[go: up one dir, main page]

WO1993017992A1 - Procede de sulfonation destine a l'acide sulfonique visqueux - Google Patents

Procede de sulfonation destine a l'acide sulfonique visqueux Download PDF

Info

Publication number
WO1993017992A1
WO1993017992A1 PCT/US1992/001684 US9201684W WO9317992A1 WO 1993017992 A1 WO1993017992 A1 WO 1993017992A1 US 9201684 W US9201684 W US 9201684W WO 9317992 A1 WO9317992 A1 WO 9317992A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
sulfonation
film
gaseous
sulfonating agent
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.)
Ceased
Application number
PCT/US1992/001684
Other languages
English (en)
Inventor
David Eugene Farmer
Norman Charles Foster
Thomas Joseph Loughney
William Bradford Sheats
Ronald Keith Borrevik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemithon Corp
Original Assignee
Chemithon Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to US07/571,751 priority Critical patent/US5136088A/en
Priority claimed from US07/571,751 external-priority patent/US5136088A/en
Application filed by Chemithon Corp filed Critical Chemithon Corp
Priority to PCT/US1992/001684 priority patent/WO1993017992A1/fr
Priority to DE69229045T priority patent/DE69229045T2/de
Priority to EP92913608A priority patent/EP0587774B1/fr
Priority to CA002102176A priority patent/CA2102176C/fr
Publication of WO1993017992A1 publication Critical patent/WO1993017992A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B45/00—Formation or introduction of functional groups containing sulfur
    • C07B45/02—Formation or introduction of functional groups containing sulfur of sulfo or sulfonyldioxy groups
    • 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

Definitions

  • the present invention relates to a process and apparatus for the sulfonation of organic reactants and particularly to an improved process and apparatus for the production of sulfonic acids such as alkyl diaryl ether disulfonic acid, alkyl diaryl disulfonic acid, high molecular weight alkyl aryl sulfonic acids, dialkyl aryl sulfonic acid and other sulfonic acids
  • sulfonic acids such as alkyl diaryl ether disulfonic acid, alkyl diaryl disulfonic acid, high molecular weight alkyl aryl sulfonic acids, dialkyl aryl sulfonic acid and other sulfonic acids
  • Organic sulfonic acids and organic sulfonates are important commercially as components of
  • Sulfonation products such as alkyl diphenyl ether disulfonic acid (ADEDS) are
  • ADEDS is particularly useful as an additive in household detergent formulations as well as a surfactant in many industrial detergent applications.
  • ADEDS is characterized by excellent properties including high thermal stability, high solubility and the ability to solubilize other detergents.
  • ADEDS is generally unsuitable for household use because of residual
  • Another sulfonation product characterized by high viscosity is high molecular weight alkyl benzene sulfonic acid (ABS) with an alkyl group of 18 or more carbons. ABS is particularly useful as a non-aqueous detergent such as an additive for high temperature lubricating oil.
  • Another sulfonation product characterized by high viscosity is dialkyl naphthalene sulfonic acid (DANS) with each alkyl group containing 5 or more carbons. In its neutral form, DANS is particularly useful as a corrosion inhibiting agent.
  • the thick films of high viscosity reaction products prevent sufficient penetration of the sulfur trioxide through the thickness of the reaction product to the unreacted feedstock to give sufficient yields of
  • the present invention provides an improved process for sulfonating an organic reactant which, upon sulfonation with a gaseous sulfonating agent (preferably sulfur trioxide), produces a viscous sulfonation
  • a gaseous sulfonating agent preferably sulfur trioxide
  • reaction product having a viscosity substantially
  • the method is capable of producing such a sulfonation reaction product which is greater than 85% by weight completely reacted.
  • dodecyl for dodecyl
  • diphenyl ether DDE
  • the method is capable of producing sulfonation reaction product which is greater than 88% by weight disulfonated.
  • the method of the invention comprises the steps including: providing an elongated, enclosed reactor surface greater than about 15 feet in length having upstream and downstream ends and equipped with a . heat exchanging surface; flowing a film of the organic reactant along the reactor surface from the upstream end to the downstream end; directing a gaseous sulfonating agent cocurrently alongside the film; confining the gaseous sulfonating agent in close proximate relation to the film.
  • a film of organic reactant is reacted with the gaseous sulfonating agent to form a film of
  • the method of the invention calls for providing a pressure drop between the upstream and downstream ends of the reactor which is sufficient to impart to the gaseous agent an increasing velocity progressively in a downstream direction.
  • the pressure drop results in an increasing velocity in a downstream direction because a given weight of gas under lower pressure at a downstream portion of the reactor has a greater volume than that gas at a higher pressure upstream portion of the reactor. This greater volume of gas must accordingly move with a greater velocity in order to progress through the reactor.
  • the increasing velocity of the gaseous agent is utilized to thin the increasingly viscous film of reaction product so as to increase the reaction product surface area and reduce the degree of penetration through the reactant/product film required for the sulfonating agent to react to form product.
  • the process of the present invention provides sulfonation product with yields in excess of 85% by weight by means of increased sulfonating agent/air mixture pressures, increased pressure drops and gas velocities through the reactor, and reactors having increased lengths but characterized by relatively small equivalent diameters.
  • the reaction conditions are preferably selected to produce a sulfonation reaction product which is greater than about 88% by weight completely reacted, and most preferably greater than about 90% by weight completely reacted.
  • reaction conditions are selected to produce sulfonation reaction products which are
  • the present invention provides an improved process for the sulfonation of organic reagents and particularly those where the sulfonation products are characterized by high viscosities.
  • the process provides high sulfonation yields in sulfonation reactions where the sulfonation product is characterized by viscosities in excess of 1,500 centipoises at reaction conditions.
  • a product of the present invention is ADEDS which, when produced according to the methods of the invention, is suitable for use in household detergents and industrial products.
  • the process of the present invention resolves the problem of reduced reactivity caused by the high viscosity of certain sulfonation products.
  • the effect of the reduced reactivity is evident in the low yields or incompletely reacted product from conventional film and jet reactors.
  • sulfur trioxide reacts rapidly with most sulfonatable organic feedstocks, the reaction rate can be severely limited by the decreased ability of sulfonating agents such as sulfur trioxide to penetrate through viscous product to unreacted sites.
  • the material becomes increasingly viscous as the sulfonation reaction proceeds. This causes the viscous product to increase in thickness on the reactor surface, inhibiting the sulfonation reaction and the passage of the gaseous agent through the reactor.
  • the reaction product layer is thinned by the sheering action of the expanding gaseous agent as it proceeds from the high to low pressure ends of the reactor.
  • the thinned layer of the reaction product reduces the degree of penetration required for the sulfonating agent to contact unreacted sites.
  • the process of the present invention provides sulfonation product with yields in excess of 85% by weight by means of increased sulfonating agent/air mixture pressures, increased pressure drops and gas velocities through the reactor and reactors having increased lengths but characterized by relatively small equivalent diameters, reduced liquid loading (mass flow per unit of reactor circumference) and higher film temperatures as manifested by higher reactor wall temperatures. While not wishing to be bound by any theory of the invention, it is believed that this combination of elevated pressure, pressure drop and gas velocities improve mixing and increase the kinetics of the sulfonation reaction thus improving the sulfonation yield.
  • Reactors suitable for use according to the present invention include virtually all falling film reactors wherein cocurrent flow of liquid and vapor-phase reactants may be maintained including multitube, parallel plate and annular reactors. While the method of the invention is preferably carried out in falling film reactors having vertically disposed reactor
  • the high velocity of the flowing gas renders it possible to dispose the reactor surfaces in
  • the lengths of reactors used according to the present invention must preferably be longer, in the range of from two to five-times, than those wherein reactions are carried out under lower pressure-drop or lower vapor flowrate conditions. Accordingly, the length of the surface where reaction occurs within the reactors is preferably between about 15 and about 60 feet and most preferably between about 20 and about 40 feet. Whatever length of reactor is chosen, it is important to maintain a relatively' small equivalent diameter for the reactor in order that an adequate velocity of the gaseous agent can be generated such that a buildup of thickness of reaction product on the reactor surface does not
  • the method of the invention is sensitive with respect to reaction temperature such that the optimum temperature for reaction may be neither too hot nor too cold.
  • a heat exchanging surface is generally
  • a preferred temperature range for heat transfer fluid in the cooling jacket contacting the reactor walls ranges from about 180°F to about 220°F.
  • Hotter heat transfer fluid tends to reduce the viscosity of the reaction product in the thin film but can induce the production of undesired oxidation by-products.
  • cooler heat transfer fluid removes more heat from the reactor and reduces the rate of side reactions but increases the viscosity of the film of reaction product which inhibits penetration of sulfur trioxide and leads to a less-completely reacted product.
  • the method of the invention requires a high inlet pressure in the range of about 30 psig to 150 psig because of the requirement that there be a large
  • dry tube gas velocities be maintained in excess of about 40 feet per second at the upstream end of said reactor surface (reactor inlet) and in excess of about 200 feet per second at the downstream end of said reactor surface (reactor outlet).
  • the thickness of the film or reaction product on the walls of the reactor gradually increases as the feedstock and product materials flow to the bottom of the reactor.
  • the area of the reactor available for gas flow gradually decreases, thus restricting the gas flow and increasing the gas velocity.
  • the drop in pressure leads to expansion of the gas, further increasing the velocity of gas flow.
  • preferred pressure drops range from about 90 psi to about 120 psi where the feedstock is a branched precursor of ADEDS, but may be in the range of from about 70 psi to about 100 psi where the feedstock is a linear precursor of ADEDS.
  • Reactor outlet gas pressure is generally less than about 15 psig but depends on the degree of pressure drop required by downstream effluent gas processing equipment. Outlet pressures preferably range from about 5 to about 15 psig where the reactor discharge is to a gas-liquid separator but can be as low as 0 psig where the discharge is not directly to another piece of processing equipment.
  • the method of the present invention preferably utilizes feed gas with a sulfonating agent (preferably sulfur trioxide) concentration ranging from about 1.4% to about 10.0% by volume, with concentrations ranging between about 1.4% and about 4.0% being
  • a sulfonating agent preferably sulfur trioxide
  • concentrations of about 2.5% sulfur trioxide being particularly preferred.
  • the reaction product is discharged from the reactor at a temperature of about 200°F. Unlike certain prior art processes, it is preferred that cooled
  • reaction product not be recycled to the reactor. While recycling material will not necessarily hurt the
  • reaction product tends to be so viscous that it cannot readily be pumped to the reactor for recycling.
  • the method of the invention is thus useful in the production of monosulfonates by
  • dialkyl benzenes having C 8 -C 20 sidechains dialkyl toluenes having C 8 -C 20 sidechains, alkyl benzenes having C 18 -C 40 sidechains, polyisopropyl naphthalenes with molecular weights ranging from 300 to 600, isobutanes with total molecular weights ranging from 300 to 500, dialkyl phenols with C 8 -C 12 sidechains, dialkyl naphthalenes with C 6 -C 12 sidechains (which can also be disulfonated), C 6 -C 12 cocomonoglycerides (ester of coconut fatty acids and glycerine).
  • Feedstocks which can be disulfonated include biphenyl alkanes with C 6 -C 18 alkane groups, diphenyl ether, diphenyl alkanes with C 6 -C 18 alkane groups, alkyl benzene sulfones with C 6 -C 18 sidechains. It would be necessary to vary specific process
  • a film reactor was used to carry out a sulfonation reaction on alkyl diphenyl ether feedstocks according to the method of the invention.
  • the film reactor had a 25 foot vertical reactor surface and was operated without a recycle quench to react a feedstock with a sulfur trioxide gas mixture.
  • the cooling water temperature is indicated for water on a single reactor cooling surface, although in certain indicated situations, multiple segment reactor cooling surfaces having
  • branched dodecyl diphenyl ether BDDE feedstock was reacted with sulfur trioxide in the 25 foot vertical film reactor according to the method of the invention as well as in a standard 5 foot film reactor under the conditions specified in

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

On décrit un procédé permettant de sulfoner un réactif organique qui donne de ce fait un produit de réaction de sulfonation visqueux à la viscosité nettement supérieure à 1500 contipoises pour une température de réaction telle que ce produit de réaction de sulfonation réagisse complétement à raison de plus de 85 % de son poids. Ce procédé implique d'utiliser un réacteur allongé clos dépassant environ 15 pieds de long et doté d'extrémités amont et aval et d'une surface échangeuse de chaleur. Il implique aussi de faire s'écouler en parallèle un film de réactif organique et un agent gazeux de sulfonation vers le bas du réacteur tout en plaçant cet agent de sulfonation sous pression sur ladite surface du réacteur et en prévoyant une chute de pression entre les extrémités amont et aval du réacteur afin de conférer assez de vélocité à l'agent gazeux de sulfonation pour que s'amincisse le film constitué par le produit visqueux de sulfonation. La surface du réacteur est suffisamment longue pour que ce film soit au contact du mélange gazeux à haute vélocité assez longtemps pour donner un produit de réaction de sulfonation ayant complètement réagi à raison d'au moins 85 % de son poids.
PCT/US1992/001684 1990-08-23 1992-03-03 Procede de sulfonation destine a l'acide sulfonique visqueux Ceased WO1993017992A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US07/571,751 US5136088A (en) 1990-08-23 1990-08-23 Sulfonation process for viscous sulfonic acid
PCT/US1992/001684 WO1993017992A1 (fr) 1990-08-23 1992-03-03 Procede de sulfonation destine a l'acide sulfonique visqueux
DE69229045T DE69229045T2 (de) 1992-03-03 1992-03-03 Sulfonierungsverfahren für viskose sulfonsäure
EP92913608A EP0587774B1 (fr) 1990-08-23 1992-03-03 Procede de sulfonation destine a l'acide sulfonique visqueux
CA002102176A CA2102176C (fr) 1990-08-23 1992-03-03 Procede de sulfonation d'acide sulfonique visqueux

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/571,751 US5136088A (en) 1990-08-23 1990-08-23 Sulfonation process for viscous sulfonic acid
PCT/US1992/001684 WO1993017992A1 (fr) 1990-08-23 1992-03-03 Procede de sulfonation destine a l'acide sulfonique visqueux
CA002102176A CA2102176C (fr) 1990-08-23 1992-03-03 Procede de sulfonation d'acide sulfonique visqueux

Publications (1)

Publication Number Publication Date
WO1993017992A1 true WO1993017992A1 (fr) 1993-09-16

Family

ID=27169530

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/001684 Ceased WO1993017992A1 (fr) 1990-08-23 1992-03-03 Procede de sulfonation destine a l'acide sulfonique visqueux

Country Status (1)

Country Link
WO (1) WO1993017992A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427342A (en) * 1962-12-12 1969-02-11 Chemithon Corp Continuous sulfonation process
US4113438A (en) * 1976-05-27 1978-09-12 The Chemithon Corporation Sulfonating apparatus
US4816185A (en) * 1987-03-04 1989-03-28 Chevron Research Company Styrene alkylbenzene copolymers and sulfonates thereof and method of making

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427342A (en) * 1962-12-12 1969-02-11 Chemithon Corp Continuous sulfonation process
US4113438A (en) * 1976-05-27 1978-09-12 The Chemithon Corporation Sulfonating apparatus
US4816185A (en) * 1987-03-04 1989-03-28 Chevron Research Company Styrene alkylbenzene copolymers and sulfonates thereof and method of making

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0587774A4 *

Similar Documents

Publication Publication Date Title
CN100516092C (zh) 制备聚烯烃的方法
US3427342A (en) Continuous sulfonation process
US3420875A (en) Olefin sulfonates
US4212544A (en) Orifice plate mixer and method of use
CA2705155C (fr) Procede de polymerisation ou d'oligomerisation d'un hydrocarbure
EP0482687B1 (fr) Composition coulable liquide concentrée
EP2217551B1 (fr) Procede de polymerisation ou d'oligomerisation d'un hydrocarbure
KR20030090639A (ko) 중간-범위 비닐리덴 함량의 폴리이소부틸렌 및 그의 제조
US3270038A (en) Sulphonation of organic compounds
US4113765A (en) Continuous process for sulfonating alkyl aromatics
US4113438A (en) Sulfonating apparatus
US2139038A (en) Process for producing polymers of olefines
US3501276A (en) Apparatus for sulfonation of organic compounds
US5136088A (en) Sulfonation process for viscous sulfonic acid
US3535339A (en) Process and apparatus for the continuous reaction of organic compounds with undiluted sulfur trioxide
WO1993017992A1 (fr) Procede de sulfonation destine a l'acide sulfonique visqueux
CN112500280B (zh) 氢溴化方法
US3505418A (en) Method for monochlorinating paraffins
US4102911A (en) Sulfonating or sulfating method
US3620684A (en) Apparatus for continuous sulfonation
JP2541774B2 (ja) 粘性スルホン酸のためのスルホン化による製造方法
JP7649380B2 (ja) 内部オレフィンの製造方法、内部オレフィンスルホン酸塩の製造方法及び低温安定化方法
US2133735A (en) Method of reacting fluid reagents
CA1117133A (fr) Melangeur a plaque ajouree, et mode d'emploi connexe
US3313838A (en) Reaction of chlorosulfonic acid with alkoxylated alkyl phenols

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IT LU MC NL SE

WWE Wipo information: entry into national phase

Ref document number: 1992913608

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2102176

Country of ref document: CA

WWP Wipo information: published in national office

Ref document number: 1992913608

Country of ref document: EP

WWG Wipo information: grant in national office

Ref document number: 1992913608

Country of ref document: EP