(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(19) World Intellectual Property Organization
`International Bureau
`
`(43) International Publication Date
`16 August 2007 (16.08.2007)
`
` (10) International Publication Number
`
`WO 2007/091862 A1
`
`(51) International Patent Classification:
`C07C 2/28 (2006.01)
`
`10371408 Chowon APT, Mahnnyunrdong
`[KR/KR];
`Seo—gu, Daejeon 302—740 (KR).
`
`(21) International Application Number:
`PCT/KR2007/000706
`
`(74) Agents: KWON, Oh-Sig et al.; 4F, Jooeun Leaderstel, 921
`Dunsan—dong Seo—gu, Daejeon 302—120 (KR).
`
`(22) International Filing Date: 9 February 2007 (09.02.2007)
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`English
`
`English
`
`(30) Priority Data:
`10—2006—0012317
`
`9February 2006 (09.02.2006)
`
`KR
`
`(71) Applicant (for all designated States except US): KO-
`REA RESEARCH INSTITUTE OF CHEMICAL
`
`TECHNOLOGY [KR/KR]; 100, Jang—dong Yuseong—gu,
`Daejeon 305—600 (KR).
`
`(72) Inventors; and
`(75) Inventors/Applicants (for US only): JHUNG,Sung-Hwa
`[KR/KR];
`5—1104 Cheongsol APT, Sahmcheon—dong
`Seo—gu, Daejeon 302—743 (KR). CHANG, Jong-San
`[KR/KR]; 103—204 Yudeungmaheul APT, Taepyung—dong
`Joong—gu, Daejeon 301—779 (KR). YOON, Ji Woong
`[KR/KR]; 301 Seongdo villa,
`98—322 Sinrim2—dong
`Gwanak—gu,
`Seoul
`151—855
`(KR). KIM, Tae-Jin
`[KR/KR];
`111—904
`Sejong APT,
`Jeonmin—dong
`Yuseong—gu, Daejeon 305—728
`(KR). CHOO, Dae
`Hyun [KR/KR]; 102—407 Doshi APT, Dongsahm—dong
`Youngdo—gu, Busan 606—080
`(KR). LEE, Hee-Du
`
`(81) Designated States (unless otherwise indicated, for every
`kind of national protection available): AE, AG, AL, AM,
`AT, AU, AZ, BA, BB, BG, BR, BW, BY, BZ, CA, CH, CN,
`CO, CR, CU, CZ, DE, DK, DM, DZ, EC, EE, EG, ES, FI,
`GB, GD, GE, GH, GM, GT, HN, HR, HU, ID, IL, IN, IS,
`JP, KE, KG, KM, KN, KP, KZ, LA, LC, LK, LR, LS, LT,
`LU, LV, LY, MA, MD, MG, MK, MN, MW, MX, MY, MZ,
`NA, NG, NI, NO, NZ, OM, PG, PH, PL, PT, RO, RS, RU,
`SC, SD, SE, SG, SK, SL, SM, SV, SY, TJ, TM, TN, TR,
`TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM, ZW.
`
`(84) Designated States (unless otherwise indicated for every
`kind of regional protection available): ARIPO (BW, GH,
`GM, KE, LS, MW, lVIZ, NA, SD, SL, SZ, TZ, UG, ZM,
`ZW), Eurasian (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM),
`European (AT, BE, BG, CH, CY, CZ, DE, DK, EE, ES, FI,
`FR, GB, GR, HU, IE, IS, IT, LT, LU, LV, MC, NL, PL, PT,
`RO, SE, SI, SK, TR), OAPI (BF, BJ, CF, CG, CI, CM, GA,
`GN, GQ, GW, ML, MR, NE, SN, TD, TG).
`
`Published:
`
`— with international search report
`
`For two—letter codes and other abbreviations, refer to the ”Guid—
`ance Notes on Codes and Abbreviations ” appearing at the begin—
`ning of each regular issue of the PCT Gazette.
`
`(54) Title: PREPARATION METHOD OF LIGHT OLEFIN TRIMERS AND PRODUCTION OF HEAVY ALKYLATES BY
`USING THEREOF
`
`(57) Abstract: The present invention relates to a preparation method of olefin trimers, and more particularly, to a preparation method
`of isobutene trimers that are useful as precursors for heavy alkylates or neo acids, performed in such a manner that a macroporous
`cation exchange resin in hydrogen form is used as a catalyst and the olefin conversion is higher than 60%. Furthermore, the present
`invention relates to a preparation method of heavy alkylates by hydrogenating olefin trimers thus formed.
`
`
`
`WO2007/091862A1|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
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`BUTAMAX l 03 7
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`

`

`WO 2007/091862
`
`PCT/KR2007/000706
`
`Description
`
`PREPARATION METHOD OF LIGHT OLEFIN TRIMERS AND
`
`PRODUCTION OF HEAVY ALKYLATES BY USING THEREOF
`
`Technical Field
`
`[1]
`
`The present invention relates to a preparation method of olefin trimers useful as
`
`precursors for heavy alkylates or neo acids. More particularly, present invention relates
`
`to a preparation method of olefin trimers, with high throughput and purity, by tuning
`
`the pore—structure of acid catalysts and by increasing olefin conversion.
`
`Background Art
`
`[2]
`
`The oligomerization reaction of olefms has been carried out by using acid catalysts
`
`such as supported phosphoric acid, and olefin dimers have been generally obtained for
`
`gasoline additive after hydrogenation of the dimers (USP 6689927, 6284938).
`
`[3]
`
`Alkylates have been prepared by the alkylation of olefms with paraffins in the
`
`presence of sulfuric acid or hydrofluoric acid (Catalysis Today, 49, 193, 1999);
`
`however, the method has a severe disadvantage of environmental problem and
`
`corrosion due to the usage of the liquid acids. Heavy alkylates with C9 or more carbons
`are obtained by the alkylation in low content of 5-10%, and are used as prime solvent
`
`or diesel additive to increase the cetane—number of diesel fuel. Therefore, development
`
`of a new process to produce heavy alkylate is necessary because the productivity is
`
`limited by conventional methods.
`
`[4]
`
`Recently, several oligomerization methods to prepare trimers are reported. Olefin
`
`trimerization has been mainly carried out by using solid acid catalysts such as
`
`heteropoly acid (JP 2005015383), zirconia (JP 2005015384), zeolite called Al-TS-l
`
`(USP 6914165) and sulfated titania (J. Molecular Catalysis A, 228, 333, 2005). Ionic
`
`liquids are also used for the reaction (CN 1379005).
`
`[5]
`
`A few examples have also been reported to utilize cation exchange resins for the
`
`oligomerization. It has been claimed that a cation exchange resin can be used in a
`
`dimerization (USP 2005/0119111A1). USP 5789643 taught that oligomerization could
`
`be catalyzed by zeolites, aluminas and ion exchange resins. Tetramers or pentamers
`
`could be obtained by the oligomerization of pre—formed dimers with ion exchange
`
`resins (US 6239321).
`
`[6]
`
`Moreover, an ion exchange resin called Amberlyst—15 was used in the
`
`oligomerization of isobutene (Catalysis Today, 100, 463, 2005). However, the
`
`conversion was less than 40% and dimers rather than trimers were the main products.
`
`[7]
`
`Hence, there is no finding to use cation exchange resins in the olefin trimerization.
`
`Furthermore, no result is reported to get olefin trimers by adjusting physical properties
`
`

`

`WO 2007/091862
`
`PCT/KR2007/000706
`
`of ion exchange resins or optimizing olefin conversion.
`
`[8]
`
`Therefore, there remains a need in the art for the development of a novel process for
`
`preparing olefin trimers by using solid acid catalysts such as ion exchange resins.
`
`Disclosure of Invention
`
`Technical Problem
`
`[9]
`
`The present inventors have made intensive researches to overcome the
`
`shortcomings described above, and as a result, found a novel trimerization process in
`
`which a macroporous cation exchange resin is used in the reaction and the olefin
`
`conversion is higher than 60%. Moreover, a heavy alkylate is obtained by the hy-
`
`drogenation of trimers that are derived from the trimerization.
`
`[10]
`
`Accordingly, the object of this invention is to provide a process for producing olefin
`
`trimers with high trimers selectivity, high throughput and long catalyst life. Moreover,
`
`this invention is also to provide a method for producing a heavy alkylate by the hy-
`
`drogenation of the trimers thus obtained.
`
`Technical Solution
`
`[11]
`
`The present invention is directed to a novel process for preparing olefin trimers by
`
`oligomerization of olefins, wherein macroporous cation exchange resins are used as
`
`catalysts and the olefin conversion is higher than 60%. The present invention is also
`
`directed to a process for preparing heavy alkylates by the hydrogenation of olefin
`
`trimers thus obtained. Olefin trimers can be effectively prepared by using macroporous
`
`cation exchange resins, rather than gel-type cation exchange resins without internal
`
`surface area, that have high internal surface area, due to pores (>5nm) even in dried
`
`state, and maintaining the olefin conversion high, preferably higher than 60 %.
`
`The present invention will be described in more detail as follows:
`
`The olefins described in this invention are any olefins composed of C2 or higher
`carbon, preferentially to be C3 or C4 unsaturated hydrocarbons, and more preferentially
`to be butenes (C4H3) and isobutene is the most suitable olefin.
`The oligomerization temperature does not have any limitation; however, the
`
`preferential temperature is from room temperature to 120 °C. The reaction rate should
`
`be low when the temperature is too low, whereas, the conversion at high temperature is
`
`not high, due to the exothermal oligomerization reaction, and the resin catalyst can be
`
`degraded if the temperature is too high. The reaction temperature of 50-100 °C is more
`
`suitable.
`
`[12]
`
`[13]
`
`[14]
`
`[15]
`
`The oligomerization reaction can be performed both in batch mode and continuous
`
`mode, and the latter method is suitable for mass production of oligomers. The
`
`continuous mode is operated well by using a fixed bed reactor, and the reactants can be
`
`flown upward or downward.
`
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`WO 2007/091862
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`PCT/KR2007/000706
`
`[16]
`
`It is advisable to use a solvent to control the heat of reaction because the
`
`oligomerization reaction is very exothermic. Moreover, a solvent is helpful to transport
`
`reactants and products easily. As a solvent, hydrocarbons such as C2-C10 paraffins can
`be used. More preferably, isobutane, n-butane, pentanes, hexanes, octanes, nonanes or
`
`decanes can be used. Cyclohexane can also be utilized as a solvent. The reactant/
`
`solvent ratio can be any value between 1/100 and 100/1 (wt/wt), and it is preferable to
`
`maintain the ratio between 1/ 10 and 10/1 because of the operation convenience and
`
`high productivity. Inert gases such as nitrogen, argon, carbon dioxide and helium can
`
`be used as a diluent instead of an organic solvent. It is good to flow the reactant and
`
`the inert gas upward when diluent is used in a fixed bed reactor.
`
`[17]
`
`Any macroporous cation exchange resins can be used in the oligomerization
`
`reaction if the resin is in a hydrogen form. The pore size of macropore should be larger
`
`than 5 nm even in dried form as described in Reactive and functional polymers, 35, 7,
`
`1997. The catalyst stability is low when the pore size is too large, whereas the
`
`diffusion of reactants and products are difficult or deactivation of the catalyst is too
`
`fast if the pore size is too small. On the other hand, gel-type ion exchange resins
`
`without macropore have the drawback of low reactivity and rapid deactivation.
`
`[18]
`
`The resins to support hydrogen ion can be any composition, and the resins
`
`composed of styrene and divinylbenzene copolymers are suitable. As the content of di-
`
`vinylbenzene increases the stability of catalyst increases due to the increased degree of
`
`crosslinkings. However, the diffusion of reactants and products will be difficult. The
`
`content of divinylbenzene should be 2—98% of the total content of divinylbenzene and
`
`styrene. The cation exchange resins should have functional group of sulfonic acid (—SO
`
`3H) because the acidity is high when the hydrogen ion exists in the form of sulfonic
`acid.
`
`[19]
`
`As the oligomerization reaction rate is high when the concentration of hydrogen ion
`
`is high, the cation exchange resins should have at least 2—equivalent Hng-resin. More
`
`preferably, the hydrogen ion concentration is at least 3-equivalent H7kg-resin. The
`
`hydrogen ion concentration of 4-6 equivalent Hng-resin is most preferable.
`
`[20]
`
`Any commercial cation exchange resins can be utilized as long as the resins are
`
`macroporous and hydrogen form. Amberlyst—35, Amberlyst—DT and Diaion-PK—228
`
`are some of the examples that can be used easily. Amberlyst—35 is the most suitable
`
`catalyst because the concentration of sulfonic acid is high. Moreover, any synthetic
`
`cation exchange resins can be used for the reaction.
`
`[21]
`
`Cation exchange resins can be used in any state such as water-containing form,
`
`dried form, alcohol-containing form and acetone-containing form. The alcohol— or
`
`acetone-containing form can be obtained by solvent exchange of water with alcohol or
`
`acetone. Alcohol- or acetone-containing resin is more suitable because the catalytic
`
`

`

`WO 2007/091862
`
`PCT/KR2007/000706
`
`performance in the earlier stage of reaction is more stable and the catalyst life is longer
`
`than any other state. This may be due to the fact that the reactants are organics similar
`
`to the alcohols or acetone incorporated in the cation resins.
`
`[22]
`
`Granular catalyst is suitable for the reaction even though no specific size and
`
`morphology are mandatory. Catalyst with size greater than 0.1 mm is more suitable,
`
`and the size of 0.2-1.0 mm is most suitable for the operation ability and low pressure
`
`drop.
`
`[23]
`
`Olefin conversion does not have any limitation as long as the conversion is higher
`
`than 60%. More preferably, the conversion should be higher than 90% because the se-
`
`lectivity of olefin trimers increases with increasing olefin conversion. If the conversion
`
`is too low the formation of impurities such as olefin dimers cannot be avoided,
`
`whereas olefin tetramers can be increased slightly when the olefin conversion is too
`
`high.
`
`[24]
`
`The productivity is low and the concentration of high molecular weight impurity is
`
`high when the flow rate or space velocity of reactant is too low. On the other hand, the
`
`olefin conversion and trimers selectivity are low if the space velocity is too high. The
`
`suitable space velocity, based on the olefin WHSV (weight hourly space velocity), is
`2-100 h'l, and more preferably the velocity is 10-50 h'l.
`
`[25]
`
`The trimers that obtained from the olefin oligomerization can be utilized directly for
`
`the production of chemicals such as neo—acid or can be converted to heavy alkylate by
`
`hydrogenation. Heavy alkylates containing C9 or higher carbons are obtained by hy-
`drogenation of the olefin trimers that are prepared by this invention. The hy-
`
`drogenation is described only briefly because hydrogenation is conducted relatively
`
`easily in the presence of a precious metal or nickel as described in 'Fine chemicals
`
`through heterogeneous catalysis, Wiley-VCH, 2001, pp. 351-426'. The hydrogenation
`
`for heavy alkylate can be performed with any conventional reactors such as a fixed bed
`
`reactor and a continuous stirred reactor. Hydrogenation catalyst can be selected from
`
`any supported catalysts such as Pd/C, Pd/alumina, Pd/silica, Pdlsilica—alumina, Pt/C,
`
`Pt/alumina, Pt/silica, Pt/silica—alumina, Ru/C, Ru/alumina, Ru/silica, Ru/
`
`silica-alumina, Ni/C, Ni/alumina, Ni/silica, Ni/silica—alumina. Or, the mixed catalysts
`
`containing two or more of above mentioned catalysts can be applicable. Furthermore
`
`supported mixed catalyst that containing two or more metals from Pd, Pt, Ru, Ni can
`
`be used for the hydrogenation. The hydrogenation reaction can be carried out in any
`
`phase such as liquid— or gas—phase and any concentration of hydrogen is affordable as
`
`long as the total amount of hydrogen is higher than the stoichiometric amount that is
`
`needed for the hydrogenation.
`
`Brief Description of the Drawings
`
`

`

`WO 2007/091862
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`PCT/KR2007/000706
`
`[26]
`
`Fig. 1 represents the change of conversion and selectivities with reaction time in the
`
`isobutene oligomerization, obtained in Example 1.
`
`[27]
`
`Fig. 2 represents the dependence of trimers selectivity on the isobutene conversion,
`
`obtained in Example 5.
`
`Mode for the Invention
`
`[28]
`
`The following specific examples are intended to be illustrative of the invention and
`
`should not be construed as limiting the scope of the invention as defined by appended
`
`[29]
`
`[30]
`
`[31]
`
`[32]
`
`[33]
`
`[34]
`
`claims.
`
`EXAMPLE 1
`
`The oligomerization reaction of isobutene was carried out at 70 °C by using a fixed
`
`bed reactor containing 2 g of dried Amberlyst—35 (size: 0.2 1.0mm, average diameter:
`
`0.5 mm) and by flowing n-butane and isobutene (1:1 wt ratio) upward. The flow rates
`
`of hydrocarbons were controlled by mass flow controllers and the isobutene flow rate
`
`was adjusted for the isobutene WHSV (weight hourly space velocity) to be 10 h'l. The
`
`reaction temperature was maintained constant by using a liquid circulator. Circulated
`
`water at fixed temperature absorbs extra heat generated from the oligomerization
`
`reaction. The isobutene conversion was calculated by the analysis of gas-phase effluent
`
`by using a GC. The isobutene conversion was cross-checked by measuring the total
`
`flow rates of n-butane and isobutene with mass flow meters. The liquid product, after
`
`trapping using a cold trap, was analyzed by a GC for the composition of dimers,
`
`trimers and tetramers. As shown in Table 1, the isobutene conversion and trimers se-
`
`lectivity were 99.4% and 75.5 wt%, respectively, through the reaction of 70 h. The
`
`dimers selectivity and tetramers selectivity were maintained low of 9.4 wt% and 15.1
`
`wt %, respectively. Detailed reaction conditions and reaction results are summarized in
`
`Table 1.
`
`EXAMPLE 2
`
`The oligomerization reaction was carried out as Example 1, except that ethanol-
`
`containing catalyst was used instead of dried catalyst. Ethanol-containing Amberlyst-
`
`35 was prepared from water-containing catalyst by replacing water with ethanol. The
`used catalyst was 2 g based on the dried catalyst, and the isobutene WHSV was 50 h-1
`instead of 10 h'l. Even though 2 h of reaction time was needed for the steady state
`
`reaction, the isobutene conversion and trimers selectivity were satisfactory after 12 h
`
`of reaction. Detailed reaction conditions and reaction results are summarized in Table
`
`1.
`
`EXAMPLE 3
`
`The oligomerization reaction was carried out as Example 1, except that water-
`
`containing catalyst was used instead of dried catalyst. Water-containing Amberlyst—35
`
`

`

`WO 2007/091862
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`PCT/KR2007/000706
`
`[35]
`
`[36]
`
`[37]
`
`[38]
`
`[39]
`
`[40]
`
`was used as-received from the maker. The catalyst was 2 g based on the dried catalyst,
`and the isobutene WHSV was 80 h'1 instead of 10 h'l. Even though 2 h of reaction time
`
`was needed for the steady state reaction, the isobutene conversion and trimers se-
`
`lectivity were satisfactory after 10 h of reaction. Detailed reaction conditions and
`
`reaction results are summarized in Table 1.
`
`EXAMPLE 4
`
`The oligomerization reaction was carried out as Example 3, except that ethanol-
`
`containing Amberlyst—DT catalyst was used instead of water-containing Amberlyst—35
`
`catalyst. Ethanol-containing Amberlyst—DT was prepared from water-containing
`
`catalyst by replacing water with ethanol. The catalyst was 2 g based on the dried
`catalyst, and the isobutene WHSV was 50 h'1 instead of 80 h'l. Even though 2 h of
`
`reaction time was needed for the steady state reaction, the isobutene conversion and
`
`trimers selectivity were higher than 50% after 12 h of reaction. Detailed reaction
`
`conditions and reaction results are summarized in Table 1.
`
`EXAMPLE 5: Dependence of trimers selectivity on conversion
`
`The oligomerization reaction was carried out as Example 3 except that process
`
`parameters such as temperature, space velocity and catalyst amount were changed to
`
`reach the isobutene conversion of 40%-100%. The trimers selectivity increased with
`
`the isobutene conversion as shown in Fig. 2. It can be known that isobutene conversion
`
`should be higher than 60% for the trimers selectivity higher than 50%.
`
`EXAMPLE 6: Hydrogenation reaction
`
`Ten(10) grams of trimers, obtained in Example 1 and purified with distillation, were
`
`loaded in a continuous stirred reactor. Cyclohexane (90 g) was added as a solvent.
`
`Catalyst basket containing 0.5 g of Pd (5%)IC was mounted on the stirring shaft. The
`
`reactor temperature was maintained at 100 °C and the reactor pressure was raised to 10
`
`atm by using hydrogen. The hydrogenation reaction was started by the onset of
`
`agitation, and the reactor pressure was maintained constant (10 atm) by using a back
`
`pressure regulator. After reaction for 1 h, the product was separated from cyclohexane
`
`by distillation. The conversion of olefins to paraffins was higher than 99% and a heavy
`
`alkylate was successfully obtained.
`
`W T
`
`he oligomerization reaction was carried out as Example 3, except that water-
`
`[41]
`
`[42]
`
`containing Amberlyst-3l catalyst was used instead of water-containing Amberlyst—35
`
`catalyst. Amberst—31 catalyst was gel—type ion exchange resin without macropore, and
`
`was used as received. The catalyst was 2 g based on the dried catalyst, and the
`isobutene WHSV was 50 h'1 instead of 80 h]. Contrary to other Examples, the
`
`isobutene conversion was less than 5 % and the trimers selectivity was less than 20%.
`
`Accordingly, the main product was dimers (C8) instead of trimers (C12). Detailed
`
`

`

`WO 2007/091862
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`PCT/KR2007/000706
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`reaction conditions and reaction results are summarized in Table 1.
`
`[43]
`
`[44]
`
`[Table 1] Reaction conditions for oligomerization and reaction results.
`
`
`
`lsobutene
`
`Example
`
`Catalyst
`
`(state or
`
`solvent
`
`Ion exchange
`
`capacity
`
`space Reaction Isobutene
`
`Trimers Dimers
`
`velocity,
`
`WHSV
`
`time
`
`(h)
`
`(96)
`
`conversion selectivity selectivity
`”
`
`(wt%)
`
`(wt%)
`
`(equivalent/
`.
`~
`incorporated)
`kg—resm)
`
`(h'l)
`
`
`
`
`
`
`
`
`
`
`
`Amberlyst—35
`1
`5.2
`10
`70
`99.4
`75.5
`9.4
`
`(dried)
`
`Amberlyst—35
`2
`5.2
`50
`12
`93.5
`68.7
`22.3
`
`(ethanol)
`
`Amberlyst—35
`3
`5.2
`80
`10
`76.9
`54.8
`40.1
`
`(water)
`
`4
`
`Amberlyst—DT
`
`(water)
`
`C0111? Amberlyst—31
`
`3.1
`
`4.8
`
`50
`
`50
`
`12
`
`71.8
`
`6
`
`4.5
`
`52.2
`
`18.9
`
`40.4
`
`76.1
`
`(water)
`Ex. 1
`
`
`
`
`
`
`
`
`Industrial Applicability
`
`[45]
`
`As described above, the present process for preparing olefin trimers is performed by
`
`use of macroporous cation exchange resins in hydrogen form and maintaining the
`
`isobutene conversion higher than 60% because the trimers selectivity increases with
`
`increasing isobutene conversion. The olefin trimers thus obtained can be used for
`
`preparing neo—acid or can be hydrogenated to heavy alkylate that is used for prime
`
`solvent or diesel additive.
`
`

`

`WO 2007/091862
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`PCT/KR2007/000706
`
`[1]
`
`[2]
`
`[3]
`
`[4]
`
`[5]
`
`[6]
`
`[7]
`
`[8]
`
`[9]
`
`Claims
`
`A preparation method of olefin trirners, wherein a macroporous cation exchange
`
`resin is used as an acid catalyst and the olefin conversion is maintained higher
`
`than 60%.
`
`The preparation method according to claim 1, wherein reaction temperature is 50
`~ 100 °C and olefin space velocity, weight hourly space velocity, is 2 ~ 100 h'].
`
`The preparation method according to claim 1, wherein said cation exchange
`
`resins have acid sites composed of functional group of -SO3H.
`The preparation method according to claim 1, wherein said cation exchange
`
`resins have hydrogen ion exchange capacity higher than 2-equivalent/kg-resin.
`
`The preparation method according to claim 4, wherein said cation exchange
`
`resins have hydrogen ion exchange capacity higher than 4-equivalent/kg-resin.
`
`The preparation method according to claim 1, wherein said olefin conversion is
`
`higher than 90%.
`
`The preparation method according to claim 1, wherein said olefin is isobutene.
`
`A preparation method of heavy alkylates by hydrogenation of olefin trirners that
`
`are obtained according to any one of claims 1 to 7.
`
`The preparation method according to claim 8, wherein hydrogenation catalyst is
`
`composed of one or more catalysts selected from supported Pd, Pt, Ru and Ni
`
`catalysts and hydrogenation agent is hydrogen.
`
`

`

`WO 2007/091862
`
`1/1
`
`[Fig. 1]
`
`PCT/KR2007/000706
`
`Conversion&Selectivity(%)
`
`+Conversion
`+SelectiviMC)
`+5e|ecuvilflcn)
`+Selectiwmcu)
`
`Time(hour)
`
`[Fig. 2]
`
`
`
`100
`
`80
`
`60
`
`40
`
`20
`
`3 z
`
`.2
`
`E g
`
`02
`
`0
`
`0
`
`20
`
`40
`
`60
`
`80
`
`100
`
`Conversion (%)
`
`

`

`
`
`INTERNATIONAL SEARCH REPORT
`
`International application No.
`
`PCT/KR2007/000706
`
`Box No. II Observations Where certain claims were found unsearchable (Continuation of item 2 of first sheet)
`
`This international search report has not been established in respect of certain claims under Article 17(2)(a) for the following reasons:
`
`1. El Claims Nos.:
`because they relate to subject matter not required to be searched by this Authority, namely:
`
`2.
`
`Claims Nos.:
`
`because they relate to parts of the international application that do not comply with the prescribed requirements to such an
`extent that no meaningful international search can be carried out, specifically:
`
`3. El Claims Nos.:
`because they are dependent claims and are not drafted in accordance with the second and third sentences of Rule 6.4(a).
`
`Box No. III Observations Where unity of invention is lacking (Continuation of item 3 of first sheet)
`
`This International Searching Authority found multiple inventions in this international application, as follows:
`
`Group I , claims 1-7 are directed to a preparation method of olefin trimer,
`Group ll , claims 8-9 are directed to a preparation method of heavy al kyl ates by hydrogenation of olefin trimers that are
`obtained according to any one of claims 1-7.
`
`
`
`
`
`do not relate to a single inventive concept under PCT Rule 13.1 because, under PCT rule
`The inventions listed as Group I ,
`13.2 they lack the same or corresponding special technical features in that olefin trimer is the already known material and
`cannot be accepted to constitute a special technical feature linking the claimed matter as a
`whole.
`
`1. El As all required addtional search fees were timely paid by the applicant, this international search report covers all searchable
`claims.
`
`2. E As all searchable claims could be searched without effort justifying an additional fee, this Authority did not invite payment
`of any additional fee.
`
`3. D As only some of the required additional search fees were timely paid by the applicant, this international search report covers
`only those claims for which fees were paid, specifically claims Nos.:
`
`4. D No required additional search fees were timely paid by the applicant. Consequently,
`restricted to the invention first mentioned in the claims;
`it is covered by claims Nos.:
`
`this international search report
`
`is
`
`Remark 011 Protest
`
`CI The additional search fees were accompanied by the applicant‘s protest and, where applicable, the
`payment of a protest fee.
`CI The additional search fees were accompanied by the applicant‘s protest but the applicable protest
`fee was not paid within the time limit specified in the invitation.
`D No protest accompanied the payment of additional search fees.
`
`Form PCT/ISA/210 (continuation of first sheet (2)) (April 2007)
`
`
`
`

`

`INTERNATIONAL SEARCH REPORT
`
`International application NO.
`PCT/KR2007/000706
`
`A.
`
`CLASSIFICATION OF SUBJECT MATTER
`
`C0 7C 2/28(2006. 01)i
`
`According to International Patent Classification (IPC) or to both national classification and IPC
`FIELDS SEARCHED
`
`Minimum documentation searched (classification system followed by classification symbols)
`IPC 8 C07C
`
`Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched
`
`
`
`Electronic data base consulted during the international search (name of data base and, Where practicable, search terms used)
`STN(CAS on line), PAJ, eKIPASS
`
`C. DOCUMENTS CONSIDERED TO BE RELEVANT
`
`Citation of document, with indication, where appropriate, of the relevant passages
`
`Relevant to claim No.
`
`US 6,800,702 B2 (BP Chemicals Limited) 5 October 2004
`See the Whole document
`
`US 2005/0182284 Al(STANAT JON E , MATHYS GEORGES M , et al.) 18 August 2005
`See the Whole document
`
`US 6,703,356 B1 (EXXONMOBIL RES & ENG CO ) 9 March 2004
`See the Whole document
`
`US 4,377,393 A (ERDOELCHEMIE GMBH ) 22 March 1983
`See the Whole document
`
`JP 2003-160526 A (MANAC INC ) 3 June 2003
`See the Whole document
`
`|:| Further documents are listed in the continuation of Box C.
`
`Scc patcnt family annex.
`
`*
`"A"
`
`"E"
`
`"Ii"
`
`"0"
`
`"P"
`
`Special categories 0f cited documents:
`document defining the general state of the art which is not considered
`to be of particular relevance
`earlier application or patent but published on or after the international
`filing date
`document which may throw doubts on priority claim(s) or which is
`cited to establish the publication date 0f citation or other
`Special reason (as Specified)
`document referring 10 an oral disclosure, use, exhibition or other
`means
`document published prior to the international filing date but later
`than the priority date claimed
`
`"T"
`
`later document published after the international filing date or priority
`date and not in conflict with the application but cited to understand
`the principle or theory underlying the invention
`" 7" document of particular relevance; the claimed invention cannot be
`considered novel or cannot be considered to involve an inventive
`step when the document is taken alone
`"Y" document of particular relevance;
`the claimed invention cannot be
`considered to involve an inventive step when the document
`is
`combined with one or more other such documents,such combination
`being obvious to a person skilled in the art
`"&" document member of the same patent family
`
`Date of the actual completion of the international search
`
`Date of mailing of the international search report
`
`10 MAY 2007 (10.05.2007)
`Name and mailing address of the ISA/KR
`
`10 MAY 2007 (10.05.2007)
`Authorized officer
`
`Korean Intellectual Property Office
`920 Dunsan—dong, Seo-gu, Daejeon 302-701,
`Republic of Korea
`Facsimile No. 82-42-472-7140
`
`Form PCT/ISA/ZIO (second sheet) (April 2007)
`
`LEE, Suk Ju
`
`Telephone No.
`
`82-42-481-8149
`
`

`

`INTERNATIONAL SEARCH REPORT
`
`Information on patent family members
`
`International application No.
`
`P(jT[KflR2007/000706
`
`09.10.2003
`
`Publication
`date
`
`21.05.2003
`21.01.2002
`21.01.2002
`30.09.2003
`29.07.2003
`17.01.2002
`17.01.2002
`22.06.2005
`30.10.2003
`09.04.2003
`09.04.2003
`30.08.2000
`28.05.2004
`29.01.2004
`29.01.2004
`03.03.2003
`05.04.2004
`13.02.2003
`09.01.2003
`23.08.2004
`11.09.2003
`21.11.2003
`04.09.2003
`04.09.2003
`27.01.2005
`27.01.2005
`05.10.2004
`28.11.2006
`17.01.2002
`17.01.2002
`05.11.2003
`
`13.10.2003
`13.10.2003
`01.02.2005
`09.10.2003
`09.10.2003
`20.07.2005
`12.01.2005
`12.01.2005
`12.11.2004
`03.02.2005
`20.10.2005
`18.08.2005
`09.10.2003
`
`AR028795A1
`AU200167743A1
`AU200167743A5
`BG107539A
`BR200112470A
`CA2412990AA
`CA2412990A1
`CN1630554A
`EG22912A
`EP01299189A1
`EP1299189A1
`GB200016895A0
`HU200400497AB
`JP16502527
`JP2004502527T2
`KR1020030017616
`MXPA03000301A
`N020030108A
`N020030108A0
`PL358746A1
`SK200300017A5
`TW562696B
`US2003166456A1
`US2003166456AA
`US20050020788A1
`US2005020788AA
`US6800702BB
`US71416338B
`W00204119A1
`W0200204119A1
`ZA200210392A
`
`AU2003259157A1
`AU2003259157AA
`BR200308851A
`CA2479466AA
`CA2479466A1
`CN1642880A
`EP01494983A1
`EP1494983A1
`KR1020040095330
`MXPA04009473A
`RU2004131684A
`US2005182284AA
`W003082780A1
`W02003082780A1
`
`Patent document
`
`cited in search report
`
`Publication
`date
`
`Patent family
`member(s)
`
`USO6800702
`
`05.10.2004
`
`US2005182284A1
`
`18.08.2005
`
`Form PCT/lSA/210 (patent family annex) (April 2007)
`
`

`

`INTERNATIONAL SEARCH REPORT
`
`Information on patent family members
`
`International application No.
`
`P(jT[KflR2007/000706
`
`Patent document
`
`cited in search report
`
`Publication
`date
`
`US6703356B1
`
`09.03.2004
`
`US4377393A
`
`22.03.1983
`
`Patent family
`member(s)
`
`AU200147402A1
`AU200147402B2
`AU200147402A5
`AU775014B2
`DE6012588400
`EP01200376A2
`EP01200376B1
`EP1200376A2
`EP1200376B1
`JP15528174
`JP2003528174T2
`KR1020020013546
`U806703356
`US6703356BA
`W00170651A2
`W0200170651A2
`W0200170651A3
`
`DE2944457A1
`EP0028377A1
`EP28377A1
`EP28377B1
`JP56075441A2
`JP56075441
`USO4377393
`US4377393A
`
`Publication
`date
`
`03.10.2001
`03.10.2001
`03.10.2001
`15.07.2004
`22.02.2007
`02.05.2002
`10.01.2007
`02.05.2002
`10.01.2007
`24.09.2003
`24.09.2003
`20.02.2002
`09.03.2004
`09.03.2004
`27.09.2001
`27.09.2001
`07.03.2002
`
`14.05.
`13.05.
`13.05.
`22.09.
`22.06.
`22.06.
`22.03.
`22.03.
`
`03.06.2003
`
`JP15160526
`
`03.06.2003
`
`JP15160526
`JP2003160526A2
`
`03.06.2003
`
`Form PCT/lSA/210 (patent family annex) (April 2007)
`
`