CN1781601B - A shaped body and its use as catalyst - Google Patents

A shaped body and its use as catalyst Download PDF

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Publication number
CN1781601B
CN1781601B CN200510127013.6A CN200510127013A CN1781601B CN 1781601 B CN1781601 B CN 1781601B CN 200510127013 A CN200510127013 A CN 200510127013A CN 1781601 B CN1781601 B CN 1781601B
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formed body
metal oxide
oxide sol
metal
mixture
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CN1781601A (en
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G·H·格罗施
U·米勒
M·赫瑟
C·洛克曼
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BASF SE
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BASF SE
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    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/08—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding porous substances
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1025—Alkali-free or very low alkali-content materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/10—Compositions or ingredients thereof characterised by the absence or the very low content of a specific material
    • C04B2111/1031—Lime-free or very low lime-content materials

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Catalysts (AREA)

Abstract

A method for producing a shaped body, consisting of at least one porous oxide material, preferably a titanium silicate, and at least one metal oxide, comprising the following step (i): (i) the porous oxide material is mixed with at least one metal oxide sol, preferably a silica sol, that has a low alkaline and alkaline-earth metal ion content and/or with at least one metal oxide that has a low alkaline and alkaline-earth metal ion content. The invention also relates to the use of said shaped body in the production of an alkene oxide.

Description

Formed body and as Application of Catalyst
The application be the application number submitted on March 10th, 2004 be being entitled as of 200410008075.0 (applying date is on April 7th, 1999) " using metal oxide sol to produce the method for formed body " divide an application divide an application.
Technical field
The present invention relates to: a kind of production comprises the method for the formed body of at least a kind of porous oxidation material and at least a kind of metal oxide; This formed body itself; And, particularly has the Application of Catalyst in the organic compound epoxidation reaction of at least 1 carbon-to-carbon double bond as the reaction of organic compound.
Background technology
The formed body that comprises the porous oxidation material is used in the number of chemical process.Therefore, need a kind of production method that meets the formed body of industrial requirements quantity with low-cost production.
For producing formed body, usually the porous oxidation material is mixed with binding agent, organic tackify material and liquid, so that mixture is made thickener, compacting in kneader or disc type mill then.Subsequently, the material that is obtained is shaped by ram extrusion machine or multiple screw extruder, and last, the formed body that is obtained carries out drying and calcining.
In order to make the formed body of producing be fit to again produce active very high product, need to adopt and to prevent planting here the further chemical inertness binding agent of reaction of product.
Suitable binding agent is a series of metal oxides.The example that can enumerate is the oxide of silicon, aluminium, titanium or zirconium.Silica as binding agent for example is disclosed in US5, in 500,199 and US4,859,785.
In this kind binding agent, the content of alkali metal and alkaline-earth metal ions should be low as far as possible, Just because of this, need to use to contain seldom or the binding agent source of alkali-free metal and alkaline-earth metal.
For producing above-mentioned metal oxide binding agent, can use the respective metal oxide sol as raw material.Preparation example as contain less or the process of the above-mentioned silica binder of alkali-free metal and alkaline-earth metal in, adopt contain less or the Ludox of alkali-free metal and alkaline-earth metal as the binding agent source.
In the preparation of Ludox, can be from alkali silicate, but this causes containing in the Ludox high unacceptable alkali metal ion usually.The preparation example of this kind Ludox is as being described in " Ullmann industrial chemistry complete works ", and volume A23 (1993) is in pp.614～629.
JP-A-07 048 117 discloses a kind of by alkoxy silane, and being hydrolyzed with ammonia in the presence of excessive greatly alcohol prepares the method for Ludox; The Ludox that obtains comprises the highest 10wt% silica.
JP-A-05 085 714 has described a kind of sour decomposition method of alkoxy silane, carries out in pure medium equally.The dioxide-containing silica of the Ludox that this method is produced is between 1～10wt%.
Disclosed Ludox preparation method's shortcoming is that the accessible dioxide-containing silica of Ludox is low excessively in the two pieces of publications in back.This makes that this method is uneconomical, because the production capacity of device has been wasted by big water gaging in colloidal sol production and further processing.
Summary of the invention
The purpose of this invention is to provide a kind of industrial usability methods that produces body, the alkali metal of this formed body and alkaline-earth metal ions content are low, and useful as catalysts, are preferred in the fixed bed.
We find, this purpose can realize by the method for such this kind of production formed body: the porous oxidation material is mixed in the 1st step of method with metal oxide sol and/or metal oxide, and wherein metal oxide sol and metal oxide have low levels of alkali metal and alkaline-earth metal ions separately.
In sum, the invention provides the method that a kind of production comprises the formed body of at least a kind of porous oxidation material and at least a kind of metal oxide, comprise the following steps (i):
(i) metal oxide of the metal oxide sol of a kind or multiple porous oxidation material and at least a kind of low levels of alkali metal and alkaline-earth metal ions and/or at least a kind of low levels of alkali metal and alkaline-earth metal ions mixes.
The present invention also provides a kind of formed body, and its available said method production and its alkali metal and alkaline-earth metal ions content are preferably less than 700ppm, especially preferably less than 600ppm, particularly less than 500ppm.
In the preferred embodiment of the inventive method, metal oxide sol is the hydrolysis preparation by at least a kind of metal acid esters (metallic acid ester).
Therefore, the present invention also provides a kind of like this method described above, and wherein metal oxide sol prepares by the hydrolysis of a kind of metal acid esters at least.
The metal acid esters that is used for hydrolysis can be purified before hydrolysis.Here, all suitable methods all can be imagined.Preferably make the metal acid esters before hydrolysis, distill.
About the hydrolysis of metal acid esters, all possible in principle method all can be used.Yet in the methods of the invention, this hydrolysis is preferably carried out in aqueous medium.The advantage of doing like this is, with for example JP07,048,117 or JP05,085,714 and so on adopts the known method for hydrolysis of alcohol excess to compare, and needs the pure much less that distill away.
This hydrolysis can give catalysis by adding alkalescence and acidic materials.The alkalescence or the acidic materials of residue can be removed and not stay to preferred those by calcining.Especially the preferred material that is selected from ammonia, alkylamine, alkanolamine, arylamine, carboxylic acid, nitric acid and hydrochloric acid that adopts.Especially preferably adopt ammonia, alkylamine, alkanolamine and carboxylic acid.
The metal acid esters that the inventive method is used is ortho-silicate preferably.
In the methods of the invention, the esterolytic implementation condition of metal acid is: temperature, 20～100 ℃, preferred 60～95 ℃; The pH value, 4～10, preferred 5～9, especially preferred 7～9.
Catalytic active substance/the mol ratio of metal acid esters is generally between 0.0001～0.11, and is preferred 0.0002～0.01, and especially 0.0005～0.008.
In the methods of the invention, hydrolysis produces metal oxide sol, preferred Ludox, its alkali metal and alkaline-earth metal ions content are less than 800ppm, preferably less than 600ppm, be more preferably less than 400ppm, be more preferably less than 200ppm, be more preferably less than 100ppm, especially preferably less than 50ppm, more specifically preferably less than 10ppm, particularly less than 5ppm.
In view of the above, the invention provides a kind of metal oxide sol, it has less than the alkali metal of 800ppm and alkaline-earth metal ions content and can prepare by the hydrolysis of at least a kind of metal acid esters.
The metal oxide content of the metal oxide sol of the inventive method preparation is the highest 50wt% generally, preferred 10～40wt%.
The alcohol that forms in hydrolysis distillation removal in the process of the inventive method usually.Yet a small amount of alcohol also allows to remain in this metal oxide sol, as long as they do not have a negative impact to later each step of the inventive method.
The metal oxide sol of the inventive method preparation is used for industrial advantage and is, they do not show the tendency that forms gel.Therefore, take extraordinary precaution just to become unnecessary for preventing that gel from generating.The metal oxide sol of the inventive method preparation can be stored several weeks, is out of question on this time coordination that makes them be prepared in further procedure of processing.
In the methods of the invention, comprising the mixture of at least a kind of porous oxidation material and at least a kind of metal oxide, is to prepare as metal oxide source with the metal oxide sol by preparation as mentioned above.
In principle, the production method of this mixture is not subjected to any restriction.Yet the inventive method preferably adopts the method for the suspended substance spraying that will comprise at least a kind of porous oxidation material and metal oxide sol.
Here, the porous oxidation material content that exists in the suspended substance is not subjected to any restriction, has machinability and can spray as long as guarantee during the preparation this suspended substance.The porous oxidation material to the weight ratio between the metal oxide of metal oxide sol preferably between 10～0.1, especially preferred 8～1.
The main component of suspended substance is generally porous oxidation material, metal oxide sol and water.This suspended substance also can comprise the organic compound of residual trace in addition.They can be to produce in the preparation by for example porous oxidation material.Equally, the alcohol that also can expect in the hydrolysis of metal acid esters, generating or, as mentioned above, be the material that promotes that the hydrolysis of metal acid esters adds.
Mixture water capacity on further processing request is decided, and can carry out drying subsequently.Here, the method that can adopt all to imagine.Spraying in the dry preferred and spray-drying step of mixture is carried out simultaneously.Spray dryer preferably adopts inert gas operation, especially preferred nitrogen or argon gas.
Produce the adoptable porous oxidation material of body as for the inventive method, do not have any specific limited, as long as can produce formed body described herein by these materials, and as long as these materials have necessary catalytic activity.
The porous oxidation material is zeolite preferably.Zeolite is that a class has orderly passage and cage structure and contains the crystal aluminosilicate of micropore as everyone knows.With regard to the object of the invention, term " micropore " is corresponding to " pure applied chemistry " 57 (1985), and p.603～619 definition in refers to the hole of aperture less than 2nm.The framework of this kind zeolite is by SiO 4And AlO 4Tetrahedron couples together formation by sharing oxygen atom.The general introduction of this kind known structure for example can be seen in W.M.Meier, D.H.Olson and Ch.Baerlocher, " zeolite structure type atlas ", Elsevier, the 4th edition, London 1996.
Also have such class zeolite, they do not comprise aluminium, and the Si in lattice silicate (IV) is partly replaced by the titanium of Ti (IV) form.This kind titanium zeolite, especially those have the MFI type crystal structure and they may prepare approach, for example be described among EP-A0 311983 and the EP-A0 405 978.Except silicon and titanium, this type of material also can comprise the element such as aluminium, zirconium, tin, iron, niobium, cobalt, nickel, gallium, boron or small amount of fluorine in addition.
In described zeolite, titanium can be partly or entirely by vanadium, zirconium, chromium, niobium or iron or among them 2 or more kinds of mixtures replace.Titanium and/or vanadium, zirconium, chromium, niobium or iron, to the mol ratio of silicon and titanium and/or vanadium, zirconium, chromium, niobium or iron sum generally between 0.01: 1～0.1: 1.
The enough specific X-ray diffraction figures of the known energy of titanium zeolite with MFI structure are differentiated, also can be by about 960cm -1Near infrared (IR) interval lattice vibration bands of a spectrum differentiate, thereby and do not come with alkali metal titanate or crystallization and amorphous titania equiphase zone.
The preferred zeolite that adopts titanium, vanadium, chromium, niobium or zirconium, more preferably titanium zeolite, especially titanium silicate (titanium silicalites).
Object lesson is that to have five silicon (pentasil) zeolite structured, particularly names titanium into following type by X-ray crystallography, vanadium, chromium, niobium and zirconium zeolite: BEA, MOR, TON, MTW, FER, MFI, MEL, CHA, ERI, RHO, GIS, BOG, NON, EMT, HEU, KFI, FAU, DDR, MTT, RUT, RTH, LTL, MAZ, GME, NES, OFF, SGT, EUO, MFS, this class zeolite of MWW or MFI/MEL structure and ITQ-4. for example is described in people's such as above-mentioned Meier the document. and also can imagine to adopt in the methods of the invention and have UTD-1, the titanium-containing zeolite of CIT-1 or CIT-5 structure.Other titanium-containing zeolites are to have those of ZSM-48 or ZSM-12 structure.
This type of zeolite is described among US-A5 430 000 and the WO94/29408 especially, and wherein relevant with this paper theme content is all received and made the application as a reference.In the methods of the invention, the especially preferred titanium zeolite that uses with MFI, MEL or MFI/MEL structure.
Also preferred, specifically, be referred to as the titanium containing zeolite catalyst of " TS-1 ", " TS-2 ", " TS-3 " usually, and have the titanium zeolite that is isomorphous frame construction with beta-zeolite.
In view of the above, the invention provides a kind of production method of formed body as mentioned above, wherein the porous oxidation material is a zeolite.
Certainly, also can use 2 or the mixture of more kinds of porous oxidation materials in the methods of the invention, especially above-mentioned those.
The preparation process of above-mentioned titanium, zirconium, chromium, niobium, iron and vanadium zeolite normally, make metal oxide source, preferred silica source, with titanium, zirconium, chromium, niobium, iron or vanadium source, for example titanium oxide or suitable vanadium oxide, pure zirconium, chromium oxide, niobium oxide or iron oxide, and as the nitrogenous organic base of model such as the aqueous mixture of tetrapropylammonium hydroxide, the words of hope add alkali compounds again, stoichiometric number hour or a few days under the pressure vessel medium and high temperature, thus crystallized product generated.It is filtered out, and washing, drying are also at high temperature calcined to remove organic nitrogen(ous) base.In the powder that so obtains, at least a portion titanium or zirconium, chromium, niobium, iron and/or vanadium in the zeolite framework in varing proportions 4-, 5-or the form existence of 6-coordination (number).For improving catalytic performance, this product can be repeatedly washs with the hydrogenperoxide steam generator of sulfuric acid acidation subsequently, and titanium or zirconium, chromium, niobium, iron and/or vanadium zeolite powder must dry once more and calcinings then.So the titanium of preparation or zirconium, chromium, niobium, iron or vanadium zeolite powder just can be used in the inventive method as the composition of above-mentioned suspended substance.
Therefore, specifically, the invention provides a kind of aforesaid method, wherein a kind or multiple porous oxidation material mix with at least a kind of metal oxide sol, and wherein a kind or multiple porous oxidation material are the method preparations by comprising the following steps one or more steps in (a)～(f):
(a) at least a kind of metal oxide source of preparation, preferred silica source, with another kind of source metal, the preferred aqueous mixture in titanium, zirconium, chromium, niobium, iron or vanadium source for example,
(b) mixture from (a) carries out crystallization in pressure vessel, wherein adds at least a kind of stereotyping compound, and the words of hope add another kind of alkali compounds again,
(c) crystallized product that exists in the suspended substance from (b) carries out drying, preferably takes spray-drying,
(d) calcine from the desciccate of (c),
(e) pulverize from the calcined product of (d), for example adopt and grind, thereby become granularity less than 500 μ m, preferably less than 300 μ m, especially preferred particle less than 200 μ m,
Wish that (f) cyclic washing is from the crushed products of (e), drying is also calcined then.
Pore structure to the porous oxidation material, do not add any restriction yet, promptly, this material can have micropore, mesopore, macropore, micropore and mesopore, micropore and macropore, mesopore and macropore or micropore, mesopore and macropore, wherein term " mesopore " reach " macropore " definition equally corresponding to the definition in the above-mentioned document " pure applied chemistry ", refer to that respectively diameter is greater than 2nm～about 50nm and greater than the hole of about 50nm.
Yet, preferably use the micropore oxidation material, as titanium silicate.
In the another kind of preferred embodiment of the inventive method, a kind or multiple porous oxidation material mix with the metal oxide of a kind of low levels of alkali metal and alkaline-earth metal ions in step (i) at least.
If the porous oxidation material mixes with two or more metal oxides, then can be at first this a kind or multiple porous oxidation material be mixed with a kind of metal oxide, then the mixture that obtains is mixed with another kind of metal oxide.Wish that this mixture can mix with another kind of metal oxide subsequently again.Similarly, also the porous oxidation material can be mixed with 2 or the mixture of more kinds of metal oxides.
This metal oxide or 2 or the mixture of more kinds of metal oxides in alkalies and alkaline earth content be generally less than 800ppm, preferably less than 600ppm, especially preferably less than 500ppm, particularly less than 200ppm.
The metal oxide of this kind low levels of alkali metal and alkaline-earth metal ions for example is high temperature (pyrolysis) method metal oxide, for example high temperature method silica.
Certainly, also can use the conventional metals oxide in the methods of the invention, as long as its alkalies and alkaline earth ion concentration is suitably low as top pointing out.
All right, alkalies and alkaline earth ion concentration at a kind or multiple conventional metals oxide is higher than under the situation of afore mentioned rules, reduce its alkalies and alkaline earth ion concentration, by washing, extraction or other adequate measures, certainly also can adopt 2 or the combination of more kinds of adequate measures, thereby metal oxide is purified to the degree that can be used for the inventive method.
Be considered as reducing the measure that the alkalies and alkaline earth ion concentration adopts and decide, might need this a kind or multiple conventional metals oxide are implemented appropriate postprocessing.For example,, need after washing, carry out drying sometimes, then it be mixed with a kind or multiple porous oxidation material again the conventional metals oxide if the alkalies and alkaline earth ion concentration of conventional metals oxide reduces by washing.
In the methods of the invention, a kind or multiple porous oxidation material can certainly be mixed the mixture that the back obtains with metal oxide, mix with the metal oxide sol of at least a kind of low levels of alkali metal and alkaline-earth metal ions.For this kind preparation process of mixture, do not add any restriction in principle, porous oxidation material as mentioned above is the same with the preparation of the mixture of metal oxide sol.Yet, preferably, will comprise a kind or multiple porous oxidation material and a kind or multiple metal oxide, and the suspension of the mixture of a kind or multiple metal oxide sol is sprayed.There is not any restriction in content as for the porous oxidation material that exists in this suspended substance, as long as just as described above, the machinability of suspended substance is guaranteed and gets final product.
Have again, can certainly, in the methods of the invention, at least a kind of porous oxidation material is mixed the mixture that forms with at least a kind of metal oxide sol, mix with the metal oxide of at least a kind of low levels of alkali metal and alkaline-earth metal ions.Here, with mixing of a kind or multiple oxide, can after the mixture preparation of a kind or multiple porous oxidation material and a kind or multiple metal oxide sol, carry out immediately.As described above,, then also this metal oxide can be mixed with dried drying composite if after the mixture preparation of a kind or multiple porous oxidation material and a kind or multiple metal oxide sol, need dryly.
In the methods of the invention, a kind or multiple porous oxidation material side by side can be mixed with at least a kind of metal oxide sol and with at least a kind of metal oxide equally.
Mixture through obtaining after one of above-mentioned embodiment of the present invention carries out compacting in the further stage of the inventive method.In this compacting or forming step, hope also can be introduced other metal oxides, can adopt by the metal oxide sol form for preparing as mentioned above as its metal oxide source.This procedure of processing can be carried out in any suitable equipment, but preferred kneader, disc type mill or extruding machine.As the commercial Application of the inventive method, especially preferably adopt the disc type mill.
If, according to embodiment described above, the mixture that at first prepares at least a kind of porous oxidation material and at least a kind of metal oxide, then, this mixture carries out compacting, and in this compacting step, add in addition the metal oxide sol of low levels of alkali metal and alkaline-earth metal ions again, then in the preferred scheme of the present invention, use 20～80wt% porous oxidation material, 10～60wt% metal oxide and 5～30wt% metal oxide sol.Especially preferably use 40～70wt% porous oxidation material, 15～30wt% metal oxide and 10～25wt% metal oxide sol.These percetages by weight are benchmark with the formed body of final generation as described below all in each case.Here preferably use porous oxidation titanium-containing materials and Ludox.
In the another embodiment of the inventive method, mixing of the metal oxide of a kind or multiple porous oxidation material and a kind or multiple low levels of alkali metal and alkaline-earth metal ions carried out during compacting step.Therefore, in this compacting step, may be that a kind or multiple porous oxidation material, a kind or multiple metal oxide and at least a kind of additional metal oxide sol mix equally.
In this forming step, also can add a kind or multiple tackify material, as the material that this mixture is converted into thickener; These materials especially can be used to improve the stability that is not sintered into body as will be described below.For this purpose, can use the known suitable material of any prior art.In the methods of the invention, make water, perhaps water and a kind or the mixture multiple and organic substance that water is miscible are so that be converted into thickener with said mixture.Remove once more during being used for mixture is converted into the formed body calcining that the material of thickener can be afterwards.
Preferred employing is organic, especially hydrophilic organic polymer, as cellulose, cellulose derivative, for example methylcellulose, ethyl cellulose or hexyl cellulose, PVP, (methyl) ammonium acrylate, Tylose are perhaps in the middle of them 2 or more kinds of mixtures.Especially preferably use methylcellulose.
As another kind of additive, can add ammonium, amine or amine compound, for example tetraalkyl ammonium compound or amino alkoxide.This another kind additive is described among EP-A0 389 041, EP-A0200 260 and the WO95/19222, and related content all is collected herein by reference.
Replace alkalinity additive, also can use acid additives.The preferred organic acidity compound that uses those can burn by the calcining after the forming step.Especially optimization acid.
The consumption of this analog assistant is a benchmark with the formed body of the following final production that will describe, preferably between 1～10wt%, and especially preferred 2～7wt%.
For to exerting one's influence such as transporting pore volume, transport bore dia and transporting the pore size distribution formed body performance, can add further material, preferably have organic compounds, especially preferably have organic polymer, as the further additive that can also influence the composition formability.Examples of such additives comprises, alginates, PVP, starch, cellulose, polyethers, polyester, polyamide, polyamine, poly-imines, polyalkenes, polystyrene, styrol copolymer, polyacrylate, polymethacrylates, aliphatic acid such as stearic acid, high-molecular-weight poly (alkylidene) glycol such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol are perhaps in the middle of them 2 or more kinds of mixtures.Total consumption of these materials is a benchmark with the formed body of the following final generation that will describe, preferably between 0.5～10wt%, and especially preferred 1～6wt%.
Therefore, the present invention also provides poly-(alkylidene) glycol, particularly polyethylene glycol, contains the titanium silicate formed body in production, the application during particularly those formed bodies of useful as selective oxidation catalyst are produced.
In preferred embodiments, the inventive method is used to produce basic for micropore but also may have the formed body of mesopore and/or macropore in addition.The void content of mesopore and macropore in the formed body of the present invention, according to DIN66133, mercury void determination method is measured, and greater than 0.1ml/g, is preferably greater than 0.2ml/g, especially is preferably greater than 0.3ml/g, particularly greater than 0.5ml/g.
With which kind of order above-mentioned additive one of is joined as stated above in the mixture that obtains and there is no strict demand.At first introduce other metal oxides with the metal oxide sol form, follow by tackify material, subsequent is to influence the material that compacted compositions transports performance and/or formability, or introduces according to the order of other requirements, all is same possible.
Before the compacting, still be pulverous mixture substantially, hope, can be in kneader or extruding machine homogenizing 10～180min.This step usually about 10 ℃～be used for mixture is converted into the boiling temperature scope of the material of thickener, and carry out under the pressure of atmospheric pressure or superatmospheric pressure.Mixture is mediated always and is formed till the extrudable material.
In the methods of the invention, the metal oxide content that the composition that is obtained by compacting step, can be used for being shaped this moment has is a benchmark with the total composition, at least be 10wt%, preferred 15wt% at least, especially preferred 20wt% at least, particularly 30wt% at least.Specifically, when adopting the titaniferous microporous oxide, the composition of producing by the inventive method can not go wrong because of thixotropic behavior in forming step subsequently.
In principle, mediate and be shaped and adopt tradition kneading known, that be fit to produce catalyst mouldings for example of any prior art and former and method to implement.
In the preferred method that adopts, by extruding realization, the extrudate of producing for example has general about 1～about 10mm, the diameter of especially about 1.5～about 5mm in habitual extruding machine in shaping.This kind extrusion apparatus for example is described in " Ullmann industrial chemistry complete works ", and the 4th edition, p.295 volume 2 (1972) rises.Except adopting the multiple screw extruder the same preferred ram extrusion machine that adopts.In the large-scale industrial application of this method, especially preferably adopt multiple screw extruder.
Extrudate can be extrude bar-shaped or cellular.Honeycomb ceramics can have the shape of any requirement.For example, they can be circular extrudate, hollow extrudate or star extrudate.Honeycomb ceramics also can have any diameter.Its profile and diameter depend on the process engineering requirement usually, just depend on the process that will use this formed body.
Before the forming step, during or after, on this material, can apply suitable noble metal composition form, for example the noble metal of water soluble salt form.This kind process is preferred for producing that to have zeolite structured be the oxidation catalyst of carrier with titanium silicate or silicic acid vanadium carrier, and the catalyst of being produced can comprise 0.01～30wt%1 kind or the multiple noble metal that is selected from ruthenium, rhodium, palladium, osmium, iridium, platinum, rhenium, Jin Jiyin.This type of catalyst for example is described in DE-A19623609.6, will wherein receive the reference of making this paper about the content of catalyst is whole at this.
Yet, in many cases, most convenient be to have only after the shaping step is finished just the noble metal composition to be loaded on the formed body, particularly when the catalyst of not wishing to comprise noble metal is subjected to high-temperature process.The noble metal composition can adopt methods such as ion-exchange, dipping or spraying to be loaded on the formed body particularly.This loading can be adopted organic solvent, ammonia spirit or implement such as the supercritical phase of carbon dioxide.
The employing of said method makes various preparation that contains noble metal catalyst become possibility.For example, the application type catalyst can prepare by precious metal solution is sprayed on the formed body.This coating or comprise the thickness of the shell of noble metal can increase greatly by dipping, and under the situation of ion-exchange, will be in catalyst granules loads noble metal substantially equably along the whole section of formed body.
After extruding from ram extrusion machine or multiple screw extruder, institute's formed body that obtains is usually at 50～250 ℃, and preferred 80～250 ℃ and generally between 0.01～5bar, the down dry about 1～20h of preferred 0.05～1.5bar pressure.
Calcining subsequently preferred 350～600 ℃, is carried out under especially preferred 400～500 ℃ of conditions at 250～800 ℃.The pressure that is adopted is close with the dry pressure that adopts.Usually, calcining is carried out in oxygen-containing atmosphere, and wherein oxygen content is between 0.1～90% (volume), preferred 0.2～22% (volume), especially preferred 0.2～10% (volume).
In view of the above, the present invention also provides a kind of production method of formed body as mentioned above, it comprise the following steps (i)～(v):
(i) metal oxide of the metal oxide sol of a kind or multiple porous oxidation material and at least a kind of low levels of alkali metal and alkaline-earth metal ions and/or at least a kind of low levels of alkali metal and alkaline-earth metal ions mixes;
(ii) compacting is from the mixture of step (i), and hope adds metal oxide sol;
(iii) form from step composition (ii);
(iv) carry out drying from step formed body (iii);
(v) calcine from the step body that is dried to (iv).
In a kind of particular of the present invention, metal oxide sol joins from the suspended substance that step more described above (b) is obtained, and formed suspended substance carries out drying, and preferably by spray-drying, formed then powder is calcined.Product dry and calcining subsequently can be according to (iii) further processing of step.
Certainly, the extrudate that is obtained also can further be processed.Any breaking method with formed body crushing or broken, also is imaginabale for example, as further chemical treatment recited above for example.If implement to pulverize, preferably produce particle diameter between 0.1～5mm, especially the pill of 0.5～2mm or fragment.
In fact the formed body of this pill or fragment and preparation does not by other means comprise the more fine grained of the smallest particles diameter of about 0.1mm.
Formed body useful as catalysts of the present invention or that produce by the present invention is especially for catalyzed conversion, in particular for the oxidation of organic molecule.The example that may react is:
Alkene epoxidation for example prepares expoxy propane by propylene and hydrogen peroxide or by propylene and the mixture that generates hydrogen peroxide on the spot;
Hydroxylating, for example monocycle, dicyclo or polycyclic aromatic hydrocarbon generate through hydroxylating and singly replace, two replace or the hydroxy arene of more senior replacement, for example phenol and hydrogen peroxide or phenol and the mixture that the generates hydrogen peroxide on the spot production quinhydrones that reacts;
Alkane is converted into alcohol, aldehyde and acid;
Ketone hydrogen peroxide or can generate the mixture of hydrogen peroxide on the spot and ammonia in the presence of generate oxime (ammonoximation (oxime is synthesized in ammoxidation)), for example prepare cyclohexanone oxime by cyclohexanone;
Isomerization reaction, for example epoxides is converted into aldehyde;
And be described to plant thus formed body catalysis, the particularly reaction of zeolite catalyst catalysis in the literature in addition, for example be described in W.H In lderich " zeolite: organic compound synthetic catalyst ", Elsevier, " Surface Science research. catalysis " 49, Amsterdam (1989), pp.69～93; And particularly, possible oxidation reaction, for example B.Notari " Surface Science research. catalysis " 37, (1987) roll up 41 in pp.413～425 or in " catalysis progress ", described in academic press (1996), pp.253～334.
Therefore, the invention provides by one of formed body of preparation as mentioned above or its 2 or more kinds of mixture as Application of Catalyst.
The zeolite of below comprehensively discussing especially is fit to the epoxidation reaction of alkene.
In view of the above, the present invention also provides the method for at least a kind of oxyalkylene of a kind of preparation, and it comprises the following steps (III):
(III) at least a kind of alkene and hydrogen peroxide react as under the catalyst at formed body or the aforesaid formed body produced according to the method described above.
May realize that functionalized alkene for example is by this kind epoxidation, ethene, propylene, the 1-butylene, the 2-butylene, isobutene, butadiene, amylene, pentadiene, hexene, hexadiene, heptene, octene, diisobutylene, trimethylpentene, nonene, dodecylene, tridecylene, four-～eicosylene, three-and tetrapropylene, polybutadiene, polyisobutene, isoprene, terpene, geraniol, linalool, linalyl acetate, the methylene cyclopropane, cyclopentene, cyclohexene, ENB, cycloheptene, vinyl cyclohexane, vinyl oxirane, VCH, styrene, cyclo-octene, cyclo-octadiene, vinyl norbornene, indenes, the tetrahydro indenes, methyl styrene, bicyclopentadiene, divinylbenzene, the ring dodecylene, cyclodoecatriene, stilbene, diphenyl diethylene, Alphalin, beta carotene, vinylidene fluoride, allyl halide, crotyl chloride, methylallyl chloride, dichloro-butenes, allyl alcohol, methallyl alcohol, butenol, butylene glycol, cyclopentene diol, pentenol, octadienol, tridecylene alcohol, unsaturated steroid, ethoxy ethylene, isoeugenol, anethole, unsaturated carboxylic acid such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, vinyl acetic acid, unrighted acid such as oleic acid, linoleic acid, palmitic acid, naturally occurring fat and oils.
The zeolite that above extensive discussions is crossed especially is suitable for the epoxidation of 2～8 carbon atom alkenes, the more preferably epoxidation of ethene, propylene or butylene, particularly propylene, and the result generates corresponding oxyalkylene.
In view of the above, the present invention provides formed body described herein as catalyst especially, from propylene and hydrogen peroxide or from propylene with can generate the application of the mixture preparation propylene oxide of hydrogen peroxide on the spot.
In the particular of this method, treat that epoxidised alkene is the dehydrogenation preparation by corresponding alkane.
In view of the above, the present invention also provides a kind of aforesaid method, and it comprises additional step (I):
(I) dehydrogenation by at least a kind of alkane prepares a kind or the multiple alkene that reacts in step (III).
This dehydrogenation reaction can adopt the known any method of prior art to implement in principle.These class methods especially are described among the EP-A0850 936, and related content all is collected herein by reference.
In the preferred embodiment of the inventive method, the hydrogen that a kind or multiple alkane dehydrogenation produce be used to preparation in reactions steps (III) with dehydrogenation after the hydrogen peroxide that reacts of generate a kind or multiple alkene.
In view of the above, the present invention also provides a kind of aforesaid method, and it comprises the following steps (II):
(II) hydrogen that generates in the step (I) the generation hydrogen peroxide that reacts, wherein hydrogen peroxide is used further in the reaction of step (III).
In view of the above, the present invention also provides a kind of integrated processes for preparing oxyalkylene, and it comprises step (A)～(C):
(A) the alkane dehydrogenation generates alkene and hydrogen,
(B) hydrogen that obtains by (A) the generation hydrogen peroxide that reacts, and
(C) by (B) hydrogen peroxide that obtains and the alkene that obtains by (A), by the formed body of the inventive method generation oxyalkylene that reacts.
Hydrogen reaction generates hydrogen peroxide, can adopt the known any method of prior art to implement.Particularly, this hydrogen can with the molecular oxygen generation hydrogen peroxide that reacts.Can expect being used to hydrogen from step (A) equally by anthraquinone preparation hydrogen peroxide.In these 2 kinds of situations, before reusing, may need the hydrogen of purification from step (A).Yet, preferably adopt anthraquinone.This method generates corresponding anthrahydroquinone compound based on the anthraquinone compounds catalytic hydrogenation, and this product and oxygen react the generation hydrogen peroxide then, subsequently the hydrogen peroxide that goes out to generate by extract and separate.This catalytic cycle is closure by the hydrogenation again of the anthraquinone compounds of acquisition in front and the oxygen reaction.Relevant anthraquinone general introduction is stated from " Ullmann industrial chemistry complete works ", and the 5th edition, volume 13 is in pp.447～456.
In adopting a kind of the present invention or the process of multiple formed body as catalyst, when latter's inactivation, can regenerate by the following method, wherein regeneration is to burn realization by carry out the part at the deposit that causes inactivation.This preferably carries out in the inert gas atmosphere that contains accurate specified quantity oxygen source material.This renovation process is described among the DE-A197 23 949.8, and related content all is collected herein by reference.
In addition, the present invention provides a kind of metal oxide sol of preparation as stated above as binding agent in its most universal embodiment, and preparation has the application of the formed body of high resistance to chemicals and high mechanical properties.
The specific embodiment
The following examples are used to illustrate the present invention.
Embodiment
Example 1: the preparation of micropore oxidation material
The 910g tetraethyl orthosilicate is put in the four neck flasks (4L capacity), and in 30min under agitation (250rpm, blade agitator) add the 15g original four-isopropyl titanate by dropping funel.Form a kind of water white transparency mixture.Add 1600g20wt% concentration hydrogen oxidation tetrapropylammonium solution (alkali metal content is less than 10ppm) subsequently, mixture stirs 1h again.The alcohol mixture (about 900g) that hydrolysis generates is distilled away at 90～100 ℃.Add 3L water, this moment, slightly opaque colloidal sol was transferred in the 5L capacity stainless steel agitated autoclave.
(anchor agitator, 200rpm) rate of heat addition with 3 ℃/min is heated to 175 ℃ of reaction temperatures to the autoclave of sealing.Reaction is finished through behind the 92h.The cooling reactant mixture (white suspension body) through centrifugation, solid with water washing repeatedly until neutrality.The solid that obtains is 110 ℃ of dry 24h (weight: 298g).Residual model in the zeolite is removed during 550 ℃ of calcining 5h in air subsequently that (calcining is weightless: 14wt%).
This white pure products is pressed wet chemical analysis, has the Ti content of 1.5wt% and less than the however, residual base tenor of 100ppm.With the silica consumption is that the yield of benchmark is 97%.Crystalline size is between 0.05～0.25 μ m, and this product demonstrates near the typical band that is positioned at the 960cm-1 in infrared spectrum.
Example 2: the preparation of Ludox
3L water joins that 10L has agitator, temperature is taken into account in the four neck flasks of reflux condenser.The pH value of solution is adjusted to 8～9 with 6g25% concentration ammonia.Subsequently, this water is heated to 50 ℃, adds the 1300g tetraethyl orthosilicate then from dropping funel.
The mixture backflow 3h of water and tetraethyl orthosilicate.Then, add the 1304g tetraethyl orthosilicate again by dropping funel.Reflux behind the 2h, the Ludox/aqueous mixtures of formation stirs 12h more again, distills out the ethanol that hydrolysis generates then.
The 3618g so Ludox of preparation contains the 20wt% silica and less than the alkali metal ion of 3ppm of having an appointment.
Example 3: the preparation of Ludox
188.6g water joins, and 500mL has agitator, temperature is taken into account in the four neck flasks of reflux condenser.The pH value of solution is adjusted to 9. subsequently with 0.3g25% concentration ammonia, and this water is heated to 50 ℃, adds the 111.65g tetraethyl orthosilicate then from dropping funel.
The mixture backflow 2h of water and tetraethyl orthosilicate.Then, add the 111.65g tetraethyl orthosilicate again by dropping funel.Reflux behind the 2h Ludox/aqueous mixtures of the formation 12h that refluxes again again.Add 50g water subsequently, distill out the ethanol that hydrolysis generates then.
The 169g so Ludox of preparation contains the 38wt% silica and less than the alkali metal ion of 5ppm of having an appointment.
Example 4: the spraying of titanium silicate
200g is as the abrasive catalyst of preparation as described in the example 1, and at first fine gtinding is suspended in the 2000g water then to the granularity less than 300 μ m.Sneak into the silica hydrosol of 245g subsequently as the dioxide-containing silica 18wt% of preparation as described in the example 2.
Continuing under the stirring condition, suspended substance is pressed into spray dryerin lab (diameter: 200mm, the column part height: 500mm), and pass through two phase flow nozzle (liquid feeding pipeline diameter: 2.5mm that glass is made by peristaltic pump; Orifice gas inlet pressure: 3bar) and micronize.
In spray dryer, suspended substance be dried gas (nitrogen, throughput: 24kg/h, inlet temperature: 210 ℃; Outlet temperature: 100 ℃) drying, thus the powder that closely mixes formed, subsequently, in the glass cyclone separator, separate.Yield is 80%.
Example 5: the spraying of titanium silicate
16.1kg as the catalyst of preparation as described in the example 1, at first rough lapping in hammer-mill utilizes impeller disintegrating machine fine gtinding to the granularity less than 300 μ m then.
Subsequently, powder suspension wherein adds the silica hydrosol of 16kg as the dioxide-containing silica 20wt% of preparation as described in the example 2 in 160L water, put into then in the uncovered stirred vessel.Continuing under the stirring condition, suspended substance is by large-scale peristaltic pump sucking-off and dry in spray-drying installation (manufacturing of Niro company), thus formation powder fine and smooth, that closely mix.
The suspended substance utilization have ceramic chamber lining the disk atomizer (rotating speed: 17,000rpm) and micronize.Drying is to carry out under the condition of 260 ℃ of temperature of inlet air, 110 ℃ of air exit temps.
Product is separated from air stream in cyclone separator.Yield is 13kg.
Comparative Examples 1: the shaping of titanium silicate (catalyst A)
Catalyst A system by 1665g by 89wt% as the catalyst of preparation as described in the example 1 and the spray-dried powders that 11wt% silica is formed, with being mixed and made between the Ludox (Ludox TM, E.I.Du Pont Company's manufacturing) of the about 50wt% of 416g dioxide-containing silica.The spray-dried powders of defined is according to being similar to example 4 preparations, and different is to press the Ludox of the present invention's preparation with Ludox (Ludox AS-40, the E.I.Du Pont Company makes) replacement of industrial sodium content 800ppm.
Mixture is converted into extrudablely by adding entry and extrusion aids methylcellulose, and extrudes extrudate into diameter 1.5mm.
This extrudate is 120 ℃ of dryings, then at 500 ℃ of heating 5h.The silica binder content of formed body is 20wt%; Sodium content, 700ppm.
Comparative Examples 2: the shaping of titanium silicate (catalyst B)
Catalyst B system by 3000g by 78wt% as the catalyst of preparation as described in the example 1 and the spray-dried powders that 22wt% silica is formed, with being mixed and made between the Ludox of the about 43wt% of 750g dioxide-containing silica (Ludox AS-40, E.I.Du Pont Company makes).
The spray-dried powders of defined is according to being similar to example 4 preparations, and different is to press the Ludox of the present invention's preparation with Ludox (Ludox AS-40, the E.I.Du Pont Company makes) replacement of industrial sodium content 800ppm.
Mixture is converted into extrudablely by adding entry and extrusion aids methylcellulose, and extrudes extrudate into diameter 2.5mm.
This extrudate is 120 ℃ of dryings, then at 500 ℃ of heating 5h.The silica binder content of formed body is 30wt%; Sodium content, 910ppm.The transverse compression intensity of extrudate is 37.9N; Anti-cutting, 10.25N.
Comparative Examples 3: the shaping of titanium silicate (catalyst C)
Catalyst C system by 7500g by 78wt% as the catalyst of preparation as described in the example 1 and the spray-dried powders that 22wt% silica is formed, be mixed and made in the disc type mill with the Ludox (Ludox AS-40, E.I.Du Pont Company makes) of the about 43wt% of 4300g dioxide-containing silica.
The spray-dried powders of defined is according to example 4 preparations, and different is to press the Ludox of the present invention's preparation with Ludox (Ludox AS-40, the E.I.Du Pont Company makes) replacement of industrial sodium content 800ppm.
Mixture is converted into extrudablely by adding entry and extrusion aids methylcellulose, and extrudes extrudate into diameter 1.5mm.
This extrudate is 120 ℃ of dryings, then at 500 ℃ of heating 5h.The silica binder content of formed body is 30wt%; Sodium content, 900ppm.
Example 6: the shaping of titanium silicate (catalyst D)
Catalyst D system by 2200g by 75wt% as the catalyst of preparation as described in the example 1 and the spray-dried powders that 25wt% silica is formed, and 1037g is as being mixed and made between the Ludox of the about 21wt% of dioxide-containing silica of preparation as described in the example 2.The spray-dried powders of defined is according to the method preparation that is similar to example 4.
Mixture is converted into extrudablely by adding entry and extrusion aids methylcellulose, and extrudes extrudate into diameter 1.5mm.
This extrudate is 120 ℃ of dryings, then at 500 ℃ of heating 5h.The silica binder content of formed body is 32wt%; Sodium content, 400ppm.
Example 7: the shaping of titanium silicate (catalyst E)
Catalyst E system is mixed and made in disc type is ground as the Ludox of the about 19wt% of dioxide-containing silica of preparation as described in the example 2 as the catalyst of preparation as described in the example 1 and spray-dried powders that 25wt% silica is formed and 13000g by 75wt% by 9700g.
The spray-dried powders of defined is according to the method preparation that is similar to example 4.
Mixture is converted into extrudablely by adding entry and extrusion aids methylcellulose, and extrudes extrudate into diameter 1.5mm.
This extrudate is 120 ℃ of dryings, then at 500 ℃ of heating 5h.The silica binder content of formed body is 40wt%; Sodium content, 420ppm.
Example 8: the shaping of titanium silicate (catalyst F)
Catalyst F system by 8000g by 70wt% as the catalyst of preparation as described in the example 1 and the spray-dried powders that 30wt% silica is formed, in disc type is ground, be mixed and made into as the Ludox of the about 19wt% of dioxide-containing silica of preparation as described in the example 2 with 4000g.
The spray-dried powders of defined is according to the method preparation that is similar to example 4.
Mixture is converted into extrudablely by adding entry and extrusion aids methylcellulose, and extrudes extrudate into diameter 1.5mm.
This extrudate is 120 ℃ of dryings, then at 500 ℃ of heating 5h.The silica binder content of formed body is 40wt%; Sodium content, 400ppm.The anti-2N that is cut into; Transverse compression intensity, 19N.
Example 9: the compacting of titanium silicate and shaping (catalyst G)
3.5kg by as the TS-1 of preparation as described in the example 1 in the disc type mill with 1.23kg
Figure S051C7013620051213D00017145424QIETU
(DEGUSSA), 6.26kg as the Ludox of preparation as described in the example 2 and 237g methylcellulose (
Figure S051C7013620051213D00017145452QIETU
) compacting 60min together.
Subsequently, add the 48g polyethylene glycol (
Figure S051C7013620051213D00018145526QIETU
), mixture is compacting 30min again, adding 96g polyethylene glycol ( ) and 450g deionized water, mixture compacting 15min once more then.
This extrudable composition utilizes extruding machine to be configured as the circular extrudate of 1.5mm.Extrusion molding pressure is between 85～100bar; The extrusion molding time is 15min.This extrudate is 120 ℃ of dryings, and calcines 5h in 500 ℃ air.
Yield is 5.1kg.The silica binder content of formed body is 40wt%; Sodium content, 500ppm; Transverse compression intensity is 17N; The macropore volume is pressed the mercury void determination method of DIN66133 regulation and is measured, and is 0.70g/ml.
Example 10: catalytic test (intermittently operated)
In each case, quantity is put in the steel autoclave that has basket shape internals and bubbling agitator corresponding to catalyst A～G of titanium silicate quality 0.5g.
Add 100g methyl alcohol in autoclave, sealing is also checked and is not had leakage.Subsequently, autoclave is heated to 40 ℃, and is metered into the 11g propylene liguid in autoclave.
Subsequently, utilize HPLC (high pressure liquid chromatography) pump in autoclave, to be pressed into 9.0g30wt% concentration aqueous hydrogen peroxide solution, adopt 16mL methyl alcohol will feed hydrogen peroxide residual in the pipeline then and be flushed in the autoclave.Initial content of hydrogen peroxide in the reaction solution is 2.5wt%.
After reaction time, autoclave cools off and emptying through 2h.Adopt content of hydrogen peroxide in the cerimetry analyzing liquid product.Adopt the gas chromatograph art to measure the propylene oxide content of product.
Analysis result is summed up in following table.
Table: example 10 (catalytic test)
Catalyst Propylene oxide content in the product, wt% Content of hydrogen peroxide in the product, wt%
A (Comparative Examples) 0，88 1，72
B (Comparative Examples) 0，86 1，74
C (Comparative Examples) 0，93 1，51
D 1，39 1，28
E 1，47 1，19
F 1，34 1，25
G 1，1 1，45
Example 11: catalytic test (continued operation)
24g/h hydrogen peroxide (40wt%), 57g/h methyl alcohol and 11.7ml/h propylene under 40 ℃ of reaction temperatures, pressure 20bar condition by the tubular reactor of 28.1g catalyst F of the present invention is housed.
Leave after the reactor, reactant mixture unzips to atmospheric pressure in the Sambay evaporimeter.The low boiling branch of separating is analyzed by online gas chromatograph.Collect liquid reaction product, weigh and similarly by the analysis of gas chromatograph art.
Total reaction time is 550h.During this period, hydrogen peroxide conversion is far above 90%.During Total Test, hydrogen peroxide is significantly higher than 90% equally to the selectivity of propylene oxide.
Example 12: catalytic test (continued operation)
9g/h hydrogen peroxide (40wt%), 49g/h methyl alcohol and 8g/h propylene under 40 ℃ of reaction temperatures, pressure 20bar condition by the tubular reactor of 20g catalyst G of the present invention is housed.
Leave after the reactor, reactant mixture unzips to atmospheric pressure in the Sambay evaporimeter.The low boiling branch of separating is analyzed by online gas chromatograph.Collect liquid reaction product, weigh and similarly by the analysis of gas chromatograph art.
Total reaction time is 850h.During this period, hydrogen peroxide conversion is far above 90%.During Total Test, hydrogen peroxide is significantly higher than 90% equally to the selectivity of propylene oxide.

Claims (10)

1. the alkali metal that contains and the content of alkaline-earth metal ions are lower than the formed body of 500ppm, and it comprises at least a titanium zeolite and at least a metal oxide, described formed body by comprise the following steps (i) to (method v) obtains:
(i) comprise that by spraying the suspended substance of at least a titanium zeolite and metal oxide sol mixes at least a titanium zeolite with at least a metal oxide sol,
(ii) compacting is wherein introduced other metal oxides from the mixture of step (i), adopts metal oxide sol as metal oxide source,
(iii) will be shaped from step composition (ii),
(iv) will be from step formed body drying (iii),
(v) will calcine from the formed body of step drying (iv),
Wherein step (i) and (ii) in the content of the alkalies and alkaline earth ion that contains of the metal oxide sol that uses less than 10ppm.
2. the formed body of claim 1, it is micropore and also has mesopore and macropore in addition that wherein the void content of mesopore and macropore is determined as greater than 0.1ml/g according to DIN 66133 substantially.
3. the alkali metal that contains and the content of alkaline-earth metal ions are lower than the formed body of 500ppm, and it comprises at least a titanium zeolite and at least a oxide, described formed body by comprise the following steps (i) to (method v) obtains:
(i) comprise that by spraying the suspended substance of at least a titanium zeolite and oxide sol mixes at least a titanium zeolite with at least a oxide sol,
(ii) compacting is wherein introduced other oxides from the mixture of step (i), adopts oxide sol as oxide source,
(iii) will be shaped from step composition (ii),
(iv) will be from step formed body drying (iii),
(v) will calcine from the formed body of step drying (iv),
Wherein step (i) and (ii) in the content of the alkalies and alkaline earth ion that contains of the oxide sol that uses less than 10ppm, and
Wherein said oxide is a silica, and described oxide sol is a Ludox.
4. the formed body of claim 3, wherein said titanium zeolite is a titanium silicate.
5. the alkali metal that contains and the content of alkaline-earth metal ions are lower than the formed body of 500ppm or its multiple mixture as Application of Catalyst, described formed body comprises at least a titanium zeolite and at least a metal oxide, described formed body by comprise the following steps (i) to (method v) obtains:
(i) comprise that by spraying the suspended substance of at least a titanium zeolite and metal oxide sol mixes at least a titanium zeolite with at least a metal oxide sol,
(ii) compacting is wherein introduced other metal oxides from the mixture of step (i), adopts metal oxide sol as metal oxide source,
(iii) will be shaped from step composition (ii),
(iv) will be from step formed body drying (iii),
(v) will calcine from the formed body of step drying (iv),
Wherein step (i) and (ii) in the content of the alkalies and alkaline earth ion that contains of the metal oxide sol that uses less than 10ppm.
6. the application of claim 5, described formed body are micropore and also have mesopore and macropore in addition that wherein the void content of mesopore and macropore is determined as greater than 0.1ml/g according to DIN 66133 substantially.
7. the alkali metal that contains and the content of alkaline-earth metal ions are lower than the formed body of 500ppm or its multiple mixture as Application of Catalyst, described formed body comprises at least a titanium zeolite and at least a oxide, described formed body by comprise the following steps (i) to (method v) obtains:
(i) comprise that by spraying the suspended substance of at least a titanium zeolite and oxide sol mixes at least a titanium zeolite with at least a oxide sol,
(ii) compacting is wherein introduced other oxides from the mixture of step (i), adopts oxide sol as oxide source,
(iii) will be shaped from step composition (ii),
(iv) will be from step formed body drying (iii),
(v) will calcine from the formed body of step drying (iv),
Wherein step (i) and (ii) in the content of the alkalies and alkaline earth ion that contains of the oxide sol that uses less than 10ppm, and
Wherein said oxide is a silica, and described oxide sol is a Ludox.
8. the application of claim 7, wherein said titanium zeolite is a titanium silicate.
9. the application of claim 7, wherein said formed body be used as by propylene and hydrogen peroxide or by propylene and the mixture that generates hydrogen peroxide on the spot prepare the catalyst of expoxy propane.
10. the application of claim 8, wherein said formed body be used as by propylene and hydrogen peroxide or by propylene and the mixture that generates hydrogen peroxide on the spot prepare the catalyst of expoxy propane.
CN200510127013.6A 1998-04-08 1999-04-07 A shaped body and its use as catalyst Expired - Fee Related CN1781601B (en)

Applications Claiming Priority (4)

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DE19815879.3 1998-04-08
DE19815879A DE19815879A1 (en) 1998-04-08 1998-04-08 Production of oxide molding useful as catalyst, especially in epoxidation of alkene
DE19859561A DE19859561A1 (en) 1998-12-22 1998-12-22 Production of shaped bodies, for example containing titanium, silicon, and lithium, using a metal oxide sol
DE19859561.1 1998-12-22

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CNB2004100080750A Division CN1240475C (en) 1998-04-08 1999-04-07 Method of using metallic oxide collosol to produce shaping body
CNB998071404A Division CN1178928C (en) 1998-04-08 1999-04-07 Method for producing shaped body using metal oxide sol, shaped body, the use thereof in production of alkene oxide

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DE19939416A1 (en) 1999-08-20 2001-02-22 Basf Ag Production of zeolite, e.g. titanium zeolite, useful as catalyst (support), sorbent, pigment or filler for plastics, involves crystallizing solid from precursor(s) and direct drying of reaction mixture
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