WO2018015191A1 - Acides alcane-sulfoniques à faible corrosion pour réactions de condensation - Google Patents

Acides alcane-sulfoniques à faible corrosion pour réactions de condensation Download PDF

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Publication number
WO2018015191A1
WO2018015191A1 PCT/EP2017/067242 EP2017067242W WO2018015191A1 WO 2018015191 A1 WO2018015191 A1 WO 2018015191A1 EP 2017067242 W EP2017067242 W EP 2017067242W WO 2018015191 A1 WO2018015191 A1 WO 2018015191A1
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Prior art keywords
aqueous solution
reactor
reaction
condensation
added
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PCT/EP2017/067242
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English (en)
Inventor
Henning Urch
Michael Koch
Thomas PAASCHE
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Basf Se
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Application filed by Basf Se filed Critical Basf Se
Priority to AU2017298882A priority Critical patent/AU2017298882A1/en
Priority to BR112019000481A priority patent/BR112019000481A2/pt
Priority to US16/318,146 priority patent/US20190301027A1/en
Priority to CA3030989A priority patent/CA3030989A1/fr
Priority to EP17735577.3A priority patent/EP3485063A1/fr
Priority to JP2019502230A priority patent/JP2019524999A/ja
Priority to CN201780044428.8A priority patent/CN109477225A/zh
Priority to KR1020197001853A priority patent/KR20190028444A/ko
Publication of WO2018015191A1 publication Critical patent/WO2018015191A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/163—Sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
    • C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
    • C11C3/04—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by esterification of fats or fatty oils
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
    • C23F11/181—Nitrogen containing compounds

Definitions

  • the present invention relates to methods for adding an aqueous solution of alkane sulfonic acids to a reactor via a pipe or container, wherein a condensation reaction takes place after addition of the aqueous solution of alkane sulfonic acid and to methods for reducing or limiting corrosion by adding said aqueous solution to a reactor.
  • the present invention also relates to the use of aqueous solutions of alkane sulfonic acids in the reduction or limitation of corrosion and to the use of such aqueous solutions in condensation reactions.
  • Condensation reactions are reactions where two or more molecules or moieties of one molecule are combined to a single molecule accompanied by the loss of small molecules.
  • Well known condensations comprise those where water is released during formation of the single molecule, but also other small molecules may be released. It is also possible that separate moieties within the same molecule may react with one another to reform the molecule (intramolecular condensation reaction) which is typically accompanied by the formation of a ring ( Bruckner, R., Reak- tionsmechanismen, 2. Aufl.; Spektrum: Heidelberg, (2002), S. 388-389; Ullmann's Encyclopedia of Industrial Chemistry, 6. Aufl.; Wiley-VCH: Weinheim, (2002), 16, 241-245).
  • a typical example of a condensation reaction is an esterification between a carboxylic acid and an alcohol, producing an ester and one water molecule.
  • Condensations may occur intramolecular or intermolecular, either between only two molecules or more molecules to form a condensation polymer (polycondensation).
  • Many condensations are acid catalyzed.
  • a variety of acids is generally suitable, e.g., organic acids or inorganic acids.
  • Strong acids like sulfuric acid, p-toluenesul- fonic acid or methanesulfonic acid are often preferred since they enable a faster reaction.
  • strong acids have the disadvantage that they induce corrosion such as formation of iron oxides (rust) on metal surfaces which are contacted with such acids, either during the condensation reaction or when adding the acid catalyst to the reaction.
  • Some strong acids are known to induce less corrosion than others.
  • alkane sulfonic acids such as methanesulfonic acid (MSA) are less corrosive towards stainless steel compared to sulfuric acid, and hence have become more popular in recent years.
  • Methods for preparing alkane sulfonic acids are known in the art, e.g., WO 2000/031027, WO 2015/086645, WO 201 1/054703, or US 4,450,047.
  • the acid catalyzed condensation reaction is an equilibrium reaction and involves the elimination of water
  • higher acid concentrations in the catalyst solution normally lead to higher corrosion rates, especially in storage tanks, pipelines, fittings, etc., which are very often made of steel materials. Higher corrosion rates may also appear in the reactor, especially at the beginning of the reactant dosage. Accordingly, it is desirable to use as little acid catalyst as possible in order to minimize corrosion.
  • a higher acid catalyst dosage normally leads to a faster reaction and hence a more efficient process.
  • the present invention relates to a method of adding an aqueous solution (A) to a reactor, wherein said aqueous solution (A) is added to the reactor via a pipe or a container,
  • reactor, pipe and/or container has a corrosive surface (e.g., a surface containing iron), and
  • said aqueous solution (A) contains about 80 to 99 w/w%, preferably about 80 to 98, 85 to 98, 88 to 98, 90 to 98, 92 to 97, 92 to 96, or 93 to 95w/w of an alkane sulfonic acid, relative to the total weight of said aqueous solution (A).
  • a reaction takes place in said reactor after the addition of said aqueous solution (A) into the reactor, wherein said aqueous solution (A) is either a reactant (e.g., an educt), a solvent, a neutralizer, or a catalyst for said reaction.
  • a reactant e.g., an educt
  • solvent e.g., a solvent
  • neutralizer e.g., sodium bicarbonate
  • catalyst for said reaction e.g., sodium bicarbonate, sodium bicarbonate
  • said aqueous solution (A) may be the catalyst for an acid catalyzed reaction or a neutralizer for a base catalyzed reaction; see, e.g., EP 2358851.
  • the reaction which takes place in the reactor after addition of the aqueous solution (A) is a condensation reaction, for example an acid catalyzed condensation reaction.
  • an aqueous solution (A) containing about 80 to 99 w/w% of an alkane sulfonic acid is able to drastically reduce the corrosion rate on a corrosive surface (e.g. a surface containing iron), compared to an aqueous solution comprising less than about 80 w/w% or more than about 99 w/w% of such alkane sulfonic acid.
  • a corrosive surface e.g. a surface containing iron
  • nitric acid or a salt thereof e.g., an (earth) alkali metal salt of nitrate
  • the addition of small amounts of nitric acid or a salt thereof can further reduce the corrosion rate.
  • the present invention also relates to a method for reducing the corrosion rate of the corrosive surface (e.g., an iron containing surface), comprising adding an aqueous solution (A) which contains about 80 to 99 w/w%, preferably about 80 to 98, 85 to 98, 88 to 98, 90 to 98, 92 to 97, 92 to 96, or 93 to 95 w/w% of an alkane sulfonic acid, relative to the total weight of said aqueous solution (A) to a corrosive surface (e.g., an iron containing surface).
  • a corrosive surface e.g., an iron containing surface
  • the corrosive (e.g., iron containing) surface may be the surface of a reactor, a pipe and/or a container.
  • said aqueous solution (A) is added to the reactor via said pipe and/or container.
  • the term "reducing" corrosion means that the corrosion rate is lower compared to when an aqueous solution containing more or less of the alkane sulfonic acid as defined herein is applied to said reactor, pipe and/or container.
  • “Lower” in this context means that the formation of corrosion is at least about 1.2-fold, at least 1.5-fold, at least 1.8-fold, or at least 2-fold or even 2.5-fold lower.
  • the present invention relates to a method for limiting the corrosion rate of a corrosive surface (e.g., an iron containing surface) to a rate of max. about 0.3 mm/year, preferably max. about 0.25 mm/year, max. 0.2 mm/year, max.
  • a corrosive surface e.g., an iron containing surface
  • aqueous solution (A) which contains about 80 to 99 w/w%, preferably about 80 to 98, 85 to 98, 88 to 98, 90 to 98, 92 to 97, 92 to 96, or 93 to 95 w/w% of an alkane sulfonic acid, relative to the total weight of said aqueous solution (A) to a corrosive surface (e.g., an iron containing surface).
  • the corrosive (e.g., iron containing) surface may be the surface of a reactor, a pipe and/or a container.
  • said aqueous solution (A) is added to the reactor via said pipe and/or container.
  • corrosion means any kind of chemical and/or electrochemical conversion of a metal to a chemically more stable form and particularly comprises the oxidation of a metal, particularly the oxidation of iron (rust formation).
  • the "corrosion rate” as used herein means the degree of the formation of corrosion and can be measured by methods known in the art and as also described and exemplified herein. Typically, the corrosion rate is indicated in mm/year. Methods for measuring the corrosion rate are described for example in DIN 50905 (part 2) or ASTM G31 -72 and as further described and exemplified herein.
  • the iron containing surface e.g. that of a reactor, a pipe and/or a container which is/are contacted with an aqueous solution (A) as described herein, may be of any material containing iron.
  • such surface is of an iron containing mate- rial which has the general ability to corrode (e.g., to rust) when exposed to oxygenizing compounds (oxidants) such as oxygen, sulfur, or organic or inorganic acids (preferably organic acids such as, e.g., alkane sulfonic acid, sulfuric acid, citric acid, acetic acid, or others).
  • oxygenizing compounds oxidants
  • oxygen, sulfur, or organic or inorganic acids preferably organic acids such as, e.g., alkane sulfonic acid, sulfuric acid, citric acid, acetic acid, or others.
  • such iron containing material may comprise any kind of iron alloys such as, e.g., cast iron alloys, austenitic steel alloys (see, e.g., Rompp Online, Version 3.5, Georg Thieme Verlag 2009), (stainless) steel alloys (e.g., steel alloys according to the SAE designation; see, e.g., Jef- fus, Cengage Learning (2002), Welding: Principles and Applications), elinvar, fernico, ferroalloys, invar, kovar, staballoys, and others.
  • iron alloys such as, e.g., cast iron alloys, austenitic steel alloys (see, e.g., Rompp Online, Version 3.5, Georg Thieme Verlag 2009), (stainless) steel alloys (e.g., steel alloys according to the SAE designation; see, e.g., Jef- fus, Cengage Learning (2002), Welding: Principles and Applications), el
  • iron alloys may comprise further (metal) compounds such as, e.g., nickel, chromium, cobalt, carbon, molybdenum, hydrogen, manganese, silicon, nitrogen, and/or others.
  • the iron containing surface may be an iron (e.g., steel) alloy comprising about 10 to 22, 12 to 20, or 13 to 17 w/w% chromium, and/or about up to 0.20 w/w% or about 0.02 to 0.15 w/w%, or 0.05 to 0.12 w/w% carbon, and/or about 15 to 22 w/w% chromium and about 9 to 15 w/w% nickel.
  • the chromium content may be about 16 to 20 w/w%, and/or the nickel content may be about 10 to 14 w/w%, and/or manganese in an amount of about 1 to 3 w/w%.
  • Other metals may be contained in various amounts, for example about 1 to 5 (preferably 1.5 to 4 or 2 to 3) w/w% molybdenum, and/or about 0.1 to 2 or 0.5 to 1 w/w% titanium. It is also possible that such steel alloys do not contain chromium, nickel, or molybdenum, for example they do not contain nickel and/or molybdenum.
  • such iron alloys may also be passivized by a passivation layer formed by, e.g., chromium in the presence of ambient air or oxygen.
  • a passivation layer formed by, e.g., chromium in the presence of ambient air or oxygen.
  • the iron containing surface which is contacted with an aqueous solution (A) as described herein may be a steel alloy, e.g., a carbon steel alloy according to DIN EN 10088, AISI, SAE designation or others.
  • Examples of steel alloys in context with the present invention comprise those listed in Table 1 , 2, 3, or 4.
  • Table 1 Steel alloy examples according to AISI and DIN EN 10088 classification including respective selected contents of Cr, Ni, Mo, and C
  • Examples for iron containing surfaces as contacted with the aqueous solution (A) as described herein comprise steel alloys listed in Table 2 herein, e.g. those selected from the group consisting of 1.4401 , 1 .4404, 1.4541 , 1.4571 , 1 .4462, 1.4539, 1.4016, and 1.4006 according to DIN EN 10088-3.
  • Particular examples comprise 1 .4401 , 1.4404, 1.4541 , 1.4571 , 1.4462, 1.4539, 1.4016, and 1.4006, more particularly 1.4401 , 1 .4404, 1.4541 , 1.4571 , 1.4016, and 1.4006, more particularly 1.4016, and 1.4006 (all numbers according to DIN EN 10088-3).
  • the term "reactor" which is contacted with the aqueous solution (A) containing an alkane sulfonic acid as described herein may be of any size and shape suitable to allow a (condensation) reaction to take place and has a corrosive surface (e.g., an iron containing surface) as defined herein above and below.
  • a corrosive surface e.g., an iron containing surface
  • Examples are batch reactors, stirred tank reactors or tubular reactors. The reactor can be operated in continuous, batch or semi-batch mode.
  • the "pipe” as used in context with the present invention has a corrosive surface (e.g., an iron containing surface) as defined herein above and below and is employed to add the aqueous solution (A) containing an alkane sulfonic acid as described herein to the reactor.
  • the pipe may be of any size or shape suitable to add the aqueous solution (A) to the reactor, e.g., it may be round or contain edges (preferably it is round), it may be a tube which is closed except the entry and the outlet opening, it may be a channel, it may have a continuous diameter or be formed as a nozzle (i.e. with a larger diameter at one end and a reduced diameter at the other end), or have other or combined forms.
  • the "container” as used in context with the present invention has a corrosive surface (e.g., an iron containing surface) as defined herein above and below and is employed to add the aqueous solution (A) containing an alkane sulfonic acid as described herein to the reactor, either in addition or as an alternative to the pipe.
  • the container may be of any size or shape suitable to add the aqueous solution (A) to the reactor, e.g., it may be a bottle, a flask, a container, a barrel, a tank, a can, or the like.
  • the corrosive (e.g., iron containing) surface e.g. that of the reactor, pipe and/or container is contacted with the aqueous solution (A) in the presence of oxygen, e.g., in the presence of ambient air.
  • the aqueous solution (A) as described herein and to be employed in context with the present invention contains an alkane sulfonic acid in an amount of about 80 to 99 w/w%, preferably about 80 to 98, 85 to 98, 88 to 98, 90 to 98, 92 to 97, 92 to 96, or 93 to 95 w/w% of an alkane sulfonic acid, relative to the total weight of said aqueous solution (A).
  • the alkane sulfonic acid may be selected from methane sulfonic acid, ethane sulfonic acid, or higher alkane sulfonic acids (e.g., Ci to C20 alkane sulfonic acid, linear or branched, preferably linear).
  • the alkane sulfonic acid of the aqueous solution (A) is methane sulfonic acid (MSA).
  • the aqueous solution (A) may further comprise nitric acid or salts thereof (e.g., (earth) alkali salts of nitrates such as Na- Nitrate, Mg-Nitrate, K-Nitrate, or others).
  • nitric acid or salts thereof e.g., (earth) alkali salts of nitrates such as Na- Nitrate, Mg-Nitrate, K-Nitrate, or others.
  • the aque- ous solution (A) may further comprise up to about 2000 ppm nitric acid or salts thereof, preferably about 100 to 1500 ppm, 300 to 1300 ppm, 500 to 1200 ppm, or 700 to 1000 ppm.
  • the aqueous solution (A) as described herein is added via a pipe and/or a container to the reactor wherein inter alia a(n) (acid catalyzed) condensation reaction may take place in said reactor after the addition of said aqueous solution (A) into the reactor.
  • a(n) (acid catalyzed) condensation reaction may be of any kind. In context of the present invention, for example it may be selected from the group consisting of esterification, etherification, Aldol condensation, intramolecular condensation (cyclization), polycondensation, silica condensation, phosphate condensation, rearrangement, dehydration, and others.
  • a typical example for a condensation reaction is a water releasing condensation reaction.
  • a more particular example in this context may be an esterification, for example an esterification between a carboxylic acid and an alcohol, producing an ester and one water molecule. Examples comprise the production of dimethyl ether or diethyl ether.
  • Esterifications as used herein comprise generally reactions between an acid and an alcohol under elimination of water.
  • Suitable acids can be inorganic or organic acids, preferably organic ac- ids.
  • Organic acids can be any kind of aliphatic or aromatic carboxylic acids.
  • Aliphatic carboxylic acids can have linear or branched hydrocarbon chains, which might be saturated or unsaturated (e.g. double bonds or triple bonds), and might have additional functional groups.
  • Alcohols can be monofunctional (e.g. methanol), diols (e.g. ethylene glycol) or polyols (e.g. glycerine).
  • esterification reactions comprise the production of acrylates, plasticizers, acetates (sol- vent esters), oleochemical esters, cellulose acetate or polyesters.
  • a specific example of oleo- chemical esters is the production of fatty acid methyl ester (FAME) from various fatty acid containing feedstocks, and methanol, which is an essential step in the production of biodiesel.
  • FAME fatty acid methyl ester
  • the esterification might also be accompanied by an acid catalyzed transesterifica- tion, as described in WO 201 1/018228.
  • esterification reactions are known in the art and also exemplified herein, see, e.g., EP127104WO 2015/063189, WO 2013/064775, or US 6,673,959.
  • Polycondensations are a specific form of polymerization reactions.
  • the polymers are produced from bifunctional or polyfunctional compounds (monomers) by elimination of small molecules (e.g. water, alcohols, hydrogen halides). Examples are the formation of polyesters, polyamides, polyacetales and resins (phenolic resins, furanic resins, epoxy resins, amino resins, etc.).
  • the reaction which takes place in the reactor as described herein is an acid catalyzed reaction, preferably an acid catalyzed condensation reaction.
  • condensation reaction is an esterification as known in the art and as also described and exemplified herein, for example an esterification of one or more carboxylic acids with one or more alcohols, an esterification of one or more fatty acids with one or more alcohols, or an esterification of one or more fatty acids with methanol.
  • condensation reactions in organic synthesis comprise acyloin condensation, aldol condensation, benzoin condensation, Claisen condensation, Claisen-Schmidt condensation, Darzens condensation, Dieckmann condensation, Guareschi-Thorpe condensation, Knoevenagel condensation, Michael condensation, Pechmann condensation, Rap-Stormer condensation, Ziegler condensation, or Beckmann rearrangement.
  • aqueous solution (A) leads to a reduced or limited corrosion rate on iron containing surfaces. Particularly acids are known to be corrosive to iron containing surfaces.
  • water oxygen comprised by water
  • water may contribute to the formation of corrosion, depending on the iron alloy which is contacted with the aqueous solution (A). Accordingly, as the amount of water in a water-releasing condensation reaction may increase over time, it is possible that the corrosion rate may increase as it exceeds the water amount which was initially comprised by the aqueous solution (A) which was added to the reactor.
  • the total water content comprised by all components added to the reactor does not exceed about 20 w/w%, preferably about 15, 12, 10, 8, 7, 6, 5, 4, 3, 2 or 1 w/w% relative to the total amount of all components added to the reactor.
  • water formed by the condensation reaction over time may be removed in order not to allow the water content of the condensation reaction mixture to exceed the water which was added to the reactor by the addition of the aqueous solution (A), or not to allow the total water content comprised by all components added to the reactor to exceed about 20 w/w%, preferably about 15, 12, 10, 8, 7, 6, 5, 4, 3, 2 or 1 w/w% relative to the total amount of all components added to the reactor.
  • Such water removal can be performed by methods known in the art, e.g., by evaporation, distillation, adsorption or phase separation.
  • the educts and further components e.g., catalysts, solvents, neutralizer, or reactants other than educts
  • the educts and further components for the (condensation) reaction may be added to the reactor before, during, or after the aqueous solution (A) is added to the reactor.
  • suitable educts and further components for respective (condensation) reactions and it is also described and exemplified herein.
  • the corrosiveness of acids and/or water increases as temperature increases. That is, the effect which has been found in context with the present invention that the aqueous solution (A) as defined and to be employed as described herein leads to an reduced or limited corrosion rates on corrosive surfaces such as iron containing surfaces may be even higher at elevated temperatures.
  • the temperature of the aqueous solution (A) as described herein or the temperature of any mixture comprising the aqueous solution (A) and further educts or further compounds as added to the reactor where the (condensation) reaction may take place is at least about 20 °C, preferably at least about 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 ° C, 70 °C, 75 °C, or 80 °C when contacted with the corrosive (e.g., iron containing) surface, either during or after addition of the (mixture comprising) the aqueous solution (A) to the pipe, to the container, and/or to the reactor as described herein.
  • the corrosive e.g., iron containing
  • the (mixture comprising) the aqueous solution (A) may have a temperature of at least about 20 °C, preferably at least about 30 °C, 35 °C, 40 °C, 45 °C, 50 °C, 55 °C, 60 °C, 65 °C, 70 °C, 75 °C, or 80 °C when added to the reactor, pipe, and/or container, or when stored in the reactor, pipe, and/or container, or before or during any reaction as described herein takes place in said reactor.
  • the temperature may increase in the reactor once a (conden- sation) reaction as described herein has started and/or it may be intentionally increased in order to have such (condensation) reaction started.
  • a water releasing reaction e.g., water releasing condensation reaction
  • the temperature in the pipe, the container, and/or the reactor may be measured before, during or after (e.g., before) the (condensation) reaction starts, either during or after addition of the (mixture comprising the) aqueous solution (A) to the pipe, to the container, and/or to the reactor.
  • the temperature may be measured before the total amount of water contained in the reactor exceeds the amount of water comprised by the aqueous solution (A) as described and to be employed as described herein.
  • further components added to the reactor such as educts and/or other components (e.g., catalysts, solvents, neutralizer, or reactants other than educts) are substantially free of water, i.e. one or more or all of such further components do not comprise more than about 5 w/w%, preferably less than about 4, 3, 2, 1 or 0.5 w/w% water, either alone or all such components in total.
  • the temperature may be measured before the total amount of water contained in the reactor exceeds about 20 w/w%, preferably about 15, 12, 10, 8, 7, 6, 5, 4, 3, 2 or 1 w/w% relative to the total amount of all components added to the reactor.
  • the educts and/or other components e.g., catalysts, solvents, neutralizer, or reactants other than educts
  • the educts and/or other components for the (condensation) reaction as added to the reactor are substantially free of water, for example they comprise water in an amount of less than about 5 w/w%, preferably less than 4, 3, 2, 1 or 0.5 w/w%.
  • the pressure applied to the reactor for the condensation reaction may be inter alia up to about 200 bar, preferably up to about 100 bar, or up to about 10 bar. In one embodiment, the pressure is up to about 5 bar, for example up to about 2 bar, ambient pressure or below about 1 bar (e.g., about 0.5 bar).
  • the aqueous solution (A) preferably acts as acid catalyst.
  • the aqueous solution (A) may be added in amount suitable for the respective (condensation) reaction which takes place after addition to the reactor.
  • the aqueous solution (A) may be added to the reactor in an amount of about 0.1 to 10 w/w%, preferably about 0.2 to 5, or 0.5 to 2 w/w%, relative to the total weight of all components added to the reactor.
  • the present invention further relates to the use of an aqueous solu- tion (A) as described herein for reducing or limiting the corrosion rate on an iron containing surface as defined herein.
  • A aqueous solu- tion
  • the present invention further relates to the use of the aqueous solution (A) in a (condensation) reaction as described herein.
  • the present invention further relates to the condensation products obtained or obtainable by a condensation reaction as described herein.
  • the singular forms "a”, “an”, and “the”, include plural references unless the context clearly indicates otherwise.
  • reference to “a reagent” includes one or more of such different reagents and reference to “the method” includes reference to equivalent steps and methods known to those of ordinary skill in the art that could be modified or substituted for the methods described herein.
  • the present invention particularly relates to the following items:
  • aqueous solution (A) is added to the reactor via a pipe or a container, wherein said reactor, pipe and/or container has a corrosive surface, and
  • said aqueous solution (A) contains about 80 w/w% to 99 w/w of an alkane sulfonic acid, relative to the total weight of said aqueous solution (A).
  • aqueous solution (A) further comprises nitric acid or salts thereof.
  • Method for reducing the corrosion rate of an iron containing surface comprising adding the aqueous solution (A) as described in any one of the preceding items to the iron con- taining surface.
  • Method for limiting the corrosion rate of an iron containing surface to a rate of max. 0.3 mm/year comprising adding an aqueous solution (A) as described in any one of the preceding items to the iron containing surface.
  • the following examples are illustrating the present invention without limiting the scope of the invention which is defined by the claims.
  • the corrosion behavior of corrosive media by means of gravimetric and visual assessment of metal coupons was determined. It was tailored to the different and therefore comprised different types of coupons, media (from acidic to alkaline), test temperature (room temperature to 80°C), potential corrosion inhibitors and test period of time.
  • the metal coupon was degreased in ethyl acetate and then rinsed with deionized water and dried. In order to avoid further contamination, the metal coupon was only touched with disposable gloves (e.g. Dermatril) after this treatment.
  • disposable gloves e.g. Dermatril
  • the coupon was charged with 100 g of the test solution in a PP beaker and then closed. 4.
  • the PP beaker with the coupon in the test solution was then stored at given temperatures (e.g., 40 °C, 60 °C, and 80 °C)
  • the coupon was removed with forceps, rinsed, dried and weighed. In addition, visual changes of the coupon and the solution were recorded. Then the coupon was placed into the test solution again.

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Abstract

La présente invention concerne des procédés pour ajouter une solution aqueuse d'acides alcane-sulfoniques à un réacteur par l'intermédiaire d'un tuyau ou d'un récipient, une réaction de condensation ayant lieu après l'addition de la solution aqueuse d'acide alcane-sulfonique, ainsi que des procédés pour réduire ou limiter la corrosion en ajoutant ladite solution aqueuse à un réacteur. L'invention concerne également l'utilisation de solutions aqueuses d'acides alcane-sulfoniques dans la réduction ou la limitation de la corrosion et l'utilisation de telles solutions aqueuses dans des réactions de condensation.
PCT/EP2017/067242 2016-07-18 2017-07-10 Acides alcane-sulfoniques à faible corrosion pour réactions de condensation WO2018015191A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
AU2017298882A AU2017298882A1 (en) 2016-07-18 2017-07-10 Low corrosion alkane sulfonic acids for condensation reactions
BR112019000481A BR112019000481A2 (pt) 2016-07-18 2017-07-10 método de adição de uma solução aquosa em um reator, e, uso de uma solução aquosa.
US16/318,146 US20190301027A1 (en) 2016-07-18 2017-07-10 Low corrosion alkane sulfonic acids for condensation reactions
CA3030989A CA3030989A1 (fr) 2016-07-18 2017-07-10 Acides alcane-sulfoniques a faible corrosion pour reactions de condensation
EP17735577.3A EP3485063A1 (fr) 2016-07-18 2017-07-10 Acides alcane-sulfoniques à faible corrosion pour réactions de condensation
JP2019502230A JP2019524999A (ja) 2016-07-18 2017-07-10 縮合反応のための低腐食性アルカンスルホン酸
CN201780044428.8A CN109477225A (zh) 2016-07-18 2017-07-10 用于缩合反应的低腐蚀链烷磺酸
KR1020197001853A KR20190028444A (ko) 2016-07-18 2017-07-10 축합 반응을 위한 낮은 부식 알칸 술폰산

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EP16179881 2016-07-18

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BR (1) BR112019000481A2 (fr)
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CA3030989A1 (fr) 2018-01-25
BR112019000481A2 (pt) 2019-04-24
US20190301027A1 (en) 2019-10-03
JP2019524999A (ja) 2019-09-05
AU2017298882A1 (en) 2019-01-17
KR20190028444A (ko) 2019-03-18
EP3485063A1 (fr) 2019-05-22

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