CN1067990C - 从肟制备酰胺的方法 - Google Patents
从肟制备酰胺的方法 Download PDFInfo
- Publication number
- CN1067990C CN1067990C CN97118502A CN97118502A CN1067990C CN 1067990 C CN1067990 C CN 1067990C CN 97118502 A CN97118502 A CN 97118502A CN 97118502 A CN97118502 A CN 97118502A CN 1067990 C CN1067990 C CN 1067990C
- Authority
- CN
- China
- Prior art keywords
- oxime
- catalyzer
- acid amides
- mol ratio
- pore size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 150000002923 oximes Chemical class 0.000 title claims abstract description 17
- 150000001408 amides Chemical class 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000005855 radiation Effects 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 5
- 230000008707 rearrangement Effects 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 3
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- WHOPEPSOPUIRQQ-UHFFFAOYSA-N oxoaluminum Chemical compound O1[Al]O[Al]1 WHOPEPSOPUIRQQ-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 10
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BMTAFVWTTFSTOG-UHFFFAOYSA-N Butylate Chemical group CCSC(=O)N(CC(C)C)CC(C)C BMTAFVWTTFSTOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 aluminum compound Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- WJLUBOLDZCQZEV-UHFFFAOYSA-M hexadecyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCCCCCCCCCCCCCCC[N+](C)(C)C WJLUBOLDZCQZEV-UHFFFAOYSA-M 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Steroid Compounds (AREA)
Abstract
通过肟的催化重排制备酰胺的方法，包括使在蒸气相中的肟与选自摩尔比SiO2/Al2O2在20-1000之间、平均孔径在20-100A之间、煅烧后粉末的X-射线衍射图形(XRD)在大于18A的d-间距(spacing)处(2θ＜4.9°，CuKα辐射)具有最强(deepest)反射的中孔硅铝催化剂相接触。
Description
本发明涉及从肟制备酰胺的方法。
更具体地，本发明涉及在肟，例如环己酮肟催化转变从而形成酰胺，例如ε-己内酰胺(己内酰胺)，也称之为贝克曼催化重排中使用具有高表面积和高孔体积的硅铝催化剂。
酰胺，尤其是己内酰胺，在文献中作为用于化学合成的重要中间体和作为用于制备聚酰胺树脂的原料是已知的。
目前，通过在液相中使用硫酸或发烟硫酸通过环己酮肟重排工业化地生产已内酰胺。该重排的产物用氨中和导致同时形成硫酸铵。这一技术有很多与使用硫酸有关，与形成大量的硫酸铵有关的问题，由于存在酸蒸气，在处理废弃物，设备腐蚀等方面有问题。
对于环己酮肟催化重排形成己内酰胺，在文献中已经提出了另一个方法，在该方法中，使用选自硼酸衍生物，沸石，非沸石分子筛，固体磷酸，混合金属氧化物等的酸性固体作为催化剂。
特别地，EP234088描述了制备己内酰胺的方法，该方法包括使气体状态的环己酮肟与沸石型硅铝酸盐相接触，上述沸石型硅铝酸盐是：例如“约束(constraint)指数”在1-12之间，Si/Al原子比至少为500(SiO2/Al2O3至少1000)和外部酸官能度低于5微当量/克的ZSM-5，ZSM-11或ZSM-23。
沸石，如在“Zeolite Molecular Sieves”,D.W.Breck,John Wiley&Sons,(1974)中或在“Nature”381(1996),295中所描述的，是结晶产物，其特征是存在规则的微孔率，具有尺寸在3-10之间的通道。在某些特定的沸石结构中，可以有较大尺寸，最大达约13腔。
另外，沸石可以通过三维晶格的典型X-射线衍射图形，用存在于宽图谱范围内的布喇格反射识别。较显著的布喇格反射通常在2θ角在3-60°的范围，CuKα辐射。
为了提供另一个制备酰胺，特别是己内酰胺的方法，本申请人现已发现了一种新方法，该方法使用选自具有特殊形态或结构性质的硅铝酸性催化剂，如下面所述，其特征在于：相当大的催化活性，高的选择性，几乎与转化率无关，和通过热处理再生的可能性。
因此，本发明涉及通过肟的催化重排制备酰胺的方法，包括使在蒸气相中的肟与选自摩尔比SiO2/Al2O2在20-1000之间、平均孔径在18-100之间、和煅烧后粉末的X-射线衍射图形(XRD)在大于18的d-间距(spacing)处(2θ＜4.9°,CuKα辐射)具有最强(deepest)反射的中孔硅铝催化剂相接触。另外，在大于10的d-间距处(2θ＜8.8°,CuKα辐射)也可以存在其它反射。因此，这些材料在比沸石材料窄得多的谱图范围内有布喇格反射。
按照本发明的优选催化剂的例子是摩尔比SiO2/Al2O2在25-500之间，比表面积在500-1500m2/g之间和平均孔径在20-60之间的硅铝催化剂。这些材料以及其制备方法在文献中是已知的并且描述于已公开的国际专利申请WO/11390、“Nature”,368(1994),321或“ChemicalCommunication”,(1996),981中。
更具体地，在本发明的方法中使用的硅铝催化剂可以从含有至少一种二氧化硅源，一种氧化铝源，和具有式R1R2R3R4-OH(Ⅰ)的有机化合物的混合物得到，在式(Ⅰ)中，R1,R2,R3和R4的至少一个表示具有长链(C6-C36)的芳基或烷基，而剩下的R1，R2，R3和R4各自选自氢和具有较短的链(C1-C5)的烷基。也可以存在具有上式的第二个季铵碱，然而，其中R1，R2，R3和R4选自氢和具有短链C1-C5的烷基，或者可以把烷基中的两个共同看作形成环状化合物。
另外，有机化合物(Ⅰ)可以用直链胺例如十二烷胺取代。
在25-250℃的温度下使该混合物经受5分钟-14天的水热处理。这样得到的催化剂当以其酸形式使用时在肟的催化重排方面是有活性的。因此，当需要时，借助通常的技术可以有阳离子交换相。
按照本发明，优选的酰胺是ε-己内酰胺(己内酰胺)，优选的肟是环己酮肟(CEOX)。特别地，在0.05-10巴的压力和250-500℃，优选300-450℃的温度下进行环己酮肟的催化重排。更具体地，在溶剂和任选地不凝性气体的存在下，将蒸气相的环己酮肟送料进含有催化剂的反应器中。环己酮肟溶解在溶剂中，然后这样得到的混合物蒸发并送料进反应器中。
优选的溶剂是R1-O-R2型的，其中R1是C1-C4烷基链，R2可以是氢原子或含有碳原子数少于或等于R1的烷基链。这些溶剂可以单独地，或者彼此混合地，或者与芳香烃例如苯或甲苯混合地使用。具有C1-C2烷基链的醇是特别优选的。
将环己酮肟送料进重排反应器，其相对于催化剂的重量比，是用kg环己酮肟/kg催化剂/时间表示的WHSV(重时空速)为0.1-50h-1，优选0.5-20h-1。
催化剂的中毒是由于形成有机残余物造成的，该有机残余物阻塞了催化剂的孔隙并毒化了其活性部位。该中毒过程是很慢的并且取决于操作条件，特别是空速，溶剂，温度，进料的组成。然而，通过使该残余物燃烧，通过在450-600℃的温度下在空气和氮气气流中处理可以有效地恢复催化活性。
为了更好地理解本发明和其实施方案，提供下面说明性的、而非限制性的实施例。
实施例1催化剂A的合成
将0.3g异丙醇铝溶解在70g通过使20％(重量)的十六烷基三甲基溴化铵与碱形式的离子交换树脂接触得到的十六烷基三甲基氢氧化铵的水溶液中。将稀释在100g乙醇中的55g原硅酸四乙酯加入到该溶液中，在室温下操作。
让得到的沉淀物在室温静置2小时，然后过滤，通过在水中的再分散洗涤并再次过滤。然后在100℃干燥该固体2小时，然后在550℃空气中煅烧5小时。
得到的产物用粉末X-射线衍射分析法进行分析，用装有比例脉冲计数器、发散和接受狭缝为1/6°和用CuKα辐射(\=1.54178)的Philips立式衍射仪进行记录，在约38处有最强反射。
根据化学分析，该样品的摩尔比SiO2/Al2O3=330。
使用Carlo Erba Sorptomatic 1900仪器在液氮温度(77K)下通过N2吸附-脱附循环用B.E.T.方法测定的比表面积是986m2/g。
通过在液氮温度下也适用于N2的吸附/脱附曲线的Dollimore/Heal加工测定的平均孔径是26。
实施例2催化剂B的合成
使用与实施例1相同的方法，但存在0.5g的异丙醇铝。
得到的产物在约38处有最强的X-射线反射。
比表面积等于1100m2/g，平均孔径为约24。
根据化学分析，该样品的摩尔比SiO2/Al2O3=190。
实施例3-7催化剂C-G的合成
向含有52g乙醇，8.3g十二烷胺和13.5g水的第一溶液中加入通过混合26g乙醇，34.7g原硅酸四乙酯和变化量的仲丁醇铝得到的第二溶液，仲丁醇铝量的变化是为了得到摩尔比SiO2/Al2O3等于50,100,300,500的试剂混合物(催化剂C-F)。为了制备催化剂G，省去添加铝化合物。
让得到的沉淀物在室温静置2小时，然后过滤，通过在水中再分散洗涤并再次过滤。然后在100℃干燥固体2小时，然后在550℃空气中煅烧5小时。
得到的所有产物均表明在d-间距为35-40处X-射线有强峰。
此表面积分别为1000,1100,955,987,795m2/g，平均孔径分别为约20,26,36,36,40。根据化学分析，它们的摩尔比SiO2/Al2O3分别为：26,75,209,442。在催化剂G中，Al2O3的摩尔含量小于50ppm。
实施例8-14
将粒化为42-80目的催化剂装进玻璃反应器(20cm长，内径1cm)中，该反应器已在氮气中预热到380℃并干燥1小时。然后将摩尔比为5/1的MeOH/N2的混合物送到催化剂中30分钟。
该预处理后，通过送入预热并蒸气化的CEOX/MeOH/N2混合物(WHSV=2.2h-1，摩尔比1/40/8)开始进行催化试验。催化床的温度维持在380℃。
冷凝从反应器流出产物的混合物并通过气相色谱法分析。
在下面表Ⅰ中给出了环己酮肟的转化数据和对己内酰胺(CPL)的选择性。表Ⅰ实施例 催化剂 时间(小时) 转化率％ 选择性％8 A 1 97.8 76.8
20 84.1 78.89 B 1 100.0 72.8
24 94.5 77.010 C 3 99.8 62.3
24 99.8 73.711 D 1 99.9 69.7
24 100.0 78.112 E 1 100.0 68.8
24 100.0 75.713 F 1 99.9 66.5
24 99.4 70.914 G 1 10.7 64.1
24 6.9 37.7
实施例15
如上述操作，评估催化剂E的性能对时间的稳定性。数据列于下面表Ⅱ。表Ⅱ时间(小时) 转化率％ 选择性％1 100.0 68.82 100.0 72.810 100.0 77.319 100.0 76.121 100.0 76.323 100.0 75.725 100.0 77.234 99.9 74.344 99.7 75.2
Claims (7)
1．一种通过肟的催化重排制备酰胺的方法，包括使在蒸气相中的肟与选自摩尔比SiO2/Al2O2在20-1000之间、平均孔径在20-100之间、煅烧后粉末的X-射线衍射图形(XRD)在大于18的d-间距处(2θ＜4.9°，CuKα辐射)具有最强反射的中孔硅铝的催化剂相接触。
2．按照权利要求1的方法，其中催化剂选自摩尔比SiO2/Al2O3在25-500之间，比表面积在500-1500m2/g之间且平均孔径在20-60之间的硅铝催化剂。
3．按照权利要求1或2的方法，其中肟是环己酮肟，酰胺是ε-己内酰胺。
4．按照权利要求3的方法，其中肟的催化重排是在0.05-10巴的压力和250-500℃的温度下进行的。
5．按照权利要求4的方法，其中肟的催化重排是在溶剂存在下进行的。
6．按照权利要求5的方法，其中溶剂选自具有式R1-O-R2的产物，式中R1是C1-C4烷基链，R2是氢原子或含有碳原子数少于或等于R1的烷基链。
7．按照权利要求3的方法，其中将肟送料进重排反应器，其相对于催化剂的重量比是用kg肟/kg催化剂/时间表示的WHSV(重时空速)为0.1-50h-1。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT96MI001716A IT1283773B1 (it) | 1996-08-07 | 1996-08-07 | Procedimento per la perparazione di ammidi da ossime |
| IT001716A/1996 | 1996-08-07 | ||
| IT001716A/96 | 1996-08-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1177594A CN1177594A (zh) | 1998-04-01 |
| CN1067990C true CN1067990C (zh) | 2001-07-04 |
Family
ID=11374783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97118502A Expired - Fee Related CN1067990C (zh) | 1996-08-07 | 1997-08-06 | 从肟制备酰胺的方法 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5942613A (zh) |
| EP (1) | EP0823422B1 (zh) |
| JP (1) | JP3130836B2 (zh) |
| KR (1) | KR100233696B1 (zh) |
| CN (1) | CN1067990C (zh) |
| DE (1) | DE69701936T2 (zh) |
| ES (1) | ES2145538T3 (zh) |
| IT (1) | IT1283773B1 (zh) |
| TW (1) | TW381072B (zh) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1314263B1 (it) * | 1999-12-03 | 2002-12-06 | Enichem Spa | Processo per la preparazione di catalizzatori zeolitici. |
| US7022844B2 (en) | 2002-09-21 | 2006-04-04 | Honeywell International Inc. | Amide-based compounds, production, recovery, purification and uses thereof |
| KR101352250B1 (ko) | 2005-12-28 | 2014-01-16 | 셰브런 유.에스.에이.인크. | 분자체 ｓｓｚ-74 조성물 및 이의 합성 |
| US20070149778A1 (en) * | 2005-12-28 | 2007-06-28 | Chevron U.S.A. Inc. | Beckmann rearrangement using molecular sieve ssz-74 |
| WO2013154671A1 (en) | 2012-04-12 | 2013-10-17 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-87 |
| WO2014123610A1 (en) | 2013-02-08 | 2014-08-14 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-85 |
| WO2015179228A1 (en) | 2014-05-21 | 2015-11-26 | Chevron U.S.A. Inc. | Processes using molecular sieve ssz-95 |
| US20160167030A1 (en) * | 2014-12-16 | 2016-06-16 | University Of Southampton | Hierarchical aluminophosphates as catalysts for the beckmann rearrangement |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0234088A2 (en) * | 1985-08-28 | 1987-09-02 | Sumitomo Chemical Company, Limited | Production of E-caprolactam |
| WO1991011390A2 (en) * | 1990-01-25 | 1991-08-08 | Mobil Oil Corp | Synthetic porous crystalline material its synthesis and use |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4281194A (en) * | 1980-02-28 | 1981-07-28 | Allied Chemical Corporation | Process for ammoximation of cyclohexanone |
| US4359421A (en) * | 1981-01-15 | 1982-11-16 | Mobil Oil Corporation | Process for making epsilon-caprolactam |
| IT1214622B (it) * | 1985-07-10 | 1990-01-18 | Montedipe Spa | Processo catalitico per laproduzione di cicloesanonossima. |
| IT1222022B (it) * | 1987-07-14 | 1990-08-31 | Montedipe Spa | Metodo per la preparazione di un catalizzatore per l' ammossimazione di composti carbonilici |
| US5334368A (en) * | 1990-01-25 | 1994-08-02 | Mobil Oil Corp. | Synthesis of mesoporous oxide |
| IT1265320B1 (it) * | 1993-12-22 | 1996-10-31 | Eniricerche Spa | Procedimento per la preparazione di silico-allumine amorfe cataliticamente attive |
-
1996
- 1996-08-07 IT IT96MI001716A patent/IT1283773B1/it active IP Right Grant
-
1997
- 1997-07-04 EP EP97111242A patent/EP0823422B1/en not_active Expired - Lifetime
- 1997-07-04 ES ES97111242T patent/ES2145538T3/es not_active Expired - Lifetime
- 1997-07-04 DE DE69701936T patent/DE69701936T2/de not_active Expired - Fee Related
- 1997-07-09 US US08/890,677 patent/US5942613A/en not_active Expired - Fee Related
- 1997-07-28 TW TW086110715A patent/TW381072B/zh not_active IP Right Cessation
- 1997-08-04 KR KR1019970037208A patent/KR100233696B1/ko not_active IP Right Cessation
- 1997-08-06 CN CN97118502A patent/CN1067990C/zh not_active Expired - Fee Related
- 1997-08-07 JP JP09213677A patent/JP3130836B2/ja not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0234088A2 (en) * | 1985-08-28 | 1987-09-02 | Sumitomo Chemical Company, Limited | Production of E-caprolactam |
| WO1991011390A2 (en) * | 1990-01-25 | 1991-08-08 | Mobil Oil Corp | Synthetic porous crystalline material its synthesis and use |
Also Published As
| Publication number | Publication date |
|---|---|
| IT1283773B1 (it) | 1998-04-30 |
| US5942613A (en) | 1999-08-24 |
| CN1177594A (zh) | 1998-04-01 |
| TW381072B (en) | 2000-02-01 |
| JPH111470A (ja) | 1999-01-06 |
| ITMI961716A0 (zh) | 1996-08-07 |
| EP0823422B1 (en) | 2000-05-10 |
| JP3130836B2 (ja) | 2001-01-31 |
| ITMI961716A1 (it) | 1998-02-07 |
| ES2145538T3 (es) | 2000-07-01 |
| DE69701936D1 (de) | 2000-06-15 |
| KR100233696B1 (ko) | 2000-02-01 |
| DE69701936T2 (de) | 2000-10-05 |
| EP0823422A1 (en) | 1998-02-11 |
| KR19980018350A (ko) | 1998-06-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2001292758B2 (en) | Method for heteroatom lattice substitution in large and extra-large pore borosilicate zeolites | |
| Bellussi et al. | Amorphous mesoporous silica-alumina with controlled pore size as acid catalysts | |
| CA1166233A (en) | Preparation of zeolites and use of these zeolites as catalysts | |
| US10974967B2 (en) | Molecular sieve SCM-15, synthesis method therefor and use thereof | |
| WO2017090751A1 (ja) | ゼオライト触媒及び低級オレフィンの製造方法 | |
| Linares et al. | Effect of hierarchical porosity in Beta zeolites on the Beckmann rearrangement of oximes | |
| IE48184B1 (en) | Modified silica and germania and their use as catalysts | |
| CN1067990C (zh) | 从肟制备酰胺的方法 | |
| JPH0542299B2 (zh) | ||
| Wu et al. | Exclusive SAPO-seeded synthesis of ZK-5 zeolite for selective synthesis of methylamines | |
| CN112239215B (zh) | Scm-27分子筛、其制造方法及其用途 | |
| US5271920A (en) | Activation of zeolites | |
| EP1101735B1 (en) | Method for the removal of the templating agent from synthetic zeolites | |
| RU2240312C1 (ru) | Способ получения эпсилон-капролактама | |
| US11643332B2 (en) | Method for preparing a high-purity AFX structural zeolite with a nitrogen-containing organic structuring agent | |
| EP0819675B1 (en) | Process for the preparation of amides from oximes | |
| US5241119A (en) | Process for the preparation of 4,4'-diaminodiphenyl-methane and its derivatives | |
| CN111099613B (zh) | 分子筛、其合成方法及其用途 | |
| CN113966251A (zh) | Iwr骨架结构类型的硅铝酸盐沸石材料的直接合成及其在催化中的用途 | |
| RU2129989C1 (ru) | Материал на основе диоксида циркония и способ его приготовления | |
| US5215736A (en) | Mordenite type zeolite and its preparation process | |
| KR100478077B1 (ko) | 알킬화 반응 촉매 및 이의 용도 | |
| JP7091768B2 (ja) | ゼオライト粉体 | |
| Bhattacharya et al. | Benzylation of naphthalene over zeolite catalysts | |
| KR20240076832A (ko) | 실리콘-알루미늄 제올라이트 scm-36, 이의 제조방법 및 응용 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1019560 Country of ref document: HK |
|
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |