CN102371158A - Catalyst of acrylic acid prepared by oxidation process and its preparation method - Google Patents

Catalyst of acrylic acid prepared by oxidation process and its preparation method Download PDF

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CN102371158A
CN102371158A CN 201010261471 CN201010261471A CN102371158A CN 102371158 A CN102371158 A CN 102371158A CN 201010261471 CN201010261471 CN 201010261471 CN 201010261471 A CN201010261471 A CN 201010261471A CN 102371158 A CN102371158 A CN 102371158A
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catalyst
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acrylic acid
acid
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CN 201010261471
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缪晓春
郑育元
杨斌
汪国军
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中国石油化工股份有限公司
中国石油化工股份有限公司上海石油化工研究院
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Abstract

The invention relates to a catalyst of acrylic acid prepared by oxidizing acrylaldehyde and its preparation method, which mainly solves the problem of low selectivity of acrylic acid in the prior art. According to the invention, at least one of SiO2, Al2O3 or TiO2 is selected as a carrier, which contains an active component shown in the following general formula of Mo12VaCubXcYdZeOx, wherein X is selected from at least one of W, Cr, Sn or Nb; Y is selected from at least one of Fe, Bi, Co, Ni, Sb, Ce, La, Zr or Sr; Z is selected from at least one of alkali metal or alkaline-earth metal, at least one organic acid is added during the catalyst preparation process. The technical scheme better solves the problem, and can be used for preparing acrylic acid by oxidizing acrylaldehyde.

Description

氧化法制丙烯酸催化剂及其制备方法 Oxidation catalyst and preparation of acrylic acid

技术领域 FIELD

[0001] 本发明涉及一种氧化法制丙烯酸催化剂及其制备方法,特别是关于丙烯醛氧化制取丙烯酸催化剂及其制备方法。 [0001] The present invention relates to a method for preparing an acrylic catalyst and oxidation process, catalyst and preparation of acrylic acid on oxidation of acrolein particular preparation.

背景技术 Background technique

[0002] 烯烃的选择氧化制备α、β不饱和醛及不饱和酸是重要的化工过程,其中由丙烯醛制丙烯酸的生产使用一种活性组分含有Mo、V的催化剂。 [0002] The selective oxidation of olefins prepared α, β-unsaturated aldehyde and unsaturated acid is an important chemical process in which the production of acrolein by the use of one active component acrylic acid containing Mo, V of the catalyst. 催化剂的改进主要是从催化剂的活性、选择性及稳定性方面进行的,如在活性组份中加入过渡金属以提高活性,增加产物的单收;加入稀土元素改善氧化还原能力,提高催化剂稳定性;加入Fe、Co、Ni等元素以抑制Mo的升华,稳定催化剂活性组分,提高催化剂的使用寿命等。 The main catalyst is improved in terms of catalyst activity, selectivity and stability, such as the addition of the transition metal in the active ingredient to increase activity, increase product yield single; rare earth elements added to improve the redox potential, to improve stability of the catalyst ; adding Fe, Co, Ni and other elements to suppress the sublimation of Mo, stabilizing the active catalyst component, to improve the life of the catalyst and the like.

[0003] 对于丙烯醛选择氧化已有很多专利报道: [0003] For the selective oxidation of acrolein has been reported in many patents:

[0004] US Pat7220698B2通过催化剂制备过程中加入一种微量的催化剂毒物,来控制催化剂反应床层热点,抑制催化剂的热降解,提高催化剂稳定性。 [0004] US Pat7220698B2 by adding a trace amount of catalyst poison the catalyst preparation process, the reaction is controlled hot catalyst bed, the catalyst to suppress thermal degradation, improved catalyst stability. 丙烯醛转化率达98. 8%,而且长时间保持稳定。 Acrolein conversion rate was 98.8%, and stable over time. US Ι^ΐ7378367Β2介绍了一种丙烯酸催化剂,丙烯酸收率高达95. 1%, 且具有很好的稳定性,使用过程中反应器温升小。 US Ι ^ ΐ7378367Β2 describes a catalyst acrylic acid, acrylic acid yields of up to 95.1%, and has good stability, small temperature increase during use of the reactor. US I^t7456U9B2通过控制载体酸强度来改善催化剂性能,丙烯醛转化率98. 9 %,丙烯酸选择性95.1%。 US I ^ t7456U9B2 be improved by controlling the acid strength of the catalyst carrier performance, 98.9% acrolein conversion, acrylic acid selectivity of 95.1%.

[0005] CN1183088C介绍一种催化剂制备方法,通过选择特定的制备原料,丙烯醛转化率高达99. 6 %,丙烯酸选择性高达96. 0 %,丙烯酸收率高达95.2%。 [0005] CN1183088C describes a catalyst preparation method, by selecting a specific preparation of starting materials, the acrolein conversion rate as high as 99.6 percent, up to 96.0% acrylic acid selectivity, acrylic acid yield up to 95.2%.

[0006] 综上所述,现有文献中均存在丙烯酸选择性低和丙烯酸收率较低的问题。 [0006] In summary, the literature exist in low acrylic acid selectivity and acrylic acid yield is low problem.

发明内容 SUMMARY

[0007] 本发明所要解决的技术问题之一是现有技术丙烯酸选择性较低,丙烯酸收率较低的问题,提供一种新的丙烯醛氧化制丙烯酸的催化剂。 One [0007] The present invention solves the technical problem of the prior art is low acrylic acid selectivity, acrylic acid yield is low problems and to provide a novel catalyst oxidation of acrolein to acrylic acid. 该催化剂用于丙烯醛选择氧化生产丙烯酸反应,具有丙烯酸选择性高、丙烯酸收率高的优点。 The catalyst for selective oxidation of acrolein production of acrylic acid, acrylic acid having high selectivity, acrylic acid yield advantages. 本发明所要解决的技术问题之二是提供一种与解决技术问题之一所用的催化剂相对应的制备方法。 Invention to two technical problem is to provide a method for the preparation of the catalyst used in one of the technical problems to be solved relatively.

[0008] 为解决上述技术问题之一,本发明采用的技术方案如下:一种氧化法制丙烯酸催化剂,以选自Si02、Al2O3或TiA中的至少一种为载体,活性组份由下列通式表示: [0008] In order to solve one of the above-described technical problem, the present invention employs the following technical solution: an oxidation catalyst SYSTEM acrylate, selected from Si02, Al2O3 or TiA at least one carrier, the active ingredient represented by the following formula :

[0009] Mo12VaCubXcYaZeOx [0009] Mo12VaCubXcYaZeOx

[0010] 式中X为选自W、Cr、Sn、Nb中的至少一种; [0010] wherein X is selected from W, Cr, Sn, Nb is at least one;

[0011] Y 为选自Fe、Bi、Co、Ni、Sb、Ce、La、Zr、Sr 中的至少一种; [0011] Y is selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr, Sr, at least one;

[0012] Z为选自碱金属或碱土金属中的至少一种; [0012] Z is at least one selected from an alkali metal or an alkaline earth metal;

[0013] a的取值范围为1.0〜10. 0 ; In the range [0013] a is 0 1.0~10.;

[0014] b的取值范围为0.5〜8.0; In the range [0014] b is 0.5~8.0;

[0015] c的取值范围为0.8〜11.0; [0015] c ranges 0.8~11.0;

[0016] d的取值范围为0.5〜6.0; In the range [0016] d is 0.5~6.0;

[0017] e的取值范围为0.5〜5.0;[0018] χ为满足其它元素化合价所需的氧原子总数; [0017] e is in the range of 0.5~5.0; [0018] χ total number of oxygen atoms required to satisfy the valence of other elements;

[0019] 催化剂中载体的用量为催化剂重量的5〜40% ; [0019] The amount of the catalyst support is 5 ~ 40% by weight of the catalyst;

[0020] 催化剂制备过程中加入至少一种有机酸。 Preparation of [0020] catalyst added during at least one organic acid.

[0021] 上述技术方案中,a的取值范围为2. 0〜7. 0 ;b的取值范围为1. 2〜5. 5 ;c的取值范围为1. 0〜7. 2 ;d的取值范围为0. 8〜4. 8 ;e的取值范围为0. 7〜3. 6 ;制备过程中加入草酸、马来酸和柠檬酸中的至少一种。 [0021] The above technical solution, a is in the range of 2. 0~7 0;. B ranges 1. 2~5 5;. C ranges from 0 to 7 1 2; d is in the range of 0. 8 8~4;. e in the range of 0. 6 7~3; preparation process of adding at least one oxalic acid, maleic acid and citric acid.

[0022] 为解决技术问题之二本发明采用的技术方案如下:一种氧化法制丙烯酸催化剂的制备方法,包括以下步骤: [0022] To solve the second technical problem aspect of the present invention used is as follows: A method for preparing acrylic catalyst oxidation process, comprising the steps of:

[0023] a)将所需量的钼酸铵溶解在水中,然后将所需量的Si02、Al203或T^2中的至少一种载体加入形成溶液I ; [0023] a) The required amount of ammonium molybdate was dissolved in water, and then the desired amount of Si02, Al203, or at least one vector T ^ 2 was added to form a solution I;

[0024] b)将所需量的偏钒酸铵及所需量的有机酸溶解在水中形成溶液II ; [0024] b) The required amount of ammonium metavanadate, and the desired amount of organic acid is dissolved in water to form a solution II;

[0025] c)将所需量的金属盐溶解在水中形成溶液III ; [0025] c) the desired amount of the metal salt is dissolved in water to form a solution III;

[0026] d)在搅拌下,将溶液II和溶液III分别加入溶液I形成催化剂浆料; [0026] d) under stirring, the solution II and solution III were added to Solution I to form a catalyst slurry;

[0027] e)浆料通过喷雾成型或蒸发大部分水分后挤出成型得到催化剂前体,催化剂前体通过400〜550°C焙烧得到催化剂成品。 [0027] e) spraying the slurry through extrusion molding or after molding most of the water was evaporated to give a catalyst precursor, the catalyst precursor finished catalyst obtained by calcining 400~550 ° C.

[0028] 上述技术方案中,催化剂制备过程中有机酸的加入量占催化剂重量的2〜10%。 [0028] In the above technical solution, the catalyst preparation process of an organic acid catalyst is added an amount of 2~10% by weight.

[0029] 本发明由于在催化剂制备过程中加入了一种有机酸,该化合物在焙烧分解过程中影响了催化剂金属氧化还原程度及催化剂成品表面积、孔分布等物性参数从而改善了催化剂的反应性能。 [0029] In the present invention, since the addition of an organic acid during the preparation of the catalyst, the catalyst metal compound affects the degree of reduction and oxidation of the surface area of ​​the finished catalyst decomposition during the firing process, the pore size distribution and other physical parameters to improve the performance of the catalyst in the reaction. 使用本发明的催化剂用于丙烯选择氧化制备丙烯醛,在反应温度为280°C、反应空速为1400小时―1的条件下,其丙烯醛转化率可达99. 6%、丙烯酸选择性可达99.1%,产物丙烯酸收率可达97. 7%,取得了较好的技术效果。 Catalyst of the present invention the selective oxidation of propylene to acrolein, at a reaction temperature of 280 ° C, a space velocity of 1400 hr -1 Reaction conditions that acrolein conversion rate of 99.6%, selectivity of acrylic acid 99.1% acrylic acid product yield of 97.7%, and achieved good results in the art.

[0030] 在以下给出的实施例中,对催化剂的考察评价条件为: [0030] In the examples given below, the inspection of Catalyst evaluation conditions are as follows:

[0031] 反应器:固定床反应器,内径25. 4毫米,反应器长度750毫米 [0031] Reactor: fixed bed reactor, an inner diameter of 25.4 mm, 750 mm reactor length

[0032] 催化剂填装量:150克 [0032] The catalyst filling amount: 150 g

[0033] 反应温度:280°C [0033] The reaction temperature: 280 ° C

[0034] 反应时间:4小时 [0034] Reaction time: 4 hours

[0035] 原料比:丙烯醛/空气/水蒸汽=15. 8/50. 9/33. 3 [0035] The ratio of starting material: Acrolein / air / water vapor = 15 8/50 9/33 3

[0036] 反应空速:1400小时— [0036] The space velocity: 1,400 hours -

[0037] 反应产物用0°C稀酸吸收,用气相色谱分析产物。 [0037] The reaction product is taken up with dilute 0 ° C, the product was analyzed by gas chromatography. 并计算碳平衡,当碳平衡在(95〜105)%时为有效数据。 And calculating the carbon balance, when the carbon balance (95~105)% valid data.

[0038] 丙烯醛转化率、产物收率和选择性的定义为: [0038] acrolein conversion rate, product yield and selectivity is defined as:

[0039] [0039]

丙烯醛转化率(o/o)-i__mmmmm_ Acrolein conversion (o / o) -i__mmmmm_

所有产物c摩尔数(包括未反应丙烯醛)xl00/o C moles of all products (including unreacted acrolein) xl00 / o

[0040] [0040]

[0041] [0041]

^r^m (rj 生成某产物c摩尔数 ^ R ^ m (rj generate a number of moles of product c

某严物收:f 所有产物c摩尔数(包括未反应丙烯醛)xl00/° Yan was a close: f c the number of moles of all products (including unreacted acrolein) xl00 / °

某产物选择性d—。 A product selectivity d-. [0042] 下面通过实施例对本发明作进一步阐述。 [0042] The following examples further illustrated the invention.

具体实施方式 Detailed ways

[0043]【比较例1】 [0043] [Comparative Example 1]

[0044] 将100克(NH4) 6ΜΟ7024 · 4H20加入到100克70°C的温水中,搅拌使其全部溶解,加入64. 4克40% (wt.)的硅溶胶和12. 7克(NH4) 6H5 [H2 (WO4) 6]制成物料A。 [0044] 100 g (NH4) 6ΜΟ7024 · 4H20 was added to 100 g of warm 70 ° C, stirring and completely dissolved, was added 64.4 g 40% (wt.) Silica sol and 12.7 g (NH4 ) 6H5 [H2 (WO4) 6] made of material A.

[0045] 将28. 5克!^e(NO3)3 · 9H20加入20克的70°C热水中,搅拌溶解后再加入34. 2克Cu (NO3) 2 · 3H20、12. 0 克Sr (NO3) 2、1. 6 克KOH 搅拌溶解后制成物料B。 [0045] A 28.5 g! ^ E (NO3) 3 · 9H20 70 ° C was added 20 g of water, stirring to dissolve and then add 34.2 g Cu (NO3) 2 · 3H20,12. 0 g of Sr (NO3) 2,1. 6 g of KOH dissolved by stirring the material B.

[0046] 在50克水中加入25. 8克NH4VO3形成物料C。 [0046] 25.8 g NH4VO3 was added 50 grams of water is formed in the material C.

[0047] 将物料B和C先后在快速搅拌下滴加于物料A中,形成催化剂浆料,并在80°C下搅拌老化2小时,浆料120°C烘干去除大部分水分后挤出成型,得到cp3.5x3.5mm的圆柱状物, 然后高温焙烧得到催化剂成品,焙烧温度为480°C,按上述考评条件,反应考评结果列于表2。 After [0047] the material B and C successively added dropwise with rapid stirring at material A to form a catalyst slurry, and stirred aged for 2 hours at 80 ° C, the slurry 120 ° C dried to remove most of the water out molding to obtain a cylindrical cp3.5x3.5mm was then high temperature firing to obtain the finished catalyst calcined at 480 ° C, according to the above evaluation condition, the evaluation results of the reaction are shown in table 2.

[0048]【实施例1】 [0048] [Example 1]

[0049] 将100克(NH4) 6Μο7024 · 4H20加入到100克70°C的温水中,搅拌使其全部溶解,加入68. 6 克40% (wt.)的硅溶胶、63. 3 克20% (wt.)的铝溶胶和16. 6 克(NH4)6H5 [H2 (WO4)6] 制成物料A。 [0049] 100 g (NH4) 6Μο7024 · 4H20 was added to 100 g of warm 70 ° C, stirring and completely dissolved, was added 68.6 g 40% (wt.) Silica sol, 63.3 g of 20% (wt.) of alumina sol and 16.6 g (NH4) 6H5 [H2 (WO4) 6] made of material A.

[0050] 将32. 8克Ce(NO3)3 · 6H20加入20克的70°C热水中,搅拌溶解后再加入26. 3克Zr (NO3)4 · 6Η20、31· 9 克Cu(NO3)2 · 3Η20、64· 1 克、Bi(NO3)3 · 5Η20、9· 2 克CsNO3>3. 3 克KOH 溶解后制成物料B。 [0050] A 32.8 g Ce (NO3) 3 · 6H20 20 g of 70 ° C hot water, stirring to dissolve and then add 26.3 grams Zr (NO3) 4 · 6Η20,31 · 9 g of Cu (NO3 ) 2 · 3Η20,64 · 1 g of, Bi (NO3) 3 · 5Η20,9 · 2 after g of CsNO3> 3. 3 g of KOH dissolved to prepare a material B.

[0051] 在50克水中加入18. 7克NH4VO3及20. 5克马来酸形成物料C。 [0051] 18.7 g NH4VO3 was added and 20.5 grams of maleic acid in 50 grams of water forming material C.

[0052] 将物料B和C先后在快速搅拌下滴加于物料A中,形成催化剂浆料,并在80°C下搅拌老化2小时,浆料120°C烘干去除大部分水分后挤出成型,得到cp3.5x3.5mm的圆柱状物, 然后高温焙烧得到催化剂成品,焙烧温度为480°C。 After [0052] the material B and C successively added dropwise with rapid stirring at material A to form a catalyst slurry, and stirred aged for 2 hours at 80 ° C, the slurry 120 ° C dried to remove most of the water out molding to obtain a cylindrical cp3.5x3.5mm was then high temperature firing to obtain the finished catalyst calcined at 480 ° C.

[0053]【实施例2〜11】 [0053] [Embodiment] Example 2~11

[0054] 按实施例1的各个步骤制得催化剂,只是改变催化剂制备条件,加入有机酸的品种及用量,具体结果列于表1,在上述相同的评价条件下,反应考评结果列于表2。 [0054] The various steps as described in Example 1 to prepare a catalyst, except for changing the preparation conditions, the types and rates of adding an organic acid, particularly the results shown in Table 1, under the same evaluation conditions as above, the reaction evaluation results are shown in Table 2 .

[0055] 表1催化剂 [0055] Table 1 Catalyst

[0056] [0056]

Figure CN102371158AD00061

7 7

[0057] 表2实施例考察结果 [0057] Table 2 Results Example Investigation

[0058] [0058]

Figure CN102371158AD00062
Figure CN102371158AD00071

Claims (5)

  1. 1. 一种氧化法制丙烯酸催化剂,以选自Si02、Al2O3或T^2中的至少一种为载体,活性组份由下列通式表示:Mo12VaCubXcYdZeOx式中X为选自W、Cr、Sn、Nb中的至少一种; Y 为选自Fe、Bi、Co、Ni、Sb、Ce、La、Zr、Sr 中的至少一种; Z为选自碱金属或碱土金属中的至少一种; a的取值范围为1.0〜10.0 ; b的取值范围为0. 5〜8. 0 ; c的取值范围为0.8〜11.0 ; d的取值范围为0. 5〜6. 0 ; e的取值范围为0. 5〜5. 0 ; χ为满足其它元素化合价所需的氧原子总数; 催化剂中载体的用量为催化剂重量的5〜40% ; 催化剂制备过程中加入至少一种有机酸。 An acrylic Oxidation catalyst selected from Si02, Al2O3, or T ^ 2 at least one active component carrier as represented by the following general formula: Mo12VaCubXcYdZeOx wherein X is selected from W, Cr, Sn, Nb at least one; Y is selected from Fe, Bi, Co, Ni, Sb, Ce, La, Zr, Sr is at least one; Z is at least one metal selected from alkali or alkaline earth metals; a of in the range of 1.0~10.0; b is in the range 0. 5~8 0;. c ranges 0.8~11.0; d is in the range 0. 5~6 0;. e values range of 0. 5~5 0;. χ total number of oxygen atoms required to satisfy the valence of other elements; the amount of the catalyst support is 5 ~ 40% by weight of the catalyst; catalyst preparation process of adding at least one organic acid.
  2. 2.根据权利要求1所述的氧化法制丙烯酸催化剂,其特征在于a的取值范围为2. 0〜 7. 0 ;b的取值范围为1. 2〜5. 5 ;c的取值范围为1. 0〜7. 2 ;d的取值范围为0. 8〜4. 8 ;e 的取值范围为0.7〜3. 6。 Acrylic 2. Oxidation catalyst according to claim 1, wherein a is in the range of 2 0~ 7.0; range of b is 1. 2~5 5;. C ranges 2 to 1. 0 to 7;. d is in the range 8~4 0. 8;. e range of 0.7~3 6.
  3. 3.根据权利要求1所述的氧化法制丙烯酸催化剂,其特征在于制备过程中加入的有机酸选自草酸、马来酸和柠檬酸中的至少一种。 Acrylic 3. Oxidation catalyst according to claim 1, characterized in that at least one organic acid added during preparation selected from oxalic acid, maleic acid and citric acid.
  4. 4.权利要求1所述的氧化法制丙烯酸催化剂制备方法,包括以下步骤:a)将所需量的钼酸铵溶解在水中,然后将所需量的Si02、Al203或T^2中的至少一种载体加入形成溶液I ;b)将所需量的偏钒酸铵及所需量的有机酸溶解在水中形成溶液II ;c)将所需量的金属盐溶解在水中形成溶液III ;d)在搅拌下,将溶液II和溶液III分别加入溶液I形成催化剂浆料;e)浆料通过喷雾成型或蒸发大部分水分后挤出成型得到催化剂前体,催化剂前体通过400〜550°C焙烧得到催化剂成品。 At least one of a) the desired amount of ammonium molybdate was dissolved in water, and then the desired amount of Si02, Al203, or the T ^ 2: The oxidation catalyst for producing acrylic acid according to claim 4. Method 1, comprising the steps of seed carrier was added to form a solution I; b) dissolving ammonium metavanadate and the required amount of the desired amount of the organic acid in water to form a solution II; c) the desired amount of the metal salt is dissolved in water to form a solution III; D) under stirring, the solution II and solution III were added to solution I to form a catalyst slurry; after e) forming a slurry by spraying or most of the water was evaporated to obtain extruded catalyst precursor, the catalyst precursor by calcining 400~550 ° C to give a finished catalyst.
  5. 5.根据权利要求书5所述的氧化法制丙烯酸催化剂的制备方法,其特征在于催化剂制备过程中有机酸的加入量占催化剂重量的2〜10%。 The preparation method according to claim 5, wherein the catalyst preparation oxidized acrylic acid, wherein the catalyst is 2~10% by weight of the amount added during preparation of the catalyst of organic acids.
CN 201010261471 2010-08-23 2010-08-23 Catalyst of acrylic acid prepared by oxidation process and its preparation method CN102371158A (en)

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CN103418402A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof
CN103521235A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof
CN103586067A (en) * 2013-07-09 2014-02-19 中国科学院过程工程研究所 Catalyst for synthesizing acrylic acid by aqueous formaldehyde solution and acetic acid and preparation and application method of catalyst
CN103769155A (en) * 2012-10-23 2014-05-07 中国石油天然气股份有限公司 Catalyst for unsaturated aldehyde selective-oxidation and preparation method thereof
CN103769149A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Catalyst for preparing propenoic acid through oxidation of propenal, as well as preparation and application of catalyst
CN103769148A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst
CN103877987A (en) * 2012-12-19 2014-06-25 中国石油化工股份有限公司 Catalyst for acrylic acid and preparation method thereof
CN103894205A (en) * 2012-12-27 2014-07-02 中国石油化工股份有限公司 Catalyst for acrylic acid synthesis and preparation method thereof
CN103894204A (en) * 2012-12-27 2014-07-02 中国石油化工股份有限公司 Catalyst for catalyzing acrolein oxidation reaction to prepare acrylic acid, and preparation method thereof
CN104107697A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Preparation method of acrylic acid catalyst
CN104107696A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Preparation method of catalyst for preparing acrylic acid through oxidizing acrolein
CN104226328A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Catalyst for synthesis of acrylic acid, preparation method thereof and synthetic method of acrylic acid
CN104275192A (en) * 2013-07-09 2015-01-14 中国石油化工股份有限公司 Catalyst for synthesis of acrolein and acrylic acid and preparation method and application thereof
CN104549350A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for preparing acrylic acid and preparation method thereof
CN104646018A (en) * 2013-11-19 2015-05-27 中国石油天然气股份有限公司 Unsaturated aldehyde selective oxidation catalyst and preparation method thereof
CN104923247A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Catalyst for synthesis of acrylic acid from acraldehyde
CN105664961A (en) * 2014-11-20 2016-06-15 中国石油化工股份有限公司 Acrylic acid catalyst

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CN103418402A (en) * 2012-05-16 2013-12-04 中国石油化工股份有限公司 Catalyst for preparing acrylic acid by acrolein oxidation and preparation method thereof
CN103521235A (en) * 2012-07-03 2014-01-22 中国石油化工股份有限公司 Catalyst for preparing acrylic acid through acrolein oxidation and preparation method thereof
CN103769155B (en) * 2012-10-23 2016-01-20 中国石油天然气股份有限公司 Unsaturated aldehyde selective oxidation catalyst and preparation method
CN103769155A (en) * 2012-10-23 2014-05-07 中国石油天然气股份有限公司 Catalyst for unsaturated aldehyde selective-oxidation and preparation method thereof
CN103769149A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Catalyst for preparing propenoic acid through oxidation of propenal, as well as preparation and application of catalyst
CN103769148A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Acrolein oxidation to acrylic acid catalyst, preparation method and application of catalyst
CN103877987A (en) * 2012-12-19 2014-06-25 中国石油化工股份有限公司 Catalyst for acrylic acid and preparation method thereof
CN103877987B (en) * 2012-12-19 2016-07-06 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method
CN103894204A (en) * 2012-12-27 2014-07-02 中国石油化工股份有限公司 Catalyst for catalyzing acrolein oxidation reaction to prepare acrylic acid, and preparation method thereof
CN103894205B (en) * 2012-12-27 2016-02-10 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method
CN103894205A (en) * 2012-12-27 2014-07-02 中国石油化工股份有限公司 Catalyst for acrylic acid synthesis and preparation method thereof
CN103894204B (en) * 2012-12-27 2016-09-07 中国石油化工股份有限公司 The catalyst for producing acrolein and acrylic acid oxidative synthesis
CN104107696A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Preparation method of catalyst for preparing acrylic acid through oxidizing acrolein
CN104107697A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Preparation method of acrylic acid catalyst
CN104107697B (en) * 2013-04-16 2016-07-13 中国石油化工股份有限公司 A catalyst for producing acrylic acid
CN104107696B (en) * 2013-04-16 2017-09-15 中国石油化工股份有限公司 Oxidation of acrolein to acrylic acid in the catalyst preparation method
CN104226328A (en) * 2013-06-17 2014-12-24 中国石油化工股份有限公司 Catalyst for synthesis of acrylic acid, preparation method thereof and synthetic method of acrylic acid
CN104226328B (en) * 2013-06-17 2016-09-07 中国石油化工股份有限公司 The catalyst for the synthesis of acrylic acid, acrylic acid and a method for preparing synthesis
CN104275192B (en) * 2013-07-09 2016-06-08 中国石油化工股份有限公司 Acrolein and acrylic acid catalyst synthesis, preparation method and application
CN104275192A (en) * 2013-07-09 2015-01-14 中国石油化工股份有限公司 Catalyst for synthesis of acrolein and acrylic acid and preparation method and application thereof
CN103586067A (en) * 2013-07-09 2014-02-19 中国科学院过程工程研究所 Catalyst for synthesizing acrylic acid by aqueous formaldehyde solution and acetic acid and preparation and application method of catalyst
CN104549350A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for preparing acrylic acid and preparation method thereof
CN104549350B (en) * 2013-10-28 2017-05-10 中国石油化工股份有限公司 Acrylic acid catalyst and preparation method
CN104646018A (en) * 2013-11-19 2015-05-27 中国石油天然气股份有限公司 Unsaturated aldehyde selective oxidation catalyst and preparation method thereof
CN104646018B (en) * 2013-11-19 2016-11-23 中国石油天然气股份有限公司 An unsaturated aldehyde selectivity of the oxidation catalyst and preparation method
CN104923247A (en) * 2014-03-17 2015-09-23 中国石油化工股份有限公司 Catalyst for synthesis of acrylic acid from acraldehyde
CN104923247B (en) * 2014-03-17 2018-06-08 中国石油化工股份有限公司 Synthesis of acrylic acid by the acrolein
CN105664961A (en) * 2014-11-20 2016-06-15 中国石油化工股份有限公司 Acrylic acid catalyst

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