｇ添加し、撹拌翼付きの反応槽にて、槽内温度を４５〜５５℃の範囲で制御するよう撹拌しながら中和を行った。中和後のｐＨが中性で、有効分が６５質量％であるアルキルベンゼンスルホン酸塩の中和物を得た。
得られた粗中和物に無水硫酸ナトリウムを３６ｋｇ添加し、撹拌して最終中和物とした。
得られた最終中和物の粘性評価を実施例１と同様にして行った結果、充填圧力は１．０〜１．８ＭＰａ、降伏応力は１６５７Ｐａであった。なお、充填圧力１．０ＭＰａで容器への充填を開始したが、配管閉塞により充填が不可能となったため、圧力を１．８ＭＰａまで上昇させて充填を行った。
Comparative Example 1
2508.7 kg of the alkylbenzene sulfonic acid obtained in Example 1 is added to 1455.3 kg of 22% by mass sodium hydroxide, and the temperature in the tank is controlled in the range of 45 to 55 ° C. in a reaction tank equipped with a stirring blade. Neutralization was carried out with stirring. A neutralized product of alkylbenzene sulfonate having a neutral pH after neutralization and an effective content of 65% by mass was obtained.
36 kg of anhydrous sodium sulfate was added to the resulting crude neutralized product and stirred to obtain a final neutralized product.
As a result of evaluating the viscosity of the final neutralized product obtained in the same manner as in Example 1, the filling pressure was 1.0 to 1.8 MPa, and the yield stress was 1657 Pa. In addition, although the filling to the container was started at a filling pressure of 1.0 MPa, the filling was impossible due to the blockage of the pipe, and thus the filling was performed by increasing the pressure to 1.8 MPa.
比較例２
実施例１で得られたアルキルベンゼンスルホン酸１６３６ｋｇを、２７質量％の水酸化ナトリウム水溶液７６３．２ｋｇに添加し、撹拌翼付きの反応槽にて、槽内温度を４５〜５５℃の範囲で制御するよう撹拌しながら中和を行った。中和後のｐＨは中性で、有効分が６０質量％のアルキルベンゼンスルホン酸塩の粗中和物を得た。
得られた粗中和物に対し、イオン交換水を１２８ｋｇ、３２質量％水酸化ナトリウム水溶液２２３．５ｋｇを添加し、混合物のｐＨを１０〜１２に維持しながら１時間撹拌した。
得られた混合物に対し、前記アルキルベンゼンスルホン酸を５７６．２ｋｇ添加して中和を行い、有効分６３質量％のアルキルベンゼンスルホン酸塩を得た。
得られたアルキルベンゼンスルホン酸塩にイオン交換水１２８ｋｇと３２質量％水酸化ナトリウム水溶液１４８．１ｋｇを添加し、ｐＨを１０〜１２に維持しながら１時間撹拌した。
得られた混合物に、前記アルキルベンゼンスルホン酸３５６．２ｋｇを添加して中和を行い、有効分が６５質量％であるアルキルベンゼンスルホン酸塩を得た。
得られた中和物に無水硫酸ナトリウムを３６ｋｇ加えて撹拌し、最終中和物とした。
得られた最終中和物の粘性評価を行った結果、充填圧力は１．０ＭＰａ、降伏応力は１５１４Ｐａであった。なお、充填圧力１．０ＭＰａで容器への充填は可能であったが、アルキルベンゼンスルホン酸塩の最終中和物の硬さは比較例１で得られた最終中和物と同程度であった。
Comparative Example 2
1636 kg of the alkylbenzene sulfonic acid obtained in Example 1 is added to 763.2 kg of a 27% by mass aqueous sodium hydroxide solution, and the temperature in the tank is controlled in the range of 45 to 55 ° C. in a reaction tank equipped with a stirring blade. Neutralization was carried out with stirring. The pH after neutralization was neutral, and a crude neutralized product of alkylbenzene sulfonate having an effective content of 60% by mass was obtained.
To the resulting crude neutralized product, 128 kg of ion-exchanged water and 223.5 kg of a 32 mass% aqueous sodium hydroxide solution were added, and the mixture was stirred for 1 hour while maintaining the pH of the mixture at 10-12.
The resulting mixture was neutralized by adding 576.2 kg of the alkylbenzene sulfonic acid to obtain an alkylbenzene sulfonate having an effective content of 63% by mass.
To the resulting alkylbenzene sulfonate, 128 kg of ion-exchanged water and 148.1 kg of a 32% by mass aqueous sodium hydroxide solution were added and stirred for 1 hour while maintaining the pH at 10-12.
The resulting mixture was neutralized by adding 356.2 kg of the alkylbenzene sulfonic acid to obtain an alkylbenzene sulfonate having an effective content of 65% by mass.
36 kg of anhydrous sodium sulfate was added to the resulting neutralized product and stirred to obtain a final neutralized product.
As a result of evaluating the viscosity of the final neutralized product, the filling pressure was 1.0 MPa and the yield stress was 1514 Pa. Although the container could be filled at a filling pressure of 1.0 MPa, the hardness of the final neutralized product of alkylbenzene sulfonate was almost the same as that of the final neutralized product obtained in Comparative Example 1.
Claims (5)
（ａ）下記式（１）で表されるアルキルベンゼンスルホン酸をアルカリ性物質にて中和し、粗中和物を得る工程
Ｒ−Ｃ6Ｈ4ＳＯ3Ｈ （１）
（式中、Ｒは炭素数６〜２０のアルキル基を示す。）
（ｂ）粗中和物に前記アルキルベンゼンスルホン酸を添加し、酸性混合物を得る工程
（ｃ）酸性混合物にアルカリ性物質を添加し、中和する工程 The manufacturing method of the alkylbenzene sulfonate composition containing the following (a), (b) and (c) process.
(A) Step of neutralizing alkylbenzenesulfonic acid represented by the following formula (1) with an alkaline substance to obtain a crude neutralized product R—C 6 H 4 SO 3 H (1)
(In the formula, R represents an alkyl group having 6 to 20 carbon atoms.)
(B) Step of adding the alkylbenzenesulfonic acid to the crude neutralized product to obtain an acidic mixture (c) Step of adding an alkaline substance to the acidic mixture for neutralization
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| JP2018518581A (en) * | 2015-06-22 | 2018-07-12 | ザ プロクター アンド ギャンブル カンパニー | Process for producing a liquid detergent composition comprising a liquid crystal phase |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02218658A (en) * | 1989-02-21 | 1990-08-31 | Kao Corp | Production of alkylbenzenesulfonate |
| JP2003073697A (en) * | 2001-08-31 | 2003-03-12 | Lion Corp | Process for producing detergent |
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2006
- 2006-10-11 JP JP2006277466A patent/JP4972372B2/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02218658A (en) * | 1989-02-21 | 1990-08-31 | Kao Corp | Production of alkylbenzenesulfonate |
| JP2003073697A (en) * | 2001-08-31 | 2003-03-12 | Lion Corp | Process for producing detergent |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018518581A (en) * | 2015-06-22 | 2018-07-12 | ザ プロクター アンド ギャンブル カンパニー | Process for producing a liquid detergent composition comprising a liquid crystal phase |
| US10640738B2 (en) | 2015-06-22 | 2020-05-05 | The Procter And Gamble Company | Processes for making liquid detergent compositions comprising a liquid crystalline phase |
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| JP4972372B2 (en) | 2012-07-11 |
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