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1. 发明申请

WO2013008279A1 PROCESS FOR PREPARING CATALYST USED IN PRODUCTION OF ACROLEIN AND/OR ACRYLIC ACID AND PROCESS FOR PREPARING ACROLEIN AND/OR ACRYLIC ACID BY DEHYDRATION REACTION OF GLYCERIN 审中-公开
标题翻译：用于制备用于制备丙烯酸和/或丙烯酸的催化剂的方法和通过脱水甘油的反应制备丙烯酸和/或丙烯酸的方法
公开(公告)号：WO2013008279A1
公开(公告)日：2013-01-17
申请号：PCT/JP2011/004040
申请日：2011-07-14
申请人： NIPPON KAYAKU KABUSHIKI KAISHA , ARKEMA FRANCE , OKUMURA, Kimito , KOBAYASHI, Yasushi , HIRAOKA, Ryota , DUBOIS, Jean-Luc , DEVAUX, Jean-Francois
发明人： OKUMURA, Kimito , KOBAYASHI, Yasushi , HIRAOKA, Ryota , DUBOIS, Jean-Luc , DEVAUX, Jean-Francois
IPC分类号： B01J23/00 , B01J23/30 , B01J27/16 , B01J27/188 , B01J37/02 , B01J35/10 , C07C45/52 , C07C47/22
CPC分类号： B01J27/16 , B01J23/007 , B01J23/30 , B01J27/188 , B01J35/1014 , B01J37/0242 , C07C45/52 , C07C51/252 , C07C47/22 , C07C57/04
摘要： A process for preparing a catalyst having a minimized amount of basic sites used in a production of acrolein and acrylic acid by dehydration reaction of glycerin, comprising more than one cycle of contacting a material with a solution of at least one acid precursor or one heteropolyacid or one heteropolyacid salt, drying and calcining the resulting solid mixture. This invention relates also to an improved catalyst used in the dehydration reaction of glycerine and further to a process for preparing acrolein and/or acrylic acid carried out in the presence of the dehydration catalyst.
摘要翻译：一种制备催化剂的方法，所述催化剂具有通过甘油的脱水反应生产丙烯醛和丙烯酸所用碱性位点的量最小，包括使材料与至少一种酸前体或一种杂多酸的溶液接触的多于一个循环，或一种杂多酸盐，干燥并煅烧所得固体混合物。本发明还涉及用于甘油脱水反应的改进的催化剂，还涉及在脱水催化剂存在下进行丙烯醛和/或丙烯酸的方法。

2. 发明申请

WO2013018915A3 IMPROVED PROCESS OF DEHYDRATION REACTIONS 审中-公开
标题翻译：改进的脱水反应过程
公开(公告)号：WO2013018915A3
公开(公告)日：2013-04-04
申请号：PCT/JP2012069934
申请日：2012-07-31
申请人： ARKEMA FRANCE , OKUMURA KIMITO , KOBAYASHI YASUSHI , HIRAOKA RYOTA , DUBOIS JEAN-LUC
发明人： OKUMURA KIMITO , KOBAYASHI YASUSHI , HIRAOKA RYOTA , DUBOIS JEAN-LUC
IPC分类号： C07C45/52 , C07C47/22 , C07C51/377 , C07C57/04
CPC分类号： C07C253/26 , C07C45/52 , C07C51/16 , C07C51/252 , C07C51/347 , C07C47/22 , C07C57/04
摘要： The present invention relates to the production of acrolein, acrylic acid or methacrylic acid by dehydration reaction of renewable raw material such as glycerin or hydroxycarboxylic acids, in the presence of a novel catalyst system supported on a carrier having a bimodal structure and a high pore volume and distribution. The dehydration reactions can be carried out for longer operation duration, so that acrolein, acrylic acid or methacrylic acid can be produced at higher productivity and for longer running time.
摘要翻译：本发明涉及通过可再生原料如甘油或羟基羧酸的脱水反应在负载在具有双峰结构和高孔体积的载体上的新型催化剂体系存在下生产丙烯醛，丙烯酸或甲基丙烯酸和分配。脱水反应可以进行较长的操作持续时间，从而可以以更高的生产率和更长的运行时间生产丙烯醛，丙烯酸或甲基丙烯酸。

3. 发明申请

WO2012102411A3 CATALYST FOR SELECTIVELY REDUCING SATURATED ALDEHYDE, AND PRODUCTION METHOD THEREFOR 审中-公开
标题翻译：用于选择性还原饱和醛的催化剂及其生产方法
公开(公告)号：WO2012102411A3
公开(公告)日：2012-10-26
申请号：PCT/JP2012052327
申请日：2012-01-26
申请人： NIPPON KAYAKU KK , OKUMURA KIMITO , KAWAGUCHI TORU , KOBAYASHI YASUSHI
发明人： OKUMURA KIMITO , KAWAGUCHI TORU , KOBAYASHI YASUSHI
IPC分类号： B01J27/199 , B01J23/88 , B01J27/19 , C07C45/85 , C07C47/22
CPC分类号： B01J27/199 , B01J21/063 , B01J23/881 , B01J23/8876 , B01J27/19 , C07C45/78 , C07C45/85 , C07C47/22
摘要： [Problem] To provide a novel catalyst for selectively reducing propionaldehyde from a starting-material acrolein in order to produce an acrolein and/or acrylic acid and/or acrylonitrile and/or methylmercaptopropionaldehyde that has a low-concentration of propionaldehyde and/or propionic acid and/or propionitrile. In particular, to provide a catalyst used to selectively reduce propionaldehyde-containing acrolein. [Solution] A catalyst used for selectively reducing propionaldehyde from propionaldehyde-containing acrolein, said catalyst including Mo as the essential component, and further containing at least one element selected from P, Si, W, Ti, Zr, V, Nb, Ta, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, In, Tl, Sn, Ag, As, Ge, B, Bi, La, Ba, Sb, Te, Ce, Pb, Mg, K, Rb, Cs and Al, and preferably from P, Si, W, Ti, Cr, Mn, Fe, Co, Ni, Zn, Sn, Bi, Sb, Ce, Mg, Cs and K.
摘要翻译：为了制备丙烯醛和/或丙烯酸和/或具有低浓度丙醛和/或丙酸的丙烯腈和/或甲基巯基丙醛，提供了一种新型催化剂，用于选择性还原起始原料丙烯醛中的丙醛和/或丙腈。特别地，提供用于选择性还原含丙醛的丙烯醛的催化剂。 [溶液]用于从含丙醛的丙烯醛中选择性还原丙醛的催化剂，所述催化剂包括Mo作为必要组分，并且还含有选自P，Si，W，Ti，Zr，V，Nb，Ta， Cr，Mn，Fe，Co，Ni，Cu，Zn，Ga，In，Tl，Sn，Ag，As，Ge，B，Bi，La，Ba，Sb，Te，Ce，Pb，Mg， Cs，Al，优选为P，Si，W，Ti，Cr，Mn，Fe，Co，Ni，Zn，Sn，Bi，Sb，Ce，Mg，Cs和K.

4. 发明申请

WO2011046232A1 PROCESS FOR PREPARING CATALYST USED IN PRODUCTION OF UNSATURATED ALDEHYDE AND/OR UNSATURATED CARBOXYLIC ACID BY DEHYDRATION REACTION OF GLYCERIN, AND CATALYST OBTAINED 审中-公开
标题翻译：制备用于生产不饱和醛和/或不饱和羧酸的催化剂的方法，通过脱胶反应甘氨酸和获得的催化剂
公开(公告)号：WO2011046232A1
公开(公告)日：2011-04-21
申请号：PCT/JP2010/068644
申请日：2010-10-15
申请人： NIPPON KAYAKU KABUSHIKI KAISHA , ARKEMA FRANCE , MAGATANI, Yasuhiro , OKUMURA, Kimito , DUBOIS, Jean-Luc
发明人： MAGATANI, Yasuhiro , OKUMURA, Kimito , DUBOIS, Jean-Luc
IPC分类号： B01J27/188 , B01J27/195 , C07B61/00 , C07C27/00 , C07C45/52 , C07C47/22 , C07C51/235 , C07C57/04
CPC分类号： B01J23/002 , B01J37/0063 , B01J37/0201 , B01J37/0234 , B01J2523/00 , C07C45/52 , C07C51/252 , C07C47/22 , C07C57/04 , B01J2523/15 , B01J2523/51 , B01J2523/69 , B01J2523/31 , B01J2523/41 , B01J2523/47 , B01J2523/56
摘要： A process for preparing a catalyst used in a production of acrolein and acrylic acid by dehydration reaction of glycerin, characterized by the steps of mixing a solution of heteropolyacid or constituents of heteropolyacid, a solution of at least one metal selected from elements belonging to Group 1 to Group 16 of the Periodic Table of Elements or its onium and a carrier to obtain a solid substance, and then of effecting at least one time of calcination before said solid substance is used in the dehydration reaction of glycerin. A catalyst obtained by the process for use in a production of acrolein and acrylic acid by dehydration reaction of glycerin. A process for preparing acrolein by catalytic dehydration of glycerin carried out in the presence of the catalyst and under a pressurized condition. A process for preparing acrylic acid obtained by oxydation of acrolein obtained. A process for preparing acrylonitrile obtained by ammoxidation of acrolein obtained.
摘要翻译：一种通过甘油脱水反应制备用于生产丙烯醛和丙烯酸的催化剂的方法，其特征在于以下步骤：将杂多酸的溶液或杂多酸的组分，选自属于第1组的元素的至少一种金属的溶液至元素周期表第16族或其鎓盐和载体以获得固体物质，然后在所述固体物质用于甘油的脱水反应之前至少进行一次煅烧。通过甘油脱水反应生产丙烯醛和丙烯酸的方法得到的催化剂。通过在催化剂存在下和在加压条件下进行的甘油的催化脱水来制备丙烯醛的方法。制备通过氧化得到的丙烯醛获得的丙烯酸的方法。制备通过丙烯醛氨氧化得到的丙烯腈制备方法。

5. 发明申请

WO2011033689A1 CATALYST AND PROCESS FOR PREPARING ACROLEIN AND/OR ACRYLIC ACID BY DEHYDRATION REACTION OF GLYCERIN 审中-公开
标题翻译：通过脱水反应制备丙烯酸和/或丙烯酸的催化剂和方法
公开(公告)号：WO2011033689A1
公开(公告)日：2011-03-24
申请号：PCT/JP2009/067115
申请日：2009-09-18
申请人： NIPPON KAYAKU KABUSHIKI KAISHA , ARKEMA FRANCE , MAGATANI, Yasuhiro , OKUMURA, Kimito , DUBOIS, Jean-Luc , DEVAUX, Jean-Francois
发明人： MAGATANI, Yasuhiro , OKUMURA, Kimito , DUBOIS, Jean-Luc , DEVAUX, Jean-Francois
IPC分类号： B01J23/30 , B01J27/188 , B01J37/02 , C07C45/52 , C07C47/22
CPC分类号： C07C45/002 , B01J21/063 , B01J21/12 , B01J23/002 , B01J23/30 , B01J27/188 , B01J37/0205 , B01J2523/00 , C07C45/52 , C07C51/235 , C07C51/252 , C07C253/26 , C07K14/78 , G01N33/6887 , G01N33/6893 , G01N2333/705 , C07C47/22 , C07C57/04 , B01J2523/15 , B01J2523/51 , B01J2523/69 , B01J2523/41
摘要： A catalyst composition comprising at least an heteropolyacid deposited on a porous titania carrier.A catalyst composition comprising at least an heteropolyacid in which protons in the heteropolyacid may be partially exchanged by at least one cation selected from elements belonging to Group 1 to Group 16 of the Periodic Table of Elements that have been deposited on a porous titania carrier.A method for preparing the catalyst composition, comprising impregnating a titania carrier with a solution of at least one metal selected from elements belonging to the Group 1 to Group 16 of the Periodic Table of Elements or onium, drying and firing the resulting solid mixture, secondly impregnating the resulting solid mixture with a solution of heteropolyacid, drying, and firing the resulting solid mixture.A process for preparing acrolein and acrylic acid by dehydration of glycerin, carried out in the presence of the catalyst.
摘要翻译：一种催化剂组合物，其至少包含沉积在多孔二氧化钛载体上的杂多酸。一种催化剂组合物，其至少包含杂多酸，其中所述杂多酸中的质子可以通过至少一种选自属于所述杂多酸的第1组至第16组的元素的阳离子部分交换已经沉积在多孔二氧化钛载体上的元素周期表.1。一种制备催化剂组合物的方法，包括用至少一种选自元素周期表第1族至第16族的金属的溶液浸渍二氧化钛载体的元素或鎓盐，干燥并焙烧得到的固体混合物，其次用杂多酸溶液浸渍所得固体混合物，干燥并焙烧所得固体混合物。一种通过甘油脱水制备丙烯醛和丙烯酸的方法，催化剂的存在。

6. 发明申请

WO2009128555A3 PROCESS FOR MANUFACTURING ACROLEIN OR ACRYLIC ACID FROM GLYCERIN 审中-公开
公开(公告)号：WO2009128555A3
公开(公告)日：2009-10-22
申请号：PCT/JP2009/057818
申请日：2009-04-14
申请人： ARKEMA FRANCE , DUBOIS, Jean-Luc , MAGATANI, Yasuhiro , OKUMURA, Kimito
发明人： DUBOIS, Jean-Luc , MAGATANI, Yasuhiro , OKUMURA, Kimito
IPC分类号： C07C45/52 , C07C47/22
摘要： The subject of the present invention is a process for preparing acrolein by dehydration of glycerin, characterized in that the dehydration is carried out in the presence of a catalyst comprising mainly a compound in which protons in a heteropolyacid are exchanged at least partially with at least one cation selected from elements belonging to Group 1 to Group 16 of the Periodic Table of Elements. The process according to the invention permits to obtain acrolein at higher yield.

7. 发明申请

WO2013084258A1 CATALYST FOR THE MANUFACTURING OF ACRYLIC ACID AND A PROCESS FOR PRODUCING ACRYLIC ACID BY USING THE CATALYST 审中-公开
标题翻译：用于制备丙烯酸的催化剂和使用催化剂生产丙烯酸的方法
公开(公告)号：WO2013084258A1
公开(公告)日：2013-06-13
申请号：PCT/JP2011/006831
申请日：2011-12-06
申请人： NIPPON KAYAKU KABUSHIKI KAISHA , OKUMURA, Kimito , KOBAYASHI, Yasushi
发明人： OKUMURA, Kimito , KOBAYASHI, Yasushi
IPC分类号： B01J23/88 , C07B61/00 , C07C27/00 , C07C45/38 , C07C47/22 , C07C51/235 , C07C57/04
CPC分类号： B01J37/0036 , B01J23/002 , B01J27/199 , B01J37/0045 , B01J37/08 , B01J2523/00 , C07C45/52 , C07C51/235 , C07C57/04 , C07C47/22 , B01J2523/17 , B01J2523/53 , B01J2523/55 , B01J2523/68 , B01J2523/69
摘要： This invention provides a catalyst for producing unsaturated carboxylic acid from unsaturated aldehyde which is obtained by dehydration reaction of alcohol. In particular, this invention provides a catalyst for producing acrylic acid from acrolein obtained by dehydration reaction of glycerin. This invention provides also a process for producing unsaturated carboxylic acid, especially acrylic acid by using the catalyst. Catalyst used contains an active ingredient having a composition represented by following formula (1): Mo 12 V a W b Cu c Sb d X e Y f Z g O h ........... (1) in which Mo, V, W, Cu, Sb and O represent respectively molybdenum, vanadium, tungsten, copper, antimony and oxygen, X is at least one element selected from a group comprising alkali metals and thallium, Y is at least one element selected from a group comprising magnesium, calcium, strontium, barium and zinc, Z is at least one element selected from a group comprising niobium, cerium, tin, chromium, manganese, iron, cobalt, samarium, germanium, titanium and arsenic, "a", "b", "c", "d", "e", "f", "g" and "h" each represents an atom ratio of element and satisfies following respective range when a value for molybdenum atom is considered as 12: "a" is greater than 0 but not greater than 10, "b" is not less than 0 but not greater than 10, "c" is greater than 0 but not greater than 6, "d" is greater than 0 but not greater than 10, "e" is not less than 0 but not greater than 0.5, "f" is not less than 0 but not greater than 1, "g" is not less than 0 but less than 6 and "h" is a number of oxygen atom required for satisfying the valences of above elements.
摘要翻译：本发明提供了通过醇的脱水反应得到的不饱和醛的不饱和羧酸的制造催化剂。特别地，本发明提供了由丙三醇的脱水反应得到的丙烯醛制造丙烯酸的催化剂。本发明还提供了使用该催化剂制备不饱和羧酸，特别是丙烯酸的方法。使用的催化剂含有具有下述式（1）表示的组成的活性成分：Mo12 Va Wb Cuc Sbd Xe Yf Zg Oh ...........（1）其中Mo，V，W，Cu， Sb和O分别代表钼，钒，钨，铜，锑和氧，X是选自碱金属和铊的至少一种元素，Y是选自镁，钙，锶，钡和锌，Z是选自铌，铈，锡，铬，锰，铁，钴，钐，锗，钛和砷中的至少一种元素，“a”，“b”，“c” d“，”e“，”f“，”g“和”h“各自表示元素的原子比，当钼原子值被认为是12时满足相应的范围：”a“大于0但不大于0 大于10，“b”不小于0但不大于10，“c”大于0但不大于6，“d”大于0但不大于10，“e”不小于 0以上且0.5以下，“f”为0以上且1以下，“g”为0以上且6以下，“h”表示满足下述式以上元素。

8. 发明申请

WO2013018752A3 CATALYST FOR MANUFACTURE OF ACROLEIN AND ACRYLIC ACID BY MEANS OF DEHYDRATION OF GLYCERIN, AND MANUFACTURING METHOD FOR SAME 审中-公开
标题翻译：通过甘油脱水制备丙烯酸和丙烯酸的催化剂及其制备方法
公开(公告)号：WO2013018752A3
公开(公告)日：2013-03-21
申请号：PCT/JP2012069305
申请日：2012-07-30
申请人： NIPPON KAYAKU KK , OKUMURA KIMITO , KOBAYASHI YASUSHI , HIRAOKA RYOTA , DUBOIS JEAN-LUC
发明人： OKUMURA KIMITO , KOBAYASHI YASUSHI , HIRAOKA RYOTA , DUBOIS JEAN-LUC
IPC分类号： B01J27/188 , B01J23/30 , B01J35/10 , B01J37/08 , C07B61/00 , C07C45/52 , C07C47/22
CPC分类号： B01J27/188 , B01J23/30 , B01J35/1038 , B01J35/108 , C07C45/52 , C07C51/235 , C07C51/25 , C07C57/04 , C07C47/22
摘要： The present invention provides a glycerin dehydration catalyst which enables the high-yield production of unsaturated aldehydes and unsaturated carboxylic acid by dehydrating glycerin, and exhibits little reduction over time in glycerin conversion ratio, or in the yield of unsaturated aldehydes and unsaturated carboxylic acid. The present invention provides, in particular, a glycerin dehydration catalyst which has a long life and can produce acrolein and acrylic acid at high yields by dehydrating glycerin. Furthermore, the present invention is for the purpose of providing a manufacturing method for such a catalyst. A catalyst for glycerin dehydration used to produce acrolein and acrylic acid by contact-dehydrating glycerin, the catalyst having a W-containing metal oxide supported on a support which contains at least one kind of metal oxide selected from TiO2, SiO2, Al2O3, ZrO2 and Nb2O5, and which has bimodal pores wherein the ratio of the pore volume of micropores of 50nm or more relative to the pore volume of mesopores, which are bigger than 2nm but smaller than 50nm, is at least 0.5; in addition to the W-containing metal oxide, at least one kind of element-containing metal oxide selected from P, Si, Mo and V can also be supported.
摘要翻译：本发明提供甘油脱水催化剂，其能够通过使甘油脱水而高收率地制造不饱和醛和不饱和羧酸，甘油转化率或不饱和醛和不饱和羧酸的收率的经时降低少。本发明特别提供甘油脱水催化剂，其具有长寿命并且可以通过使甘油脱水以高产率生产丙烯醛和丙烯酸。此外，本发明的目的在于提供这种催化剂的制造方法。甘油脱水用催化剂，用于通过使甘油接触 - 脱水来生产丙烯醛和丙烯酸，所述催化剂具有负载在载体上的含W的金属氧化物，所述载体含有选自TiO 2，SiO 2，Al 2 O 3，ZrO 2和ZrO 2中的至少一种金属氧化物; Nb2O5，其具有双峰孔径，其中，50nm以上的微孔的孔体积相对于大于2nm小于50nm的中孔孔隙体积的比例至少为0.5; 除了含W的金属氧化物之外，还可以负载选自P，Si，Mo和V中的至少一种含元素的金属氧化物。

9. 发明申请

WO2013018915A2 IMPROVED PROCESS OF DEHYDRATION REACTIONS 审中-公开
标题翻译：改进的脱水反应过程
公开(公告)号：WO2013018915A2
公开(公告)日：2013-02-07
申请号：PCT/JP2012/069934
申请日：2012-07-31
申请人： ARKEMA FRANCE , OKUMURA, Kimito , KOBAYASHI, Yasushi , HIRAOKA, Ryota , DUBOIS, Jean-Luc
发明人： OKUMURA, Kimito , KOBAYASHI, Yasushi , HIRAOKA, Ryota , DUBOIS, Jean-Luc
IPC分类号： C07C45/52 , C07C51/377 , C07C47/22 , C07C57/04
CPC分类号： C07C253/26 , C07C45/52 , C07C51/16 , C07C51/252 , C07C51/347 , C07C47/22 , C07C57/04
摘要： The present invention relates to the production of acrolein, acrylic acid or methacrylic acid by dehydration reaction of renewable raw material such as glycerin or hydroxycarboxylic acids, in the presence of a novel catalyst system supported on a carrier having a bimodal structure and a high pore volume and distribution. The dehydration reactions can be carried out for longer operation duration, so that acrolein, acrylic acid or methacrylic acid can be produced at higher productivity and for longer running time.
摘要翻译：本发明涉及丙烯醛，丙烯酸或甲基丙烯酸通过可再生原料如甘油或羟基羧酸的脱水反应在负载于载体上的新型催化剂体系存在下生产丙烯醛，丙烯酸或甲基丙烯酸，双峰结构和高孔隙体积和分布。脱水反应可以在较长的操作时间内进行，从而可以以更高的生产率和更长的运行时间生产丙烯醛，丙烯酸或甲基丙烯酸。

10. 发明申请

WO2013017904A1 IMPROVED PROCESS OF DEHYDRATION REACTIONS 审中-公开
公开(公告)号：WO2013017904A1
公开(公告)日：2013-02-07
申请号：PCT/IB2011/002068
申请日：2011-07-29
申请人： ARKEMA FRANCE , DUBOIS, Jean-Luc , OKUMURA, Kimito , KOBAYASHI, Yasushi , HIRAOKA, Ryota
发明人： DUBOIS, Jean-Luc , OKUMURA, Kimito , KOBAYASHI, Yasushi , HIRAOKA, Ryota
IPC分类号： C07C45/52 , C07C51/377 , C07C47/22 , C07C57/04
CPC分类号： C07C253/26 , C07C45/52 , C07C51/16 , C07C51/252 , C07C51/347 , C07C47/22 , C07C57/04
摘要： The present invention relates to the production of acrolein, acrylic acid or methacrylic acid by dehydration reaction of renewable raw material such as glycerin or hydroxycarboxylic acids, in the presence of a novel catalyst system supported on a carrier having a bimodal structure and a high pore volume and distribution. The dehydration reactions can be carried out for longer operation duration, so that acrolein, acrylic acid or methacrylic acid can be produced at higher productivity and for longer running time.

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