公开(公告)号：US4496770A

公开(公告)日：1985-01-29

申请号：US479475

申请日：1983-03-28

申请人： Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Ekhart Lucas ,  Franz Merger ,  Friedbert Nees

发明人： Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Ekhart Lucas ,  Franz Merger ,  Friedbert Nees

IPC分类号： B01J31/00 ,  B01J31/04 ,  C07B61/00 ,  C07C45/00 ,  C07C45/75 ,  C07C47/21 ,  C07C47/22 ,  C07C67/00

CPC分类号： C07C45/75

摘要： .alpha.-Alkylacroleins are prepared by a process wherein an alkanal is reacted with formaldehyde in the presence of a secondary amine and in the presence or absence, of an acid, in the liquid phase, under superatmospheric pressure and at above 150.degree. C., for not more than 25 minutes.The .alpha.-alkylacroleins obtainable by the process are useful starting materials for dyes, drugs and pesticides.

摘要翻译： α-烷基丙烯醛通过一种方法制备，其中在超级大气压和高于150℃的温度下，在仲胺的存在下，在存在或不存在酸的条件下，在液相中，在超临界压力和150℃以上，使链烷醛与甲醛反应， 不超过25分钟。 通过该方法获得的α-烷基丙烯醛可用于染料，药物和农药的起始材料。

公开(公告)号：US4638085A

公开(公告)日：1987-01-20

申请号：US660978

申请日：1984-11-21

申请人： Franz J. Broecker ,  Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Franz Merger ,  Friedbert Nees

发明人： Franz J. Broecker ,  Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Franz Merger ,  Friedbert Nees

IPC分类号： C07C69/00 ,  B01J21/06 ,  B01J23/06 ,  B01J23/10 ,  B01J23/62 ,  B01J23/63 ,  C07B61/00 ,  C07C67/00 ,  C07C67/39 ,  C07C69/54

CPC分类号： B01J23/63 ,  B01J23/628 ,  C07C67/39

摘要： A catalyst which is free from alkali metal compounds and alkaline earth metal compounds, contains palladium and lead as active constituents and is supported on a carrier which contains two or more of the oxides ZnO, Al.sub.2 O.sub.3, La.sub.2 O.sub.3 and TiO.sub.2, and the use of this catalyst for the preparation of methyl methacrylate from methacrolein, methanol and oxygen.

摘要翻译： 不含碱金属化合物和碱土金属化合物的催化剂含有钯和铅作为活性成分，负载在含有两种或多种氧化物ZnO，Al 2 O 3，La 2 O 3和TiO 2的载体上，并且使用该催化剂 用于从甲基丙烯醛，甲醇和氧气制备甲基丙烯酸甲酯。

公开(公告)号：US4520125A

公开(公告)日：1985-05-28

申请号：US582727

申请日：1984-02-23

申请人： Karl Baer ,  Peter Bassler ,  Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Franz Merger ,  Friedbert Nees

发明人： Karl Baer ,  Peter Bassler ,  Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Franz Merger ,  Friedbert Nees

IPC分类号： C07C69/54 ,  B01J23/00 ,  B01J23/06 ,  B01J23/62 ,  C07B61/00 ,  C07C67/39 ,  B01J31/04 ,  C07C67/00

CPC分类号： B01J23/628 ,  C07C67/39

摘要： Catalysts for the preparation of carboxylates from an aldehyde and an alkanol in the presence of oxygen, which contain palladium and lead as active components, these being present on a carrier containing zinc oxide, and the palladium being applied as a palladium salt in a solution containing hydrochloric acid and then being liberated by reduction, and whose carrier consists solely of zinc oxide, are particularly active and selective.

摘要翻译： 在含有钯和铅作为活性组分的氧的存在下由醛和链烷醇制备羧酸盐的催化剂存在于含有氧化锌的载体上，钯作为钯盐以含有 然后通过还原释放，并且其载体仅由氧化锌组成，具有特别的活性和选择性。

公开(公告)号：US4925823A

公开(公告)日：1990-05-15

申请号：US875516

申请日：1986-06-19

申请人： Richard Krabetz ,  Gerd Duembgen ,  Friedbert Nees ,  Franz Merger ,  Gerd Fouquet

发明人： Richard Krabetz ,  Gerd Duembgen ,  Friedbert Nees ,  Franz Merger ,  Gerd Fouquet

IPC分类号： B01J27/188 ,  B01J27/19 ,  B01J27/195 ,  C07B61/00 ,  C07C51/00 ,  C07C51/235 ,  C07C57/055 ,  C07C67/00

CPC分类号： B01J27/19 ,  C07C51/235

摘要： Oxidation catalysts of the general formulaMo.sub.12 P.sub.a W.sub.b Sb.sub.c As.sub.d Cu.sub.e X.sub.f O.sub.xwhereX is Nb, Fe, Mn, Sn and/or Cr,a is 0.1-3,b is 0.1-4,c is

摘要翻译： 通式为Mo12PaWbSbcAsdCueXfOx的氧化催化剂，其中X为Nb，Fe，Mn，Sn和/或Cr，a为0.1-3，b为0.1-4，c为<0-2，d为0-1，e为0 -1，d + e为<0-2，f为0-1.5，e + f为0-2，x为饱和其它催化剂组分的正离子所需的氧原子数，可以特别有利地使用 用于通过甲基丙烯醛的气相氧化制备甲基丙烯酸。

公开(公告)号：US4595778A

公开(公告)日：1986-06-17

申请号：US587118

申请日：1984-03-07

申请人： Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Franz Merger ,  Friedbert Nees

发明人： Gerd Duembgen ,  Gerd Fouquet ,  Richard Krabetz ,  Franz Merger ,  Friedbert Nees

IPC分类号： B01J27/19 ,  B01J27/198 ,  B01J27/199 ,  C07B61/00 ,  C07C51/00 ,  C07C51/25 ,  C07C57/055 ,  C07C67/00 ,  C07C51/235 ,  C07C67/08

CPC分类号： B01J23/002 ,  B01J27/19 ,  B01J27/199 ,  C07C51/252 ,  B01J2523/00 ,  Y10S203/22

摘要： Oxidation catalysts of the general formulaW.sub.6 Mo.sub.a V.sub.b P.sub.c Cu.sub.d As.sub.e Sb.sub.f X.sub.g Y.sub.h O.sub.xwhere X is K, Rb and/or Cs, Y is Nb, Fe, Mn, Sn, Li, Na, Sr, Rh, Ce, Ti and/or Cr, a is from 2.0 to 6, b is from 0 to 3, c is from 0.1 to 3, d is from 0.01 to 1, e is from 0 to 1, f is from 0 to 2, g is from 0.01 to 3, h is from 0 to 1 and x is the number of oxygen atoms formally required to saturate the valencies of the catalyst components, give high conversions and particularly high selectivity in the oxidation of methacrolein in the gas phase to methacrylic acid.

摘要翻译： 通式为W6MoaVbPcCudAseSbfXgYhOx的氧化催化剂，其中X为K，Rb和/或Cs，Y为Nb，Fe，Mn，Sn，Li，Na，Sr，Rh，Ce，Ti和/或Cr，a为2.0至6 b为0〜3，c为0.1〜3，d为0.01〜1，e为0〜1，f为0〜2，g为0.01〜3，h为0〜1， x是使催化剂组分的价态饱和所需的氧原子数，在气相中甲基丙烯醛氧化成甲基丙烯酸时产生高转化率和特别高的选择性。

公开(公告)号：US5087744A

公开(公告)日：1992-02-11

申请号：US213837

申请日：1988-06-30

申请人： Richard Krabetz ,  Gerd Duembgen ,  Franz Merger ,  Michael Jaeger ,  Fritz Thiessen ,  Herbert Vogal

发明人： Richard Krabetz ,  Gerd Duembgen ,  Franz Merger ,  Michael Jaeger ,  Fritz Thiessen ,  Herbert Vogal

IPC分类号： B01J27/19 ,  C07B63/04 ,  C07C51/00 ,  C07C51/235 ,  C07C51/25 ,  C07C57/055 ,  C07C57/07 ,  C07C67/00

CPC分类号： C07C51/252

摘要： Methacrylic acid can be prepared with advantage by gas phase oxidation of methacrolein or isobutyraldehyde over Mo- and P-containing catalysts at from 250.degree. to 400.degree. C. with cooling of the hot reaction gas to below 100.degree. C., absorption of the methacrylic acid in a water-operated absorption column, at below 100.degree. C. and partial recycling into the oxidation reactor after admixture of methacrolein or isobutyraldehyde and oxygen by feeding a quantity of methacrolein or isobutyraldehyde equal to the quantity of methacrolein or isobutyraldehyde consumed in the reaction in liquid form together with a polymerization inhibitor into the reactor gas in the lower two-thirds of the absorber column and upstream of the feed point for the fresh methacrolein or isobutyraldehyde or down-stream of the absorption column splitting off the reactor off-gas a side stream which is washed in a wash column operated with water at

摘要翻译： 甲基丙烯酸可以通过在250℃至400℃的含Mo和P的催化剂上甲基丙烯醛或异丁醛的气相氧化来制备，同时将热反应气体冷却至低于100℃，吸收甲基丙烯酸 酸在水性吸收塔中，低于100℃，并通过加入与反应中消耗的甲基丙烯醛或异丁醛的量相等的量的异丁烯醛或异丁醛，将甲基丙烯醛或异丁醛和氧气混合后，部分再循环进入氧化反应器 液体形式与聚合抑制剂一起在吸收塔的下三分之二的反应器气体中，在新鲜的甲基丙烯醛或异丁醛的进料点的上游或吸收塔的下游分离反应器废气a 侧流在洗涤塔中用水在<10℃下洗涤以除去未转化的异丁烯醛或异丁醛，其为f 作为吸收塔顶部的水溶液。

公开(公告)号：US5173468A

公开(公告)日：1992-12-22

申请号：US729169

申请日：1991-07-12

申请人： Karl-Heinz Boehning ,  Gerd Duembgen ,  Ulrich Hammon ,  Richard Krabetz ,  Franz Merger ,  Matthias Schwarzmann ,  Fritz Thiessen ,  Herbert Vogel

发明人： Karl-Heinz Boehning ,  Gerd Duembgen ,  Ulrich Hammon ,  Richard Krabetz ,  Franz Merger ,  Matthias Schwarzmann ,  Fritz Thiessen ,  Herbert Vogel

IPC分类号： B01J27/19 ,  B01J27/199 ,  C07B61/00 ,  C07C57/055

CPC分类号： B01J23/002 ,  B01J27/199 ,  B01J2523/00

摘要： Compositions of the formula IMO.sub.12 P.sub.a V.sub.b X.sup.1.sub.c X.sup.2.sub.d X.sup.3.sub.e Sb.sub.f Re.sub.g S.sub.h O.sub.n (I)whereX.sup.1 is potassium, rubidium and/or cesium,X.sup.2 is copper and/or silver,X.sup.3 is cerium, boron, zirconium, manganese and/or bismuth,a is from 0.5 to 3.0,b is from 0.01 to 3.0,c is from 0.2 to 3.0,d is from 0.01 to 2.0,e is from 0 to 2.0,f is from 0.01 to 2.0,g is from 0 to 1.0,h is from 0.001 to 0.5 andn is a number determined by the valency and content ofthe elements different from oxygen in I, are used as catalysts for preparing methacrylic acid by gas-phase oxidation of methacrolein.

摘要翻译： 式I MO12PaVbX1cX2dX3eSbfRegShOn（I）的组成，其中X1是钾，铷和/或铯，X2是铜和/或银，X3是铈，硼，锆，锰和/或铋，a是0.5-3.0，b 为0.01〜3.0，c为0.2〜3.0，d为0.01〜2.0，e为0〜2.0，f为0.01〜2.0，g为0〜1.0，h为0.001〜0.5，n为 由I中不同于氧的元素的化合价和含量确定的数字被用作通过甲基丙烯醛的气相氧化制备甲基丙烯酸的催化剂。

公开(公告)号：US5221767A

公开(公告)日：1993-06-22

申请号：US928334

申请日：1992-08-12

申请人： Karl-Heinz Boehning ,  Gerd Duembgen ,  Ulrich Hammon ,  Richard Krabetz ,  Franz Merger ,  Matthias Schwarzmann ,  Fritz Thiessen ,  Herbert Vogel

发明人： Karl-Heinz Boehning ,  Gerd Duembgen ,  Ulrich Hammon ,  Richard Krabetz ,  Franz Merger ,  Matthias Schwarzmann ,  Fritz Thiessen ,  Herbert Vogel

IPC分类号： B01J27/199

CPC分类号： B01J23/002 ,  B01J27/199 ,  B01J2523/00

摘要： Compositions of the formula IMo.sub.12 P.sub.a V.sub.b X.sub.c.sup.1 X.sub.d.sup.2 X.sub.e.sup.3 Sb.sub.f Re.sub.g S.sub.h O.sub.n (I),whereX.sup.1 is potassium, rubidium and/or cesium,X.sup.2 is copper and/or silver,X.sup.3 is cerium, boron, zirconium, manganese and/or bismuth,a is from 0.5 to 3.0,b is from 0.01 to 3.0,c is from 0.2 to 3.0,d is from 0.01 to 2.0,e is from 0 to 2.0,f is from 0.01 to 2.0,g is from 0 to 1.0,h is from 0.001 to 0.5 andn is a number determined by the valency and content of the elements different from oxygen in I, are used as catalysts for preparing methacrylic acid by gas-phase oxidation of methacrolein.

摘要翻译： 式I Mo12Pa VbXc1Xd2Xe3SbfRegShOn（I）的组成，其中X1是钾，铷和/或铯，X2是铜和/或银，X3是铈，硼，锆，锰和/或铋，a是0.5-3.0 ，b为0.01〜3.0，c为0.2〜3.0，d为0.01〜2.0，e为0〜2.0，f为0.01〜2.0，g为0〜1.0，h为0.001〜0.5， n是由I中不同于氧的元素的化合价和含量确定的数，用作通过甲基丙烯醛的气相氧化制备甲基丙烯酸的催化剂。

公开(公告)号：US4259211A

公开(公告)日：1981-03-31

申请号：US963203

申请日：1978-11-24

申请人： Richard Krabetz ,  Walter Herrmann ,  Norbert Scholz ,  Heinz Engelbach ,  Gerd-Juergen Engert ,  Carl-Heinz Willersinn ,  Gerd Duembgen ,  Fritz Thiessen

发明人： Richard Krabetz ,  Walter Herrmann ,  Norbert Scholz ,  Heinz Engelbach ,  Gerd-Juergen Engert ,  Carl-Heinz Willersinn ,  Gerd Duembgen ,  Fritz Thiessen

IPC分类号： B01J23/00 ,  B01J23/24 ,  B01J23/28 ,  B01J23/30 ,  B01J23/31 ,  B01J23/34 ,  B01J23/88 ,  B01J23/89 ,  B01J37/02 ,  C07B61/00 ,  C07C51/00 ,  C07C51/25 ,  C07C57/055 ,  C07C67/00 ,  B01J23/22 ,  B01J23/72

CPC分类号： B01J23/887 ,  B01J23/002 ,  B01J23/24 ,  B01J23/34 ,  B01J37/0221 ,  B01J37/0236 ,  C07C51/252 ,  B01J2523/00

摘要： Catalysts which consist of a molded carrier, the surface of which is coated with an active catalyst composition of the general formula Mo.sub.12 A.sub.a B.sub.b C.sub.c D.sub.d O.sub.x, where A is V and/or W, B is Cu and/or Fe and/or Mn and/or Ni and/or Cr, C is Nb and/or Ta and/or Bi and/or Sb and/or Sn and/or Th and/or Ce and/or U, D is Li and/or Na and/or K and/or Rb and/or Cs and/or Tl and a is from 0.1 to 18, b is from 0 to 8, c is from 0 to 10, d is from 0 to 2 and x is from 36 to 135, which are particularly active and selective for the oxidation of acrolein and methacrolein with oxygen-containing gases to give acrylic acid and methacrylic acid, respectively, are obtained by first manufacturing the catalyst composition, before applying it to the carrier, from thermally easily decomposed salts of the components by mixing aqueous solutions, slurries or moist solid masses of the salts of the components, drying the mixture and calcining the dried composition at from 140.degree. to 600.degree. C., then milling it to a particle size of less than 150 .mu.m and thereafter applying it, as a mixture with water, as a layer from 10 to 1,500 .mu.m thick, to the premolded carrier, which has a rough surface.

摘要翻译： 催化剂由模制载体组成，其表面涂覆有通式为Mo12AaBbCcDdOx的活性催化剂组合物，其中A为V和/或W，B为Cu和/或Fe和/或Mn和/或Ni，和 /或Cr，C是Nb和/或Ta和/或Bi和/或Sb和/或Sn和/或Th和/或Ce和/或U，D是Li和/或Na和/或K和/或 Rb和/或Cs和/或T1和a为0.1至18，b为0至8，c为0至10，d为0至2，x为36至135，特别有活性， 选择性地分别用含氧气体氧化丙烯醛和甲基丙烯醛以产生丙烯酸和甲基丙烯酸，这是通过首先在将催化剂组合物施加到载体上之前通过将组分的热容易分解的盐混合 溶液，浆液或湿固体组分的盐的组分，干燥混合物并在140℃至600℃下煅烧干燥的组合物，然后将其研磨成颗粒 尺寸小于150μm，然后将其作为与水混合的10至1,500μm厚的层涂于具有粗糙表面的预成型载体上。

公开(公告)号：US4031135A

公开(公告)日：1977-06-21

申请号：US595321

申请日：1975-07-11

申请人： Heinz Engelbach ,  Richard Krabetz ,  Gerd Duembgen ,  Carl-Heinz Willersinn ,  Ulrich Lebert ,  Fritz Thiessen

发明人： Heinz Engelbach ,  Richard Krabetz ,  Gerd Duembgen ,  Carl-Heinz Willersinn ,  Ulrich Lebert ,  Fritz Thiessen

IPC分类号： C07C57/05 ,  C07C45/35 ,  C07C51/00 ,  C07C51/25 ,  C07C57/055 ,  C07C67/00 ,  C07C51/32

CPC分类号： C07C45/35 ,  C07C51/252

摘要： In the oxidation of propylene to acrylic acid in the gas phase in two spatially separate oxidation stages, a part of the off-gas, which has been freed from condensable products, is fed to the oxidation stages in addition to freshly charged propylene and air, under the following conditions:A. The recycled off-gas and air are in part fed to the first oxidation stage and in part to the second oxidation stage,B. The molar ratio of propylene : oxygen : residual gases fed to the first stage is 1 : 1.5-2.3 : 11-19,C. The molar ratio of the total propylene fed in, to the total oxygen fed in, in the form of air or off-gas, before and after the first stage, and to the total residual gases fed in is 1 : 1.9-2.5 : 13-25, with the proviso thatD. The air and the recycled off-gas are divided between the two feed points in such a way that from 10 to 50% by volume of the total quantity of air and off-gas fed in are added after the first stage andE. The air and off-gas are admixed to the reaction gas mixture after the first stage, immediately after it leaves the catalyst zone, so that the mixture is rapidly cooled to a temperature of from 150.degree. to 320.degree. C.

摘要翻译： 在两个空间分离的氧化阶段中，在气相中将丙烯氧化成丙烯酸，除了新鲜电荷的丙烯和空气之外，将一部分已经脱除可冷凝产物的废气进料到氧化阶段， 在以下条件下：