Certificate of Experiment
`
`I, Ryuji SAlTO, majored in Production System in Graduate School of Science
`
`and Technology, Niigata University of 8050. lgarashi 2-Nocho, Nishi-ku, Niigata,
`
`Japan, and graduated therefrom in March 1998, employed by Daicel Chemical
`
`Industries, Ltd, Japan since April 1998, and currently work as a researcher for a
`
`process development, hereby declare that all statements made herein of any own
`
`knowledge are true and that all statements made on information and belief are
`
`believed to be true.
`
`l have conducted experiments which prove that not only that the second
`
`overhead of document D1 comprises dimethyl ether recited in the granted claims
`
`3, 15 and 27 (new claims 18, 30 and 51 as well as new claims 2, 22 and 39) but
`
`also that the process of document D1 forms dimethyl ether during the distillation
`
`recited in the granted claims 5, 18 and 35 (new claims 4, 24 and 44). Further,
`
`the experiments prove the presence of methanol in the mixture recited in the
`
`granted claim 24 (new claims 36).
`
`That is, Example and Example 1 of D1 were repeated twice according to the
`
`descriptions of D1 to prove that the second overhead of document D1 comprises
`
`dimethyl ether and that dimethyl ether is formed during the distillation of Di, and
`
`that methanol is inherently present in the mixture (the first overhead 20) of D1,
`
`as shown in the experimental data.
`
`In more details, the experiments were
`
`conducted as follows.
`
`000001
`
`Exh. 1025
`
`000001
`
`Exh. 1025
`
`
`
`I, Ryuji SAlTO, majored in Production System in Graduate School of Science
`
`and Technology, Niigata University of 8050. lgarashi 2-Nocho, Nishi-ku, Niigata,
`
`Japan, and graduated therefrom in March 1998, employed by Daicel Chemical
`
`Industries, Ltd, Japan since April 1998, and currently work as a researcher for a
`
`process development, hereby declare that all statements made herein of any own
`
`knowledge are true and that all statements made on information and belief are
`
`believed to be true.
`
`l have conducted experiments which prove that not only that the second
`
`overhead of document D1 comprises dimethyl ether recited in the granted claims
`
`3, 15 and 27 (new claims 18, 30 and 51 as well as new claims 2, 22 and 39) but
`
`also that the process of document D1 forms dimethyl ether during the distillation
`
`recited in the granted claims 5, 18 and 35 (new claims 4, 24 and 44). Further,
`
`the experiments prove the presence of methanol in the mixture recited in the
`
`granted claim 24 (new claims 36).
`
`That is, Example and Example 1 of D1 were repeated twice according to the
`
`descriptions of D1 to prove that the second overhead of document D1 comprises
`
`dimethyl ether and that dimethyl ether is formed during the distillation of Di, and
`
`that methanol is inherently present in the mixture (the first overhead 20) of D1,
`
`as shown in the experimental data.
`
`In more details, the experiments were
`
`conducted as follows.
`
`000001
`
`Exh. 1025
`
`000001
`
`Exh. 1025
`
`
`
`imam:
`
`A reaction liquid (a composition: methyl iodide of 7.3 weight %, water of 5.2
`
`weight %, methyl acetate of 1.4 weight %, acetic acid of 73.5 weight "/0, lithium
`
`iodide of 12.4 weight %, and rhodium of 938 ppm) was subjected to the flasher
`
`(conventionally used flasher) to obtain a volatile phase containing acetic acid
`
`and the volatile phase was subjected to the splittercolumn (conventionally used
`
`column) to obtain a first overhead, and, the first overhead from the top of the
`
`splitter column was condensed, and a part of the lower phase in the separator
`
`bath was distilled in the distillation column of 80 plates in accordance with the
`
`“Distillation condition" shown in Example of D1. The top withdrawn liquid (the
`
`second overhead) from the 80-plates distillation column was subjected to water
`
`extraction and the obtained extract was distilled for separating acetaldehyde
`
`from the extract.
`
`The extraction was carried out with a ratio S/F of water which was a solvent to
`
`the top withdrawn liquid from the 80-plates distillation column being set to 1
`
`(weight ratio) and a theoretical plate being two plates. An extractability of
`
`acetaldehyde was 98 by weight%. Acetaldehyde of 39.5 by weight% could be
`
`removed by processing the whole amount of the top withdrawn liquid from the
`
`80-plates distillation column. This could lead to removal of 69 by weight% of
`the amount of acetaldehyde formed in the reactor. A raffinate'(methyl
`
`iodide-rich liquid), which had been refined by removing acetaldehyde, was
`
`recirculated into the 26th plate from the top of the above 80-plates distillation
`
`column to thereby recirculate it (i.e., methyl iodide stream) into the reactor as a
`
`000002
`
`Exh. 1025
`
`000002
`
`Exh. 1025
`
`
`
`bottom withdrawn liquid from the above 80-plates distillation column. An
`
`extract (aqueous phase stream) with which acetaldehyde had been extracted
`
`was supplied to the subsequent distillation column, wherein acetaldehyde was
`
`withdrawn as a distillate, and water was withdrawn as a bottom product.
`
`In this
`
`distillation, separation could sufficiently be made at a theoretical plate of 8
`
`plates and a reflux ratio of 4.5. The acetaldehyde concentration in the reactor
`
`was 220 ppm. A wet product stream withdrawn from the vicinity of the bottom
`
`of the methyl iodide-acetic acid splitter column 14 was dried by distillation. The
`
`concentration otpropionic acid in this dried product liquid was 220 ppm. The
`
`dehydrated product acetic acid was further distilled for removing high boiling
`
`matters to obtain the product acetic acid.
`
`Experiment 2:
`
`The reaction and the purifying processes were repeated as same manner as in
`
`the Experiment 1 except that the following reaction liquid was subjected to the
`
`flasher and the extraction and the other subsequent processing processes were
`
`conducted as described below.
`
`The reaction liquid has a composition: methyl iodide of 7.1 weight %, water of
`
`2.6 weight %, methyl acetate of 1.8 weight %, acetic acid of 68.3 weight %,
`
`lithium iodide of 13.3 weight %, and rhodium of 963 ppm.
`
`000003
`
`Exh. 1025
`
`000003
`
`Exh. 1025
`
`
`
`Extraction was carried outwith a ratio S/F of water which was a solvent to the
`
`top withdrawn liquid from the 80-plates distillation column being set to 1 (weight
`
`ratio) and a theoretical plate being two plates. An extractability of
`
`acetaldehyde was 98 % by weight. Acetaldehyde of 29 % by weight could be
`
`removed by processing the whole amount of the top withdrawn liquid from the
`
`80-plates distillation column. This could lead to removal of 81 % by weight of
`
`the amount of acetaldehyde formed in the reactor. A raffinate (methyl
`
`iodide-rich liquid), which had been refined by removing acetaldehyde, was
`
`recirculated into the 26‘h plate from the top of the above 80-plates distillation
`
`column, and a bottom withdrawn liquid from the above 80-plates distillation
`
`column was recirculated into the reactor. An extract (aqueous phase stream)
`
`with which acetaldehyde had been extracted was supplied to the subsequent
`
`distillation column, wherein acetaldehyde was withdrawn as a distillate, and
`
`water was withdrawn as a bottom product.
`
`in this distillation, separation could
`
`sufficiently be made at a theoretical plate of 8 plates and a reflux ratio of 4.8.
`
`The acetaldehyde concentration in the reactor was 146 ppm. A wet product
`
`stream withdrawn from the vicinity of the bottom of the methyl iodide-acetic acid
`
`splitter column 14 was dried by distillation. The concentrations of hexyl iodide
`
`and propionic acid in’this dried product liquid were 13 ppb and 105 ppm,
`
`respectively. The dehydrated product acetic acid was further distilled for
`
`removing high boiling matters to obtain the product acetic acid.
`
`Results are shown in the following Table 1.
`
`000004
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`Exh. 1025
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`000004
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`Exh. 1025
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`
`
`In the Table 1, “Alkanes” means the total amount of decane and undecane by
`
`the quantitative analysis, and the symbol “-" shows that the amount of the
`
`component was not measured.
`
`In the Table 1, the amount of each component was measured by an instrument
`
`suitably selected from plurality of instmments, depending on components.
`
`Table 1
`
`Condensed and
`.
`.
`Separated Uquxd
`Phases of the
`Overhead 20
`
`.
`.
`80 Plates Distillation
`
`Water-E I ctor
`
`Subsequent
`Distillation
`
`The Upper
`Phase 32
`
`Charged
`.
`.
`L'qu‘d
`
`Top
`Vlfithdrawn
`Liv id
`
`Extract
`(column
`to
`
`Raffinate
`(column
`
`Column
`Bottom
`
`Column .
`“’9
`
`x:cg3|3::-o a)
`
`tou4:.e:
`
`_tSo:.‘la)T"F”—~«3on\I
`
`Methyl lodide (Mel)
`Methyl Acetate (MA)
`
`Acetic Acid (AC)
`Acetaldehyde (AD)
`para-Aldehyde (p-AD)
`Alkanes
`Methanol
`Dimeth Ether (DME)
`others
`Math Hodlde (Mel)
`
`fififififiéfififififi
`
`“-—
`
`Dimethyl Ether (DME)
`
`§EEE
`
`As apparent from the Table 1, the second overhead (the top withdrawn liquid
`
`from the 80-plates distillation column) of document D1 comprises dimethyl ether
`
`000005
`
`Exh. 1025
`
`000005
`
`Exh. 1025
`
`
`
`and dimethyl ether is formed during the distillation (splitter column and 80-plates
`
`distillation column) of D1.
`
`Incidentally, the charged liquid, which is charged to
`
`the 80 plates distillation column, corresponds to the lower phase 30, obtained by
`
`condensing the overhead 20. Thus, the first overhead 20 (Le, the upper
`
`phase 32 and the lower phase 30) of D1 contains methanol.
`
`Incidentally, the composition (proportion of the components) of each of the
`
`reaction liquids used in Experiments 1 and 2 is within the scope of the invention
`
`of D1. Further, although the raffinate (methyl iodide-rich liquid) was
`
`recirculated into the 26"1 plate from the top of the above 80-plates distillation
`
`column in Experiments 1 and 2, the plate of the above 80-plates distillation
`
`column to be recirculated with the raffinate does not affect the formation of
`
`dimethyl ether, as apparent from the fact that dimethyl ether (DME) is inevitably
`formed by the presence of the reactants formable dimethyl ether (DME).
`
`Furthermore, the distillation of the extract (aqueous phase stream) by the
`
`subsequent distillation column with a reflux ratio of 4.5 or 4.8 is also irrelevant
`
`with the formation of dimethyl ether, since this distillation operations are not
`
`defined by any of claims of the opposed patent.
`
`Dated: September 10, 2010
`
`Respectfully submitted.
`
`By W 15m
`
`Ryuji SAITO
`
`000006
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`Exh. 1025
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`000006
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`Exh. 1025
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`
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