CN101448572A - Method for producing chlorine by gas phase oxidation - Google Patents
Method for producing chlorine by gas phase oxidation Download PDFInfo
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- CN101448572A CN101448572A CNA2007800186761A CN200780018676A CN101448572A CN 101448572 A CN101448572 A CN 101448572A CN A2007800186761 A CNA2007800186761 A CN A2007800186761A CN 200780018676 A CN200780018676 A CN 200780018676A CN 101448572 A CN101448572 A CN 101448572A
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Abstract
The invention relates to a method for producing chlorine by catalytic gas phase oxidation of hydrogen chloride with oxygen, a catalyst composition and the use thereof, wherein the catalyst comprises tin dioxide and at least one halogen-containing ruthenium compound.
Description
The present invention relates to by method with oxygen catalytic vapor phase oxidation hydrogen chloride production chlorine, carbon monoxide-olefin polymeric and uses thereof, wherein catalyst comprises tin ash and at least a halogen-containing ruthenium compound.
Is the beginning of industrial chlorine chemistry by Deacon (Deacon) in the method with Oxygen Catalytic Oxidation hydrogen chloride in the exothermic equilibrium reaction of exploitation in 1868:
Yet deacon process is subjected to squeezing strongly of chloric alkali electrolysis.By the almost whole chlorine (Ullmann Encyclopedia of industrial chemistry, the 7th edition, 2006) of electrolytic aqueous solution of salt production.Yet recently the attraction of deacon process improves again because the whole world to the demand growth of chlorine faster than demand to sodium hydrate aqueous solution.The method of passing through oxidation chlorination hydrogen production chlorine irrelevant with the preparation sodium hydrate aqueous solution satisfies this development.In addition, a large amount of acquisition in for example phosgenation reaction that for example prepares in the isocyanates as the hydrogen chloride that closes co-product.
Chloration hydro-oxidation is that chlorine is balanced reaction.The equilbrium position is to being unfavorable for required end product direction migration when temperature increases.Therefore use that to have the catalyst that the highest possible activity carries out reaction at low temperatures be favourable.
First catalyst that is used for oxidation chlorination hydrogen comprises copper chloride or the cupric oxide as active component, and Deacon was described in 1868.Yet these catalyst only have low activity under low temperature (＜400 ℃).Improve reaction temperature and can improve activity really, but disadvantageously active component volatilization at high temperature causes activity of such catalysts sharply to descend.
Nineteen sixty-five has been described first catalyst that comprises the ruthenium catalytic active component that is used for oxidation chlorination hydrogen in DE 1 567 788.In this case, from loading on the RuCl on for example silica and aluminium oxide
3/ SiO
2Beginning.Yet, these RuCl
3/ SiO
2Activity of such catalysts is very low.Claimed among this external DE-A 197 48 299 have ruthenium-oxide or ruthenium mixed oxidization active substances and for example the Ru of titanium dioxide, zirconium dioxide etc. is catalyst based as the various oxides of carrier material.In this connection, the content of ruthenium-oxide be 0.1 weight % to 20 weight %, and the average grain diameter of ruthenium-oxide is that 1.0nm is to 10.0nm.In addition by the Ru catalyst of DE-A 197 34 412 known load on titanium dioxide or zirconium dioxide.Mentioned that for example ruthenium salt, ruthenium-nitrosyl radical complex compound, ruthenium-amine complex, the ruthenium complex or the ruthenium-acetylacetonate complex of organic amine of ruthenium-carbonyl complex, inorganic acid are used for preparing ruthenic chloride and the ruthenium oxide catalysts that comprises titanium dioxide and at least a compound of zirconia described herein to many Ru precursor compounds.In preferred embodiments, adopt the TiO of rutile form
2As carrier.Ruthenium oxide catalysts has quite high activity, but its preparation is expensive and need many operations, for example precipitates, flood subsequently precipitation etc., and industrial its scale expansion is difficult.In addition, ruthenium oxide catalysts also tends to sintering and tends to suffer inactivation thus under the high temperature.
Kai Fa deacon process has many weak points with catalyst up to now.They is active not enough at low temperatures.Improve reaction temperature and may improve activity really, but this causes sintering/inactivation or causes losing catalyst component.
The purpose of this invention is to provide influences oxidation of hydrogen chloride at low temperatures and has highly active catalyst system and catalyzing.Very the catalytic active component and the specific carrier material of particular combinations are realized this purpose by developing.
Be surprised to find that by on purpose loading on halogen-containing ruthenium compound on the tin ash, owing to interact especially between catalytic active component and the carrier, new high activated catalyst is provided, and it especially has high catalytic activity under≤350 ℃ temperature in oxidation chlorination hydrogen.The further advantage of catalyst according to the invention system is that catalytic active component simple and easy and be applied on the carrier with being easy to the expansion scale.In addition, saved the halogen-containing material of catalytic activity has been converted into oxide.
The present invention provides the method for producing chlorine by with oxygen catalytic vapor phase oxidation hydrogen chloride thus, and wherein catalyst comprises tin ash and at least a halogen-containing ruthenium compound.
In preferred embodiments, adopt the carrier of tin oxide (IV), the tin ash of preferred especially rutile structure as catalytic active component.
According to the present invention halogen-containing ruthenium compound is used as catalytic active component.This is a kind of compound, wherein halogen with ion to the covalency form that polarizes in conjunction with ruthenium atom.
Halogen in the halogen-containing ruthenium compound is preferably selected from chlorine, bromine and iodine.Preferred chlorine.
Halogen-containing ruthenium compound only comprises those that be made up of halogen and ruthenium.Yet particularly chlorine or muriatic those are preferred to comprise oxygen and halogen.Especially preferably at least a oxychloride ruthenium compound is used as catalytic active substance.In the context of the present invention the oxychloride ruthenium compound be wherein oxygen and chlorine with ion to the compound of covalency form that polarize in conjunction with ruthenium.Thereby such compound has general composition RuO
xCl
yAccording to the present invention, various such oxychloride ruthenium compounds can adjacent existence in catalyst.The example of the oxychloride ruthenium compound that limits is particularly including following composition: Ru
2OCl
4, RuOCl
2, Ru
2OCl
5And Ru
2OCl
6
Halogen-containing ruthenium compound is to be equivalent to general formula R uCl in particularly preferred method
xO
yMixing cpd, wherein x represents from 0.8 to 1.5 numeral, and y represents from 0.7 to 1.6 numeral.
Preferably can obtain catalytic activity oxychloride ruthenium compound in the context of the invention by a kind of method, this method comprises that at first the aqueous solution of at least a halogen-containing ruthenium compound or suspension are applied to tin ash to be removed then and desolvate.
Other possible method comprises for example hydroxide ruthenium chlorination before or after absorbing on the carrier of not chloride ruthenium compound.
Preferable methods comprises RuCl
3The aqueous solution be applied on the tin ash.
The described tin ash that randomly newly precipitates particularly including solution impregnation that applies with halogen-containing ruthenium compound.
Apply after the halogen-containing ruthenium compound, in order to be converted into preferred oxychloride ruthenium compound at least in part, carry out drying steps usually, it conforms with the destination and carries out under the situation that has oxygen or air.Be converted into ruthenium-oxide for fear of preferred oxychloride ruthenium compound, preferably should under being lower than 280 ℃, carry out drying, especially preferably at least 100 ℃ under the special temperature at least 80 ℃.
Preferable methods is characterised in that, described catalyst can obtain in the following way: at least 200 ℃, preferably at least 220 ℃, especially under preferred at least 250 ℃ to 500 ℃ the temperature, in oxygen containing atmosphere, the tin ash carrier of halogen-containing ruthenium compound is arranged particularly preferably in roasting load under the air especially.
In particularly preferred method, especially after roasting,, be 0.5 to 5 weight % from the ratio of the ruthenium of halogen-containing ruthenium compound with respect to whole carbon monoxide-olefin polymeric, preferred 1.0 to 3 weight %, preferred especially 1.5 to 3 weight %.
If oxygen-free halogen-ruthenium compound will be absorbed as catalytic active substance, can also at high temperature completely cut off oxygen and carry out drying.
Preferably halogen-ruthenium compound is converted into preferred zirconyl oxyhalides ruthenium compound basically in the reactor under being in the oxidation technology condition.Ruthenic chloride-SnO
2The evaluation of the HR-TEM of catalyst (high resolution transmission electron microscope) dot matrix interplanar distance is presented at thus that it is converted into the oxychloride ruthenium under the condition of gaseous oxidation hydrogen chloride.
Preferably can obtain this catalyst by a kind of method, this method comprises the aqueous solution of at least a halogen-containing ruthenium compound or suspension is applied to tin ash, be lower than 280 ℃ of dryings down subsequently, and under the condition of gaseous oxidation hydrogen chloride, activate subsequently, be converted into the oxychloride ruthenium during this period basically.Existing under the situation of oxygen drying of a specified duration more, form many more oxychlorides.
Based on the gross weight of catalyst (catalytic component and carrier), catalytic active component is that the load of halogen-containing ruthenium compound is usually in the scope of 0.1～80 weight %, preferably in the scope of 1～50 weight %, in the scope particularly preferably in 1～20 weight %.
Especially preferably by for example with the suitable precursor compound that exists in solution or the wetting and wet impregnated carrier of precursor compound of liquid or colloidal form, precipitation and coprecipitation, and ion-exchange and gas phase to apply (CVD, PVD) can be that halogen-containing ruthenium compound is applied on the carrier with catalyst component.
Possible promoter being has the metal of alkali effect, for example alkali metal, alkaline-earth metal and rare earth metal, and preferred as alkali is Na and Cs particularly, and alkaline-earth metal, special preferred bases earth metal, especially Sr and Ba.
Promoter can be applied on the catalyst by dipping and CVD method, but be not limited to this, preferably flood, particularly preferably in applying after the main catalyst component.
In order to make the stably dispersing of main catalyst component on carrier, can adopt for example various dispersion stabilizers for example scandium oxide, manganese oxide and lanthana etc., but be not limited to this.Preferred stabilizer floods and/or precipitates with main catalyst component and applies.
According to the present invention used tin ash be commercial the acquisition (for example from Chempur, AlfaAesar) or can be for example alkali precipitation and subsequent drying by stannic chloride (IV) obtain.It has from about 1 especially to 300m
2The BET surface area of/g.
Be exposed to heat (for example surpassing under 250 ℃ the temperature) according to the present invention as the tin ash of carrier and may reduce specific area, this may be attended by activity of such catalysts and reduce.SnO
2The preliminary treatment of carrier may be by for example carrying out 250～1500 ℃ of following roastings, but particularly preferably in 300～1200 ℃.Above-mentioned dispersion stabilizer can also be used to the surface of stabilized chlorine tin at high temperature.
Further the preferable methods feature also is 450 ℃ at the most of reaction temperatures in the catalytic vapor phase oxidation, preferably at the most 420 ℃.
Can be under normal pressure or preferably under the pressure that reduces preferably at 40 to 200 ℃ of dry catalysts.Dry preferred 10min of duration is to 6h.
According to the characteristics of oxidation chlorination catalyst for hydrogen of the present invention is at low temperatures high activity.
The preferred new carbon monoxide-olefin polymeric of use in being called as the catalysis process of deacon process as mentioned above.Here, in exothermic equilibrium reaction with hydrogen chloride oxidation with oxygen so that chlorine to be provided, wherein form water vapour.Normally 180 to 500 ℃ of reaction temperatures, preferred especially 200 to 400 ℃, preferred especially 220 to 350 ℃, and normal reaction pressure is 1 to 25bar, preferred 1.2 to 20bar, preferred especially 1.5 to 17bar, the most preferred 2 to 15bar.Because relate to balanced reaction, demonstrate still at catalyst that operation conforms with purpose under the alap temperature of enough activity.Use the oxygen of hyperstoichiometry quantity to conform with purpose with respect to hydrogen chloride in addition.For example use the oxygen excess of twice to four times usually.Because loss is optionally not dangerous, operating under than the time of staying longer under the normal pressure under the high relatively pressure and therefore, may be favourable economically.
The suitable preferred deacon process that can combine with new catalyst carrier is included in ruthenium-oxide, ruthenic chloride or other ruthenium compound on silica, aluminium oxide, titanium dioxide or the zirconium dioxide as carrier with catalyst.
As replenishing of ruthenium compound, suitable catalyst can also comprise for example compound of gold, palladium, platinum, osmium, iridium, silver, copper or rhenium of other noble metal.Shi Yi catalyst can comprise chromated oxide in addition.
Catalytic oxidation hydrogen chloride can thermal insulation or isothermal or approximate isothermal, intermittently but continuously preferred, as fluid bed or fixed bed process preferably as fixed bed process, particularly preferably in the bundled tube reactor on heterogeneous catalyst with 180 to 500 ℃ of preferred 200 to 400 ℃ of preferred especially temperature of reactor of 220 to 350 ℃, and 1 to 25bar (1,000 to 25,000hPa) carry out under preferred 1.2 to 20bar preferred especially 1.5 to 17bar and especially 2.0 to 15bar the pressure.
The popular response device that carries out catalytic oxidation hydrogen chloride is fixed bed or flowing bed reactor.Preferred catalytic oxidation chlorination hydrogen can also divide several stages to carry out.
In the mode of operation of thermal insulation, isothermal or approximate isothermal, can adopt several reactors that have intercooler unit of series connection, promptly 2 to 10, preferred 2 to 6, preferred especially 2 to 5 and especially 2 to 3.Can add whole oxygen and hydrogen chloride in the upstream of first reactor, perhaps can be dispersed on each reactor and add.Being connected in series of this separate reactors can also be combined in the device.
Another preferred embodiment that is applicable to the device of this method is to adopt structurized catalyst bed, and wherein the catalyst activity streamwise improves.Can realize such catalyst bed structuring to the different degree of impregnation of catalyst carrier or by inert material to the different dilution factors of catalyst by active material.For example can adopt ring, cylinder or the spheroid of tin ash, titanium dioxide, zirconium dioxide or its mixture, aluminium oxide, talcum, pottery, glass, graphite or high-quality steel as inert material.Under the situation of preferred use molded catalyst bodies, inert material preferably should have similar external dimensions.
The formed body of arbitrary shape is suitable to molded catalyst bodies, preferred sheet, annular, cylinder, star, wheel or sphere, and preferred especially annular, cylinder, spheroid or star strand.Preferred spherical.The size of molded catalyst bodies is diameter under the situation of spheroid for example, and perhaps the maximum cross-section width on average is in particular 0.3 to 7mm, very preferably 0.8 arrives 5mm.
As substituting of finely grained catalyst (moulding) body as mentioned above, carrier can also be carrier material monolithic (Monolith), for example is not only " routine " carrier with parallel channels that non-radioactive each other connects; In carrier, have the foam, sponge etc. of three-dimensional contact and have and intersect the carrier of logistics corridor and also belong to monolithic.
Monolithic support can have honeycomb, and can have cross channel structure open or sealing.Monolithic support has the preferred cell density (Zelldicht) of 100 to 900 unit (cpsi) per square inch, and preferred especially 200 to 600cpsi.
For example at " Monoliths in multiphase catalytic processes-aspects andprospects ", F.Kapteijn, J.J.Heiszwolf T.A.Nijhuis and J.A.Moulign, Cattech 3, monolithic in the context of the invention is disclosed in 1999, the 24 pages.
Suitable extra carrier material or the adhesive that is used for carrier especially comprise for example silica, graphite, rutile or anatase structured titanium dioxide, zirconium dioxide, aluminium oxide or their mixture, preferred titanium dioxide, zirconium dioxide, aluminium oxide or their mixture, preferred especially γ-or δ-aluminium oxide or their mixture.Preferred adhesive is aluminium oxide or zirconia.Adhesive can be 1 to 70 weight % based on the ratio of final catalyst, preferred 2 to 50 weight % and 5 to 30 weight % very preferably.Adhesive improves the mechanical stability (intensity) of molded catalyst bodies.
In the particularly preferred modification of the present invention, catalytic active component is present in the actual vector material for example on the surface of tin oxide basically, rather than on the surface of adhesive.
The suitable promoter that is used for extra doped catalyst is for example lithium, sodium, potassium, rubidium and caesium of alkali metal, preferred lithium, sodium and potassium, preferred especially potassium, alkaline-earth metal is magnesium, calcium, strontium and barium for example, preferably magnesium and calcium, special preferably magnesium, and rare earth metal for example scandium, yttrium, lanthanum, cerium, praseodymium and neodymium, preferred scandium, yttrium, lanthanum and cerium, preferred especially lanthanum and cerium, or their mixture.
The conversion per pass of hydrogen chloride can preferably be limited to 15 to 90%, and preferred 40 to 85%, preferred especially 50 to 70%.Unreacted hydrogen chloride can partly or entirely be back to catalytic oxidation hydrogen chloride at after separating.Preferably 1:1 is to 20:1 than the volume ratio of oxygen for Reactor inlet place hydrogen chloride, and more preferably 2:1 is to 8:1, and preferred especially 2:1 is to 5:1.
Can be advantageously the reaction heat of catalytic oxidation hydrogen chloride be used to produce high-pressure steam.This may be used for operational light gasification reactor or destilling tower, particularly the isocyanates destilling tower.
In another step, separate the chlorine that forms.This separable programming generally includes several stages, promptly separates unreacted hydrogen chloride and the optional catalytic oxidation hydrogen chloride that is back to from product gas flow, the dry logistics that mainly comprises chlorine and oxygen that obtains, and from dry logistics, separate chlorine.
The separation of the water vapour of unreacted hydrogen chloride and formation can be implemented by the cooling aqueous hydrochloric acid that condensation is got off from the product gas flow of chloration hydro-oxidation.Also can be in watery hydrochloric acid or water absorbing hydrogen chloride.
Theme of the present invention is that also tin ash is as the purposes of using catalyst carrier with catalyst in the oxygen catalytic vapor phase oxidation hydrogen chloride.
Theme of the present invention in addition also is to comprise the carbon monoxide-olefin polymeric of tin ash and at least a halogen-containing ruthenium compound.
Preferably such composition is characterized in that halogen is selected from chlorine, bromine and iodine series.
Halogen-containing ruthenium compound preferably includes the oxychloride ruthenium compound especially.
The most preferred halogen-containing ruthenium compound is to be equivalent to general formula R uCl
xO
yMixing cpd, wherein x represents from 0.8 to 1.5 numeral, and y represents from 0.7 to 1.6 numeral.
Preferably can obtain this carbon monoxide-olefin polymeric by a kind of method, this method comprises particularly the aqueous solution or the suspension of at least a halogen-containing ruthenium compound are applied to tin ash then except that desolvating.
In this connection, halogen-containing ruthenium compound RuCl especially preferably
3
Preferably can obtain this carbon monoxide-olefin polymeric by a kind of method, this method comprises that the aqueous solution of at least a halogen-containing ruthenium compound or suspension are applied to tin ash is dry under at least 80 ℃ temperature subsequently, preferably at least 100 ℃.
Especially preferably can obtain this carbon monoxide-olefin polymeric by a kind of method, wherein at least 200 ℃, preferably at least 240 ℃, especially under preferred at least 270 ℃ to 500 ℃ the temperature, in oxygen containing atmosphere, the tin ash carrier of halogen-containing ruthenium compound is arranged particularly preferably in roasting load under the air especially.
After roasting, halogen-containing ruthenium compound is 0.5 to 5 weight % with respect to the ratio of whole carbon monoxide-olefin polymeric, preferred 1.0 to 3 weight % especially.
Theme of the present invention also is the purposes of this carbon monoxide-olefin polymeric as catalyst, is used in particular for oxidation reaction, particularly preferably in using in the oxygen catalytic vapor phase oxidation hydrogen chloride as catalyst.
The following example explanation the present invention:
Embodiment
Embodiment 1 (the present invention)
At SnO
2Last load ruthenic chloride
In the round-bottomed flask that has dropping funel and reflux cooler, make the commercial available tin oxide of 20g (IV) (Chempur; Has 4.4m
2The BET surface area of/g) is suspended in the solution of the commercial available n hydration ruthenic chloride of 2.35g in 50ml water, and at room temperature stirs this mixture 180min, stir 120min down at 65 ℃.Filter out excessive solution, and in vacuum drying chamber in 120 ℃ of dry moist solids 4h, in air stream, reach 3 hours in all cases then in 250 ℃ of dry 5g, obtain to load on the ruthenic chloride catalyst on the tin oxide (IV).Amount by the definite Ru of elementary analysis (ICP-OES) is 4.1 weight %, and the amount of Cl is 1.1 weight %.
Embodiment 2 (the present invention):
In the round-bottomed flask that dropping funel and reflux cooler are housed, make the commercial available tin oxide of 20g (IV) (Sigma-Aldrich; Has 15m
2The BET surface area of/g) is suspended in the solution of the commercial available n hydration ruthenic chloride of 2.35g in 50ml water, and at room temperature stirred 60 minutes.Dried up in 60 ℃ of branches in air stream then.In air stream, be carried out at 250 ℃ of roastings 16 hours, obtain to load on the ruthenic chloride catalyst on the tin oxide (IV).Amount by the definite Ru of elementary analysis (ICP-OES) is 3.8 weight %, and the amount of Cl is 1.6 weight %.
Embodiment 3 (comparison):
At silica gel (SiO
2) last load ruthenic chloride
According to the method among the embodiment 1 preparation silica (silica gel 100, the Merck) catalyst of the ruthenic chloride on, and in air stream in 250 ℃ of roasting 3h.Amount by the definite Ru of elementary analysis (ICP-OES) is 4.1 weight %, and the amount of Cl is 0.8 weight %.
Embodiment 4 (comparison):
At titanium dioxide (TiO
2) last load ruthenium-oxide
20g carrier (titanium dioxide: the Sachtleben of manufacturer at room temperature suspends in 1 liter of capacity three-neck flask; 90m
2The BET surface of/g) and use magnetic stirrer.Be dissolved in 1.93gn hydration ruthenic chloride in the 50ml water and add in the suspension.Stirred this suspension then 30 minutes.In 15 minutes, drip after 24g 10% sodium hydrate aqueous solution, further stirred this mixture 30 minutes.In 10 minutes, drip other 12g 10% sodium hydrate aqueous solution then.Then reactant mixture is heated to 65 ℃ and under this temperature, kept 1 hour, when stirring, is cooled to 40 ℃ then.Next filter this suspension and use 50ml water washing solid five times.In vacuum drying chamber in 120 ℃ of dry moist solids 4 hours, then in Muffle furnace in 300 ℃ of roastings 2 hours.Determine that by elementary analysis (ICP-OES) amount of Ru is 4.0 weight %, and the amount of Cl is＜0.2 weight %.
Embodiment 5 (reference):
Adopt the blank test of tin ash
As blank test, replace catalyst and test as described below with tin ash.The small amounts of chlorine that produces is owing to gas-phase reaction.
The catalyst test of embodiment 1～5
In oxidation HCl, use catalyst
The admixture of gas of under 300 ℃, forming the catalyst in the fixed bed in crystal reaction tube (internal diameter 10mm) of flowing through from embodiment 1 to 5 by 80ml/min (STP) hydrogen chloride and 80ml/min (STP) oxygen.Sand flow movable bed by electric heating heats this crystal reaction tube.Behind the 30min product gas flow fed 16% liquor kalii iodide 10min.Use the iodine of 0.1N thiosulfate standard liquid back titration formation then so that the amount of the chlorine of determining to feed.Table 1 shows the result.
Table 1: the activity among the oxidation HCl
Study for a long period of time: the long-time stability that load on the catalyst on the tin oxide
Test catalyst as mentioned above, but prolong experimental period and got a plurality of samples in 10 minutes by the liquor kalii iodide that they is fed 16% concentration from embodiment 1.Find the amount of chlorine shown in Fig. 1.
Embodiment 6
The commercial available n hydration ruthenic chloride of 4.994g is dissolved in 16.62g H
2Among the O.In solution, add average diameter, 45.1m with 1.9mm
2The BET of/g surface and as 15 weight %Al of adhesive
2O
3Spherical SnO
2Formed body 100g, and fully mix up to the complete suppressed by vector absorption of solution.After 1 hour standing time in air stream in 60 ℃ whole night with solid drying.Then this catalyst of 250 ℃ of roastings 16 hours.Amount by the definite Ru of elementary analysis (ICP-OES) is 1.9%, and the amount of Cl is 0.5 weight %.
Only in electron micrograph/analysis (EDX), find on tin oxide, rather than on the surface of aluminium oxide (adhesive), comprise catalytic active substance (oxychloride ruthenium).
The catalyst test of embodiment 6
In oxidation HCl, use this catalyst
In nickel fixed bed reactors (diameter 10mm, length 800mm), 25g is combined from the uncoated carrier of the catalyst of embodiment 6 and 75g.Obtain the fixed bed filler of about 150mm thus.The admixture of gas of under the pressure of 300 ℃ and 4bar, forming this fixed bed filler of flowing through by 56 liters of/hour (STP) hydrogen chloride and 28 liters of/hour (STP) oxygen.Heat this Ni reactor by means of heat-carrying agent.After 30 minutes product gas flow was fed 16% liquor kalii iodide 5 minutes.Use the iodine of 0.1N thiosulfate standard liquid back titration formation then so that the amount of the chlorine of determining to introduce.The catalyst activity of Ji Suaning is 0.40kg thus
C12/ kg
KAT.h.
Compared by the comparable formed body of forming as the tin oxide of carrier material in addition with only, the aluminium oxide that adds as adhesive gives spheric catalyst bigger intensity significantly.
Embodiment 7
Apply Sn
(hollow extrudate, 4x9mm Sasol) are placed in the conical flask that cools off with frozen water, use 93.34g SnCl with 20g aluminium oxide formed body
4Coating also keeps placing 30 minutes.Then with SnCl
4Be decanted in second conical flask.Cover this formed body through dropping funel with 150ml water, and keep placing 30 minutes.The formed body that washes coating in this way with water is dried to constant weight (21.51g) then until neutrality under 60 ℃/10mbar in drying box.Repeat this program once more.Then in Muffle furnace in 750 ℃ of roasting 5g formed bodys 4 hours.
Embodiment 8
Dipping Ru
0.078gn hydration ruthenic chloride (Heraeus) is dissolved in the 0.39ml water, then to wherein adding the carrier that 2.5g prepares in embodiment 7, and fully mix up to solution suppressed by vector absorb.Dip time is 1.5 hours.Then in baking oven (air-oven) in about 5 hours of 60 ℃ of dry moist solids.Output is 2.615g.The ruthenium-containing catalyst for preparing in this way in 250 ℃ of roastings in Muffle furnace is 16 hours then.Ruthenium content is 1.1 weight % based on catalyst material.
Fig. 2 shows the electron scanning micrograph of extrudate cross section.Fig. 3 and 4 shows the distribution of the tin and the ruthenium in this cross section respectively.Consider carrier-free image cross section, can recognize the even distribution of ruthenium in the carrier extrudate.
The catalyst test of embodiment 8
In oxidation HCl, use catalyst
The catalysis test
Under 300 ℃, allow the flow through catalyst of in crystal reaction tube (internal diameter 10mm) embodiment 8 in the fixed bed filler of the admixture of gas formed by 80ml/min (STP) hydrogen chloride and 80ml/min (STP) oxygen.Sand flow movable bed by electric heating heats this crystal reaction tube.After 30 minutes product gas flow was fed 16% liquor kalii iodide 10 minutes.Use the iodine of 0.1N thiosulfate standard liquid back titration formation then so that the amount of the chlorine of determining to introduce.Find 1.46kg
C12/ kg
Kat.h space-time yield.
Claims (27)
1. the method by producing chlorine with oxygen catalytic vapor phase oxidation hydrogen chloride is characterised in that catalyst comprises tin ash and at least a halogen-containing ruthenium compound at least.
2. according to the method for claim 1, be characterised in that as the halogen of halogen selection from chlorine, bromine and iodine series.
3. according to the method for claim 1 or 2, be characterised in that halogen-containing ruthenium compound comprises the oxychloride ruthenium compound.
4. according to the method for claim 3, be characterised in that halogen-containing ruthenium compound is to be equivalent to general formula R uCl
xO
yCompound, wherein x represents from 0.8 to 1.5 numeral, and y represents from 0.7 to 1.6 numeral.
5. according to the method for one of claim 1 to 4, be characterised in that by such method to obtain described catalyst that this method comprises that particularly aqueous solution or the suspension with at least a halogen-containing ruthenium compound is applied to tin ash, and remove and desolvate.
6. according to the method for claim 5, be characterised in that halogen-containing ruthenium compound is RuCl
3
7. according to the method for claim 5 or 6, be characterised in that by such method and can obtain described catalyst, this method comprises the aqueous solution of at least a halogen-containing ruthenium compound or suspension are applied to tin ash, and is dry under at least 80 ℃ temperature subsequently, preferably at least 100 ℃.
8. according to the method for one of claim 1 to 7, be characterised in that described catalyst can obtain in the following way: at least 200 ℃, preferably at least 220 ℃, especially under preferred at least 250 ℃ to 500 ℃ the temperature, in oxygen containing atmosphere, the tin ash carrier of halogen-containing ruthenium compound is arranged particularly preferably in roasting load under the air especially.
9. according to the method for one of claim 1 to 8, be characterised in that especially after roasting, with respect to whole carbon monoxide-olefin polymeric, be 0.5 to 5 weight % from the ratio of the ruthenium of halogen-containing ruthenium compound, preferred 1.0 to 3 weight %, preferred especially 1.5 to 3 weight %.
10. according to the method for one of claim 1 to 9, be characterised in that tin ash to small part preferably all exists with rutile form.
11. according to the method for one of claim 1 to 10, be characterised in that gas phase oxidation of hydrogen chloride is included under 180 to 500 ℃ the temperature by comprising the gas of hydrogen chloride and oxygen, preferred 200 to 450 ℃, preferred especially 220 to 380 ℃.
12. according to the method for one of claim 1 to 11, be characterised in that and under 1 to 25bar pressure, carry out gaseous oxidation, preferred 1.2 to 20bar, preferred especially 1.5 to 17bar and especially preferred 2.0 to 15bar.
13., be characterised in that thermal insulation or isothermal carry out gaseous oxidation particularly adiabaticly according to the method for one of claim 1 to 12.
14. tin ash is as the purposes of the catalyst carrier of using with catalyst in the oxygen catalytic vapor phase oxidation hydrogen chloride.
15. comprise the carbon monoxide-olefin polymeric of tin ash and at least a halogen-containing ruthenium compound.
16., be characterised in that halogen is selected from chlorine, bromine and iodine series according to the composition of claim 15.
17., be characterised in that halogen-containing ruthenium compound comprises the oxychloride ruthenium compound according to the composition of claim 15 or 16.
18., be characterised in that halogen-containing ruthenium compound is corresponding to general formula R uCl according to the composition of claim 17
xO
yMixing cpd, wherein x represents from 0.8 to 1.5 numeral, and y represents from 0.7 to 1.6 numeral.
19. composition according to one of claim 15 to 18, be characterised in that by such method and can obtain this catalyst, this method comprises that particularly aqueous solution or the suspension with at least a halogen-containing ruthenium compound is applied to tin ash, and removes and desolvate.
20., be characterised in that halogen-containing ruthenium compound is RuCl according to the composition of claim 19
3
21. composition according to claim 19 or 20, be characterised in that by such method and can obtain catalyst, this method comprises the aqueous solution of at least a halogen-containing ruthenium compound or suspension are applied to tin ash, and is dry under at least 80 ℃ temperature subsequently, preferably at least 100 ℃.
22. composition according to one of claim 15 to 21, be characterised in that described catalyst can obtain in the following way: at least 200 ℃, preferably at least 220 ℃, especially under preferred at least 250 ℃ to 500 ℃ the temperature, in oxygen containing atmosphere, the tin ash carrier of halogen-containing ruthenium compound is arranged particularly preferably in roasting load under the air especially.
23., be characterised in that especially after roasting, with respect to whole carbon monoxide-olefin polymeric, the ratio of halogen-containing ruthenium compound is 1 to 5 weight %, preferred 1.5 to 3 weight % according to the composition of one of claim 15 to 22.
24. composition according to one of claim 15 to 23, be characterised in that said composition comprises the adhesive that is used for carrier, described carrier is selected from following series: silica, graphite, rutile or anatase structured titanium dioxide, zirconium dioxide, aluminium oxide or their mixture, preferred titanium dioxide, zirconium dioxide, aluminium oxide or their mixture, preferred especially aluminium oxide or zirconia, and wherein adhesive is preferred 1 to 70 weight % based on the ratio of final catalyst, preferred especially 2 to 50 weight %, and 5 to 30 weight % very preferably.
25. according to the composition of one of claim 15 to 24 purposes as catalyst.
26. according to the purposes of claim 25, as the catalyst that is used for oxidation reaction.
27. according to the purposes of claim 25 or 26, in oxygen catalytic vapor phase oxidation hydrogen chloride as catalyst.
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| DE102006024545 | 2006-05-23 | ||
| DE102006024545.8 | 2006-05-23 | ||
| DE102007020154.2 | 2007-04-26 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103167906A (en) * | 2010-08-25 | 2013-06-19 | 拜耳知识产权有限责任公司 | Catalyst and method for the production of chlorine by gas phase oxidation |
| CN115052679A (en) * | 2020-04-01 | 2022-09-13 | 住友化学株式会社 | Catalyst for halogen production, package, and method for producing package |
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2007
- 2007-05-16 CN CNA2007800186761A patent/CN101448572A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103167906A (en) * | 2010-08-25 | 2013-06-19 | 拜耳知识产权有限责任公司 | Catalyst and method for the production of chlorine by gas phase oxidation |
| CN110548526A (en) * | 2010-08-25 | 2019-12-10 | 科思创德国股份有限公司 | Catalyst and process for the production of chlorine by gas phase oxidation |
| CN115052679A (en) * | 2020-04-01 | 2022-09-13 | 住友化学株式会社 | Catalyst for halogen production, package, and method for producing package |
| CN115052679B (en) * | 2020-04-01 | 2023-09-12 | 住友化学株式会社 | Catalyst for halogen production, package, and method for producing package |
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