US20020026070A1 - Process for the production of dimethylesters of dicarboxylic acids or anhydrides - Google Patents
Process for the production of dimethylesters of dicarboxylic acids or anhydrides Download PDFInfo
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- US20020026070A1 US20020026070A1 US09/446,394 US44639400A US2002026070A1 US 20020026070 A1 US20020026070 A1 US 20020026070A1 US 44639400 A US44639400 A US 44639400A US 2002026070 A1 US2002026070 A1 US 2002026070A1
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- 238000000034 method Methods 0.000 title claims abstract description 38
- 150000008064 anhydrides Chemical class 0.000 title claims abstract description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 108
- 238000005886 esterification reaction Methods 0.000 claims abstract description 47
- 230000032050 esterification Effects 0.000 claims abstract description 37
- 239000003054 catalyst Substances 0.000 claims abstract description 23
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 14
- 150000004996 alkyl benzenes Chemical class 0.000 claims abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003377 acid catalyst Substances 0.000 claims description 10
- 230000014759 maintenance of location Effects 0.000 claims description 8
- 150000005690 diesters Chemical class 0.000 claims description 7
- -1 alkylbenzene sulfonic acids Chemical class 0.000 claims description 6
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 229910006069 SO3H Inorganic materials 0.000 claims 2
- 238000004064 recycling Methods 0.000 claims 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims 2
- 125000004018 acid anhydride group Chemical group 0.000 claims 1
- 239000012445 acidic reagent Substances 0.000 claims 1
- 239000012263 liquid product Substances 0.000 claims 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 22
- 150000002148 esters Chemical class 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 10
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 7
- LPTWEDZIPSKWDG-UHFFFAOYSA-N benzenesulfonic acid;dodecane Chemical compound OS(=O)(=O)C1=CC=CC=C1.CCCCCCCCCCCC LPTWEDZIPSKWDG-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 0 *#*#*.*#*#N.CC(=O)/C=C\C(=O)O.CO.O.O=C1C=CC(=O)O1 Chemical compound *#*#*.*#*#N.CC(=O)/C=C\C(=O)O.CO.O.O=C1C=CC(=O)O1 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 2
- 229960001826 dimethylphthalate Drugs 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000003459 sulfonic acid esters Chemical class 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UAZLASMTBCLJKO-UHFFFAOYSA-N 2-decylbenzenesulfonic acid Chemical compound CCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O UAZLASMTBCLJKO-UHFFFAOYSA-N 0.000 description 1
- PVXSFEGIHWMAOD-UHFFFAOYSA-N 2-tridecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O PVXSFEGIHWMAOD-UHFFFAOYSA-N 0.000 description 1
- UCDCOJNNUVYFKJ-UHFFFAOYSA-N 4-undecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCC1=CC=C(S(O)(=O)=O)C=C1 UCDCOJNNUVYFKJ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Definitions
- the present invention relates to an improved process for the production of esters by reacting dicarboxylic acids or anhydrides (typically maleic anhydride or phthalic anhydride) with methanol, in the presence of a catalyst consisting of an alkyl benzene sulfonic acid with an alkyl radical containing from 8 to 16 carbon atoms, preferably from 10 to 13 carbon atoms.
- dicarboxylic acids or anhydrides typically maleic anhydride or phthalic anhydride
- DMM dimethyl maleate
- MAN maleic anhydride
- BDO butanediol
- the monoesterification reaction is normally effected non catalytically, while the esterification reaction is carried out in the presence of a catalyst in order to accelerate the reaction.
- the most widely used catalysts are strong homogeneous acid compounds, such as sulfuric acid or sulfonic acids (typically p-toluene sulfonic acid) as suggested in British Patents 1,173,089 and 1,262,645.
- the aforementioned catalysts tend to form sulfonate esters which derive from the esterification of the acid catalyst obtained by reacting it with the alcohol reagent.
- sulfur impurities shall be absent, or limited to a fraction of a part per million (say 0.5 ppm. or less).
- DAVY McKEE described the production of esters of maleic anhydride, preferably diethylmaleate, using a solid ion exchange resin containing S03H groups.
- the present invention provides a process for producing esters from a dicarboxylic acid or anhydride that react with methanol in the presence of a homogeneous type catalyst, characterized by the fact that the amount of sulfur in the product meets the specifications required by the further processing of the abovementioned ester product consisting of hydrogenations and also by the fact that the catalyst can be recovered and reused in the process causing no major enviromental problems.
- alkylbenzene sulfonic acid having an alkyl radical containing from 8 to 16 carbon atoms, preferably from 10 to 13 carbon atoms (i.e.: n-decylbenzene sulfonic acid, n-undecylbenzene sulfonic acid, n-dodecylbenzene sulfonic acid, n-tridecylbenzene sulfonic acid) as esterification catalyst.
- UNION CARBIDE concerns the esterification of monocarboxylic acids having from 1 to 4 carbon atoms ( acetic acid, propionic acid, butyric acid and alikes) with alcohols having from 2 to 8 carbon atoms.
- UNION CARBIDE Furthermore the process described by UNION CARBIDE concerns the production of esters which vaporize together with water in the esterification.
- the process object of the present invention applies to dicarboxylic acids or anhydrides esterified with an alcohol only containing one carbon atom (i.e. methanol).
- the esterification is performed in a reactor consisting of a multi-tray column where the liquid phase containing the mono and diester mixture flows downwards from each tray coming to contact with a progressively drier upflowing stream of vapors in countercurrent, which remove the water formed in the reaction from the liquid phase.
- the esterification reaction is carried out at operating conditions (i.e. number of trays, retention time, operating pressure and temperature) which are selected so as to cause all of the MAN and MMM to be converted into DMM with high selectivity.
- operating conditions i.e. number of trays, retention time, operating pressure and temperature
- FIG. 1 shows a procedure for putting this invention in practice for the production of DMM from MAN and methanol.
- Fresh methanol (line 1 ) is mixed with recycle methanol (line 2 ) to form a methanol stream (line 3 ) that feeds the process.
- Molten MAN (line 4 ) joins the methanol stream in monoesterification reactor 5 , where MAN is to a large extent converted into MMM.
- the operating conditions at the monoesterification reactor 5 are: Pressure: from 0.1 to 5 bar preferably from 2 to 4 bar Temperature: from 20 to 160° C. preferably from 100 to 130° C. Methanol:MAN molar ratio: from 1.1:1 to 5:1 preferably from 1.5:1 to 3:1 Retention time: from 5 to 60 min. preferably from 10 to 30 min.
- Methanol vapours from exchanger 7 (line 9 ) are fed to the bottom of esterification column 13 for heat recovery purposes.
- N-dodecyl benzene sulfonic acid (DBSA) is used as a catalyst.
- the operating conditions in the esterification section of column 13 are: Pressure: from 0.1 to 5 bar preferably from 0.1 to 1 bar Temperature: from 80 to 150° C. preferably from 90 to 130° C. Retention time: from 1 to 5 hr. preferably from 1.5 to 3 hr.
- DBSA concentration (as S03H): from 0.1 to 2.0% wt. preferably from 0.3 to 0.8% wt.
- the heat needed to vaporize and remove the water present in the reaction and the excess methanol is supplied by vaporizing a methanol stream (line 15 ) in heater 16 and feeding the methanol vapours (lime 17 ) at the bottom end of esterification colunm 13 .
- This stream is first processed in stripper 22 where excess methanol is recovered and recycled (line 23 ).
- Column 25 separates the DMM product at the top from the bottom stream that contains DMM and any non-converted MMM and DBSA catalyst (line 26 ). This is recycled to esterification column 13 .
- a small fraction of recycle stream 11 is intermittently purged out (line 27 ) for control of by-product accumulation.
- Freshly made DBSA catalyst (line 28 ) is intermittently added to compensate for the negligible losses of catalyst that occur in the process.
- the DMM produced in the process object of the present invention meets very high purity standards and is fully adequate to be converted into derivatives such as GBL, THF and BDO by selective hydrogenation.
- the sulfur content of the DMM will be less than 500 ppb.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
- The present invention relates to an improved process for the production of esters by reacting dicarboxylic acids or anhydrides (typically maleic anhydride or phthalic anhydride) with methanol, in the presence of a catalyst consisting of an alkyl benzene sulfonic acid with an alkyl radical containing from 8 to 16 carbon atoms, preferably from 10 to 13 carbon atoms.
- The production of dimethyl maleate (DMM) from maleic anhydride (MAN) and methanol has received special attention and interest due to the increasing use of DMM as feedstock for the production of derivatives such as gamma butyrolactone (GBL), tetrahydrofuran (THF) and butanediol (BDO).
- Various methods for production of DMM have been described in the literature.
-
- Other esterifications, like the production of dimethylphthalate from phthalic anhydride and methanol, proceed in the same way.
- These reactions are normally carried out in two separate reactors.
- The monoesterification reaction is normally effected non catalytically, while the esterification reaction is carried out in the presence of a catalyst in order to accelerate the reaction.
- Because the esterification is an equilibrium reaction, various methods have been described in the literature in which the equilibrium is displaced by removal of water in order to allow a high yield, high conversion rate production of the ester.
- In the esterifications, the most widely used catalysts are strong homogeneous acid compounds, such as sulfuric acid or sulfonic acids (typically p-toluene sulfonic acid) as suggested in British Patents 1,173,089 and 1,262,645.
- Other patents, such as European Patent Publications 009,886 and 158,499 suggest the use of alkyl sulfonic acids having formula RSO3H.
- The above catalysts, however, present several disadvantages in the preparation of an ester like DMM, which must meet critical purity specifications.
- In fact, in order to recover the DMM produced, the catalyst must be removed.
- Neutralisation with alkali, followed by washing with water, is a standard method employed by the esterification industry for the above removal.
- The neutralisation and washing steps, however, produce significant quantities of waste water, where besides the catalyst, salts of acid compounds such as maleic anhydride or MMM in traces are present, as well as DMM which is somewhat soluble in water, resulting in a loss of process efficiency and major environmental problems.
- Moreover, since the acid catalyst is destroyed in the neutralisation, its consumption penalizes production costs.
- According to the present invention, to avoid the problems that arise from the neutralisation it has been thought to vaporize and distill the ester product by separating it from a residue containing the acid catalyst which is bound to be recycled to the esterification, as an integral part of the process object of the invention
- However, such procedure results non-satisfactory in case standard acid catalysts are employed in the esterification.
- In fact, the aforementioned catalysts tend to form sulfonate esters which derive from the esterification of the acid catalyst obtained by reacting it with the alcohol reagent.
- No matter whether the sulfonic esters are distilled with DMM or are subject to thermal decomposition, they release sulfur compounds which contaminate the ester product.
- In case the DMM produced is used as a feed for the production of GBL, THF and BDO, sulfur impurities shall be absent, or limited to a fraction of a part per million (say 0.5 ppm. or less).
- In fact, the presence of sulfur in DMM would result in rapid poisoning of the hydrogenation catalyst employed in the conversion of DMM into GBL, THF and BDO.
- Furthermore, because of the formation of sulfonic esters and their contamination either with metals resulting from corrosion or with heavy organic by-products, the standard acid catalysts have shown to rapidly lose their activity and as a result of that to be only partly reusable if an ester vaporization and distillation process is employed.
- To avoid the disadvantages associated with the use of standard homogeneous acid catalysts, various methods have been described.
- In WO 88/00937 DAVY McKEE described the production of esters of maleic anhydride, preferably diethylmaleate, using a solid ion exchange resin containing S03H groups.
- Although feasible, the use of a heterogeneous catalyst complicates the process because of the complex design the multistage esterification system is based on, and in principle it cannot grant a completely sulfur free product. This ought to be ascribed to the tendency the resins have to lose part of their active sulfonic groups at the start and in the course of the operation, with the associated gradual decrease in their catalytic activity.
- To completely overcome the abovementioned drawbacks and complications, the present invention provides a process for producing esters from a dicarboxylic acid or anhydride that react with methanol in the presence of a homogeneous type catalyst, characterized by the fact that the amount of sulfur in the product meets the specifications required by the further processing of the abovementioned ester product consisting of hydrogenations and also by the fact that the catalyst can be recovered and reused in the process causing no major enviromental problems.
- The abovementioned results are obtained by using an alkylbenzene sulfonic acid having an alkyl radical containing from 8 to 16 carbon atoms, preferably from 10 to 13 carbon atoms (i.e.: n-decylbenzene sulfonic acid, n-undecylbenzene sulfonic acid, n-dodecylbenzene sulfonic acid, n-tridecylbenzene sulfonic acid) as esterification catalyst.
- Mixtures of alkylbenzene sulfonic acids containing alkyl chains formed by between 8 and 16 carbon atoms are also adequate.
- Similar esterification catalysts have been suggested by UNION CARBIDE in E.P. 0521 488 A2.
- However, it can be noted that the above mentioned patent owned by UNION CARBIDE concerns the esterification of monocarboxylic acids having from 1 to 4 carbon atoms ( acetic acid, propionic acid, butyric acid and alikes) with alcohols having from 2 to 8 carbon atoms.
- Furthermore the process described by UNION CARBIDE concerns the production of esters which vaporize together with water in the esterification.
- Instead, the process object of the present invention applies to dicarboxylic acids or anhydrides esterified with an alcohol only containing one carbon atom (i.e. methanol). The product of the esterification—DMM, dimethylphthalate and alikes—does not vaporize during the process.
- Furthermore, in the process object of the present invention the esterification is performed in a reactor consisting of a multi-tray column where the liquid phase containing the mono and diester mixture flows downwards from each tray coming to contact with a progressively drier upflowing stream of vapors in countercurrent, which remove the water formed in the reaction from the liquid phase.
- The esterification reaction is carried out at operating conditions (i.e. number of trays, retention time, operating pressure and temperature) which are selected so as to cause all of the MAN and MMM to be converted into DMM with high selectivity.
- The preferred embodiments of the process object of the present invention can be illustrated with reference to the attached flow diagram of FIG. 1, which shows a procedure for putting this invention in practice for the production of DMM from MAN and methanol.
- Fresh methanol (line1) is mixed with recycle methanol (line 2) to form a methanol stream (line 3) that feeds the process.
- Molten MAN (line4) joins the methanol stream in
monoesterification reactor 5, where MAN is to a large extent converted into MMM. - The operating conditions at the
monoesterification reactor 5 are:Pressure: from 0.1 to 5 bar preferably from 2 to 4 bar Temperature: from 20 to 160° C. preferably from 100 to 130° C. Methanol:MAN molar ratio: from 1.1:1 to 5:1 preferably from 1.5:1 to 3:1 Retention time: from 5 to 60 min. preferably from 10 to 30 min. - The effluent from monoesterification reactor5 (line 6) is cooled in exchanger 7 where it vapourises a liquid methanol stream (line 8).
- Methanol vapours from exchanger7 (line 9) are fed to the bottom of
esterification column 13 for heat recovery purposes. - The cooled monoester stream from exchanger7 (line 10), is mixed with a DMM recycle stream containing the acid esterification catalyst (line 11) and the resulting mixture (line 12) flows to
esterification column 13. - N-dodecyl benzene sulfonic acid (DBSA) is used as a catalyst.
- In
column 13 the esterification is completed by a further MMM reaction of with methanol and production of DMM. - There are some trays in the section. above the feed inlet (line12) of
esterification column 13 for washing out and recovering by means of liquid methanol (line 14) any MAN, MMM or DMM present in the vapours leaving the esterification section of the column itself. - The operating conditions in the esterification section of
column 13 are:Pressure: from 0.1 to 5 bar preferably from 0.1 to 1 bar Temperature: from 80 to 150° C. preferably from 90 to 130° C. Retention time: from 1 to 5 hr. preferably from 1.5 to 3 hr. DBSA concentration (as S03H): from 0.1 to 2.0% wt. preferably from 0.3 to 0.8% wt. - In the esterification column the liquid stream passes downwards from each tray to the next lower tray against an upflowing stream of methanol and water vapours produced in the esterification.
- Flowing downwards, the unreacted acid or anhydride fractions come in contact with progressively drier methanol vapours. By providing an adequate number of trays with appropriate retention times, at the bottom of
esterification column 13 it is possible to produce DMM with some methanol in it, but with a very low MMM and water content. - The heat needed to vaporize and remove the water present in the reaction and the excess methanol is supplied by vaporizing a methanol stream (line15) in
heater 16 and feeding the methanol vapours (lime 17) at the bottom end ofesterification colunm 13. - After leaving esterification column13 (line 18) the vapours flow to
column 19 where dry methanol is separated at the top (line 20) to be reused in the process, while reaction water is collected at the bottom ofcolumn 19 to be disposed of (line 29). - When the crude ester produced leaves the esterification column (line21) besides DMM it contains methanol and DBSA catalyst, with only little amounts of free acids and water.
- This stream is first processed in
stripper 22 where excess methanol is recovered and recycled (line 23). - The crude ester that leaves stripper22 (line 24) is eventually processed in
column 25 that operates under vacuum. -
Column 25 separates the DMM product at the top from the bottom stream that contains DMM and any non-converted MMM and DBSA catalyst (line 26). This is recycled toesterification column 13. - A small fraction of
recycle stream 11 is intermittently purged out (line 27) for control of by-product accumulation. - Freshly made DBSA catalyst (line28) is intermittently added to compensate for the negligible losses of catalyst that occur in the process.
- The DMM produced in the process object of the present invention meets very high purity standards and is fully adequate to be converted into derivatives such as GBL, THF and BDO by selective hydrogenation.
- The sulfur content of the DMM will be less than 500 ppb.
- Similar esterification catalysts have also been suagested by HULS in DE 4241448 and in DE 1910564.
- It can be noted that the abovementioned patents of HULS concern the esterification of aliphatic dicarboxylic acids containing from 4 to 20 carbon atoms or of aromatic dicarboxylic acids containing from 8 to 12 carbon atoms.
- The abovementioned patents of HULS do not apply to the esterification of unsaturated dicarboxylic anhydrides, as maleic anhydride.
- As a matter of fact the operating temperatures of esterification and of distillation of the ester product described in the mentioned patents of HULS result too high if applied to the esterification of maleic anhydride with methanol, in consideration of the fact that, at relatively high temperature, MMM tends to decompose into maleic anhydride and methanol.
Claims (13)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE9700535A BE1011230A6 (en) | 1997-06-24 | 1997-06-24 | METHOD FOR PRODUCTION dimethyl esters ACID OR ANHYDRIDES DICARBOXYLIC. |
BE9700535 | 1997-06-24 | ||
BE97/00535 | 1997-06-24 | ||
PCT/EP1997/006738 WO1998058897A1 (en) | 1997-06-24 | 1997-12-02 | Process for the production of dimethylesters of dicarboxylic acids or anhydrides |
Publications (2)
Publication Number | Publication Date |
---|---|
US20020026070A1 true US20020026070A1 (en) | 2002-02-28 |
US6392088B1 US6392088B1 (en) | 2002-05-21 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/446,394 Expired - Fee Related US6392088B1 (en) | 1997-06-24 | 1997-12-02 | Process for the production of dimethylesters of unsaturated dicarboxylic anhydrides |
Country Status (13)
Country | Link |
---|---|
US (1) | US6392088B1 (en) |
EP (1) | EP0996610B1 (en) |
JP (1) | JP2002511081A (en) |
KR (1) | KR20010014093A (en) |
CN (1) | CN1259931A (en) |
AT (1) | ATE240930T1 (en) |
AU (1) | AU5658598A (en) |
BE (1) | BE1011230A6 (en) |
BR (1) | BR9714744A (en) |
CA (1) | CA2293630A1 (en) |
DE (1) | DE69722262T2 (en) |
ES (1) | ES2200213T3 (en) |
WO (1) | WO1998058897A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100314243A1 (en) * | 2009-06-16 | 2010-12-16 | Draths Corporation | Preparation of trans,trans muconic acid and trans,trans muconates |
US8367858B2 (en) | 2009-06-16 | 2013-02-05 | Amyris, Inc. | Terephthalic and trimellitic based acids and carboxylate derivatives thereof |
US8367859B2 (en) | 2009-06-16 | 2013-02-05 | Amyris, Inc. | Cyclohexane 1,4 carboxylates |
US8415496B2 (en) | 2009-06-16 | 2013-04-09 | Amyris, Inc. | Biobased polyesters |
US8809583B2 (en) | 2010-01-08 | 2014-08-19 | Amyris, Inc. | Methods for producing isomers of muconic acid and muconate salts |
WO2016151289A1 (en) * | 2015-03-24 | 2016-09-29 | Johnson Matthey Davy Technologies Limited | Process for carrying out a reaction in a reaction column |
GB202404471D0 (en) | 2024-03-28 | 2024-05-15 | Johnson Matthey Davy Technologies Ltd | Process for the production of diamethyl succinate and 1,4 butanediol |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101314564A (en) * | 2007-06-01 | 2008-12-03 | 上海焦化有限公司 | Preparation of maleic acid di-methyl ester |
CN103360252B (en) * | 2012-04-01 | 2015-04-08 | 中国石油化工股份有限公司 | Method for producing maleic acid methyl ester |
CN106565488B (en) * | 2016-10-21 | 2019-05-14 | 华南理工大学 | A kind of method that lignin selective catalytic oxidation prepares maleate |
CN106631784A (en) * | 2016-11-18 | 2017-05-10 | 山东泰和水处理科技股份有限公司 | Synthesis process of dimethyl maleate |
KR20230156824A (en) | 2021-03-12 | 2023-11-14 | 꼰세르 엣세.삐.아. | Process for co-production of dialkyl succinate and 1,4-butanediol by hydrogenating dialkyl maleate in two stages |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1173089A (en) | 1967-06-06 | 1969-12-03 | Bp Chem Int Ltd | Production of Esters |
GB1262645A (en) | 1968-05-14 | 1972-02-02 | B P Chemicals Uk Ltd | Production of butyl esters |
ZA794513B (en) | 1978-09-12 | 1981-04-29 | Bp Chem Int Ltd | Process for the production of esters employing superatmospheric pressure |
US4331812A (en) * | 1980-10-30 | 1982-05-25 | E. I. Du Pont De Nemours And Company | Treatment of dibasic esters with alkali metal methylates |
GB8408801D0 (en) | 1984-04-05 | 1984-05-16 | Bp Chem Int Ltd | Process for making esters |
WO1988000937A1 (en) | 1986-08-01 | 1988-02-11 | Davy Mckee (London) Limited | Process for the co-production of butane-1,4-diol and gamma-butyrolactone |
DE69027304T2 (en) * | 1989-01-17 | 1997-01-23 | Davy Process Technology Ltd., London | Continuous process for the production of carboxylic acid esters |
US5231222A (en) | 1991-07-02 | 1993-07-27 | Union Carbide Chemicals & Plastics Technology Corporation | Esterification process |
DE4241448C2 (en) * | 1992-12-09 | 1996-09-05 | Huels Chemische Werke Ag | Process for the preparation of sulfur-free dicarboxylic acid dimethyl esters |
DE19610564A1 (en) * | 1996-03-18 | 1997-09-25 | Huels Chemische Werke Ag | Preparation of di:carboxylic acid di:ester(s) |
-
1997
- 1997-06-24 BE BE9700535A patent/BE1011230A6/en not_active IP Right Cessation
- 1997-12-02 EP EP97952854A patent/EP0996610B1/en not_active Expired - Lifetime
- 1997-12-02 US US09/446,394 patent/US6392088B1/en not_active Expired - Fee Related
- 1997-12-02 CA CA002293630A patent/CA2293630A1/en not_active Abandoned
- 1997-12-02 BR BR9714744-3A patent/BR9714744A/en not_active Application Discontinuation
- 1997-12-02 ES ES97952854T patent/ES2200213T3/en not_active Expired - Lifetime
- 1997-12-02 DE DE69722262T patent/DE69722262T2/en not_active Expired - Fee Related
- 1997-12-02 AT AT97952854T patent/ATE240930T1/en not_active IP Right Cessation
- 1997-12-02 KR KR19997012133A patent/KR20010014093A/en not_active Application Discontinuation
- 1997-12-02 AU AU56585/98A patent/AU5658598A/en not_active Abandoned
- 1997-12-02 CN CN97182264A patent/CN1259931A/en active Pending
- 1997-12-02 WO PCT/EP1997/006738 patent/WO1998058897A1/en active IP Right Grant
- 1997-12-02 JP JP50362599A patent/JP2002511081A/en active Pending
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100314243A1 (en) * | 2009-06-16 | 2010-12-16 | Draths Corporation | Preparation of trans,trans muconic acid and trans,trans muconates |
US8367858B2 (en) | 2009-06-16 | 2013-02-05 | Amyris, Inc. | Terephthalic and trimellitic based acids and carboxylate derivatives thereof |
US8367859B2 (en) | 2009-06-16 | 2013-02-05 | Amyris, Inc. | Cyclohexane 1,4 carboxylates |
US8415496B2 (en) | 2009-06-16 | 2013-04-09 | Amyris, Inc. | Biobased polyesters |
US8426639B2 (en) | 2009-06-16 | 2013-04-23 | Amyris, Inc. | Preparation of trans, trans muconic acid and trans, trans muconates |
US8809583B2 (en) | 2010-01-08 | 2014-08-19 | Amyris, Inc. | Methods for producing isomers of muconic acid and muconate salts |
WO2016151289A1 (en) * | 2015-03-24 | 2016-09-29 | Johnson Matthey Davy Technologies Limited | Process for carrying out a reaction in a reaction column |
GB2539063A (en) * | 2015-03-24 | 2016-12-07 | Johnson Matthey Davy Technologies Ltd | Process |
GB2539063B (en) * | 2015-03-24 | 2019-11-20 | Johnson Matthey Davy Technologies Ltd | Reaction Process |
US10538476B2 (en) * | 2015-03-24 | 2020-01-21 | Johnson Matthey Davy Technologies Limited | Process for carrying out a reaction in a reaction column |
EA036198B1 (en) * | 2015-03-24 | 2020-10-13 | Джонсон Мэтти Дэйви Текнолоджиз Лимитед | Process for carrying out a reaction in a reaction column |
AU2016238646B2 (en) * | 2015-03-24 | 2021-01-28 | Johnson Matthey Davy Technologies Limited | Process for carrying out a reaction in a reaction column |
GB202404471D0 (en) | 2024-03-28 | 2024-05-15 | Johnson Matthey Davy Technologies Ltd | Process for the production of diamethyl succinate and 1,4 butanediol |
Also Published As
Publication number | Publication date |
---|---|
KR20010014093A (en) | 2001-02-26 |
EP0996610B1 (en) | 2003-05-21 |
EP0996610A1 (en) | 2000-05-03 |
US6392088B1 (en) | 2002-05-21 |
ES2200213T3 (en) | 2004-03-01 |
DE69722262D1 (en) | 2003-06-26 |
DE69722262T2 (en) | 2004-03-25 |
BE1011230A6 (en) | 1999-06-01 |
CA2293630A1 (en) | 1998-12-30 |
ATE240930T1 (en) | 2003-06-15 |
JP2002511081A (en) | 2002-04-09 |
BR9714744A (en) | 2000-07-25 |
WO1998058897A1 (en) | 1998-12-30 |
AU5658598A (en) | 1999-01-04 |
CN1259931A (en) | 2000-07-12 |
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