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`GRUNECKER
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`Certificate of Experiment
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`I, Hiroyuki MIURA. majored in Industrial Organic Chemistry in Graduate School of
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`Engineering, Muroran Institute of Technology of 27-1 Mizumoto-cho, Muroran
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`0506585. Japan, and graduated therefrom in March 1983. employed by Daicel
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`Chemical Industries, Ltd, Japan since April 1983, and currently work as a researcher
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`for a catalysis and a process development of the production (manufacture) of acetic
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`acid, hereby declare that all statements made herein of any own knowledge are true
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`and that all statements made on information and belief are believed to be true.
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`I have conducted experiment which proves that not only that the second overhead of
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`document D1 comprises dimethyl ether recited in claims 3, 15 and 27 (new claims 2.
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`18, 22, 30, 39 and 51 in Auxiliary Request) but also that the process of document D1
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`forms dimethyl ether during the distillation recited in claims 5, 18 and 35 (new claims 4,
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`24 and 44 in Auxiliary Request).
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`Further, the experiment was conducted to prove the
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`presence of methanol in the mixture recited in claims 24 and 28 (new claims 36. 48 and
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`53 in Auxiliary Request).
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`That is. the experiment was conducted according to Example and Example 1 of the
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`descriptions of 01 to prove that the second overhead of document D1 comprises
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`dimethyl ether and that dimethyl ether is formed during the distillation of D1, and that
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`20
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`methanol is inherently present in the mixture (the first overhead 20) of D1, as shown in
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`the experimental data.
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`In more details. the experiments were conducted as follows.
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`Experiment 1:
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`A reaction liquid (a composition; methyl iodide of 8.2 weight %, water of 2.7 weight %.
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`methyl acetate of 1.6 weight %, acetic acid of 73.5 weight %,
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`lithium iodide of 12.3
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`weight %, and rhodium of 910 ppm) was subjected to the flasher (conventionally used
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`flasher) to obtain a volatile phase containing acetic acid, and the volatile phase was
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`subjected to the splitter column (conventionally used column) to obtain a first overhead.
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`and, the first overhead from the top of the splitter column was condensed. and a part of
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`the lower phase in the separator bath was distilled in the distillation column of 80 plates
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`in accordance with the “Distillation condition" shown in Example of D1. The top
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`withdrawn liquid (the second overhead) from the 80-plate distillation column was
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`subjected to water extraction and the obtained extract was distilled for separating
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`acetaldehyde from the extract.
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`The extraction was carried out with a ratio S/F of water which was a solvent to the top
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`withdrawn liquid from the 8o-plate distillation column being set to 0.9 (weight ratio) and
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`a theoretical plate being two plates. An extractability of acetaldehyde was 99.7 by
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`weight%. This could lead to removal of 80 by weight% of the amount of acetaldehyde
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`formed in the reactor. A ratfinate (methyl iodide-rich liquid), which had been refined
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`by removing acetaldehyde, was recirculated into the 26m plate from the top of the
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`above 80-plate distillation column to thereby recirculate it (i.e.. methyl iodide stream)
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`into the reactor as a bottom withdrawn liquid from the above 80-plate distillation column.
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`An extract (aqueous phase stream) with which acetaldehyde had been extracted was
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`supplied to the subsequent distillation column, wherein acetaldehyde was withdrawn
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`as a distillate. and water was withdrawn as a bottom product.
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`In this distillation,
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`separation could sufficiently be made at a theoretical plate of 8 plates and a reflux ratio
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`of 4.8. The acetaldehyde concentration in the reactor was 210 ppm. A wet product
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`stream withdrawn from the vicinity of the bottom of the methyl iodide-acetic acid splitter
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`20
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`column 14 was dried by distillation. The concentration of propionic acid in this dried
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`product liquid was 130 ppm. The dehydrated product acetic acid was further distilled
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`for removing high boiling matters to obtain the product acetic acid.
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`Results are shown in the following Table 1.
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`In the Table 1, “ND" means “not detectable” by the quantitative analysis, and the
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`symbol “-” shows that the amount of the component was not measured.
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`The amount of each of the components was measured quantitatively by an instrument
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`suitably selected from plurality of instruments. depending on components, and the
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`results were shown in Table 1.
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`The sum (total) of the analysis value (wt%) of each process liquid in Table 1 is not just
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`100 exactly because of rounding error of each analysis value.
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`Table 1
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`Condensed
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`80 Plates Distillation
`Column
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`Water-Extractor
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`Subsequent
`Distillation
`Column
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`and
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`Separated
`Liquid
`Phases of
`the
`Overhead
`20
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`Methyl Iodide wt%
`(Mel)
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`Extract Ratfinate Column Column
`Top
`The Upper Charged
`Phase 32
`Liquid Withdrawn (column
`(column
`top
`bottom
`Liuid
`to-
`bottom
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`88.0
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`49.4
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`Acetate MA
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`wt%“I-WMMEM
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`Acetic Acid
`(AC)
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`wt%
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`17.4
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`1.8
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`0.15
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`Acetaldehyde wt%
`(A0)
`0.49
`0.14
`47.1
`0.17
`83.4
`Methanol
`wt%—-lIl--mmmm
`--------m
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`—-m---mmm
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`As apparent from the Table 1, the second overhead (the top withdrawn liquid from the
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`80—plate distillation column) of document D1 comprises dimethyl ether and dimethyl
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`ether is formed during the distillation (splitter column and 80-plate distillation column) of
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`D1. The charged liquid, which is charged to the 80 plates distillation column,
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`corresponds to the lower phase 30 obtained by condensing the overhead 20.
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`Further,
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`both of the upper phase 32 and the lower phase 30 (charged liquid to the 80 plates
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`distillation column) contain not only dimethyl ether but also components forming
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`dimethyl ether (methyl acetate and methyl iodide. water and methanol). Thus.
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`distillation of the upper phase 32 and/or the lower phase 30 forms dimethyl ether
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`inevitably. Moreover, the first overhead 20 (|.e.. the upper phase 82 and the lower
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`phase 30) of D1 contains methanol.
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`11-08-11;01:i3vm;fimfi§§¥m KUWATA&CO
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`GRUNECKER
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`The composition (proportion of the components) of the reaction liquid used in
`Experiment 1 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
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`80-plate distillation column in Experiment 1, the position of the plate of the above
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`80-plate distillation column to be recirculated with the raffinate does not affect the
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`formation of dimethyl ether, as apparent from the fact that dimethyl ether (DME) is
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`inevitably formed by the presence of the reactants formable dimethyl ether (DM E).
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`Furthermore, the distillation of the extract (aqueous phase stream) by the subsequent
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`distillation column with a reflux ratio of 4.8 is also irrelevant with the formation of
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`dimethyl ether, since this distillation operations are not defined by any of claims of the
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`opposed patent.
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`Respectfully submitted,
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`Dated:
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`July 29, 2011
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`WWW
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`Hiroyuki MIUFlA
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