(19)
(11)EP 3 183 100 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
31.03.2021 Bulletin 2021/13

(21)Application number: 15757169.6

(22)Date of filing:  13.08.2015
(51)Int. Cl.: 
C07C 51/42  (2006.01)
B27N 1/00  (2006.01)
C08H 8/00  (2010.01)
C07C 51/44  (2006.01)
C07C 57/08  (2006.01)
(86)International application number:
PCT/EP2015/068679
(87)International publication number:
WO 2016/026768 (25.02.2016 Gazette  2016/08)

(54)

PROCESS FOR THE RECOVERY OF CARBOXYLIC ACID AND WOOD TREATMENT PROCESS

VERFAHREN ZUR RÜCKGEWINNUNG VON CARBONSÄURE UND HOLZBEHANDLUNGSVERFAHREN

PROCÉDÉ DE RÉCUPÉRATION D'ACIDE CARBOXYLIQUE ET PROCÉDÉ DE TRAITEMENT DU BOIS


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 19.08.2014 EP 14181419

(43)Date of publication of application:
28.06.2017 Bulletin 2017/26

(73)Proprietor: Rhodia Acetow GmbH
79108 Freiburg (DE)

(72)Inventors:
  • KRUMREY, Thomas
    79331 Teningen (DE)
  • HUMMEL, Andreas
    79108 Freiburg (DE)
  • HÖLTER, Dirk
    79312 Emmendingen (DE)

(74)Representative: Trinks, Ole et al
Meissner Bolte Patentanwälte Rechtsanwälte Partnerschaft mbB Postfach 10 26 05
86016 Augsburg
86016 Augsburg (DE)


(56)References cited: : 
EP-A1- 2 546 228
GB-A- 2 301 101
US-A- 4 221 921
WO-A2-2011/022801
US-A- 3 132 177
US-A- 5 777 101
  
  • JEROEN VAN BUIJTENEN ET AL: "Furfural Production by 'Acidic Steam Stripping' of Lignocellulose", CHEMSUSCHEM, vol. 6, no. 11, 31 July 2013 (2013-07-31), pages 2132-2136, XP055124101, ISSN: 1864-5631, DOI: 10.1002/cssc.201300234
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

Amended description



[0001] The present invention concerns a process for the recovery of carboxylic acid from a fraction comprising carboxylic acid and impurities, and a process for the manufacture of treated wood. Such a recovery process is advantageous in various industries to enhance the cost-efficiency by recycling of carboxylic acid from impure carboxylic acid, for example from an acylation process, in particular in wood treatment processes such as wood acetylation. Wood acetylation uses acetic anhydride as acetylation reagent, yielding an impure carboxylic acid fraction as waste stream. Treated wood, in particular acetylated wood, is industrially valuable e.g. as construction material, presenting high service life and excellent resistance against environmental conditions and pathogens.

[0002] A wood acetylation process is described, for example in EP 0680810.

[0003] In order to enhance the efficiency and overall economics of chemical processes using carboxylic acid derivatives, which are preferably processes of acylation, in particular acetylation; often, of materials comprising polysaccharides, such as cellulose; often in particular a wood treatment process, the present invention now proposes a process for the recovery of carboxylic acid from a fraction comprising carboxylic acid and impurities.

[0004] US2012/0123160 A1 discloses a process for the recovery of acetic acid from a stream containing carboxylic acid anhydride and carboxylic acid by hydrolysis of the carboxylic acid anhydride and subsequent distillation of the hydrolyzed stream to produce a separated stream containing carboxylic acid and water and a product stream comprising carboxylic acid.

[0005] US 5,777,101 discloses a process for the acetylation of lignocellulosic materials such as wood, wherein the lignocellulosic material is reacted with a mixture of acetic acid an acetic anhydride and wherein the thus treated lignocellulosic material is then contaced with a heated gas such as nitrogen to remove excess acetic acid or acetic anhydride by stripping to provide acetylated product.

[0006] It has been found, surprisingly, that the process according to the invention, in all its embodiments, allows for efficient recovery of carboxylic acid from waste carboxylic acid fractions, in particular waste carboxylic acid fractions obtained from a process of acylation, in particular acetylation, often of materials comprising polysaccharides, such as cellulose; often in particular a wood acetylation process. By applying a stripping operation to a fraction containing carboxylic acid and impurities, it is possible to substantially reduce the impurities in the carboxylic acid fraction. Often, impurities are substantially removed by this operation. This is especially the case of halogenated organic and inorganic impurities; other organic impurities typically found in carboxylic acid waste streams coming from a process of acylation, in particular acetylation; often, of materials comprising polysaccharides, such as cellulose; often in particular wood acetylation processes, such as terpenes, are also substantially reduced. The recovered carboxylic acid fraction often is found to be sufficiently pure to be used as starting material, in particular for recycling in the wood treatment industry, e.g. for further production of acylating agents. A significant improvement has been surprisingly found in the reduced corrosivity of the recovered carboxylic acid fraction. The process according to the invention has important advantages concerning process operation, e.g. avoiding corrosion of apparatus, avoidance of additional separation steps, such as distillation, and reduction of impurities during the stripping procedure. The process therefore displays significant economic and environmental advantages over known recovery processes of carboxylic acid.

[0007] Consequently, in its broadest embodiment, the present invention concerns a process for the recovery of carboxylic acid, in particular acetic acid, from a fraction containing carboxylic acid and impurities, as described in claim 1. I.a. the process comprises submitting said fraction to a gas stripping operation and recovering at least a purified carboxylic acid fraction. In a preferred embodiment, the invention concerns the recovery of carboxylic acid, in particular acetic acid, from a fraction containing carboxylic acid and impurities, which comprises the steps of pretreating the carboxylic acid fraction with water, submitting said fraction to a gas stripping operation and recovering at least a purified carboxylic acid fraction. A process of manufacturing treated wood, in particular acetylated wood, comprising the aforementioned process steps is also object of the present invention.

[0008] In the process according to the invention, the carboxylic acid is a carboxylic acid selected from C1 to C6 alkyl carboxylic acids, wherein the term "C1 to C6 alkyl carboxylic acids" includes C1 to C6 linear carboxylic acids as well as C4 to C6 branched carboxylic acids. Particular examples include propionic and, preferably, acetic acid. The alkyl carboxylic acids can optionally be substituted by at least one substituent selected from the group consisting of halogen atoms (in particular F, Cl or Br), OH, CN and COOR, R denoting a C1 to C4 linear or branched alkyl group. The term "fraction containing carboxylic acid" also concerns fractions containing mixtures of two or more of the previously described carboxylic acids.

[0009] In the process according to the invention the fraction containing carboxylic acid and impurities contains hydrogen halides, and/or carboxylic acid halides. The term "impurities" intends to denote inorganic and organic impurities. Typically, the impurities originate from the process by which the fraction containing carboxylic acid and impurities in generated. The process by which the fraction is generated often is a process of acylation, in particular acetylation, often of materials comprising polysaccharides, such as cellulose; often in particular a wood acetylation process. Non-limiting examples of organic impurities are carboxylic acid anhydride, halogenated organic impurities such as carboxylic acid halides, which include carboxylic acid chlorides, bromides and iodides, in particular acetyl chloride, and terpenes and/or terpenoids. Inorganic impurities which can be present are, for example, hydrogen halides HCI, HBr, HI, and also metal salts, for example chlorides or bromides such as NaBr or NaCl. The salts are typically found in a fraction which is generated by a process of acylation, in particularly acetylation, of materials which comprise polysaccharides, such as cellulose; in particular, a wood treatment process. A number of impurities, such as hydrogen halides and/or carboxylic acid halides, and salts have corrosive characteristics which necessitate expensive, corrosion resistant equipment downstream, quality problems such as discoloration in the product and other issues. Reducing the corrosive and other impurities therefore is of great importance.

[0010] Often, the fraction containing carboxylic acid and impurities contains carboxylic acid anhydride as impurity. The carboxylic acid anhydride typically corresponds to the carboxylic acid contained in said fraction in the sense that the carboxylic acid anhydride is the anhydride of the carboxylic acid contained in the fraction. If a mixture of two or more carboxylic acids is contained in the fraction, one or more carboxylic acid anhydrides can be present, which can either be symmetrical carboxylic acid anhydride or mixed carboxylic acid anhydride. A mixed carboxylic acid anhydride yields two different carboxylic acids upon hydrolysis, whereas a symmetrical anhydride yields one carboxylic acid upon hydrolysis. Often, the carboxylic acid fraction containing impurities contains up to 80 weight %, preferably up to 70 weight %, more preferably up to 60 weight % and most preferably up to 50 weight % of carboxylic acid anhydride or mixtures of more than one carboxylic acid anhydrides. Non-limiting examples of inorganic impurities which can be comprised in the fraction containing carboxylic acid and impurities are metal salts and/or hydrogen halides, such as HCI and/or HBr. In a preferred embodiment of the invention, the fraction containing carboxylic acid and impurities is a waste stream generated by a process of acylation, in particular acetylation; often, of materials comprising polysaccharides, such as cellulose; often in particular wood treatment processes.

[0011] It has been found that the content of impurities of a fraction containing carboxylic acid and impurities can effectively be reduced by subjecting said fraction to a stripping operation to obtain at least a purified carboxylic acid fraction.

[0012] The term "stripping operation" denotes the introduction of a gas stream into a liquid volume containing a mixture of at least two substances of differing volatility. The term "stripping" also includes the terms sparging, bubbling or gas flushing. Generally, the at least one impurity which is at least partially removed by stripping out of the fraction containing carboxylic acid and impurities possesses a higher volatility than the carboxylic acid remaining in the liquid phase. The at least one impurity which is at least partially removed out of the fraction containing carboxylic acid and impurities by stripping can be an absorbed gas, which is desorbed by stripping, or a liquid with a higher volatility compared to the carboxylic acid. Non-limiting examples of impurities, whose content in the fraction containing carboxylic acid is reduced by stripping, include halogenated impurities such as hydrogen halides, for example HCI or HBr; halogenated, preferably chlorinated, organic impurities such as carboxylic acid chloride, preferably acetyl chloride; or other organic impurities such as carboxylic acid anhydride or terpenes and/or terpenoids. The stripping operation is performed using at least one gas selected from the group consisting of air, oxygen, CO2, exhaust gas, and inert gases, preferably helium, nitrogen, argon or xenon. Gas mixtures of two or more of the foregoing gases are also suitable. The stripping operation according to the present invention is performed in an apparatus suitable for a gas stripping operation. Such apparatus includes, but is not limited to, packed tower strippers, diffused gas (aeration) strippers, tray strippers or mechanical strippers such as the Hazleton Maxi-strip® System. Packed tower strippers are preferred. Depending on the stripping apparatus, the stripping gas or stripping gas mixture is introduced to the fraction containing carboxylic acid and impurities by introducing the fraction containing carboxylic acid and impurities descending over porous packings, wherein the gas is blown through the packing pores, stripping off the volatile compounds. In other stripping systems, gas diffusers are placed near the bottom of a reservoir containing the fraction containing carboxylic acid and impurities, introducing the stripping gas below the surface of the fraction. The stripping operation can be performed continuously, in a countercurrent or co-current way, or batchwise. The efficiency of removal of impurities, in particular impurities containing halides such as carboxylic halides and hydrogen halides, is suitably measured by methods known to the person skilled in the art, for example GC-MS using calibration with an external standard, or titration. Suitable measurements are also explained in the examples.

[0013] According to the present invention, the stripping operation is generally performed at temperatures of from 10 to 90°C. Generally, the temperature of the fraction containing carboxylic acid and impurities in the stripping step is equal to or higher than 10°C. More preferably, the temperature of the fraction containing carboxylic acid and impurities in the stripping step is equal to or higher than 15°C. Most preferably, temperature of the fraction containing carboxylic acid and impurities in the stripping step is equal to or higher than 20°C. Generally, the temperature of the fraction containing carboxylic acid and impurities in the stripping step is equal to or lower than 90°C. Preferably, the temperature of the fraction containing carboxylic acid and impurities in the stripping step is equal to or lower than 85°C. Even more preferably, the temperature of the fraction containing carboxylic acid and impurities in the stripping step is equal to or lower than 80°C. In a most preferred aspect of the invention, the temperature of the fraction containing carboxylic acid and impurities in the stripping step is from 15°C to 30°C. The temperatures are selected such that, under the given pressure of the stripping operation, the carboxylic acid contained in the fraction stays predominantly in the liquid phase. Often, heating and/or cooling is not required during the stripping step, which makes the stripping operation economically advantageous.

[0014] In the process according to the invention the content of carboxylic acid in the fraction to which the stripping operation is applied, is not substantially reduced by the stripping operation so that the content of carboxylic acid in the fraction to which the stripping operation is applied after the stripping operation is equal to or more than 90 %, preferably equal to or more than 93 %, more preferably equal to or more than 95 %, even more preferably equal to or more than 97 %, and most preferably equal to or more than 99 % in relation to the amount of carboxylic acid comprised in the fraction to which the stripping operation is applied before the stripping operation.

[0015] In one aspect of the present invention, the stripping operation is performed at ambient pressure. In another aspect of the invention, the pressure in the stripping apparatus is controlled in a desired pressure range. Pressures below or above ambient pressure can be employed. In one aspect of the invention, the pressure in the stripping apparatus is from 50 to 200 mbar. Often, the pressure in the stripping apparatus is equal to or more than 50 mbar. More preferably, the pressure in the stripping apparatus is equal to or more than 60 mbar. Most preferably, the pressure in the stripping apparatus is equal to or more than 70 mbar. Often, the pressure in the stripping apparatus is equal to or lower than 200 mbar. More preferably, the pressure in the stripping apparatus is equal to or lower than 190 mbar. Most preferably, the pressure in the stripping apparatus is equal to or lower than 180 mbar.

[0016] In a first embodiment of the invention, the fraction containing carboxylic acid and impurities is submitted to the gas stripping operation without any further preceding process steps.

[0017] In a second embodiment of the invention, the process for the recovery of carboxylic acid further comprises an additional separation step, preferably a distillation step, prior to the gas stripping operation. Often, the additional separation step is particularly advantageous if the fraction containing carboxylic acid and impurities has a content of carboxylic acid anhydride of from about 5 weight % to about 80 weight %. Generally, in this embodiment, the content of carboxylic acid anhydride in the fraction containing carboxylic acid and impurities before the additional separation step is more than 5 weight %, preferably more than 10 weight %, more preferably more than 15 weight % and most preferably more than 20 weight %. Further, the content of carboxylic acid anhydride in the fraction containing carboxylic acid and impurities before the additional separation step often is less than 80 weight %, preferably less than 75 weight %, preferably less than 70 weight % and most preferably less than 65 weight %. The additional distillation step is often applied prior to the gas stripping operation if the weight % ratio of carboxylic acid versus carboxylic acid anhydride is about 1:1 in the fraction containing carboxylic acid and impurities. The additional separation step, in particular distillation step, can be performed continuously or batchwise. In one aspect of the invention, the mixture separated from the fraction containing carboxylic acid and impurities by said separation step, contains more than about 30 weight %, more preferably more than about 40 weight % and most preferably more than about 50 weight % of carboxylic acid anhydride or it can be rich in carboxylic acid anhydride. Said mixture, is suitably recovered as a side stream or a bottom stream from the separation step and may be purified further, or may be used as recovered, for example for recycling back to its originating process. The originating process often is a process of acylation, in particular acetylation; often, of materials comprising polysaccharides, such as cellulose; often in particular a wood treatment process. The term "rich in carboxylic acid anhydride" intends to denote that the content of carboxylic acid anhydride in the side stream is equal to or greater than 70 weight %.

[0018] In another aspect of the second embodiment, the fraction containing carboxylic acid and impurities is treated with a metal salt in the presence of water before the separation step, as described in the application EP No. 14167588.4.

[0019] In a third embodiment of the invention, the fraction containing carboxylic acid and impurities is treated by a gas stripping step, followed by a separation, in particular a distillation step as described in the second embodiment. This is in particular advantageous in order to reduce or substantially remove corrosive impurities by the stripping step, such as carboxylic acid chlorides, hydrogen halide such as HCI or HBr. The resulting fraction containing carboxylic acid and impurities with a reduced content of corrosive impurities can then be submitted to the next separation, in particular distillation step, in equipment which does not need to be corrosion resistant, or of a lesser corrosion resistance, which makes the process economically more advantageous and can also avoid issues of quality (e.g. metal content, discoloration) in the product. The fraction treated by stripping and subsequent separation, in particular distillation, can then further be submitted to a stripping procedure and/or other process steps, or used in other processes as recovered from the distillation procedure. The one or more steps of this embodiment can be performed continuously or batchwise.

[0020] In the fourth embodiment of this invention, the process for the recovery of carboxylic acid further comprises the additional step of pretreating the fraction containing carboxylic acid and impurities to be introduced in the gas stripping operation with an aqueous phase. Advantageously, the fraction containing carboxylic acid and impurities has a content of less than 20 weight % carboxylic acid anhydride prior to the addition of the aqueous phase. Preferably, the fraction containing carboxylic acid and impurities has a content of less than 10 weight % carboxylic acid anhydride prior to the addition of the aqueous phase. More preferably, the fraction containing carboxylic acid and impurities has a content of less than 5 weight % carboxylic acid anhydride prior to the addition of the aqueous phase. Even more preferably, the fraction containing carboxylic acid and impurities has a content of less than 2 weight % carboxylic acid anhydride prior to the addition of the aqueous phase. A content of less than 1 weight % is even more preferred. The term "aqueous phase" denotes water of any quality (e.g. deionized water, purified water, distilled water, double-distilled water, filtered water, water from industrial processes or also municipal water, tap water, hard water, soft water), as well as an aqueous phase containing one or more metal salts or an aqueous phase further containing organic substances. The one or more metal salt which can be contained in the aqueous phase generally is a non-halogenated salt. Often, the one or more metal salt is a basic salt, suitably selected from metal hydroxides, carbonates or carboxylates, in particular acetate.

[0021] Preferably the one or more metal salt is a non-halogenated alkali salt, specifically. Potassium and sodium salts are preferred, sodium salts are more particularly preferred. Most preferably, the metal salt is selected from sodium carboxylate, in particular sodium acetate, sodium hydroxide and their mixtures. An aqueous phase containing water or water and organic substances is preferred. In the case that the aqueous phase comprises organic substances, the term "organic substances" is not limited to a specific organic substance. Often, in order to avoid further addition of contaminants to the fraction containing carboxylic acid and impurities, preferably the organic substances are carboxylic acids corresponding to the carboxylic acids contained in the fraction containing carboxylic acid and impurities. Such an aqueous phase, containing carboxylic acid, can be recycled into this step from subsequent process steps, such as a subsequent distillation step. The amount of aqueous phase supplied to the aqueous phase treatment step is controlled such that the water content of the fraction obtained by the water treatment step generally is from 0.01 weight % to 20 weight %. More preferable is the control of addition of aqueous phase to the fraction containing carboxylic acid and impurities such that the water content of the fraction obtained by the water treatment step is from 0.02 weight % to 10 weight %; even more preferable is a water content in the fraction obtained by the water treatment step from 0.05 weight % to 2 weight %. Without wishing to be bound by theory, it is believed that the addition of an aqueous phase not only converts residual carboxylic acid anhydride to carboxylic acid in the treated fraction, but also converts carboxylic acid halide to its corresponding carboxylic acid, thereby releasing hydrogen halide which can be removed by a gas stripping operation or remains in the aqueous phase. Other corrosive impurities are also removed from the fraction containing carboxylic acid and impurities by the addition of the aqueous phase, or made removable by a subsequent gas stripping operation.

[0022] The step of adding an aqueous phase to the fraction containing carboxylic acid and impurities is preferably performed either in the stripping apparatus, or in a vessel or apparatus separate from the stripping apparatus. Generally, the addition of an aqueous phase to the fraction containing carboxylic acid and impurities can be performed at temperatures of from 0 to 80°C. Often, the temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is equal to or higher than 0°C. More preferably, the temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is equal to or higher than 10°C. Most preferably, temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is equal to or higher than 15°C. Generally, the temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is equal to or lower than 80°C. Preferably, the temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is equal to or lower than 60°C. Even more preferably, the temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is equal to or lower than 50°C. Most preferably, the temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is equal to or lower than 30°C. In a most preferred aspect, the temperature of the fraction containing carboxylic acid and impurities in the step of adding an aqueous phase is from 15°C to 30°C.

[0023] In another aspect of the invention, the third embodiment is preceded by one or more steps according to the second and/or third embodiment of the invention. In this case, the aqueous step of embodiment preferably does not contain a metal salt.

[0024] The following list is non-limiting and summarizes some preferred embodiments, process variants and aspects described before:

Embodiment A



[0025] Stripping of fraction containing carboxylic acid and impurities as indicated in claim 1.

Embodiment B



[0026] Distillation of a fraction containing carboxylic acid and impurities to obtain a fraction containing carboxylic acid and a reduced amount of impurities; stripping of the fraction containing carboxylic acid and a reduced amount of impurities as indicated in claim 1.

[0027] This embodiment is particularly preferred, in particular if the fraction containing carboxylic acid and impurities contains equal to or more than 50 weight % of carboxylic acid anhydride.

Embodiment C



[0028] Distillation of a fraction containing carboxylic acid and impurities to obtain a fraction containing carboxylic acid and a reduced amount of impurities; addition of an aqueous phase; stripping of the pretreated fraction containing carboxylic acid and a reduced amount of impurities as indicated in claim 1.

[0029] This embodiment is particularly preferred, in particular if the fraction containing carboxylic acid and impurities contains equal to or more than 50 weight % of carboxylic acid anhydride.

Embodiment D



[0030] Stripping of a fraction containing carboxylic acid and impurities as indicated in claim 1 to obtain a fraction containing carboxylic acid and a reduced amount of impurities; distillation of the fraction containing carboxylic acid and a reduced amount of impurities.

Embodiment E



[0031] Addition of an aqueous phase to a fraction containing carboxylic acid and impurities; distillation of the pretreated fraction; stripping the pretreated fraction containing carboxylic acid and impurities as indicated in claim 1.

Embodiment F



[0032] Stripping of a fraction containing carboxylic acid and impurities as indicated in claim 1 to obtain a fraction containing carboxylic acid and a reduced amount of impurities; distillation of the fraction; stripping of the pretreated fraction.

Embodiment G



[0033] Stripping of a fraction containing carboxylic acid and impurities as indicated in claim 1 to obtain a fraction containing carboxylic acid and a reduced amount of impurities; distillation of the fraction; addition of an aqueous phase to the fraction; stripping of the pretreated fraction.

[0034] In a preferred aspect, the fraction being submitted to stripping, which is either the fraction containing carboxylic acid and impurities or a fraction containing carboxylic acid and a reduced amount of impurities, comprises equal to or more than 50 weight%, preferably equal to or more than 60 weight%, and more preferably equal to or more than 70 weight%, and most preferably equal to or more than 80 weight% of a mixture consisting of carboxylic acid anhydride and carboxylic acid. In one aspect, the fraction submitted to a stripping step consists of a mixture consisting of carboxylic acid anhydride and carboxylic acid, thus the content of the mixture in the fraction containing carboxylic acid and impurities or carboxylic acid and a reduced amount of impurities is 100 weight%. In another aspect, the fraction submitted to a stripping step comprises equal to or less than 99 weight%, preferably equal to or less than 97 weight%, and more preferably equal to or less than 95 weight% of a mixture consisting of carboxylic acid anhydride and carboxylic acid. In one aspect, the fraction submitted to a stripping step comprises equal to or less than 92 weight% of a mixture consisting of carboxylic acid anhydride and carboxylic acid. In yet another aspect, which is preferred in some embodiments, the fraction submitted to a stripping step comprises equal to or less than 90 weight% of a mixture consisting of carboxylic acid anhydride and carboxylic acid. The mixture consisting of carboxylic acid anhydride and carboxylic acid generally has a weight ratio of carboxylic acid anhydride versus carboxylic acid of from 1:99 to 99:1. Often, the content of carboxylic acid anhydride in the mixture consisting of carboxylic acid anhydride and carboxylic acid is equal to or greater than 1 weight%, preferably equal to or greater than 10 weight%, more preferably equal to or greater than 30%, and most preferably equal to or greater than 45 weight%. Generally, the content of carboxylic acid anhydride in the mixture consisting of carboxylic acid anhydride and carboxylic acid is equal to or lower than 99 weight%, preferably equal to or lower than 80 weight%, more preferably equal to or lower than 70 %, and most preferably equal to or lower than 50 weight%. Often, the content of carboxylic acid in the mixture consisting of carboxylic acid anhydride and carboxylic acid is equal to or greater than 1 weight%, preferably equal to or greater than 10 weight%, more preferably equal to or greater than 30 %, and most preferably equal to or greater than 45 weight%. Generally, the content of carboxylic acid in the mixture consisting of carboxylic acid anhydride and carboxylic acid is equal to or lower than 99 weight%, preferably equal to or lower than 80 weight%, more preferably equal to or lower than 70 %, and most preferably equal to or lower than 50 weight%. It is understood that the weight fractions of carboxylic acid and carboxylic acid anhydride in the mixture consisting of carboxylic acid anhydride and carboxylic acid make up the sum of 100 weight% of the mixture consisting of carboxylic acid anhydride and carboxylic acid.

[0035] Often, the purified carboxylic acid fraction recovered by the process according to the present invention is sufficiently pure to use in downstream processes such as the production of carboxylic acid anhydride. In this case, no further steps are required to recover the purified carboxylic acid fraction after the stripping operation. If necessary, the purified carboxylic acid fraction can be further purified by additional separation steps such as distillation or liquid-liquid-extraction.

[0036] In one aspect of the present invention, at least one impurity contained in the fraction containing carboxylic acid and impurities was applied to the wood. In particular, the at least one impurity contained in the fraction containing carboxylic acid and impurities which was applied to the wood originates from one or more wood preservatives or wood preservation agents. Often, the at least one impurity was applied to the wood before the wood treatment process. Application of wood preservatives or wood preservation agents for preserving the wood, and thus, impurities originating therefrom, e.g. during shipping of the wood to the wood treatment plant (and thus, before the wood treatment process), is common. Examples of impurities which originate from such wood preservatives and/or wood preservative agents are Benzalkonium chloride, iodocarb, Propiconazole, Iodofon, Propylene Glycol, Dipropylene glycol methyl ether, Dipropylene glycol, Didecyl-dimethly ammonium chloride, 5 -Chloro-2-methyl-4-isothiazolin-3-one, 2-Methyl-4-isothiazolin-3-one, Petroleum distillates, ethyl alcohol, Chlorothalonil, Methylene Bis Thiocyanate, Sodium nitrite, Guazatine and Phosphonic acid. The process according to the present invention substantially reduces or removes the content of the at least one impurity applied to the wood.

[0037] The invention also concerns a process for the manufacture of treated wood, e.g. as disclosed in EP-A-0680810, in particular acetylated wood, which comprises the process for the recovery of carboxylic acid according to the invention. Generally, wood is treated with carboxylic acid anhydride, in particular acetic anhydride, by which an effluent rich in carboxylic anhydride and carboxylic acid, also comprising other impurities, is generated next to the treated wood product. This effluent is advantageously treated by the process according to the present invention as fraction containing carboxylic acid and impurities to generate at least a purified carboxylic acid. In one aspect, the purified carboxylic acid is used, either directly or after other process steps, such as separation steps, as reaction medium in the process for the manufacture of treated wood. In another aspect, the purified carboxylic acid is used, either directly or after other process steps, such as separation steps, for the manufacture of carboxylic acid anhydride by known processes, for example ketene process. The carboxylic acid anhydride generated by these aspects is then recycled to its originating process, in particular into the wood treatment process. In another aspect, it is used for other processes. A side stream rich in carboxylic acid anhydride, as generated during the process according to the present invention, for example by a separation step as described in the second embodiment, can also be recycled. For the recycling of said side stream, the side stream can be used as recovered, or after further treatment steps. The side stream can be recycled to the originating process, which is in particular a wood treatment process. In another aspect, the side stream rich in carboxylic acid anhydride is used for other processes.

[0038] Should the disclosure of any patents, patent applications, and publications which are mentioned herein be conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

[0039] The following examples further illustrate the invention but are not to be construed as limiting its scope.

Example 1



[0040] 250 mL of a liquid phase containing 50/50 w/w acetic acid anhydride and acetic acid and 2000 mg/L acetyl chloride (mixture M1) were left to stand at room temperature under an argon blanket, measured for acetyl chloride. Argon was bubbled through the mixture using a glass fritt at 1 L/min for 1 hour, and the mixture (mixture M2) was again measured for acetyl chloride.
StepTotal Time [h]Process stepAmount acetylchlorid GC-MS-SIM
1 0 Initial measurement Initial concentration
2 1 Leaving to stand under arqon blanket 1 hour Initial concentration
3 2 1 hour bubbling argon 0 ppm


[0041] The content of acetyl chloride was measured by GC-MS in SIM-SCAN-mode using external standard calibration (mass spectrometer Agilent MSD-5975, gas chromatograph Agilent 7890 using HP-5 capillary column).

Example 2



[0042] To 200 mL of a liquid phase originating from a wood acetylation process containing 50/50 w/w acetic acid anhydride and acetic acid, 200 µl of acetyl chloride were added to bring the concentration of acetyl chloride to 1000 mg/L (mixture M3). Dry Air was bubbled through the mixture using a glass fritt at 1 L/min for 90 minutes hour, and the mixture was measured for acetyl chloride at 1, 30, 60 and 90 minutes (after 90 minutes: M4).
StepTotal Time [h]Process stepChloride
1 0 Initial measurement 1141ppm
2 1 min Bubbling air 1L/min 1135ppm
3 30 min Bubbling air 1L/min 760ppm
4 60 min Bubbling air 1L/min 634ppm
5 90 min Bubbling air 1L/min 0ppm


[0043] The content of chloride was measured by titration (Metrohm Titroprocessor 686, 0,01m AgNO3 titration agent).

Example 3



[0044] A 250 mL sample of M1, M2, M3, M4 and technical grade acetic acid was submitted to a corrosion test according to the following procedure:

Procedure 3a: The sample was contacted at 70°C temperature with coupons of AISI316L, AISI904L, Alloy C276 and alloy C22. After 650 hours, the coupons contacted with samples M1 and M3 showed extensive pitting, while for samples M2, M4 and technical grade acetic acid, no pitting was observed.

Procedure 3b: Samples M2, M4 and technical grade acetic acid were contacted at 115°C temperature with coupons of AISI316L, AISI904L, Alloy C276 and alloy C22. After 650 hours, the coupons contacted with samples M2 and M4 showed no deterioation of the coupons, similar to the coupons contacted with technical grade acetic acid.




Claims

1. Process for the recovery of carboxylic acid, in particular acetic acid, from a fraction containing carboxylic acid and impurities, which comprises submitting said fraction to a gas stripping operation and recovering at least a purified carboxylic acid fraction, wherein the content of carboxylic acid in the fraction to which the stripping operation is applied is not substantially reduced by the stripping operation so that the content of carboxylic acid in the fraction to which the stripping operation is applied after the stripping reaction is equal to or more than 90% in realtion to the amount of carboxylic acid comprised in the fraction to which the stripping operation is applied before the stripping operation,
wherein the gas stripping operation is performed using at least one gas selected from the group consisting of air, oxygen, CO2, exhaust gas, and inert gases, preferably helium, nitrogen, argon, xenon,
and wherein the fraction containing carboxylic acid and impurities contains hydrogen halides, and/or carboxylic acid halides and wherein the carboxylic acid is selected from C1 to C6 alkyl carboxylic acids which can be optionally substituted by at least one substituents selected from the group consisting of halogen atoms, OH, and CN and COOR, wherein R denotes a C1-C4 linear or branched alkyl .
 
2. The process according to claim 1,
further comprising an additional separation step, preferably a distillation step, prior to the gas stripping operation.
 
3. Process according to claim 1 or 2,
which comprises the additional step of pretreating the fraction containing carboxylic acid and impurities to be introduced in the gas stripping operation with an aqueous phase.
 
4. Process according to claim 3,
wherein the fraction containing carboxylic acid and impurities contains carboxylic anhydride, wherein the content of carboxylic anhydride in the fraction containing carboxylic acid and impurities prior to the addition of the aqueous phase is less than 20 weight %.
 
5. Process according to claim 3 or 4,
wherein the amount of aqueous phase supplied to the aqueous phase treatment step is controlled such that the water content of the fraction obtained by the water treatment step is from 0.01 weight % to 20 weight %.
 
6. Process according to anyone of claims 1 to 5,
wherein the fraction containing carboxylic acid and impurities contains impurities originating from wood, in particular terpenes and/or terpenoids.
 
7. Process according to anyone of claims 1 to 6,
wherein the fraction containing carboxylic acid and impurities contains at least one impurity which was applied to the wood, in particular wherein in the impurity which was applied to the wood originated from one or more wood preservatives or preservation agents.
 
8. Process according to anyone of claims 1 to 7,
wherein the gas stripping operation is performed continuously in a countercurrent or co-current way, or batchwise.
 
9. Process according to anyone of claims 1 to 8,
wherein the carboxylic acid fraction submitted to the gas stripping operation has a temperature of from 10 to 90°C in the gas stripping operation.
 
10. Process according to anyone of claims 1 to 9,
wherein the carboxylic acid fraction containing carboxylic acid, in particular acetic acid, and impurities originates from an acylation process, in particular an acetylation process, preferably wherein the acylation process concerns acylation, in particular acetylation, of materials comprising polysaccharides, preferably starch or cellulose.
 
11. Process according to claim 10,
wherein the process from which the carboxylic acid fraction containing carboxylic acid, in particular acetic acid, and impurities originates is a wood treatment process, in particular a wood acylation, more particularly a wood acetylation process.
 
12. Process according to claim 1,
which comprises withdrawing a mixture rich in carboxylic anhydride as a side stream or a bottom stream from a separation step, in particular a distillation step.
 
13. Process according to claim 12, which further comprises recycling the mixture rich in carboxylic anhydride to the wood treatment process.
 
14. Process for the manufacture of treated wood, in particular acetylated wood, comprising the process for the recovery of carboxylic acid according to anyone of claims 1 to 11 or claim 13.
 


Ansprüche

1. Verfahren zur Rückgewinnung von Carbonsäure, insbesondere Essigsäure, aus einer Fraktion, die Carbonsäure und Verunreinigungen enthält, wobei die genannte Fraktion einem Gas-Stripping-Vorgang unterzogen wird und mindestens eine gereinigte Carbonsäurefraktion zurückgewonnen wird, wobei der Gehalt an Carbonsäure in der Fraktion, auf die der Stripping-Vorgang angewendet wird, durch den Stripping-Vorgang nicht wesentlich verringert wird, so dass der Gehalt an Carbonsäure in der Fraktion, auf die der Strippingvorgang angewendet wird, nach der Stripping-Reaktion gleich oder mehr als 90 % in Bezug auf die Menge an Carbonsäure ist, die in der Fraktion enthalten ist, auf die der Stripping-Vorgang angewendet wird, vor dem Stripping-Vorgang,
wobei der Gas-Stripping-Vorgang unter Verwendung mindestens eines Gases, ausgewählt aus der Gruppe bestehend aus Luft, Sauerstoff, CO2, Abgas und Inertgasen, vorzugsweise Helium, Stickstoff, Argon, Xenon, durchgeführt wird,
und wobei die Carbonsäure und Verunreinigungen enthaltende Fraktion Halogenwasserstoffe und/oder Carbonsäurehalogenide enthält und wobei die Carbonsäure ausgewählt ist aus C1- bis C6-Alkylcarbonsäuren, die gegebenenfalls mit mindestens einem Substituenten, ausgewählt aus der Gruppe bestehend aus Halogenatomen, OH und CN und COOR, substituiert sein können, wobei R ein lineares oder verzweigtes C1-C4-Alkyl bezeichnet.
 
2. Verfahren nach Anspruch 1,
ferner aufweisend einen zusätzlichen Abtrennungsschritt, vorzugsweise einen Destillationsschritt, vor dem Gas-Stripping-Vorgang.
 
3. Verfahren nach Anspruch 1 oder 2,
das den zusätzlichen Schritt der Vorbehandlung der Carbonsäure und Verunreinigungen enthaltenden Fraktion, die in den Gas-Stripping-Vorgang eingebracht werden soll, mit einer wässrigen Phase aufweist.
 
4. Verfahren nach Anspruch 3,
wobei die Carbonsäure und Verunreinigungen enthaltende Fraktion Carbonsäureanhydrid enthält, wobei der Gehalt an Carbonsäureanhydrid in der Carbonsäure und Verunreinigungen enthaltenden Fraktion vor der Zugabe der wässrigen Phase weniger als 20 Gew.-% beträgt.
 
5. Verfahren nach Anspruch 3 oder 4,
wobei die Menge der wässrigen Phase, die dem Behandlungsschritt der wässrigen Phase zugeführt wird, so gesteuert wird, dass der Wassergehalt der durch den Schritt der Wasserbehandlung erhaltenen Fraktion 0,01 Gew.-% bis 20 Gew.-% beträgt.
 
6. Verfahren nach einem der Ansprüche 1 bis 5,
wobei die Carbonsäure und Verunreinigungen enthaltende Fraktion Verunreinigungen enthält, die aus Holz stammen, insbesondere Terpene und/oder Terpenoide.
 
7. Verfahren nach einem der Ansprüche 1 bis 6,
wobei die Carbonsäure und Verunreinigungen enthaltende Fraktion mindestens eine Verunreinigung enthält, die auf das Holz aufgebracht wurde, insbesondere wobei die auf das Holz aufgebrachte Verunreinigung aus einem oder mehreren Holzschutzmitteln oder Konservierungsstoffen stammt.
 
8. Verfahren nach einem der Ansprüche 1 bis 7,
wobei der Gas-Stripping-Vorgang kontinuierlich im Gegen- oder Gleichstrom oder chargenweise durchgeführt wird.
 
9. Verfahren nach einem der Ansprüche 1 bis 8,
wobei die dem Gas-Stripping-Vorgang unterzogene Carbonsäurefraktion im Gas-Stripping-Vorgang eine Temperatur von 10 bis 90°C aufweist.
 
10. Verfahren nach einem der Ansprüche 1 bis 9,
wobei die Carbonsäurefraktion, die Carbonsäure, insbesondere Essigsäure, und Verunreinigungen enthält, aus einem Acylierungsprozess, insbesondere einem Acetylierungsprozess, stammt, wobei es sich bei dem Acylierungsprozess vorzugsweise um die Acylierung, insbesondere die Acetylierung, von Materialien handelt, die Polysaccharide, vorzugsweise Stärke oder Cellulose, aufweisen.
 
11. Verfahren nach Anspruch 10,
wobei es sich bei dem Verfahren, aus dem die Carbonsäure, insbesondere Essigsäure, und Verunreinigungen enthaltende Carbonsäurefraktion stammt, um ein Holzbehandlungsverfahren, insbesondere um ein Holzacylierungs-, vor allem um ein Holzacetylierungsverfahren handelt.
 
12. Verfahren nach Anspruch 1,
welches das Abziehen eines an Carbonsäureanhydrid reichen Gemisches als Seiten- oder Bodenstrom aus einem Abtrennungsschritt, insbesondere einem Destillationsschritt, aufweist.
 
13. Verfahren nach Anspruch 12, welches ferner das Zurückführen des an Carbonsäureanhydrid reichen Gemisches in den Holzbehandlungsprozess aufweist.
 
14. Verfahren zur Herstellung von behandeltem Holz, insbesondere acetyliertem Holz, welches das Verfahren zur Rückgewinnung von Carbonsäure nach einem der Ansprüche 1 bis 11 oder Anspruch 13 aufweist.
 


Revendications

1. Procédé de récupération d'acide carboxylique, en particulier d'acide acétique, à partir d'une fraction contenant de l'acide carboxylique et des impuretés, qui comprend l'étape consistant à soumettre ladite fraction à une opération de stripage gazeux et à récupérer au moins une fraction d'acide carboxylique purifiée, dans lequel la teneur en acide carboxylique dans la fraction à laquelle l'opération de stripage est appliquée n'est pas sensiblement réduite par l'opération de stripage, de sorte que la teneur en acide carboxylique dans la fraction à laquelle l'opération de stripage est appliquée après la réaction de stripage est égale ou supérieure à 90 % par rapport à la quantité d'acide carboxylique comprise dans la fraction à laquelle l'opération de stripage est appliquée avant l'opération de stripage, dans lequel l'opération de stripage gazeux est exécutée en utilisant au moins un gaz sectionné parmi le groupe constitué de : air, oxygène, CO2, gaz d'échappement, et gaz inertes, de préférence hélium, azote, argon, xénon, et
dans lequel la fraction contenant de l'acide carboxylique et des impuretés contient des halogénures d'hydrogène, et/ou des halogénures d'acide carboxylique, l'acide carboxylique étant sélectionné parmi les acides carboxyliques alkyles de C1 à C6 auxquels peut être substitué en option au moins un substituant sélectionné parmi le groupe constitué de : atomes d'halogène, OH, et CN et COOR, où R désigne un alkyle ramifié ou linéaire en C1-C4.
 
2. Procédé selon la revendication 1,
comprenant en outre une étape de séparation additionnelle, de préférence une étape de distillation, avant l'opération de stripage gazeux.
 
3. Procédé selon la revendication 1 ou 2,
qui comprend l'étape additionnelle consistant à prétraiter la fraction contenant de l'acide carboxylique et des impuretés qu'il s'agit d'introduire dans l'opération de stripage gazeux avec une phase aqueuse.
 
4. Procédé selon la revendication 3,
dans lequel la fraction contenant de l'acide carboxylique et des impuretés contient de l'anhydride carboxylique, dans lequel la teneur en anhydride carboxylique dans la fraction contenant de l'acide carboxylique et des impuretés avant l'addition de la phase aqueuse est inférieure à 20 % en poids.
 
5. Procédé selon la revendication 3 ou 4,
dans lequel la quantité de phase aqueuse fournie à l'étape de traitement de phase aqueuse est commandée de sorte que la teneur en eau de la fraction obtenue par l'étape de traitement aqueux est de 0,01 % en poids à 20 % en poids.
 
6. Procédé selon l'une quelconque des revendications 1 à 5,
dans lequel la fraction contenant de l'acide carboxylique et des impuretés contient des impuretés provenant du bois, en particulier des terpènes et/ou des terpénoïdes.
 
7. Procédé selon l'une quelconque des revendications 1 à 6,
dans lequel la fraction contenant de l'acide carboxylique et des impuretés contient au moins une impureté qui a été appliquée au bois, en particulier dans lequel l'impureté qui a été appliquée au bois provient d'un ou de plusieurs conservateurs ou agents de conservation du bois.
 
8. Procédé selon l'une quelconque des revendications 1 à 7,
dans lequel l'opération de stripage gazeux est exécutée soit de manière continue à contre-courant ou à courant parallèle, soit par lots.
 
9. Procédé selon l'une quelconque des revendications 1 à 8,
dans lequel la fraction d'acide carboxylique soumise à l'opération de stripage gazeux a une température allant de 10 à 90 °C dans l'opération de stripage gazeux.
 
10. Procédé selon l'une quelconque des revendications 1 à 9,
dans lequel la fraction d'acide carboxylique contenant de l'acide carboxylique, en particulier de l'acide acétique, et des impuretés provient d'un procédé d'acylation, en particulier d'un procédé d'acétylation, de préférence dans lequel le procédé d'acylation concerne une acylation, en particulier une acétylation, de matériaux comprenant des polysaccharides, de préférence de l'amidon ou de la cellulose.
 
11. Procédé selon la revendication 10,
dans lequel le procédé à partir duquel provient la fraction d'acide carboxylique contenant de l'acide carboxylique, en particulier de l'acide acétique, et des impuretés est un procédé de traitement du bois, en particulier une acylation du bois, de manière plus particulière un procédé d'acétylation du bois.
 
12. Procédé selon la revendication 1,
qui comprend l'étape consistant à soutirer un mélange riche en anhydride carboxylique comme flux latéral ou flux de fond à partir d'une étape de séparation, en particulier d'une étape de distillation.
 
13. Procédé selon la revendication 12, qui comprend en outre l'étape consistant à recycler le mélange riche en anhydride carboxylique vers le procédé de traitement du bois.
 
14. Procédé de fabrication de bois traité, en particulier de bois acétylé, comprenant le procédé de récupération d'acide carboxylique selon l'une quelconque des revendications 1 à 11 ou selon la revendication 13.
 




REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description