CN101722052A

CN101722052A - Catalyst carrier

Info

Publication number: CN101722052A
Application number: CN200810247085A
Authority: CN
Inventors: H·克劳泽; H·G·J·兰辛克勒特格因克; H·里德曼
Original assignee: Evonik Degussa GmbH
Current assignee: Evonik Operations GmbH
Priority date: 2008-10-15
Filing date: 2008-10-15
Publication date: 2010-06-09

Abstract

The invention relates to a catalyst carrier which mainly comprises synthetic silica and 0.5-10 weight parts of one or more oxides or phosphates of elements selected form the Group IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, and IVA and lanthanide. The catalyst carrier is characterized in that the preparation method comprises the steps of mixing the granular synthetic silica with the granular oxides or phosphates or precursors of the elements selected from the Group IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, and IVA and the lanthanide, molding and calcining. The catalyst carrier and phosphoric acid are used together for preparing alcohol by olefin through hydration.

Description

Catalyst carrier

Technical field

The present invention relates to catalyst carrier, especially load on the catalyst on the following catalyst carrier, described catalyst is used for olefin hydration technology, for example, produces ethanol or isopropyl alcohol.The present invention also relates to olefin hydration technology, the phosphoric acid of described technology working load on described catalyst carrier comes the catalysis hydration reaction.

Background technology

Hydration catalyst can wear out in operation, and it shows activity and/or optionally reduces.Because the reduction of the carrier specific area that the temperature rising causes, inactivation is recurrent.Specific area is meant the BET surface area that is obtained by DIN 66 132 nitrogen adsorption assays according to known Brunauer, Emmett and Teller method in this application.

The specific area of carrier is closely related with pore structure.And the solid with high surface has usually fully or accounts for main impalpable structure, and it has strong trend to be transformed into the thermodynamics stable state by the decline of crystal growth simultaneous specific area.

Have now found that the catalyst carrier that contains silica also can produce such wearing out.Hydrothermal condition accelerated ageing process.When temperature surpasses the boiling point of water and pressure and is above standard pressure, account for leading role in the chemical reaction of hydrothermal condition in water solution system.Recognize that further impurity is alkali metal especially, under hydrothermal condition, can quicken silica containing carrier aging (referring to, R.K.Iler silica chemistry for example, the 544th page, John Wiley ﹠amp; Sons (1979)).

EP 0578441B1 has described the application of catalyst carrier in olefin hydration.The active constituent that loads on the carrier by immersion is a phosphoric acid.This specific carrier contain have high crush strength, the synthetic silica particle of high porosity and few metal impurities.The effect in the hole of carrier is to hold active constituent.Pore volume is preferably greater than 0.8ml/g.Average pore radius before being used for hydro-combination process is in the 1-50nm scope.

In order to reach optimum hydration effect, specified among the EP 0578441B1 that dioxide-containing silica is at least 99 weight % in the carrier, impurity is lower than 1 weight %, preferably is lower than 0.3 weight %.This class catalyst carrier is described in EP 0393356B1 and US 5,086,031.

Be surprisingly found out that now the catalyst carrier of describing among the EP 0393356B1 based on synthetic pyrogenic silica also can cause wearing out under hydrothermal condition.Aperture can become bigger hole and follow the loss of specific area in this case.At first, in such ageing process, pore volume is actual to remain unchanged.Like this aging is unexpected, because research by ESEM, the contained pyrogenic silica of carrier has good temperature resistance ability, heating is up to 1000 ℃ temperature, continue 7 days time, the form of pyrogenic silica can not change (Schriftenreihe Pigmente Nr.11:Grundlage von

Degussa publication, the 5th edition, 1993.6, the 20 pages).

Klimenko (US 3,311,568) has set forth TiO ₂In the aquation of unsaturated hydrocarbons to the positive impact in life-span of the natural siliceous carrier of phosphoric acid load.Thinking natural siliceous supports at that time, as diatomite (diatomite), diatomite (kieselguhr) or diatomaceous soil, is only carrier in these are used.Yet natural siliceous material always contains the impurity that the catalytic performance aspect is had some adverse effects.Described in some patents, can eliminate these adverse effects, for example, and DE 3709401A1, EP 0018022B1, DE 2929919, and DE 2908491, and DE 1156772.Yet this need increase some extra steps in the support/catalyst preparation.

In order to obtain enough physical strengths, Klimenko has at 1050-1350 ℃ temperature lower calcination, and calcination time is 5-24 hour.

Schluechter etc. (US 5,208,195) recognize based on the synthesized silicon rubber carrier and contain H3PO ₄Catalyst be high activity and have enough initial mechanical intensity.Yet as described in them, still there is the partially-crystallized drawback of meeting in the prolongation use of some amorphous silicas under the hydration reaction condition in these carriers.The rapid decline of this and specific area, thus cause catalytic activity to descend and the decline of mechanical strength is associated.Because these shortcomings, they more are ready need to select the natural material of a large amount of procedure of processings, for example, in order to reduce alumina content, handle with acid, are suitable for use as the carrier of hydro-combination process up to it.

Schluechter etc. have described for the crushing strength that increases the catalyst spheroid and have used titanium dioxide, and these catalyst spheroids are most of clays based on actual montmorillonoid-containing, are a kind of natural materials therefore.Titanium dioxide with mix with the clay of acid treatment, the silica gel of fine dispersion, content of titanium dioxide is the 1.5-2.5 weight portion, the content of the synthetic silica gel of producing is the 20-40 weight portion.Randomly with mixture moulding and calcining.

By prior art as can be known, come the silica of modification to show the stability of raising, referring to as EP 0792859A2 by dipping with the IVB compounds of group of solubility.Titanium is one of element of IVB family.Silica supports is by impregnation technology, and preferred pore volume impregnation is carried out modification with stabilizing element.

Pore volume impregnation is dissolved in the solvent of certain volume by the soluble compound with stabilizing element, this volume equals the pore volume of catalyst carrier, distributes solution then to carrier, for example by spray, in order to ensure the homogeneous dipping, carrier can rotate in the sample coater in the spray process.

Aqueous solvent and organic solvent or its mixture all can be used for dipping.In the industrial production, preferred water is as solvent usually.Yet the selection of suitable solvent depends on used stabilizing element compound.Organic titanic compound, for example four titanium butoxide (Ti (C ₄H ₉O) ₄), can be used to replace titanium chloride (III) aqueous solution.In this case, butanols is suitable solvent.

EP 0792859 (A2) shows that the extent of stability of pyrogenic silica increases along with the increase of Ti content.Yet, add titanium and can cause the reduction of pore volume, thereby cause low catalyst activity.Therefore, need to keep alap Ti content.

As shown in the embodiment of the above-mentioned patent application of mentioning, use TiCl ₃Aqueous solution dipping obtains the material of limited stability.The situation of contrast Ti load uses the titanium alkoxide can obtain better effect.Therefore, can be significantly preferably as the titanium source.Because the titanium alkoxide can not be water-soluble, need with an organic solvent in order to flood stabilizing element.Therefore must take suitable and expensive precautionary measures to avoid any explosion accident in the Catalyst Production process.

Before obtaining final stable carrier, the dipping method by stabilizing element comes modified support to need some steps.At first, must carry out the moulding of carrier, such as extruding or compressing tablet, dry then and calcining.Next need to flood stabilizing element, and then dry.At last, the carrier that calcination processing is crossed in the temperature range between 160-900 ℃.

Therefore need a kind of still less cost and still less dangerous preparing carriers method, can provide required high stability simultaneously, and high activity and catalyst optionally are provided simultaneously.

Summary of the invention

Therefore, an object of the present invention is to provide the catalyst carrier that mainly contains synthetic silica, it combines with phosphoric acid, shows the ageing resistance of improvement when using under hydrothermal condition, possesses the good activity and the selectivity that olefin hydration are converted into correspondent alcohol simultaneously.

Further purpose of the present invention is based on the hydration catalyst of the carrier of improvement of the present invention, and it has good activity and selectivity in the aquation that olefin hydration is changed into corresponding alcohol.

Above-mentioned and other purpose of the present invention is realized by a kind of catalyst carrier, this carrier mainly comprises synthetic silica, 0.5-10 weight portion be selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, one or more oxides or the phosphate of the element of IVA family and lanthanide series, the preparation method who it is characterized in that carrier comprises: with the graininess synthetic silica be selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, the oxide particle of the element of IVA family and lanthanide series or phosphate, or the mixing of their precursor, carry out forming step and calcining.

Above-mentioned and other purposes of the present invention also realize by the phosphoric acid catalyst of load, the catalyst carrier that wherein mainly contains synthetic silica is come modification by 0.5-10 parts by weight of titanium oxide and/or the zirconium dioxide in the gross weight of calcinated support, wherein preferably before forming step silica and titanium dioxide and/or zirconia is mixed.

Like this, on the one hand, the invention provides a kind of catalyst carrier, it mainly contains synthetic silica, the IIA that is selected from the 0.5-10 weight portion, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, the oxide particle of the element of IVA family and lanthanide series or phosphate, or their precursor, preferred titanium dioxide and/or zirconium dioxide, the preparation method who it is characterized in that carrier comprises: with the graininess synthetic silica, with be selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, the oxide particle of the element of IVA family and lanthanide series or phosphate, or their precursor, preferred titanium dioxide and/or zirconium dioxide mix, and carry out forming step and calcining.

In preferred implementation of the present invention, catalyst carrier comprises silica, titanium dioxide or zirconium dioxide.

By in this way with IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, the oxide particle of the element of IVA family and lanthanide series or phosphate, or their precursor, preferred titanium dioxide and/or zirconium dioxide, mix with silica, be selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, the oxide particle of the element of IVA family and lanthanide series or phosphate, or their precursor, preferred titanium dioxide and/or zirconium dioxide form the zone in the structural framing of calcinated support, and are not only the surface coating.Like this, according to a further aspect in the invention, a kind of catalyst carrier that contains the synthetic silica structural framing is provided, this framework comprises oxide particle or the phosphate or their precursor of the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, the zone of preferred titanium dioxide and/or zirconium dioxide.Wherein be selected from oxide particle or the phosphate or their precursor of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, preferred titanium dioxide and/or zirconium dioxide account for the 0.5-10 weight portion in total weight of carrier in described zone.

The gained carrier has the stability of improvement aspect anti-aging, in fact also than the easier production of any material of prior art.And it changes in the pure hydration reaction at alkene and demonstrates good activity and selectivity.Thereby, according to another aspect, the invention provides the method for olefin hydration, described method is included in and makes alkene and water reaction under the existence of the phosphoric acid that loads on a kind of catalyst carrier as mentioned above.

Another object of the present invention is the preparation method of these carriers.Described method comprises: the silica of hybrid particles shape and based on oxide particle or the phosphate or their precursor of the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series of the 0.5-10 weight portion of the gross weight of carrier before the forming step, preferred titanium dioxide and/or zirconium dioxide; The material of forming step and calcining moulding in 400-1050 ℃ of scope.

The inventive method is not only more simple to operation than existing production technology, and activity with improvement and stability and good material optionally also are provided simultaneously.

Detailed Description Of The Invention

Be surprisingly found out that, when before forming step with the graininess synthetic silica be selected from oxide particle or the phosphate or their precursor of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, when preferred particulates titanium dioxide and/or zirconium dioxide carry out physical mixed, based on the raising of the stability highly significant of the phosphoric acid catalyst of synthetic silica.

The silica used according to the present invention mainly contains synthetic silica.Silica gel and precipitated silica by the wet chemistry method preparation are appropriate synthetic materials.Preferred synthetic silica, so-called high temperature or the pyrogenic silica that makes by flame hydrolysis that use.

Pyrolysismethod or high temperature silica are that the commodity that Degussa-Huels provides are called

Product.

In order to prepare

Nonvolatile silicon compound is sprayed in the oxyhydrogen flame that contains hydrogen and air.In most cases, use similar silicon tetrachloride or SiMeCl ₃Compound.The hydrolysis under the influence of the water that the oxyhydrogen flame reaction produces of these materials obtains silica and hydrochloric acid.Silica enters so-called condensing zone after leaving flame, condense at this

Primary granule and elementary aggregation.In cyclone separator, from gaseous state association material, separate as a class aerosol at the product that this stage generates, in damp-heat air, carry out post processing then.The result of this method is that residual hydrochloric acid composition can be reduced to below 0.025%.Because when this method finishes, obtain

The bulk density 15g/l that only has an appointment, so next carry out the vacuum compression process, can obtain about 50g/l or higher pressed density thus.

The particle size of the product that obtains with the method changes along with the difference of reaction condition, for example flame temperature, the ratio of hydrogen or oxygen, the consumption of silicon tetrachloride, the time of staying in flame and the length of condensing zone.

Titanium dioxide used according to the invention can be any source, as precipitation or pyrogenic titanium dioxide.Pyrolysismethod or high temperature titanium dioxide also can be provided by Degussa-Huels, are by nonvolatile Ti compound, for example, and TiCl ₄Flame hydrolysis generate.Preparation high temperature or pyrolysismethod TiO ₂Method and above-mentioned

The preparation method similar.

Titanium dioxide can contain any its crystal habit, for example, anatase phase or rutile phase, perhaps it can be all or part of amorphous.These out of phase mixtures also allow.

Zirconium dioxide used according to the invention is any source, for example precipitation or pyrolysismethod zirconium dioxide.

Zirconium dioxide used according to the invention for example is as described below, Ullmann ' the s Encyclopedia of Industrial Chemistry that VCH-Verlagsgesellschaft publishes, the 5th edition, the A28 volume, the thesis for the doctorate of 543-571 and Patrick D.L.Mercera, title is " as the zirconia of catalyst carrier ", Universiteit Twente, the Netherlands (1991).

Be selected from the oxide particle or the phosphate of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series except use, preferred particulates titanium dioxide and/or zirconium dioxide, also can use one or more their precursors, convert it into corresponding oxide form by calcining.For example, can use particle Zr (OH) ₄Replace or join in the particle zirconium dioxide.

For carrier as the phosphoric acid hydration catalyst, in final carrier, be selected from oxide particle or the phosphate or their precursor of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, the content of preferred titanium dioxide and/or zirconium dioxide is 0.5-10 weight % in the gross weight of carrier, preferred 1-9 weight %, more preferably 2.6-8 weight %.Too high concentration can the minimizing of pore volume cause active loss when forming Ti-and/or Zr-phosphate.Conversely, low excessively concentration can cause the stability of catalyst deficiency, therefore has only the too short life-span.

The content of synthetic silica is at least 80% in the calcinated support.Carrier preferably contains the particle that is of a size of 0.8-10mm, more preferably 1.5-8mm.Too little particle can cause unacceptable pressure drop of beds, and too big particle can cause diffusion limited, thereby reduces activity of such catalysts.The surface area of the carrier of fresh not load depends mainly on initial compounds silica and is selected from oxide particle or the phosphate or their precursor of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, preferred titanium dioxide and/or zirconium dioxide, it is 5-600m ²/ g, preferred 10-400m ²/ g.

One of most important properties of used carrier material is its pore volume in hydration catalyst.Higher pore volume can better absorb phosphoric acid, can obtain higher catalyst activity like this.Pore volume can be 0.5-1.8ml/g, preferred 0.8-1.5ml/g, more preferably 0.9-1.5ml/g.

Carrier can exist with lamellar body, extrudate, spheroid or granular form.For extrudate and lamellar body, standard shape is a cylinder, but known other shape in all documents also can be used as ring-type, four-wheel shape, clover, star etc.The front and back end of lamellar body flat or the cap shape.

The bulk density of carrier is mainly determined by the content of pore volume, titanium dioxide and/or zirconium dioxide and the shape and the size of single carrier granular.Bulk density can change in the scope of broad, can be 300-800g/l.

Moulding comprises any forming technique.The preferred forming method of the carrier that uses in the fixed bed hydration process is compressing tablet, compress or extrude.

In the preparation process of carrier, the particle synthetic silica that preferred fine dispersion is formed with also preferably with oxide particle or the phosphate or their precursor of the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series of fine dispersion form, preferred particulates titanium dioxide and/or zirconium dioxide; And water and moulding additive, mix as lubricant and/or pore creating material.Randomly, can add silica gel or natural silica, its maximum level is counted 10 weight portions based on the weight of calcinated support.Then mixture is fully mixed or mediate.Randomly, before forming step especially compressing tablet process, carry out partially or completely drying.With mixture by selected forming technique, as, extrude, compressing tablet or compacting carry out last moulding.

The implication of fine dispersion herein is silica and oxide particle or phosphate or their precursor that is selected from the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, preferred titanium dioxide and/or zirconium dioxide, before mixing or kneading step, be limited to 100 μ m on the aggregation preferable range that comprises, be limited to 50 μ m on more preferably.Thereby the aggregation in this scope should be a loosely bonds them, in mixing or kneading step, the degree that size is reduced to makes final carrier contain to be selected from oxide particle or the phosphate or their precursor of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, the zonule of preferred particulates titanium dioxide and/or zirconium dioxide.

Because forming process comprises the physical mixed particulate silica and is selected from oxide particle or the phosphate or their precursor of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, preferred particulates titanium dioxide and/or zirconium dioxide, final carrier contains oxide particle or the phosphate or their precursor of the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, the zone of preferred titanium dioxide and/or zirconium dioxide.It is important spreading all over the size in these zones in the whole shaping carrier and distributing for stability.Mix or kneading process after be forming step as, extrude or compressing tablet, and calcining, in the carrier after calcining, 50% or more be selected from oxide particle or the phosphate or their precursor of the element of IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series, the zone of preferred particulates titanium dioxide and/or zirconium dioxide is less than 2 μ m.Preferably, the oxide particle of at least 50% the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series or phosphate or their precursor, the zone of preferred particulates titanium dioxide and/or zirconium dioxide is less than 1 μ m.Preferred, the oxide particle of at least 50% the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series or phosphate or their precursor, the zone of preferred titanium dioxide and/or zirconium dioxide is in the scope less than 0.8 μ m.The most preferably oxide particle of at least 90% the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series or phosphate or their precursor, the zone of preferred titanium dioxide and/or zirconium dioxide is less than the scope of 0.8 μ m.

The moulding additive can be an auxiliary agent known in all documents, and for example, they can have bonding or lubricated or pore-creating function.Example has cellulose and derivative, polyethylene glycol, wax, ammonia or discharges the compound of ammonia, polyvinyl alcohol, starch, sugar etc.

The content that can regulate different material in the mixture is so that the forming technique of the viscosity of mixture and selection adapts.Randomly, mixture carried out part or all of drying before forming step.

After forming step, randomly formed body is carried out drying, calcine then.Wherein drying is carried out being lower than under 200 ℃ of scopes usually, and calcining is preferably carried out in 400-1050 ℃ of scope, most preferably in 450-1000 ℃ of scope.Because the support according to the present invention material has wonderful good thermal stability, high calcining heat is no problem.The duration of calcining can be in 15 minutes to several hours scopes, and this depends on the type and the size of the kiln of calcining.Preferably calcine and in air, carry out.

Catalyst carrier described herein is particularly advantageous in hydration alkene with the preparation lower alcohol.For olefin hydration, phosphoric acid is introduced in the catalyst carrier as active constituent.At last, in case the calcining of the carrier of stabilisation process, it can adopt the aqueous solution load of phosphoric acid.Phosphoric acid solution comprises the phosphoric acid in the 15-85 weight % of the gross weight of solution, preferred 30-65 weight %.Randomly, the carrier of dipping carries out dry to obtain dry catalyst system before use.Under dry status, the phosphoric acid that catalyst has 5-55 weight % concentration in dry catalyst system gross weight, preferred 20-50 weight %.

The phosphoric acid loading process can comprise any suitable technique, for example, and the dipping of excess phosphoric acid solution, immersion, spray dipping, dry impregnating.The amount of solution can equal, be greater than or less than the pore volume of carrier amount.Load can be carried out under any pressure.In order to promote to absorb very glutinous phosphoric acid solution, carrier load on that operation also is favourable under the low pressure.

Catalyst according to the invention for example, has good stable under the condition that is run at hydrothermal condition aspect anti-aging in olefin hydration.If catalyst according to the invention is 350-370 ℃ of temperature, the 15-18bar water vapor pressure wore out after turning round about 40-45 hour, and their pore-size distribution is that most of pore volume is relevant less than the hole of 5 μ m with diameter.

In the back the variation of catalyst carrier pore structure under hydrothermal condition of containing silica is studied.Compare with traditional unstabilized and stable carrier and new stable carrier.

As above discuss described, the present invention also provides the method for olefin hydration, described method comprises: contain the catalyst that loads on the phosphoric acid on the catalyst carrier in the presence of with alkene and water reaction, it is characterized in that described catalyst carrier contains the structural framing of synthetic silica, this framework comprises at least a IIA in the periodic table of elements that is selected from, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, the oxide particle of the element of IVA family and lanthanide series or phosphatic zone, described oxide or phosphate account for the 0.5-10 weight portion of total weight of carrier.

Preferably, the catalyst carrier framework contains titanium dioxide and/or zirconium dioxide zone.

The suitable alkene by hydration is ethene or propylene.When using ethene, gained alcohol is ethanol.When using propylene, obtain isopropyl alcohol and normal propyl alcohol.The ether of corresponding alkene can generate as accessory substance in reaction.Hydration is preferably carried out under gaseous state, and promptly alkene and water all are in gas phase in reaction.

Hydration reaction is placed on the catalyst soakage carrier in the reactor when operation usually, with the reactor sealing, then supported catalyst is warmed up to reaction temperature.Preferably supported catalyst is heated to 170-300 ℃, temperature depends on required target product.For example, if target product is the ethanol from ethene, supported catalyst is fit to be heated to 225-280 ℃, and preferred 230-260 ℃, more preferably 235-245 ℃.In addition, if target product is isopropyl alcohol and normal propyl alcohol from propylene, supported catalyst is fit to be heated to 180-225 ℃, preferred 185-205 ℃.

When the supported catalyst bed reached temperature required, the alkene of vapor phase and water material transmitted by reactor.The water by reactor and the mol ratio of alkene in the 0.15-0.50 scope, preferred 0.25-0.45, more preferably 0.30-0.40.The air speed of the water vapour/alkene mixture by reactor may stand the variation of a little, and this depends on that reactant olefin is ethene or propylene.For example, under the situation of ethene, the air speed of this mixture and water vapour is adapted in the 0.010-0.100 scope, preferred every cubic centimetre of supported catalyst of 0.020-0.050 grams per minute (g/ (min cm ³Cat)).For the situation of propylene and steam, air speed is adapted in the 0.010-0.100 scope, preferred 0.02-0.07g/min/cm ³Supported catalyst.

Hydration reaction can be carried out under the pressure of 2000-24000Kpa.In this scope, the hydration of ethene suits to carry out under the pressure of 3000-10000Kpa, and the hydration of propylene suits to carry out under the pressure of 2000-7600Kpa.

Continue to set forth these and other aspect of the present invention with reference to following embodiment and accompanying drawing.

Description of drawings

Fig. 1 is that the difference of catalyst carrier after the hydrothermal aging test of not stabilisation is invaded (differential intrusion) curve map (Comparative Examples 1) with respect to the aperture of pore structure;

Fig. 2 invades curve map (Comparative Examples 2) with respect to the aperture of pore structure according to the difference of catalyst carrier after the hydrothermal aging test with the 1.5%Ti stabilisation of prior art;

Fig. 3 invades curve map (Comparative Examples 3) with respect to the aperture of pore structure according to the difference of catalyst carrier after the hydrothermal aging test with the 4%Ti stabilisation of prior art;

Fig. 4 invades curve map (Comparative Examples 4) with respect to the aperture of pore structure according to the difference of catalyst carrier after the hydrothermal aging test with the 5%Ti stabilisation of prior art;

Fig. 5 invades curve map (Comparative Examples 5) with respect to the aperture of pore structure according to the difference of catalyst carrier after the hydrothermal aging test with the 5%Ti stabilisation of prior art;

Fig. 6 is that the difference of catalyst carrier after the hydrothermal aging test with the 3%Ti stabilisation according to the present invention is invaded the curve map (embodiment 6) with respect to the aperture of pore structure;

Fig. 7 is that the difference of catalyst carrier after the hydrothermal aging test with the 1.8%Ti stabilisation according to the present invention is invaded the curve map (embodiment 7) with respect to the aperture of pore structure;

Fig. 8 is that the difference of catalyst carrier after the hydrothermal aging test with the 1.8%Ti stabilisation according to the present invention is invaded the curve map (embodiment 8) with respect to the aperture of pore structure;

Fig. 9 is according to used catalyst (embodiment 17), the space time yield of ethanol (STY) curve over time in the olefin hydration process.

Figure 10 is that the usefulness 5% Zirconia-stabilized difference of catalyst carrier after the hydrothermal aging test according to the present invention is invaded the curve map (embodiment 22) with respect to the aperture of pore structure.

The pore size distribution curve of Fig. 1-8 and 10 expressions is recorded by known mercury injection method.They show because the difference of the mercury that the effect in aperture causes penetrates (intrusion).Invade for difference and to select unit arbitrarily, and every curve all can utilize in the scope at Tu Nei and extends.

Embodiment

Comparative Examples 1

The carrier for preparing prior aries according to the embodiment 2 of EP 393356B1.

Catalyst prepares by following process: heat of mixing solution silica (

200, from Degussa-Huels), dolomol, methylcellulose and urea carry out drying and compressing tablet subsequently.Calcination process comprises two steps: carry out earlier the calcining first time under 250 ℃ of temperature, carry out last calcining then under 750 ℃ of temperature.This product by Degussa-Huels with Degussa 350, Trager 350, Support 350 or Aerolyst ^TM350 title is sold, and it has following feature: specific area is about 180m ²/ g; Bulk density is about 490g/l; Total pore volume is about 0.8cm ³/ g.It contains diameter is that 6mm highly is the lamellar body of 5.5mm.

Be heated to 350 ℃, heat treated 41 hours with 60 weight % phosphoric acid solution load carriers materials and in steam pressure is the high-pressure installation of 15bar.

The pore-size distribution of aging rear catalyst is measured with mercury injection method.The pore-size distribution that records as shown in Figure 1.

In the bore dia 20-30 of pore-size distribution mu m range, has maximum through the carrier behind the hydrothermal aging.

Comparative Examples 2

Ti with 1.5 weight % carries out modification to the catalyst carrier from Comparative Examples 1.For Ti modification 100g carrier, with 15% titanium chloride (the III) (TiCl of 33g with 1.5 weight % ₃) solution with water is diluted to 80ml, this volume is corresponding to the pore volume of carrier material.Carrier material floods with this solution.

Be exposed in the solution after 30 minutes, 100 ℃ of dry supports are 3 hours in hothouse, 600 ℃ of calcinings 4 hours in heating furnace then.Use 60 weight % phosphoric acid solution load carriers then, placed high-pressure installation 40 hours, steam pressure is 15bar in it, and temperature is 350 ℃.The pore-size distribution of aging catalyst is measured with mercury injection method once more.Pore-size distribution as shown in Figure 2.

The maximum of pore-size distribution is between 10-20 μ m.Compare with not impregnated catalyst used in the Comparative Examples 1, after aging, have the more a high proportion of aperture that is lower than 10 μ m diameters with this catalyst of 1.5 weight %Ti dipping.

Comparative Examples 3

Ti with 4 weight % carries out modification to the catalyst carrier in the Comparative Examples 1.For Ti modification 100g carrier with 4 weight %, 15% titanium chloride (III) solution with water of 85.93g is diluted to 80ml, spread on the carrier to flood it.

Be exposed in the solution after 30 minutes, 100 ℃ of dry supports are 3 hours in hothouse, 600 ℃ of calcinings 4 hours in heating furnace then.Use 60 weight % phosphoric acid solution load carriers then, placed high-pressure installation 43 hours, steam pressure is 15bar in it, and temperature is 350 ℃.The non-constant width of the pore-size distribution of this sample.The maximum of pore-size distribution is about 2 μ m.Compare with not impregnated catalyst used in the Comparative Examples 1, this catalyst that floods with 4 weight %Ti has a high proportion of hole that is lower than 10 μ m apertures.Compare with not impregnated catalyst used in the Comparative Examples 1, obviously more stable with this catalyst of 4 weight %Ti dipping, the expansion in aperture also obviously still less.

Comparative Examples 4

Ti with 5 weight % carries out modification to the catalyst carrier of Comparative Examples 1.For Ti modification 100g carrier, with 35.5g four titanium butoxide (Ti (C with 5 weight % ₄H ₉O) ₄) be diluted to 80ml with butanols, and spread on the carrier.For fear of any danger of blast, in dipping and dry run, use special explosion-protection equipment.

Be exposed in the solution after 30 minutes, 100 ℃ of dry supports are 3 hours in hothouse, 600 ℃ of calcinings 4 hours in heating furnace then.

Use the phosphoric acid load carriers then, place high-pressure installation to be heated to 350 ℃, continue 41.5 hours, steam pressure is 15bar in it.The pore-size distribution of aging catalyst is measured with mercury injection method.Pore-size distribution as shown in Figure 4.

The maximum of pore-size distribution is about 0.7 μ m.Basically there be not the hole of diameter greater than 3 μ m.Compare with not impregnated catalyst used in the Comparative Examples 1, obviously more stable with this catalyst of 5 weight %Ti dipping.With in the average pore size of this catalyst of 5 weight %Ti dipping and the Comparative Examples 1 not supported catalyst compare little 35 times.

The preparation method of this embodiment is based on an organic solvent.The industrial production of this titaniferous carrier material need be used special explosion-protection equipment and building.And, have to handle a large amount of organic solvents, organic waste materials has to burn or recycle.Therefore this material is difficult to produce, and also is expensive therefore.

Comparative Examples 5

As described in the Comparative Examples 1 similarly preparation have a catalyst carrier than macropore volume 1.0ml/g, it is by titanyl sulfate (TiOSO ₄) flood and carry out 5 weight %Ti modifications, titanyl sulfate is dissolved in and contains some H ₂O ₂Water in.This solution is spread on the carrier.

Be exposed in the solution after 30 minutes, 100 ℃ of dry supports are 3 hours in hothouse, 600 ℃ of calcinings 4 hours in heating furnace then.Use the phosphoric acid load carriers then, place high-pressure installation to be heated to 350 ℃, continue 45 hours, steam pressure is 15bar in it.The pore-size distribution of aging catalyst is measured with mercury injection method.Pore-size distribution as shown in Figure 5.

Compare with not impregnated catalyst used in the Comparative Examples 1, obviously more stable with this catalyst of 5 weight %Ti dipping.

Embodiment 6

By mix the 1.0kg pyrogenic silica (

200V,, amorphous from Degussa Huels), the 52.5g pyrogenic titanium dioxide (P25, from Degussa Huels, contain have an appointment the 70-80% anatase mutually with the 20-30% rutile mutually, surface area 50m ²/ g, d ₅₀3-4 μ m), the water of the ammonia solution of 21g methylcellulose, 50g wax, 5g polysaccharide, 10g 30% and 1.9kg prepares catalyst carrier of the present invention.Mediated this mixture about 30 minutes, and extruded subsequently.After 110 ℃ of dryings, in air, calcined this material 3 hours for 750 ℃.The gained extrudate contains the TiO of 5 weight % ₂SiO with 95 weight % ₂, 5%TiO ₂Corresponding to 3 weight %Ti content.The diameter of extrudate is 4.0mm, and surface area is 175m ²/ g, pore volume are 0.99ml/g, and bulk density is 450g/l, and crushing strength is 47N.

The carrier of this embodiment is analyzed with ESEM (TEM).High-visible titanium dioxide zone in the amorphous silica matrix.The full-size in titanium dioxide zone is about 0.3 μ m.

The carrier of this embodiment is also analyzed with XRD.Do not find the silica crystals peak.The titanium dioxide peak with anatase mutually with rutile mutually form exist.

The phosphoric acid load of this carrier is heated to 370 ℃ in high-pressure installation, continue about 45 hours, and steam pressure is 15bar in the device.The pore-size distribution of aging catalyst is measured with mercury injection method.Pore-size distribution as shown in Figure 6.Although Ti content only is 3 weight %, there is not diameter to exist basically greater than the hole of 3 μ m.

Embodiment 7

Prepare another kind of catalyst carrier of the present invention by mixing 970g pyrogenic silica, 30g pyrogenic titanium dioxide, 21g methylcellulose, 50g wax, 5g polysaccharide, the ammonia solution of 10g 30% and the water of 1.9kg.Mediated this mixture about 30 minutes, and extruded subsequently.After 110 ℃ of dryings, in air, calcined this material 3 hours for 850 ℃.The gained extrudate contains 3 weight %TiO ₂With 97 weight %SiO ₂, 3%TiO2 is corresponding to 1.8 weight %Ti content.The diameter of extrudate is 3.5mm, and surface area is 165m ²/ g, pore volume are 1.0ml/g, and bulk density is 440g/l, and crushing strength is 50N.

The phosphoric acid load of this carrier is heated to 370 ℃ in high-pressure installation, continue about 43 hours, and steam pressure is 15bar in the device.The pore-size distribution of aging catalyst is measured with mercury injection method.Pore-size distribution as shown in Figure 7.Basically there is not diameter to exist greater than the hole of 3 μ m.In Comparative Examples 2, the Ti load capacity is 1.5 weight %, and it equals the Ti content of this embodiment carrier substantially.It is more stable that the contrast of aperture data demonstrates carrier of the present invention.And, the easier production of carrier of the present invention.

Embodiment 8

Prepare another kind of catalyst carrier of the present invention by mixing 970g pyrogenic silica, 30g pyrogenic titanium dioxide (anatase phase), 21g methylcellulose, 50g wax, 5g polysaccharide, the ammonia solution of 10g 30% and the water of 1.9kg.Mediated this mixture about 30 minutes, and extruded subsequently.After 110 ℃ of dryings, in air, calcined this material 3 hours for 850 ℃.The gained extrudate contains the TiO of 3 weight % ₂SiO with 97 weight % ₂, 3%TiO ₂The corresponding only Ti content of 1.8 weight %.The diameter of extrudate is 3.5mm, and surface area is 165m ²/ g, pore volume are 1.0ml/g, and bulk density is that 440g/l and crushing strength are 50N.

The phosphoric acid load of this carrier is heated to 370 ℃ in high-pressure installation, continue 43 hours, and steam pressure is 15bar in the device.The pore-size distribution of aging catalyst is measured with mercury injection method.Pore-size distribution as shown in Figure 8.Basically there is not diameter to exist greater than the hole of 3.5 μ m.In Comparative Examples 2, the Ti load capacity is 1.5 weight %, and it equals the Ti content of this embodiment carrier substantially.It is more stable that the contrast of aperture data demonstrates carrier of the present invention.And, the easier production of carrier of the present invention.

Embodiment 9

The sourest loading process of normal application comprises carrier is dipped in excessive about 60 weight % phosphoric acid solutions.After this immersion process, the excessive solution of draining, dry catalyst.In immersion process, some titanium dioxide that exist on the carrier may dissolve.Therefore, such loading process can cause undesirable loss of titanium dioxide.

More above-described embodiment analyze the acid that emits and whether have titanium.By with some H ₂O ₂Join and carry out half component analysis in the acid solution.Under the existence of a little amount of titanium, solution becomes yellow, and solution can become orange or red under the higher titanium concentration.

Embodiment	Observed color
Embodiment	Observed color	1 (Comparative Examples) do not contain Ti	No
3 (Comparative Examples)	Yellow	1 (Comparative Examples) do not contain Ti	No
3 (Comparative Examples)	Yellow	4 (Comparative Examples)	Orange-redness
5 (Comparative Examples)	Orange	4 (Comparative Examples)	Orange-redness
5 (Comparative Examples)	Orange	?6	Very light yellow
?7	Very light yellow	?6	Very light yellow

As can be seen, stable state carrier of the prior art (embodiment 3,4 and 5) exists a large amount of Ti to run off in sour loading process from these results.Minute quantity Ti is not lost or only lose to support according to the present invention.This is the advantage of carrier of the present invention.

Proved in the aforementioned embodiment and also had other advantages: compare with carrier in the existing document, they have better or identical hydrothermal stability after load phosphoric acid, and their preparation method is more simple, and their content of titanium dioxide is also lower.

Embodiment 10

Form with the 3.5mm columnar extrudate provides the catalyst according to the invention carrier.The method of catalyst carrier for preparing this embodiment is identical with the method for catalyst carrier of preparation embodiment 6.The Ti content of carrier is 3.9%wt/wt, is measured by x-ray fluorescence.The bulk density of carrier is 480g/l, and pore volume is that 0.96ml/g is (by H ₂O absorption records), breaking strength 45N (average of 50 broken lamellar bodies uses Mecmesin breaking strength detector), pore-size distribution is characterised in that at the 16nm place and exists point unimodal, measured by mercury injection method.

Embodiment 11

Carrier with 1 liter of embodiment 10 of phosphate impregnation prepares catalyst.This can be submerged into the carrier of finding time the orthophosphoric acid solution (H of 55.3 w/w % then by the Kong Zhiyue 35mmHg of emptying carrier ₃PO ₄) realize.Under atmospheric pressure, carrier was soaked 1 hour with solution then.

After the immersion, filtration supports is removed excessive acid, and drying is 24 hours under 120 ℃.The bulk density of finding the gained catalyst is 874g/l.The sour load capacity that calculates catalyst according to the bulk density that deducts carrier is 394g/l.

The breaking strength of the gained catalyst of measuring is 49N (average of 50 broken lamellar bodies uses Mecmesin breaking strength detector)

Embodiment 12

Use the catalyst ethylene hydration reaction of embodiment 11.

Hydration reaction is carried out in 1 liter of continuous-flow experimental rig, and this device is designed to simulate the reactive moieties of gaseous ethene hydration plant, and device is operation as follows:

Fresh ethylene gas is infeeded device from the high-pressure ethylene compressor reducer.With diaphragm metering pump aqueous water is infeeded device.Before being introduced into catalyst bed, charging mixes with cyclic ethylene and by preheater/vaporizer.

Catalyst is placed copper liner tubular reactor, and it is equipped with the catalyst temperature of central multiple spot thermocouple with accurate measurement beds difference (fixing) degree of depth.With simple shell-and-tube exchanger the Gas-phase reactor logistics is cooled to room temperature, the liquids and gases mixture of products is separated in gases at high pressure/liquid separator.

Subsequently, the gas-phase product that still contains a certain amount of ethanol further processes in water scrubber, and water-soluble compositions a large amount of in tower are removed.Liquid phase stream in the water scrubber mixes the logistics of formation major product with the liquid phase stream in the gas/liquid separation device.Collect this logistics and analyze (using gas-chromatography).

The gas of removing in the water scrubber infeeds recycle compressor and turns back in the reactor once more.The circulating air flow velocity is controlled to guarantee by approaching the commercial used time of ethanol device the time of contact of beds with coriolis meter (Coriolis meter) is strict.Use the analysis cycle logistics in per 15 minutes of online gas-chromatography to form to measure circulating air.

Device turns round under the pressure of 1000psig (68atm); Reactor inlet temperature is 240 ℃, and the reactor outlet temperature is 260 ℃; Water: the ethylene feed mol ratio is 0.35-0.36; Ethene GHSV=1350hr (1); Water vapour GHSV=485hr (1).

Catalyst keeps 2 weeks of steam, during this period, measures ethanol, the space time yield of ether and acetaldehyde (STYs).The result lists in the following table 1.

Comparative Examples 13

With with embodiment 11 described similar methods by preparing catalyst with phosphate impregnation Degussa 350 carriers.Degussa 350 carriers are existing detailed description in Comparative Examples 1.

Use as above-mentioned embodiment 12 described 1 liter of continuous-flow experimental rig the gained catalyst is used for the catalyzed ethylene hydration reaction.

Following table 1 compares working load at space time yield (STY) and the phosphoric acid catalyst gained STYs of working load on Degussa 350 (Comparative Examples 13) carrier that embodiment 10 supported catalysts obtain.

Table 1

Carrier	Ethanol STY (g/Lcat/hr)	Ether STY (g/Lcat/hr)	Acetaldehyde STY (g/Lcat/hr)	Ethanol selectivity %
Carrier	Ethanol STY (g/Lcat/hr)	Ether STY (g/Lcat/hr)	Acetaldehyde STY (g/Lcat/hr)	Ethanol selectivity %	Comparative Examples 13	??120	??6.35	??0.37	??93.6
Embodiment 10	??136	??6.5	??0.45	??94.1	Comparative Examples 13	??120	??6.35	??0.37	??93.6

The result shows that loading on embodiment 10 supported catalysts (being the catalyst of embodiment 11) has better ethanol activity and selectivity than the catalyst (comparative example 13) that loads on the Degussa 350.

Embodiment 14

In this embodiment, the catalyst of embodiment 11 carries out the mensuration of pore-size distribution (PSD) before use.The pore-size distribution feature of finding fresh catalyst is at the 16nm place unicuspid peak to be arranged, and is measured by mercury injection method.As above-mentioned embodiment 12 described experimental rigs in use after, find catalyst 165 and the 380nm place exist bimodal.

Comparative Examples 15

Repeat the foregoing description 14 with the catalyst that loads on the Degussa 350.In Comparative Examples 1, Degussa 350 carriers are had detailed description.The pore-size distribution feature of finding fresh catalyst is at the 17nm place unicuspid peak to be arranged, and measures with mercury injection method.After the use, find that the PSD of catalyst is bimodal, the peak is arranged at 200nm and 3000nm place.Contrast by the result with embodiment 14 and Comparative Examples 15, the variation of the PSD of catalyst of the present invention obviously is less than and loads on no titania support as can be seen, for example the PSD of the catalyst of Degussa 350.

Embodiment 16

The catalyst according to the invention carrier of 4mm columnar extrudate form is provided.The method that is used for preparing this embodiment carrier is consistent with the method for the carrier of preparation embodiment 6.The Ti content of carrier is 4%wt/wt, measures with XRF.The bulk density of carrier is 457.3g/l, pore volume is 1.01ml/g (by mercury injection method and water absorption), and breaking strength is 44.8N (mean value of 50 broken lamellar bodies is with Mecmesin breaking strength detector), pore-size distribution is characterised in that have sharply unimodally at the 14.8nm place, is measured by mercury injection method.

Embodiment 17

Carrier with phosphate impregnation 8L embodiment 16 prepares catalyst.Be less than 40mmHg by pore volume is evacuated down to, the carrier that will take out vacuum then immerses the orthophosphoric acid (H of 52 w/w % ₃PO ₄) realize this method in the solution.Carrier under atmospheric pressure soaked 2 hours in solution.

After the immersion, filtration supports is removed excess acid, and 120 ℃ following dry 3 days.The bulk density of finding the gained catalyst is 755.5g/l.The calculating of the bulk density through deducting carrier, the sour load capacity of catalyst is 298.2g/l.

The breaking strength of catalyst is 92.6N.

Embodiment 18

The catalyst of embodiment 17 is used for the catalyzed ethylene hydration reaction.

Hydration reaction is carried out in 8L continuous-flow experimental rig, and this device is designed to simulate the reactive moieties of gaseous ethene hydration plant, and device is operation as follows:

Fresh ethylene is fed in the device from the high-pressure ethylene compressor reducer.Liquid water feed (using diaphragm metering pump) changes steam at this aqueous water in " dropping-charging " vaporizer.Charging mixes with cyclic ethylene, and passes through beds.

Catalyst is placed copper liner tubular reactor, and it is equipped with the catalyst temperature of central multiple spot thermocouple with accurate measurement beds difference (fixing) degree of depth.With simple shell-and-tube exchanger the Gas-phase reactor logistics is cooled to room temperature, the liquids and gases mixture of products is separated in gases at high pressure/liquid separator.Subsequently, the gas-phase product that still contains a certain amount of ethanol further processes in water scrubber, and water-soluble compositions a large amount of in water scrubber are removed from gaseous product.

Liquid phase stream in the water scrubber mixes the logistics of formation major product with the liquid phase stream in the gas/liquid separation device.Collect this logistics and analyze (using gas-chromatography) according to conventional methods to obtain catalyst activity and selective data.

The gas of removing in the water scrubber infeeds recycle compressor and turns back in the reactor once more.Control the circulating air flow velocity to guarantee with the coriolis meter strictness by approaching the commercial used time of ethanol device the time of contact of beds.Use online gas chromatographic analysis recycle stream.

Device turns round under the pressure of 1000psig (68atm); Reactor inlet temperature is 240 ℃, and the reactor outlet temperature is 265 ℃; Water: the ethylene feed mol ratio is 0.28-0.30; Typical ethene GHSV is 1250hr ⁽¹⁾Typical water vapour GHSV is 357.6hr ⁽¹⁾

Catalyst keeps 2 weeks of running, during this period, with regular intertrial interval, measures the ethene STY of 20 these methods.The results are shown in following Fig. 9.

From the curve of Fig. 9 as can be seen, with the prior art catalyst, the phosphoric acid (Comparative Examples 13) that for example loads on the Degussa 350 is compared, and the catalyst of embodiment 17 obviously has better activity.

In fact, yield aspects is suitable with the catalyst such as the Grace 57 that load on traditional silica gel at the scene for the performance of embodiment 17.Yet as shown in the result of embodiment 19 and Comparative Examples 20 (following), aspect attrition resistance, the catalyst of embodiment 17 obviously is better than Grace 57.

After the use, find that the lamellar body breaking strength of catalyst is brought up to 169.4N (using catalyst) from 92.6N (fresh catalyst).This advantageously is equivalent to load on the breaking strength of the catalyst on the Degussa 350, and its fresh and breaking strength used catalyst are respectively 77N and 148N.

The used catalyst of also finding embodiment 17 is different with the pore-size distribution (PSD) of fresh catalyst.Through after the test run, it is one wide unimodal to find that carrier with mistake has at the 171nm place.Although the PSD of this carrier is open, the carrier of itself and prior art is in various degree such as Degussa 350.After the use, find that Degussa 350 carriers have bimodal at 200nm and 3000nm place.

Embodiment 19

The attrition resistance of embodiment 17 catalyst uses amount preceding and dust/particle (tiny) that the use back produces to measure by measuring.

When fresh catalyst sieves with 2mm, when the fine powder of collection carries out weighing with assay balance, find only to produce the particulate of 0.05%wt.

After moving for 2 weeks, sieve filtering catalyst with 2mm.The fine powder of collecting carries out weighing with assay balance.Only produce the particulate (some of them shift out catalyst and produce from reactor, rather than technology produces) of 0.6%wt.

Comparative Examples 20

In this embodiment, the attrition resistance that loads on the phosphoric acid catalyst on silica gel (Grace 57) carrier is to measure with the method for embodiment 19.

After moving for 2 weeks, with 2mm sieve screening silica-gel catalyst.The fine powder of collecting carries out weighing with assay balance.Produce the fine powder of 10 weight %.

The comparing result of embodiment 19 and Comparative Examples 20 shows that the catalyst of embodiment 18 obviously is better than Grace 57 aspect attrition resistance.

Embodiment 21

Since with titanium add in the catalyst carrier can stable carrier physical arrangement, not run off from carrier be important to titanium in course of reaction.Therefore, use the Ti content of the used catalyst sample of x-ray fluorescence analysis embodiment 18.The result with do not use the Ti content of catalyst to compare.Should be pointed out that in order to remove the titanium of orthophosphoric acid catalyst and any dissolving, before analyzing, used catalyst is handled with Suo Gesi Li Te (Soxhlet) extractor.

For the first time in service, the Ti content of carrier is reduced to 3.8%wt/wt slightly from 4.0.Yet, residual about 3% phosphorus of used catalyst, so variation has taken place in the bulk density of carrier.When considering this, there is not evidence shows titanium on the carrier loss (in the accuracy rating of XRF technology).

In addition, in Preparation of Catalyst and operation process, there is not evidence to show the leaching of Ti.

Embodiment 22

By mix the 1.0kg pyrogenic silica (

200V,, amorphous from Degussa Huels), 30% the ammonia solution of 60g zirconium hydroxide, 20g methylcellulose, 50g wax, 5g polysaccharide, 10g and the water of 1.85kg prepares catalyst carrier of the present invention.Mediated this mixture about 30 minutes, and extruded subsequently.After 110 ℃ of dryings, in air, calcined this material 3 hours for 850 ℃.The gained extrudate contains the ZrO of 5 weight % ₂SiO with 95 weight % ₂The diameter of extrudate is 4.0mm, and pore volume is 0.97ml/g, and bulk density is 460g/l, and crushing strength is 58N.

The phosphoric acid load of this carrier is heated to 370 ℃ in high-pressure installation, continue about 45 hours, and steam pressure is 15bar in the device.The pore-size distribution of aging catalyst is measured with mercury injection method.Pore-size distribution as shown in figure 10.The diameter in most of hole is less than 5 μ m.

More variation of aforementioned content and change are that significantly it is included in these claims for those of ordinary skills.

Claims

1. catalyst carrier, mainly contain synthetic silica, and one or more oxides or the phosphate of the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series of 0.5-10 weight portion, it is characterized in that the preparation method of described carrier comprises: with oxide particle or the phosphate or the mixing of their precursor of granular synthetic silica and the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series; Forming step and calcining.

2. according to the catalyst carrier of claim 1, mainly contain synthetic silica, and 0.5-10 parts by weight of titanium oxide and/or zirconium dioxide, the preparation method who it is characterized in that described carrier comprises: with granular synthetic silica and granular titanium dioxide and/or zirconium dioxide, or the mixing of their precursor, carry out forming step and calcining.

3. according to the catalyst carrier of claim 1, wherein in the carrier after calcining, the content of synthetic silica is at least 80%.

4. according to the catalyst carrier of claim 1 or 2, wherein in the carrier after calcining, at least 50% the titanium dioxide and/or the zone of zirconium dioxide are less than 2 μ m.

5. will go 1 or 2 catalyst carrier according to right, wherein in the carrier after calcining, at least 50% the titanium dioxide and/or the zone of zirconium dioxide are less than 1 μ m.

6. according to the catalyst carrier of claim 1 or 2, wherein in the carrier after calcining, at least 50% the titanium dioxide and/or the zone of zirconium dioxide are less than 0.8 μ m.

7. according to the catalyst carrier of claim 1 or 2, wherein in the carrier after calcining, at least 90% the titanium dioxide and/or the zone of zirconium dioxide are less than 0.8 μ m.

8. according to the catalyst carrier of claim 1, wherein synthetic silica contains pyrogenic silica.

9. according to the catalyst carrier of claim 1, wherein synthetic silica all is a pyrogenic silica.

10. according to the catalyst carrier of claim 1, wherein synthetic silica comprises silica gel.

11. according to the catalyst carrier of claim 1, wherein titanium dioxide comprises pyrogenic titanium dioxide.

12. according to the catalyst carrier of claim 1, wherein titanium dioxide all is pyrogenic titanium dioxide.

13. according to the catalyst carrier of claim 1, wherein titanium dioxide comprises precipitated titania.

14. according to the catalyst carrier of claim 1, wherein titanium dioxide all is precipitated titania.

15. according to the catalyst carrier of claim 1, wherein zirconium dioxide comprises the pyrolysismethod zirconium dioxide.

16. according to the catalyst carrier of claim 1, wherein zirconium dioxide all is the pyrolysismethod zirconium dioxide.

17. according to the catalyst carrier of claim 1, wherein zirconium dioxide comprises the precipitation zirconium dioxide.

18. according to the catalyst carrier of claim 1, wherein zirconium dioxide all is the precipitation zirconium dioxide.

19. according to the preparation method of the catalyst carrier of claim 1, it is included in before the forming step with the graininess synthetic silica with based on the gross weight of carrier is that the oxide particle of the element that is selected from IIA, IIIB, IVB, VB, VIB, VIIB, VIII, IB, IIB, IIIA, IVA family and lanthanide series of 0.5-10 weight portion or phosphate or their precursor mix; The material of forming step and calcining moulding in 400-1050 ℃ of scope.

20. according to the preparation method of the catalyst carrier of claim 2, it is included in before the forming step particulate silica and counts the particulate titanium dioxide of 0.5-10 weight portion and/or zirconium dioxide or their precursor based on the gross weight of carrier and mix; The material of forming step and calcining moulding in 400-1050 ℃ of scope.

21. a catalyst, its gross weight based on dry catalyst that contains on the catalyst carrier that loads on claim 1 is the phosphoric acid of 5-55 weight %.