外文专利的说明书.docx

1、外文专利的说明书ISOPROPYL ALCOHOL FROM PROPYLENE USING ZIRCONIUM BASED MIXED METAL OXIDESFIELD OF THE INVENTION0001 The invention relates to the production of isopropyl alcohol (IPA) by direct hydration of propylene over mixed metal oxides.BACKGROUND OF THE INVENTION0002 Hydration of propylene to make isopr

2、opyl alcohol (IPA) has been practiced commercially for many years. Commercial processes may be classified as indirect or direct hydration processes. Indirect hydration processes contact propylene (C3=) with strong mineral acids such a sulfuric acid or phosphoric acid to form a sulfate/phosphate este

3、r which is then hydrolyzed to reform the acid and produce the IPA product. Direct hydration (DH) processes feed propylene and water over a solid acid catalyst that hydrolyzes the olefin to produce IPA.0003 DH processes typically use solid acid catalyst or heterogeneous catalyst for the hydration of

4、the propylene directly to IPA. In the direct process, the hydration of the olefins to alcohols is carried out directly and in a single step, by contacting the olefin with the hydration water in the presence of an acidic catalyst. DH processes typically require chemical grade propylene or better as f

5、eed to decrease impurities produced and maintain catalyst life. DH may be carried out in vapor-phase, liquid-phase or mixed phase. IPE is the major by-product from the C3 direct hydration processes.0004 Solid acid catalysts that have been utilized for DH include functionalized divinylbenzene polymer

6、 catalysts such as sulfonic acid resins (i.e. Amberlysts(TM), Dowexs(TM), solid phosphoric acid (SPA), various types of zeolites, metal impregnated silica and aluminas. Although these catalysts are capable of DH chemistry they all are subject to various limitations that impact how they can be used.

7、Resin catalysts are very active but are not intrinsically selective and chemically degrade over 150C. To manage the non- selectivity, high water to C3= ratios are used to drive the equilibrium towards IPA. These high water systems create more costly processes for separation and purification of IPA.

8、Many zeolites/molecular sieves and other silica/alumina catalysts are intrinsically selective to IPA due to microporous structure, but these have hydro lytic stability problems. 0005 Accordingly, this very important commercial process is an area of active research to overcome the problems with prior

9、 art processes. 0006 One specific area of research involves catalysts based on the modification one metal oxide by incorporation of other metal oxides, generally referred to as mixed metal oxides (MMOs). Typically, at least one of the metals is a transition metal (i.e., Groups 3-11 according to the

10、Periodic Table from Chemical and Engineering News, 63(5), 27, 1985). As used herein, the term transition metal includes the members of the Lanthanide and Actinide families of said Table.0007 Work by Hoecker in 1996 (DE 1012783) identified ZrO2 for use as a substrate for a phosphoric acid coated cata

11、lyst. The activity from that catalyst is believed due to the inclusion of phosphoric acid.0008 Krause (WO 200234390) described catalysts comprised silica plus 5-50% oxides of the transition metals, including ZrO2. These mixed metal oxides are based primarily on the silica substrate.0009 Chiyoda Corp

12、 (JP 08224472) reported a water insoluble zirconium hydroxide coated with a tungsten compound.0010 See also recent work directed to IPA production as disclosed in U.S. Patent No.7,173,158; U.S. Patent Application Publication No. 20060269462 and 20060270883; andPCT publication WO 2006/135475.0011 In

13、previous work described by one or more of the present inventors, a CeO/ZrO2 mixed metal oxide catalyst was identified as active for the decomposition of isopropyl ether(IPE). See U.S. 7,102,037, and U.S. Application Publication No. 2006-0281954. High purityC3= was produced, along with some isopropyl

14、 alcohol (IPA) was produced as a side reaction.Since these reactions are reversible, either IPE or IPA can be optimized as the main product by selection of the reaction conditions.0012 While it has been found that the CeO/ZrO2 catalyst previously described promotes direct hydration of propylene, the

15、 activity is insufficient for commercial production.0013 The present inventors have found, however, that by proper incorporation of certain other metal oxides by the use of co-precipitation, an MMO catalysts based on ZrO2 for the direct hydration of propylene may be achieved.SUMMARY OF THE INVENTION

16、0014 The invention is directed to mixed metal oxide (MMO) catalysts based on ZrO2. The mixed metal oxide comprises at least two metals, at least one of which is zirconium (Zr) and having at least one other metal selected from transition metals other than Zr. The mixed metal oxides of the invention a

17、re made by co-precipitation of the at least two metals. The mixed metal oxides according to the invention are useful for the production of isopropyl alcohol (IPA), as well as other olefins in the range of C2 to C5 carbon length.0015 In preferred embodiments, the DH catalysts according to the inventi

18、on are stable for the conversion of propylene to IPA at higher temperatures than the acidic resins and strong acid solid catalysts.0016 In another preferred embodiments, the catalysts of the invention function as DH catalysts for the conversion of propylene to IPA over a wider operational range.0017

19、 In still another embodiment, the DH catalysts of the invention have good hydrolytic stability.0018 In yet still another embodiment, the DH catalysts of the invention are regenerable.0019 Moreover, in other embodiments, the DH catalyst of the invention can be run at low water to propylene ratios (Q

20、ratio) without the co-production of large amounts of IPE for the conversion of propylene to IPA.0020 It is an object of the invention to provide MMOs that are active for the direct hydration of propylene to produce isopropyl alcohol (IPA) without co-production of large amounts of isopropyl ether (IP

21、E).0021 It is an object of the invention to provide high-temperature stable Zrtheta2-basedMMOs operating over a wide variation of operating conditions, having good hydrolytic stability, that produce IPA at low water propylene ratios and which are regenerable.0022 These and other objects, features, a

22、nd advantages will become apparent as reference is made to the following detailed description, preferred embodiments, examples, and appended claims.DETAILED DESCRIPTION OF THE INVENTION0023 According to the invention, mixed metal oxide (MMO) catalysts based on ZrO2 are made by a process comprising c

23、o-precipitation of the metal species from solution, followed by calcination. The MMOs of the invention are useful for the production of isopropyl alcohol (IPA).0024 The mixed metal oxide of the invention comprises at least two metals, at least one of which is zirconium (Zr) and having at least one o

24、ther metal selected from transition metals other than Zr.0025 The mixed metal oxide of the invention is zirconium-based (or Zrtheta2-based), wherein the term zirconium-based means that zirconium metal, regardless of oxidation state, is present in the amount of at least greater than 50 wt%, based on

25、the weight of the metals present in the mixed metal oxide catalyst. It is preferred that zirconium be present in the amount of greater than 50.0 wt% to 99.5 wt%, or 60.0 wt%, to 99.0 wt%, or 70.0 wt% to 98.5 wt%, or 80 wt% to 98.0 wt%, balance the at least one other metal. Useful ranges include from

26、 any of the minimum amount specified above to any of the maximum amount specified above, e.g., ranges such as 50 wt% to 98.0 wt% and 80 wt% to 99.0 wt% are also contemplated.0026 The at least one other metal in the mixed metal oxide of the invention is selected from Groups 3-11 of the Periodic Table

27、, i.e., the transition metals, which includes the Lanthanides and Actinides. More than one metal other than zirconium may be present in the MMO, provided that the one or more metals other than zirconium are co-precipitated along with zirconium.0027 In an embodiment, the transition metal other than Z

28、r is selected from at least one of Groups 3-9 (again, the transition metals including Lanthanides and Actinides. In another embodiment, the transition metal other than Zr is selected from at least one of Ce, Mn, W, Cu, Mo, Fe, and Cr. In still another embodiment the metal is selected from at least o

29、ne of the transition metals in Groups 3-9. In yet another embodiment they are selected from Ce, W, Mo, and mixtures thereof. In yet another embodiment the metals used are selected from tungsten, molybdenum, copper, manganese, iron and mixtures thereof.0028 The mixed metal oxides of the invention are

30、 made by co-precipitation of the at least two metals from solution. The metal salts used to co-precipitate with the ZrO can include one, two or more metals. The at least two metals are dissolved in a suitable solvent, such as water, and caused to be simultaneously precipitated, such as by addition o

31、f a suitable base. A soluble salt of the metal is preferably used, for example: halides, sulfates, nitrates, and polymetallates such as zirconyl chloride, ammonium metal tungstate, cerium sulfate and the like. More than one different salt containing the same metal may be used. The non-metal counter

32、ion (e.g., halide, sulfate, nitrate, and the like) may be the same or different for the at least two metals and may be independently selected.0029 The term soluble salt would be understood by one of ordinary skill in the art to be a relative term and depends on the solvent used. The exact amount of salt that needs to be dissolved is not particularly important except with respect to the time and effort it takes to obtain a useful amount of the mixed metal, but this is no more than routine experimentation by one of ordinary skill in posse