Process for the preparation of succinic acid ester
09776948 · 2017-10-03
Assignee
Inventors
- Martin Lucas Smidt (London, GB)
- Ian Campbell (LONDON, GB)
- Graham Reed (London, GB)
- Paul Gordon (Durham, GB)
- Christopher Ferguson (Durham, GB)
Cpc classification
C07C67/08
CHEMISTRY; METALLURGY
B01D3/009
PERFORMING OPERATIONS; TRANSPORTING
International classification
C07C67/30
CHEMISTRY; METALLURGY
C07C67/08
CHEMISTRY; METALLURGY
Abstract
A process for production of dialkyl succinate from bio-succinic acid feedstock where solid bio-succinic acid is fed to a reactor to react with alkanol by autocatalytic esterification. Products from the reactor including unreacted succinic acid, mono alkyl ester, dialkyl ester, alkanol, water and impurities are sent to a reaction distillation column for esterification of succinic acid and further esterification of mono alkyl ester with upflowing alkanol. The bottoms products from the reaction distillation column including residual succinic acid, mono alkyl ester, dialkyl ester, impurities and alkanol are sent to a bottoms stream separation zone where di-alkyl ester is separated from alkanol, succinic acid, mono alkyl ester and impurities. The tops products from the reaction distillation column including alkanol, water and organic components are sent to a top stream distillation zone where alkanol is separated from water and organic components. The organic components are recycled to the reaction zone column.
Claims
1. A process for the production of dialkyl succinate from a bio-succinic acid feedstock comprising the steps of: (a) feeding solid bio-succinic acid to a first reactor where it is contacted with alkanol, said first reactor being operated at a suitable temperature and pressure to enable autocatalytic esterification to occur; (b) passing a stream removed from the first reactor comprising unreacted succinic acid, mono alkyl ester, dialkyl ester, alkanol, water and impurities to a point at or near the top of a reaction zone column operated at temperatures and pressures to enable esterification of the succinic acid and further esterification of the mono alkyl ester, and passing said stream in counter-current reaction to upflowing additional alkanol; (c) removing a stream from at or near the bottom of the reaction zone column comprising components selected from residual succinic acid, mono alkyl ester, dialkyl ester, impurities and alkanol and passing said stream to a bottoms stream separation zone where said di-alkyl ester is separated from alkanol, and from the succinic acid, mono alkyl ester and impurities; (d) recycling the succinic acid and mono alkyl ester to the reaction zone column; (e) removing at least some of the impurities as a purge; and (f) removing a stream comprising alkanol, water and organic components from at or near the top of the reaction zone column and passing said stream to a top stream distillation zone where the alkanol is separated, from the water and from the organic components and recycling the organic components to the reaction zone column.
2. The process according to claim 1 wherein said first reactor is a stirred tank reactor.
3. The process according to claim 2, wherein the stirred tank reactor is operated at a temperature in the region of from about 120° C. to about 140° C.
4. The process according to claim 2 wherein the pressure within the stirred tank reactor is in the region of from about 5 bara to about 10 bara.
5. The process according to claim 1 wherein the stream from the first reactor comprising unreacted succinic acid, mono alkyl ester, dialkyl ester, alkanol, water and impurities is passed via a subsequent reaction vessel.
6. The process according to claim 5 wherein the subsequent reaction vessel is a plug flow reaction vessel.
7. The process according to claim 1 wherein the stream is passed through a distillation column before being fed to the reaction zone column.
8. The process according to claim 1 wherein the reaction zone column is operated at an overhead pressure of about 1.3 bara to about 10 bara.
9. The process according to claim 1 wherein the reaction zone column is operated at a temperature of about 100° C. to about 300° C.
10. The process according to claim 1 wherein an alkanol wash is applied at or near the top of the reaction zone column.
11. The process according to claim 1 wherein the bottoms stream separation zone is a hydrogen stripping zone.
12. The process according to claim 1 wherein the bottoms stream separation zone is a bottom stream distillation zone.
13. The process according to claim 12 wherein the bottoms stream separation zone is operated at an overhead pressure of from about 0.1 bara to about 1 bara.
14. The process according to claim 12 wherein the dialkyl succinate is removed as a liquid side draw.
15. The process according to claim 14 wherein the liquid side draw is removed from a point above the feed point to the bottoms stream distillation zone.
16. The process according to claim 1 wherein the recovered alkanol from the bottoms stream separation zone is recycled to one or both of the first reactor and the reaction zone column.
17. The process according to claim 1 wherein the residual succinic acid and any mono-ester are recycled to the reaction zone column.
18. The process according to claim 17 wherein the recycled residual succinic acid any mono-ester are recycled to the reaction zone column at a point below the point at which the feed from the first reactor is added.
19. The process according to claim 1 wherein the impurities are removed as a purge from the bottoms stream separation zone.
20. The process according to claim 1 wherein the overhead from the reaction column zone comprising alkanol, water and organic components is passed to a condenser before being passed to a top stream distillation column.
21. The process according to claim 1 wherein the top stream distillation column is operated at an overhead pressure of about 1.3 bara to about 2 bara.
22. The process according to claim 1 wherein a liquid side draw is taken from the top stream distillation column.
23. The process according to claim 22 wherein the side draw is passed to a separator to separate an aqueous phase form an organic phase.
24. The process according to claim 23 wherein the organic phase is recycled to the reaction zone column.
25. The process according to claim 23 wherein the aqueous phase is returned to the top stream distillation column.
26. The process according to claim 25 wherein the aqueous phase is returned to the column at a point below the draw point for the liquid side draw.
27. The process according to claim 1 wherein the esterification in the reaction zone column and one or both of the distillation zones can be located in separate columns.
28. The process according to claim 1 wherein the alkanol is methanol.
Description
(1) The present invention will now be described by way of example with reference to the accompanying drawings in which:
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(10) It will be understood by those skilled in the art that the drawings are diagrammatic and that further items of equipment such as reflux drums, pumps, vacuum pumps, temperature sensors, pressure sensors, pressure relief valves, control valves, flow controllers, level controllers, holding tanks, storage tanks, and the like may be required in a commercial plant. The provision of such ancillary items of equipment forms no part of the present invention and is in accordance with conventional chemical engineering practice.
(11) The invention will be discussed with reference to the methylation of succinic acid. However, it is equally applicable to the use of other alkanols.
(12) As noted in
(13) As illustrated in
(14) The pre-converted feed in line 3 whether fed directly from continuous stirred tank reactor A or via optional plug flow reaction vessel B and/or distillation column M is fed near to the top of the reaction zone column C where it flows downwardly to react counter-currently with upflowing methanol which is fed to the base of the reaction zone column C in line 4. A reboiler H may be located at the base of the reaction zone column C. A methanol wash may be applied to the reaction zone column C in line 5.
(15) A stream comprising the reaction zone column bottoms is removed in line 6 and passed to the bottom stream separation column D. A liquid draw 9 comprising the dialkyl succinate is removed from the bottom stream separation column D above the point at which line 6 is introduced. The bottom stream separation column D may include a reboiler I and an overhead condenser J.
(16) Methanol and other light components are removed from the bottom stream separation column D as an overhead stream 10 and may be recycled to the continuous stirred tank reactor A or the reaction zone column C. A lights purge, not shown, may be removed. Succinic acid and mono-ester are concentrated in the bottom of the column and removed in line 8. Impurities from the feed are purged in line 11. The rest of the column bottoms are recycled in line 8 to the reaction zone column and introduced below the pre-converted feed which is added in line 3.
(17) The overheads from the reaction zone column C are passed in line 7 to the top stream distillation zone E. They may optionally first be passed through condenser G. Methanol is removed in stream 12. A liquid side draw 13 is generally taken from the top stream distillation zone E. The side draw stream will include any di-ester carried over from the reaction zone column C. The stream which also includes water is passed to decanter F in which partially immiscible organic and aqueous phases are separated. The aqueous phase is returned to the top stream distillation zone E in line 15 just below the draw point 13. Water is removed from the column in line 16. The organics phase is recycled to the reaction zone column C in line 14. A reboiler L and a condenser K may be present on the top stream distillation column E.
(18) Where the top stream distillation zone is used to process recycle streams containing water and methanol from a butanediol distillation train, butanol may be purged as a liquid draw in line 17. A decanter, not shown, may be used to separate butanol from methanol and water which may be recycled.
(19) The present invention will now be described with reference to the following examples.
(20) Background Example 1—Deactivation of Esterification Catalyst by Bio-Succinic Acid
(21) A 1 liter autoclave was charged with Myriant bio-succinic acid (500 g, 4.2 mol) and methanol (149 g, 4.7 mol, 1.1 equivalent). The vessel was sealed, pressurised to 40 bar(g) under nitrogen and heated to 200° C. at which point the reaction mixture was agitated by stirring at 300 rpm. After 3 hours the vessel was cooled and the product discharged as a light-brown slurry. This process was repeated until sufficient monomethyl succinate had been prepared for further esterification testwork.
(22) The testwork was repeated to obtain discrete samples of monomethyl succinate derived from crude and pure Myriant bio-succinic acid samples.
(23) A 500 ml reaction vessel was charged with 300 g of the crude bio-mono-methyl succinate and 30 g of DPT-2 resin (available from Johnson Matthey Davy Technologies Limited). The vessel was then heated to give an approximate pot temperature of 115° C., with the flange heated to a temperature of 120° C. to reduce internal reflux. Methanol was then introduced directly into the liquor at 3 molar equivalents per hour. The resulting vapour was removed and condensed. Samples of the liquor were taken with time and analysed by titration against 0.1 M potassium hydroxide using phenolphthalein as the indicator and acetone as the solvent. The reaction was continued until the monomethyl succinate concentration was <0.5 wt %.
(24) The experiment was repeated to give 4 runs, the results of which can be seen in
(25) Analysis of the deactivated resin by XRF indicated the presence of relatively large amounts of Fe, however, this was not seen in the crude bio-monomethyl succinate.
(26) Background Example 2
(27) The experiment described above was repeated using bio-monomethyl succinate derived from pure Myriant bio-succinic acid. Five repeat runs were performed using the same charge of ion exchange resin, the results of which can be seen in
(28) To confirm the efficacy of the experiments on the Myriant bio-succinic acid samples the process described above was repeated, for a mono-ester feed derived from maleic anhydride. To a 3-necked round-bottomed flask was added maleic anhydride (2 kg, 20.4 mol). The vessel was heated to 60° C. with stirring, at which point methanol (784 g, 3 mol equivalent) was added drop-wise, maintaining an exotherm of less than 10° C. Once the methanol addition was complete the vessel was crash cooled under running water and discharged.
(29) Background Example 3
(30) Four repeat esterifications were performed using the monomethyl maleate synthesised above according to the procedure described previously using the same sample of resin. There was no evidence of deactivation as illustrated in
EXAMPLE 1—DISTILLATION OF BIO-MONOMETHYL SUCCINATE/DIMETHYL SUCCINATE
(31) A 500 ml 3 necked round bottomed flask was charged a dimethyl succinate/monomethyl succinate mixture synthesized using the mono ester preparation method described in Background Example 1 with a 2:1 methanol to bio-succinic acid ratio. The vessel was placed under vacuum (<50 mmHg) and heated to a maximum temperature of 180° C. over time. The initial overheads fractions were liquid at room temperature (methanol and dimethyl succinate), however, over time a white crystalline solid began to form on the condenser (monomethyl succinate). At this point the cooling water was reduced and the condenser was heated to 70° C. the combined overheads were collected as a colourless liquid which contained 37 wt % monomethyl succinate by titration. A black residue of monomethyl succinate remained in the vessel.
(32) Analysis by x-ray fluorescence (XRF) of the liquid feed and overhead product showed that levels of metal and chloride impurities in monomethyl succinate derived by bio-succinic acid can be significantly reduced by simple distillation. The results are set out in Table 1.
(33) TABLE-US-00001 TABLE 1 Feed Before Distillation Overheads After Metal/Element (ppm) Distillation (ppm) Silicon 334 <120 Chromium 34 14 Iron 41 18 Calcium 230 186 Phosphorous 479 495 Chloride 78 37
EXAMPLE 2
(34) A 10 liter flask was charged with 5000 g (156.25 mol) of methanol with stirring. 3000 g of bio-succinic acid A (25.42 mol), was slowly charged to the flask. This was heated under reflux at 70° C. for 4 hours until all the bio-succinic acid had dissolved. A further 2000 g (16.95 mol) of bio-succinic acid was added and stirred. The configuration was changed from reflux to a standard continuous stirred tank reactor set up with the ½ inch glass column attached to minimise dimethyl succinate losses. This was heated to 115° C. and methanol was then pumped in at 7 mLmin.sup.−1.
(35) Reactor samples were taken at regular intervals for wt % acid (as monomethyl succinate) until equilibrium was reached. The equilibrium point was typically 8-12 wt % monomethyl succinate by titration. The crude dimethyl succinate was cooled and the contents discharged. This process was repeated. Three batches (Nos. 1-3) of crude dimethyl succinate were produced for distillation. The same procedure was repeated for 6 batches (Nos. 4-9) of bio-succinic acid B and for 6 batches (Nos. 10-15) of bio-succinic acid C.
(36) Distillation of each of the batches of crude dimethyl succinate was performed using a 1″ glass column operated in batch mode.
(37) 4000 g of the crude dimethyl succinate was charged to a flask and heated to 180° C. to remove the methanol and water. Once the lights had been removed, the temperature was increased to 200° C. A 2:1 reflux ratio was employed until approximately 300 mL of overheads were obtained. The reflux was then turned off and the remaining material allowed to distill over. Finally the temperature was increased to bring over any remaining dimethyl succinate in the pot.
(38) Mass balances were typically >96 wt % with approximately 90 wt % of the material removed overhead. The dimethyl succinate material that was distilled had an acid content of 0.05 wt % (as monomethyl succinate). This process was repeated until all the crude dimethyl succinate material had been purified by distillation.
(39) The bio-dimethyl succinate material from each of the 15 distillations were analysed for sulphur and chloride. Minimal (ppb) concentrations of chloride were detected in all batches. The sulphur concentrations are detailed in Table 2. It can be seen that distillation of dimethyl succinate from bio-succinic acid samples A and B produced dimethyl succinate with sulphur levels of less than 1 ppm, whilst the distilled dimethyl succinate from Bio-succinic acid C has a substantially higher sulphur level.
(40) TABLE-US-00002 TABLE 2 Esterification of bio-succinic samples A, B & C and Batch Distillation of the resulting dimethyl succinate. Sulphur level ppm wt Bio-succinic Bio-succinic Bio-succinic acid A acid B acid C (Batch 1) (Batch 5) (Batch 14) Esterification Succinic acid crystals 6 18 159 Crude dimethyl succinate 2 NA 89 Distillation Light fractions 1.6 1.8 370 Dimethyl succinate 0.2 0.3 18 fractions Residue NA 4.8 795
(41) A hydrogenation reactor was charged with 250 mL of catalyst of 1.45 for catalyst DRD-92/89-A and 1.35 for PG-85/1. Both catalysts are available from Johnson Matthey Davy Technologies Ltd
(42) Dimethyl maleate (85 wt %) produced from maleic anhydride and methanol was fed to the reactor to provide an initial activity check prior to the bio-succinic acid being introduced. This was to confirm catalyst performance.
(43) Distilled bio-dimethyl succinate made from bio-succinic acid samples A & B, with a low sulphur concentration (ppb) was introduced. The feed composition was 85 wt % DMS and 15 wt % methanol. The reactor was operated at the following conditions:
(44) TABLE-US-00003 Exit Temperature, ° C. 190 Pressure, psi (g) 885 LHSV, hr.sup.−1 0.34 H.sub.2:Ester (molar) 350:1
(45) This process gave a dimethyl succinate conversion of 99.67 mol %, with selectivity to tetrahydrofuran, butanol, γ-butyrolactone and butanediol of 3.91 mol %, 0.97 mol %, 11.77 mol % and 83.24 mol % respectively.
(46) The results indicate that the conversion was slightly higher on bio-dimethyl succinate feed compared to dimethyl maleate feed (99.67 vs. 99.13 mol % respectively). The butanol selectivity was marginally higher for the dimethyl succinate feed (0.97 vs. 0.87 mol %). The upper limit for butanol selectivity is 2.0 mol %.
(47) A second run was performed using the same bio-dimethyl succinate feedstock at an increased LHSV to reduce conversion and assess selectivity. The feed rate was increased to a LHSV of 0.5 hr-1. All other parameters remained consistent with the run described above. The feed composition was 85 wt % dimethylsuccinate and 15 wt % methanol. The reactor was operated at the following conditions:
(48) TABLE-US-00004 Exit Temperature, ° C. 190 Pressure, psi (g) 885 LHSV, hr−1 0.5 H2:Ester (molar) 350:1
(49) Operation at these conditions resulted in a dimethyl succinate conversion of 97.78 mol %, with selectivity to tetrahydrofuran, butanol, γ-butyrolactone and butanediol of 3.33 mol %, 0.65 mol %, 13.30 mol % and 82.48 mol % respectively. Results from the dimethyl maleate activity check and the two runs on bio-dimethyl succinate made from bio-succinic acid samples A & B are given in Table 3.
(50) The results indicate that the activity dropped approximately 3% after the bio-dimethyl succinate feed was first introduced. The bio-dimethyl succinate feed results in a slower deactivation rate than a commercial dimethyl maleate test.
(51) TABLE-US-00005 TABLE 3 Results of Vapour Phase Hydrogenation of Distilled Dimethylsuccinate made from Bio-succinic Acid Samples A & B Activity Dimethyl Dimethyl succinate Run ID Check succinate High LHSV Feed Dimethyl bio-dimethyl bio-dimethyl maleate succinate from succinate from bio-succinic bio-succinic acid acid A & B A & B Time-on-Line, h 141 197 378 LHSV, h.sup.−1 0.342 0.339 0.496 Pressure, psi (g) 885 884 885 Inlet Temp, ° C. 176.5 185.5 186.1 Exit Temp, ° C. 190.2 190.0 190.2 H.sub.2: Ester 344 354 350 Residence Time, s 6.16 6.29 4.35 Analysis, wt % Methanol 50.28 52.33 51.60 Tetrahydrofuran 1.48 1.47 1.23 Butanol 0.35 0.37 0.25 γ-butyrolactone 5.70 5.30 5.90 Butanediol 39.30 39.25 38.28 Dimethyl succinate 0.68 0.26 1.71 Water 1.09 0.70 0.67 Unknowns 0.10 0.06 0.16 Selectivity, mol % Dimethyl succinate 99.13 99.67 97.78 Conversion Tetrahydrofuran 3.83 3.91 3.33 Selectivity Butanol Selectivity 0.873 0.97 0.65 γ-butyrolactone 12.43 11.77 13.30 Selectivity Butanediol Selectivity 81.84 83.24 82.48
EXAMPLE 3
(52) Succinic acid crystals with up to 160 ppm sulphur were made up to a dimethyl succinate feed for hydrogenation using the procedure described above. The resulting dimethyl succinate was also clear and colourless, but its sulphur level was around 40 ppm, far in excess of the normal 1 ppm limit; this material rapidly deactivated the hydrogenation catalyst when introduced as feed.
(53) Following a second activity check of the hydrogenation catalyst with dimethyl maleate feed, another bio-dimethyl succinate run was performed at an increased LHSV of 0.4 hr.sup.−1. The bio-dimethyl succinate batches 10-15 (excluding 14), made from bio-succinic acid C as described in Example 2 were blended together. The feed contained a sulphur concentration of 33 ppm. The feed composition was 85 wt % dimethyl succinate and 15 wt % methanol. The reactor was operated at the following conditions:
(54) TABLE-US-00006 Exit Temperature, ° C. 190 Pressure, psi (g) 885 LHSV, hr.sup.−1 0.4 H.sub.2:Ester (molar) 350:1
(55) Operation at these conditions on the bio-dimethyl succinate feed resulted in a rapid deactivation of the catalyst. The dimethylsuccinate conversion reduced from 99.05 mol % to 90.52 mol % before the feed was exhausted. Results from the dimethyl maleate activity check and the run on (once distilled) bio-dimethyls succinate made from bio-succinic acid samples C are given in Table 4.
(56) TABLE-US-00007 TABLE 4 Results of Vapour Phase Hydrogenation of (once) Distilled Dimethyl Succinate made from Bio-succinic Acid Sample C Activity Run ID Check Dimethyl Succinate High LHSV Feed Dimethyl bio-dimethyl succinate from bio- maleate succinic acid C Time-on-Line, h 697 823 LHSV, h.sup.−1 0.337 0.400 Pressure, psi (g) 885 884 Inlet Temp, ° C. 174.7 187.4 Exit Temp, ° C. 190.0 189.9 H.sub.2: Ester 349 348 Residence Time, s 4.18 5.44 Analysis, wt % Methanol 51.55 50.97 Tetrahydrofuran 1.23 1.43 Butanol 0.35 0.33 γ-butyrolactone 5.52 6.15 Butanediol 39.53 33.00 Dimethyl succinate 0.73 7.07 Water 0.62 0.59 Unknowns 0.06 0.18 Selectivity, mol % Dimethyl succinate 99.05 90.52 Conversion Tetrahydrofuran Selectivity 3.24 4.28 Butanol Selectivity 0.89 0.95 γ-butyrolactone Selectivity 12.20 15.37 Butanediol Selectivity 83.48 78.76
EXAMPLE 4
(57) High sulphur dimethyl succinate from Example 3 was purified to a level where it would be suitable for feed to hydrogenation by performing a more rigorous distillation.
(58) A second distillation was performed on the distilled dimethyl succinate from batch 14 of the bio-succinic acid C which had a high sulphur concentration (18 ppm) after the first distillation (as described in Example 3). A 5 liter flask was charged 2766 g of dimethyl succinate which had already undergone a previous distillation as described above. The temperature was slowly increased to afford a process temperature of 200° C. Both the top and bottom column heaters were set to maintain the process temperature inside the column to minimise heat loss. A 10:1 reflux ratio was employed to attempt to fractionate the sulphur species. A total of 8 overhead fractions were obtained using a 10:1 reflux ratio.
(59) The sulphur content of the fractions were measured and the concentrations are reported in Table 5 below. A high concentration of sulphur was noted in the first fraction (50 ppm) with ppb levels in all subsequent fractions. The pot contents contained a sulphur concentration of 35 ppm. Mass balances for this second distillation were >98 wt % with approximately 78 wt % of the material removed overhead. The sulphur component balance was >99%.
(60) TABLE-US-00008 TABLE 5 Repeat Distillation of Dimethyl Succinate Fraction of Bio-Succinic Acid C (Batch 14) Weight (g) Sulphur level ppm wt Feedstock (from 1.sup.st distillation) 2766 14 Fraction 1 (Lights) 348 50 Fraction 2 (dimethyl succinate) 336 1 Fraction 3 (dimethyl succinate) 269 1.2 Fraction 4 (dimethyl succinate) 268 0.7 Fraction 5 (dimethyl succinate) 265 0.7 Fraction 6 (dimethyl succinate) 258 0.3 Fraction 7 (dimethyl succinate) 299 0.4 Fraction 8 (dimethyl succinate) 115 0.7 Residue 572 35
EXAMPLE 5
(61) High sulphur dimethyl succinate from Example 4 was purified by treating it with a weak base anion exchange resin (Dow IRA-67) which reduced its sulphur content to an acceptable level for feeding to hydrogenation.
(62) Samples of the high sulphur distilled dimethyl succinate made from Bio-succinic acid C (described in Examples 3 & 4) were treated with Amberlite IRA67 (base resin) with the intention of removing the sulphur from the dimethyl succinate.
(63) Oven dried IRA67 was added to each of the dimethyl succinate samples and shaken at regular intervals for 2-3 hours. Each sample was left to stand for 1 hour and a sample of dimethyl succinate was taken for sulphur analysis. The results of sulphur analysis before and after treatment with IRA67 are presented in Table 6.
(64) TABLE-US-00009 TABLE 6 IRA67 Treatment of Dimethyl Succinate samples from Bio-Succinic Acid C Sulphur Level (ppb) Before After Sample Treatment Treatment Dimethyl succinate Fraction from Distillation 1 12,000 883 of Batch 14 Fraction 1 from Distillation 2 of Batch 14 42,000 1,000 Fraction 2 from Distillation 2 of Batch 14 1,450 661 Pot Residual from Distillation 2 of Batch 14 30,000 9,840 Blend of dimethyl succinate fractions from 33,000 743 Distillation 1 of batches 10-13 & 15.
EXAMPLE 6
(65) This example demonstrates esterification of succinic acid with methanol at temperatures of 190-210° C. in batch autoclaves.
(66) Studies on succinic acid conversion were undertaken using 6×100 cm.sup.3 Hastelloy™ autoclaves each containing a cross-shaped magnetic follower. Heating was provided by a metallic block-heater which was close-fitted to each autoclave. Heating was controlled by a suitable temperature controller and each autoclave was individually magnetically stirred. The block was pre-heated to the desired reaction temperature prior to the addition of the autoclaves.
(67) Each autoclave was individually charged with the desired starting composition of succinic acid and methanol (up to 30 g) and the resulting suspension sealed and pressured with 150 psig N.sub.2 at room temperature, to minimise component vapour losses during reaction. The autoclaves were leak-tested for 45 minutes and all six placed into the pre-heated block together. An initial run had determined that a maximum autoclave pressure (ca. 390 psig at 190° C.) was obtained after 25 minutes in the heated block (30 minutes at 210° C.) and these timings were therefore used as the “T=0” start times for sampling.
(68) Autoclaves were then removed from the block upon reaching their desired sample timings and immediately submerged in ice-water for 15 minutes in order to rapidly quench the reaction. Mass balances were calculated from comparison of the autoclave masses after reaction (vented) with that of the empty autoclave. All samples were analysed for water (coulometric Karl-Fisher) and by GC (Regisil-treated, 50 m DB-1 column, HY 381 method).
(69) Starting molar compositions of succinic acid to methanol of 1:2 and 1:4 were employed at reaction temperatures of 190° C. and 210° C., above the melting point of succinic acid. Data was collected at 10 or 15 minute intervals starting from T=0 giving data for 50 or 75 minutes per run. Mass balances were generally good (>98%) which is likely to be due to good retention of volatiles with the cold-sampling method employed. Methanol levels by GC, however, are still considered unreliable due to the rapid exotherm present upon Regisil treatment of samples. This is likely to be due to the high levels of water present in these samples, typically being in excess of 10 wt %.
(70) The data obtained, which is presented in Tables 7-10 shows trends in the components as expected, with greater conversion to dimethyl succinate at increased temperature and increased methanol to succinic acid ratio.
(71) TABLE-US-00010 TABLE 7 Results of esterification of succinic acid in a 1:4 ratio with methanol at 190° C. in 6 × batch autoclaves Experiment Description 1:4, Methanol:Succinic acid - 190° C; 6 × 100 ml Autoclaves Autoclave Charge (per Autoclave) Component Mass/g RMM/g mol-1 Mols Mol Fraction Methanol 15.2 32 0.475 80.0% Succinic Acid 14.0 118 0.119 20.0% Totals 29.2 0.593 Autoclave Number N/A 1 2 3 4 5 6 Time/min Initial 0 15 30 48 60 75 Mass Discharged/g 29.1 29.0 28.9 29.2 29.2 29.2 Components Methanol/GC, wt % 52.033 33.304 30.328 30.221 29.618 29.014 27.828 Dimethyl Succinate/ 0.000 19.053 30.190 34.492 42.416 37.548 37.279 GC, wt % Monomethyl 0.000 28.830 22.852 21.035 19.242 18.684 18.480 succinate/GC, wt % Succinic acid/GC, 47.967 11.093 4.591 3.153 2.533 2.332 2.281 wt % Water/KFT, wt % 0.000 7.172 9.792 10.344 13.245 11.682 13.407 Sum of Knowns 100.0% 99.5% 97.8% 99.2% 107.1% 99.3% 99.3% Methanol/mol 1.626 1.041 0.948 0.944 0.926 0.907 0.870 Dimethyl succinate/mol 0.000 0.130 0.207 0.236 0.291 0.257 0.255 Monomethyl succinate/ 0.000 0.218 0.173 0.159 0.146 0.142 0.140 mol Succinic acid/mol 0.407 0.094 0.039 0.027 0.021 0.020 0.019 Water/mol 0.000 0.398 0.544 0.575 0.736 0.649 0.745 MOL Total 203.3 188.2 191.1 194.1 211.9 197.4 202.9 Methanol/mol fraction 0.800 0.553 0.496 0.486 0.437 0.459 0.429 Dimethyl succinate/ 0.000 0.069 0.108 0.122 0.137 0.130 0.126 mol fraction Monomethyl succinate/ 0.000 0.116 0.091 0.082 0.069 0.072 0.069 mol fraction Succinic acid/mol 0.200 0.050 0.020 0.014 0.010 0.010 0.010 fraction Water/mol fraction 0.000 0.212 0.285 0.296 0.347 0.329 0.367 Mass Balance 99.7% 99.7% 99.4% 99.0% 100.0% 100.0% 100.0% Methanol Balance 100.0% 101.0% 100.4% 101.5% 97.5% 98.9% 93.7% Conversion to dimethyl 0.0% 29.5% 49.4% 55.9% 63.5% 61.5% 61.6% succinate (C.sub.4 basis)
(72) TABLE-US-00011 TABLE 8 Results of esterification of succinic acid in a 1:2 ratio with methanol at 190° C. in 6 × batch autoclaves Experiment Description 1:2, Methanol:succinic acid - 190° C; 6 × 100 ml Autoclaves Autoclave Charge (per Autoclave) Component Mass/g RMM/g mol-1 Mols Mol Fraction Methanol 7.6 32 0.238 66.7% Succinic Acid 14.0 118 0.119 33.3% Totals 21.6 g 0.356 Autoclave Number N/A 1 2 3 4 5 6 Time/min Initial 0 15 30 45 60 78 Mass Discharged/g N/A 21.2 21.4 21.3 21.4 21.4 21.5 Components Methanol/GC, wt % 35.185 12.062 11.235 9.940 9.704 9.468 9.165 Dimethylsuccinate/ 0.000 27.351 32.232 35.455 35.820 36.613 36.517 GC wt % Monomethylsuccinate/ 0.000 36.783 33.649 32.319 32.464 31.168 31.767 GC wt % Succinic acid/GC, 64.815 12.571 9.831 8.585 8.181 7.766 8.115 wt % Water/KFT, wt % 0.000 10.000 12.317 13.066 13.298 13.419 13.388 Sum of Knowns % 100.0 98.8 99.3 99.4 99.5 98.4 99.0 Methanol/mol 1.100 0.377 0.351 0.311 0.303 0.296 0.286 Dimethyl succinate/mol 0.000 0.187 0.221 0.243 0.245 0.251 0.250 Monomethyl succinate/ 0.000 0.279 0.255 0.245 0.246 0.236 0.241 mol Succinic acid/mol 0.549 0.107 0.083 0.073 0.069 0.066 0.069 Water/mol 0.000 0.556 0.684 0.726 0.739 0.746 0.744 MOL Total 164.9 150.5 159.4 159.7 160.3 159.4 159.0 Methanol/mol fraction 0.667 0.250 0.220 0.195 0.189 0.186 0.180 Dimehtyl succinate/ 0.000 0.124 0.138 0.152 0.153 0.157 0.157 mol fraction Monomethyl succinate/ 0.000 0.185 0.160 0.153 0.153 0.148 0.151 mol fraction Succinic acid/mol 0.333 0.071 0.052 0.046 0.043 0.041 0.043 fraction Water/mol fraction 0.000 0.369 0.429 0.455 0.461 0.468 0.468 Mass Balance % N/A 98.1 99.1 98.6 99.1 99.1 99.5 Methanol Balance % 100.0 102.7 98.5 97.8 97.3 97.2 96.9 Conversion to 0.0 32.7 39.5 43.3 43.8 45.4 44.7 Dimethyl succinate (C.sub.4 basis)
(73) TABLE-US-00012 TABLE 9 Results of esterification of succinic acid in a 1:4 ratio with methanol at 210° C. in 6 × batch autoclaves Experiment Description 1:4, Methanol:Succinic acid - 210° C; 6 × 100 ml Autoclaves Autoclave Charge (per Autoclave) Component Mass/g RMM/g mol-1 Mols Mol Fraction Methanol 15.2 32 0.475 80.0% Succinic acid 14.0 118 0.119 20.0% TOTALS 29.2 g 0.594 Autoclave Number N/A 1 2 3 4 5 6 Time/min Initial 0 15 30 45 60 78 Mass Discharged/g N/A 21.2 21.4 21.3 21.4 21.4 21.5 Components Methnaol/GC, wt % 52.055 26.547 28.503 27.002 27.633 28.177 27.437 Dimethyl succinate/ 0.000 30.617 34.013 37.628 38.581 38.136 40.186 GC. wt % Monomethylsuccinate/ 0.000 26.719 22.433 20.103 16.900 16.032 16.749 GC wt % Succinic acid/GC, 47.945 5.454 3.458 2.695 1.981 1.883 1.888 wt % Water/KFT, wt % 0.000 10.222 10.809 11.561 11.785 12.221 12.657 Sum of Knowns (%) 100.0 99.6 99.2 99.0 96.9 96.4 98.9 Methanol/mol (%) 162.7 83.0 89.1 84.4 86.4 88.1 85.7 Dimethyl succinate/mol (%) 0.0 21.0 23.3 25.8 26.4 26.1 27.5 Monomethyl succinate/ 0.0 20.2 17.0 15.2 12.8 12.1 12.7 mol (% Succinic acid/mol (%) 40.6 4.6 2.9 2.3 1.7 1.6 1.6 Water/mol (%) 0.0 56.8 60.1 64.2 65.5 67.9 70.3 MOL Total 203.3 185.6 192.3 191.9 192.7 195.8 197.9 Methanol/mol fraction 0.800 0.447 0.463 0.440 0.448 0.450 0.433 Dimethyl succinate/ 0.000 0.113 0.121 0.134 0.137 0.133 0.139 mol fraction Monomethyl succinate/ 0.000 0.109 0.088 0.079 0.066 0.062 0.064 mol fraction Succinic acid/mol 0.200 0.025 0.015 0.012 0.009 0.008 0.008 fraction Water/mol fraction 0.000 0.306 0.312 0.335 0.340 0.347 0.355 Mass Balance N/A 72.6% 73.3% 72.9% 73.3% 73.3% 73.6% Methanol Balance 100.0% 97.7% 99.2% 98.4% 98.6% 97.3% 96.9% Conversion to 0.0% 45.8% 53.9% 59.5% 64.6% 65.5% 65.8% dimethyl succinate (C.sub.4 basis)
(74) TABLE-US-00013 TABLE 10 Results of esterification of succinic acid in a 1:2 ratio with methanol at 210° C. in 6 × batch autoclaves Experiment Description 1:2 Methanol:Succinic acid - 210° C; 6 × 100 ml Autoclaves Autoclave Charge (per Autoclave) Component Mass/g RMM/g mol-1 Mols Mol Fraction Methanol 7.6 32 0.238 66.7% Succinic acid 14.0 118 0.119 33.3% TOTALS 21.6 g 0.356 Autoclave Number N/A 1 2 3 4 5 6 Time/min Initial 0 15 30 48 60 75 Mass Discharged/g N/A 21.3 21.4 21.4 21.3 21.6 21.4 Components Methanol/GC, wt % 35.185 11.974 10.015 9.914 10.467 9.261 9.531 Dimethylsuccinate/ 0.000 34.477 35.544 36.478 36.246 36.944 36.116 GC wt % Monomethylsuccinate/ 0.000 32.082 32.488 31.692 30.645 31.474 31.242 GC wt % Succinic acid/GC, 64.815 8.305 8.491 8.291 7.958 8.002 7.745 wt % Water/KFT, wt % 0.000 11.989 12.521 12.915 13.787 13.919 14.111 Sum of Knowns % 100.0 98.8 99.1 99.3 99.1 99.6 98.7 Methanol/mol % 110.0 37.4 31.3 31.0 32.7 28.9 29.8 Dimethyl succinate/mol 0.0 23.6 24.3 25.0 24.8 25.3 24.7 (%) Monomethyl succinate/ 0.0 24.3 24.6 24.0 23.2 23.8 23.7 mol (%) Succinic acid/mol (%) 54.9 7.0 7.2 7.0 6.7 6.8 6.6 Water/mol (%) 0.0 66.6 69.6 71.8 76.6 77.3 78.4 MOL Total 164.9 159.0 157.0 158.8 164.1 162.2 163.1 Methanol/mol fraction 0.667 0.235 0.199 0.195 0.199 0.178 0.183 Dimthyl succinate/ 0.000 0.149 0.155 0.157 0.151 0.156 0.152 mol fraction Monomethyl succinate/ 0.000 0.153 0.157 0.151 0.141 0.147 0.145 mol fraction Succinic acid/mol 0.333 0.044 0.046 0.044 0.041 0.042 0.040 fraction Water/mol fraction 0.000 0.419 0.443 0.452 0.467 0.477 0.481 Mass Balance (%) N/A 98.6 99.1 99.1 98.6 100.0 99.1 Methanol Balance (%) 100.0 102.8 99.9 99.1 96.5 95.6 94.6 Conversion to DMS 0.0% 43.0% 43.4% 44.6% 45.3% 45.2% 45.0% (C.sub.4 basis)
(75) The results of Example 6 are illustrated in the graph of
EXAMPLE 7
(76) In this example mono-methyl succinate is esterified with methanol to the di-ester with conversion of almost 90% at a temperature of 190° C.
(77) The monomethyl succinate for this testwork was synthesized in-house from commercially available succinic anhydride and used in its crude form. A 1 dm.sup.3 stainless steel autoclave fitted with a bottoms sample point was charged with MMS and made up to 200 psig with nitrogen to minimise component vapour pressures. The reactor was then heated to the desired reaction temperature of 190° C. and methanol pumped to the autoclave via an HPLC pump at a desired rate this was called time zero (“T=0”). Overheads were extracted via an electrically traced heated line to avoid condensation and reflux of the product mixture. This was then condensed and collected via a water cooled catch-pot. This is detailed schematically in
(78) Samples from the autoclave itself and of the overheads collected were taken at periodic time intervals and subsequently analysed for water (coulometric Karl-Fisher) and by GC. Autoclave samples were analysed after Regisil treatment on a 50 m DB-1 column, and overheads directly analysed for methanol and dimethyl ether on a 60 m DB-1 column. Masses of all samples and reactor contents were noted to allow mass balances to be calculated.
(79) A reaction temperature of 190° C. and a feed rate of 2 mols methanol per mole of monomethyl succinate per hour was chosen; 3 mols of monomethyl succinate were charged to the autoclave requiring a methanol flow rate of 4.05 mL min.sup.−1 for the run. A second run was performed at double this flow rate. When the system was at temperature, methanol flow commenced for 120 minute, with periodic sampling throughout the run. The feed composition and conditions used for each test, Runs 1 & 2 are given in Tables 11 & 14 respectively, while the results are given in Tables 12, 13, 15 and 16.
(80) TABLE-US-00014 TABLE 11 Feed composition and test conditions for Run 1 at 2 mol Methanol per hour per mol succinic acid Experiment Description Example 7 Run 1 2 mol methanol hr.sup.−1 per mol succinic acid charged at 190° C. Autoclave Charge (1 L Parr) Component Mass, g RMM/g mol.sup.−1 Mol Mol Fraction Monomethyl Succinate 396.0 132 3.0 1.00 (Crude) Theoretical Yield (of 438.0 Dimethyl succinate) Crude Monomethyl succinate Analysis Component Mass RMM/g mol.sup.−1 Mols Mol Fraction Methanol 0.9 32 0.027 0.01 Dimethyl succinate 62.5 146 0.428 0.14 Monomethyl succinate 284.3 132 2.154 0.70 Succinic Acid 47.4 118 0.402 0.13 Water 0.9 18 0.048 0.02 Total 396.0 3.060 Methanol Flow Target, molar 2.0 mol hr−1 mol.sup.−1 6.0 mol (MMS) MeOH h.sup.−1 Flow 192.0 g hr.sup.−1 Density (Methanol) 0.79 g ml.sup.−1 Target Flow Rate 4.05 ml min.sup.−1
(81) TABLE-US-00015 TABLE 12 Results of Example 7 Run 1 Example 7 Run 1 Time, min 0 11 22 32 42 52 61 Mass Discharged 14.5 8.3 10.4 8.2 9.8 13.6 13.0 (autoclave), g Methanol Flow Rate/ml 4.05 4.05 4.10 4.05 4.05 4.05 4.05 min.sup.−1 Reaction Temperature, ° C. 190 188 188 188 187 188 187 System Pressure, psig 169 158 165 165 164 163 167 Autoclave Components Methanol/GC, wt % 1.097 3.341 6.881 11.123 12.683 12.315 11.946 Dimethyl succinate/GC, wt % 29.214 33.185 41.273 46.738 50.692 54.770 58.932 Monomethyl succinate/ 48.730 44.418 37.632 31.405 27.408 22.714 22.849 GC, wt % Succinic acid AC/GC, wt % 18.440 15.476 9.613 5.918 4.152 2.745 2.416 Water/KFT, wt % 1.950 2.789 4.081 4.386 4.518 3.773 3.205 Sum of Knowns, % 99.4 99.2 99.5 99.6 99.5 96.3 99.3 Conversion to Dimethyl 27.6 32.7 43.5 52.6 58.8 65.8 67.6 succinate (C.sub.4 Basis), % Overheads Collected, g 0.0 0.0 0.1 13.4 30.8 40.8 27.4 Overheads, analysis Methanol/GC, wt % 80.939 79.238 86.252 88.699 Dimethyl succinate/GC, wt % 2.613 4.100 Monomethyl succinate/ 0.361 0.332 GC, wt % Succinic acid/GC, wt % 0.131 0.113 Water/KFT, wt % 12.021 13.303 13.708 11.301 Methanol/GC, wt %
(82) TABLE-US-00016 TABLE 13 Results of Example 7 Run 1 continued Example 7 Run 1 (cont'd) Time, min 72 81 91 101 111 121 Final Mass Discharged 16.8 11.4 13.7 15.7 16.5 12.9 731.5 (autoclave), g Methanol Flow Rate, ml 4.10 4.05 4.05 4.05 4.05 4.05 min.sup.−1 Reaction Temperature, ° C. 188 189 188 188 188 190 System Pressure, psig 165 167 166 167 166 161 Autoclave Components Methanol/GC, wt % 11.349 13.560 12.833 12.814 12.651 13.512 13.560 Dimethyl succinate/GC, wt % 63.176 64.074 66.316 69.566 71.106 72.303 64.074 Monomethyl succinate/ 20.537 18.388 17.281 15.056 13.945 12.136 18.388 GC, wt % Succinic acid/GC, wt % 1.879 1.506 1.275 0.957 0.759 0.535 1.506 Water/KFT, wt % 2.511 1.941 1.550 1.073 0.920 0.822 1.941 Sum of Knowns, % 99.5 99.5 99.3 99.5 99.4 99.3 99.5 Conversion to Dimethyl 71.6 74.3 76.2 79.6 81.3 83.7 88.2 succinate (C.sub.4 Basis), % Overheads Collected, g 40.4 30.2 35.2 35.5 37.9 36.8 292.8 Overheads, analysis 3.4 3.5 3.6 3.8 3.7 Methanol/GC, wt % 88.838 90.803 92.240 94.859 95.399 96.787 97.165 Dimethyl succinate/GC, wt % Monomethyl succinate/ GC, wt % Succinic acid/GC, wt % Water/KFT, wt % 11.162 9.197 7.760 5.141 4.601 3.213 2.835 Methanol/GC, wt %
(83) The results of run 1 of Example 7 are illustrated in
(84) TABLE-US-00017 TABLE 14 Feed composition and test conditions for Example 7 Run 2 at 4 mol Methanol per hour per mol succinic acid Experiment Description Example 7 Run 2 4 mol MeOH hr.sup.−1 per mol SAC charged at 190° C. Autoclave Charge (1 L Parr) Component Mass/g RMM/g mol.sup.−1 Mols Mol Fraction Monomethyl succinate 396.0 132 3.0 1.00 (Crude) Theoretical Yield (of 438.0 dimethyl succinate) Crude Monomethyl Succinate Analysis Component Mass RMM/g mol.sup.−1 Mols Mol Fraction Methanol 0.9 32 0.027 0.01 Dimethyl succinate 62.5 146 0.428 0.14 Monomethyl succinate 284.3 132 2.154 0.70 Succinic acid 47.4 118 0.402 0.13 Water 0.9 18 0.048 0.02 Total 396.0 3.060 Methanol Flow Target (molar) 4.0 mol h.sup.−1 mol.sup.−1 12.0 mol (MMS) MeOH h.sup.−1 Flow 384.0 g h.sup.−1 Density (Methanol) 0.79 g ml.sup.−1 Target Flow Rate 8.10 mL min.sup.−1
(85) TABLE-US-00018 TABLE 15 Results of Example 7 Run 2 Example 7 Run 2 Time, min 0 16 25 35 46 59 Mass Discharged 14.5 9.7 5.7 10.0 5.6 7.0 (autoclave), g Methnaol Flow Rate, ml 8.10 8.10 8.10 8.10 8.10 8.10 min.sup.−1 Reaction Temperature, ° C. 188 184 183 186 187 187 System Pressure, psig 168 170 164 164 163 Autoclave Components Methanol/GC, wt % 1.097 12.053 12.823 11.526 12.693 12.709 Dimethyl succinate/GC, wt % 29.214 42.354 44.027 49.981 53.980 59.055 Monomethyl succinate/ 48.730 34.006 32.199 27.850 25.688 22.081 GC, wt % Succinic acid/GC, wt % 18.440 6.156 5.372 3.860 2.948 2.209 Water/KFT, wt % 1.950 3.994 4.187 3.524 2.987 2.127 Sum of Knowns, % 99.4 98.6 98.6 96.7 98.3 98.2 Conversion to Dimethyl 27.6 48.4 51.0 58.4 62.7 68.5 succinate (C.sub.4 Basis), % Overheads Collected, g 0.0 11.1 32.1 86.4 77.4 89.5 Overheads, analysis Methanol/GC, wt % 77.745 86.517 89.292 91.903 92.810 Dimethyl succinate/GC, wt % 5.611 5.611 6.500 8.500 10.882 Monomethyl succinate/ 0.431 0.431 0.431 0.431 0.478 GC, wt % Succinic acid/GC, wt % 0.104 0.114 Water/KFT, wt % 22.255 13.483 10.708 80.97 7.190 Sums of Knowns 0.0 106.0 106.1 106.9 108.9 111.5
(86) TABLE-US-00019 TABLE 16 Results of Run 2 continued Example 7 Run 2 (cont'd) Time, min 73 90 105 Final Mass discharged (autoclave), g 11.3 9.0 6.0 316.3 Methanol Flow Rate, ml min.sup.−1 8.10 8.10 8.10 Reaction Temperature, ° C. 187 187 187 System Pressure, psig 160 154 162 Autoclave Components Methanol/GC, wt % 13.647 12.668 14.231 13.412 Dimethyl succinate/GC, wt % 64.972 68.887 70.613 75.011 Monomethyl succinate/GC, wt % 17.891 14.889 12.290 9.788 Succinic acid/GC, wt % 1.234 0.836 0.577 0.322 Water/KFT, wt % 1.265 0.795 0.537 0.529 Sum of Knowns, % 99.0 98.1 98.2 99.1 Conversion to DMS (C.sub.4 Basis), % 75.3 79.7 83.2 87.0 Overheads Collected, g 103.9 126.8 103.8 19.6 Overheads, analysis MeOH/GC, wt % 95.608 97.724 98.185 90.656 Dimethyl succinate/GC, wt % 11.500 12.399 13.399 16.000 Monomethyl succinate/GC, wt % 0.478 0.471 0.471 0.471 Succinic acid/GC, wt % 0.142 Water/KFT, wt % 4.392 2.276 1.815 9.344 Sum of Knowns 112.0 113.0 113.9 116.5
EXAMPLE 8
(87) This example demonstrates separation of di-methyl succinate from mono-methyl succinate by distillation under vacuum.
(88) The expected stream composition from the bottom of an autocatalytic reaction column was made up artificially as feed using petrochemical dimethyl succinate, monomethyl succinate and succinic acid from previous experiments. The resulting composition in weight percents was:
(89) TABLE-US-00020 Methanol 7.0 Di-methyl Succinate 63 Mono-methyl Succinate 27 Succinic Acid 2.9 Others 0.1
(90) 1032 g of this material was charged to an insulated 2 L round bottom flask, which heated by an isomantle acted as the reboiler for the batch distillation. The temperature of the isomantle was controlled using a Watlow burst fire module with a k type thermocouple attached to the skin of the vessel. A further k type thermocouple was located inside the reboiler to determine the actual process temperature.
(91) The distillation was performed using a 1″ diameter glass column containing twelve pieces of Sulzer type EX structured packing, operated in continuous mode. The column also had two zones heated by electrical heating tape enabling the temperature of both the top and bottom areas of the column to be controlled.
(92) A Liebig condenser was used on the top of the column to cool/condense the overheads. The overheads were connected to a vacuum pump, with a target overheads pressure of 400 mbar to allow the separation to be performed at reduced reboiler temperature. Overheads were removed on a continuous basis, with the mass withdrawn measured periodically and compositional analysis performed. Overheads were analysed for water (HP08) and dimethyl succinate/methanol AS08 (30 m×0.32 mm DB-FFAP column), with the acid content (as mono-methyl succinate) determined by titration with 0.1N KOH using methanolic phenolphthalein indicator solution.
(93) Analysis of the chemical composition of the reboiler was carried out by gas chromatography (GC) using N,O-bis trimethylsilylacetamide (Regisil) to allow the resolution of acidic species to be achieved. The level of methanol, dimethyl succinate, monomethyl succinate, and succinic acid were determined (Sil8 column 50 m×0.32 mm). Reboiler samples were also analysed for acid content by means of a base titration with 0.1N KOH using methanolic phenolphthalein indicator solution. Water analysis was performed on HP08 which as was fitted with a thermal conductivity detector (TCD).
(94) The overheads and reboiler compositions measured, along with temperature and pressure data for this test are set out in Table 17.
(95) TABLE-US-00021 TABLE 17 Results of Distillation of Dimethyl Succinate and Monomethyl Succinate At 400 mbar Pressure Time on Line (hours) 0 0.25 0.75 1.75 3 Temperatures Reboiler Skin (° C.) 196 210 225 224 Reboiler Pot (° C.) 106 153 181 185 Column Wall TWI 84.3 103.3 159.5 154 (bottom) (° C.) Column Heater, TTI 92.3 82.7 177.9 164.4 (bottom) (° C.) Column Wall TWI 21.8 34.9 110.9 117 (top) (° C.) Column Heater, TTI 41.7 26 147.3 149.5 (top) (° C.) Overheads (° C.) 37.6 28.8 138.8 Pressure (mbar) 490 399 374 429 Pot Contents (g) 1032 982.1 949.2 933.5 920.4 Overheads Weight 48.86 30.94 12.72 11.09 (g) Bottoms Sample 1 2 3 2 Weight (g) Overheads Analysis Methanol wt % 86.42 27.11 2.067 0.375 Dimethyl Succinate 0.312 56.76 92.06 96.99 wt % Acid (as 0.537 0.038 0.11 0.147 Monomethyl Succinate) wt % Water wt % 12.73 15.36 4.627 1.129 Others wt % 0 0.736 1.1340 1.353 Total 100 100 100 100 Pot Analysis Methanol wt % 7.00 0.27 0 0 0 Dimethyl Succinate 63.00 65.73 65.99 65.71 66.19 wt % Monomethyl 27.00 29.68 29.25 29.86 30.08 Succinate wt % Succinic acid wt % 2.90 3.43 2.80 2.07 1.176 Water wt % 0.00 0.88 1.76 1.63 0 Succinic anhydride 0.00 0.00 0.19 0.72 0.589 wt % Others wt % 0.10 0.00 0.00 0.00 2.554 Total 100.00 100.00 100.00 100.00 100.59 Time on Line (hours) 4 5 6 7 8 8.67 Temperatures Reboiler Skin (° C.) 230 225 226 226 223 223 Reboiler Pot (° C.) 192 198 200 200 197 197 Column Wall TWI 159.5 158.7 158.6 158.2 159.2 159.2 (bottom) (° C.) Column Heater, TTI 161.8 153 157 164.5 159.6 159.6 (bottom) (° C.) Column Wall TWI 121.6 122.9 120.1 135.6 132.5 132.5 (top) (° C.) Column Heater, TTI 155.1 157.6 151 86 103.3 103.3 (top) (° C.) Overheads (° C.) 145.2 145.1 135.1 128.5 113.3 113.3 Pressure (mbar) 501 637 638 600 450 450 Pot Contents (g) 872.0 801.2 660.9 576.6 438.4 420.1 Overheads Weight 46.38 68.86 138.3 82.22 136.2 16.35 (g) Bottoms Sample 2 2 2 2 2 2 Weight (g) Overheads Analysis Methanol wt % 0.199 0 0 0 0 0 Dimethyl Succinate 98.36 98.61 99.08 94.36 99.22 98.99 wt % Acid (as 0.01 0.006 0.01 4.933 0.17 0.1 Monomethyl Succinate) wt % Water wt % 0.288 0.164 0.074 0.104 0.056 0.084 Others wt % 1.147 1.218 0.839 0.608 0.559 0.828 Total 100 100 100 100 100 100 Pot Analysis Methanol wt % 0 0 0 0 0 0 Dimethyl Succinate 66.77 66.16 60.36 48.16 40.06 41.38 wt % Monomethyl 29.25 29.32 34.02 46.53 53.44 51.88 Succinate wt % Succinic acid wt % 1.022 0.9683 1.190 2.113 2.623 3.411 Water wt % 0.0036 0.0667 0 0.1445 0 0 Succinic anhydride 1.730 2.279 2.751 1.875 2.565 1.695 wt % Others wt % 2.955 3.4855 4.428 3.056 3.880 3.319 Total 101.73 102.28 102.75 101.88 102.56 101.69