CN101371984B - CO removing catalyst as well as preparation method and use thereof - Google Patents
CO removing catalyst as well as preparation method and use thereof Download PDFInfo
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- CN101371984B CN101371984B CN2007101206529A CN200710120652A CN101371984B CN 101371984 B CN101371984 B CN 101371984B CN 2007101206529 A CN2007101206529 A CN 2007101206529A CN 200710120652 A CN200710120652 A CN 200710120652A CN 101371984 B CN101371984 B CN 101371984B
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Abstract
The present invention relates to a CO removal catalyst in olefin and/or saturated hydrocarbon stream and a preparation method and the application thereof. The catalyst comprises a porous inorganic vector, main active component Au loaded on the vector and at least one aided active component selected from Ce, W, Mg and Mo. The porous inorganic vector is one or more than one selected from La2O3-Al2O3 compound and/or La2O3-TiO2-Al2O3 compound. An impregnation method is adopted by the catalyst to load the active component on the vector. The catalyst has high activity at low temperature. Under the condition that the room temperature reaches 70 DEG C, trace CO in the olefin and/or the saturated hydrocarbon stream can be oxidized into CO2 without the loss of olefin.
Description
Technical field
The present invention relates to a kind of CO and remove Catalysts and its preparation method and application, specifically, the present invention relates to a kind of Catalysts and its preparation method and application that removes trace impurity CO in alkene and/or the saturated hydrocarbons logistics.
Background technology
As everyone knows, in the logistics of polymer grade olefinic monomer, usually contain the CO impurity of content≤5ppm, under this concentration, the existence of CO can make polymerization catalyst poison and lose activity, and CO must be removed before olefinic monomer enters polymerization process.For many years, how from the olefinic monomer logistics, to remove trace amounts of CO, receive personnel's in the industry concern always and carried out a large amount of research work.
Removing CO is C
2-C
4One step of key in the olefin polymetiation process, industrial widely used C at present
2-C
4It is catalytic oxidation that alkene purifies the method that removes CO, is about to contain the C of trace amounts of CO
2-C
4The olefinic monomer logistics contacts with CO selective oxidation catalyst, makes CO change into CO
2Thereby, CO is removed.Employed catalyst mainly is a copper-based catalysts.
Selective oxidation CO in the presence of olefinic monomer is disclosed as CA1115495, and the technology of oxyalkylene monomer not, its catalyst that uses is copper-based catalysts; US5387408 discloses a kind of cupric oxide-aluminium oxide-magnesia catalyst; CN1117956 uses the CuO/ZnO catalyst, removes CO from the alpha-olefin that contains trace amounts of CO and/or saturated hydrocarbon; JP05070376 discloses a kind of method that can remove carbonyl sulfide and carbon monoxide in the propylene simultaneously, uses Al
2O
3-CuO-SiO
2Catalyst, the impurity removal in the 0-80 ℃ of propylene that will contain COS and CO; WO9521146 discloses with Cu and/or Cu/MnO
2Adsorbent, the method for adsorbing and removing carbon monoxide and arsenide from hydrocarbon can make in the hydrocarbon impurity content less than 5ppb; EP537628 also disclose a kind of from alpha-olefin and/or saturated hydrocarbon the copper-based catalysts of removal of carbon monoxide.
Copper-based catalysts has been widely used in industrial production, as the C-18 catalyst that removes starting monomer and the contained trace amounts of CO impurity of other auxiliary gas in the manufacture of polyolefins of Shanghai chemical research institute development; The BR-9201 catalyst of Beijing Chemical Research Institute's exploitation.
Copper-based catalysts generally adopts the coprecipitation method preparation, and the characteristics of its preparation method are: preparation section is long, and consumption of raw materials is big, and is more serious to the damage ratio of environment.Because copper-based catalysts is in use, reaction temperature height (generally at 90～150 ℃), the reaction logistics must be carried out under gas phase state, and this relatively uses for gas-phase polymerization process.But, for liquid phase polymerization technology, if trace impurity CO in the logistics is removed, need add heat transmission equipment on the flow process at device, at first make the liquid phase stream vaporization after, remove CO through purification again, the logistics that is removed CO then liquefies through heat exchanger again, just can enter polymerization process.Owing in the logistics phase transition process, increase heat transmission equipment, make that the device flow process increases, equipment investment increases, also caused operational inconvenience.
Exist above-mentioned weak point just because of Cu-series catalyst, therefore, people begin to seek novel catalyst with the Alloy instead of Copper series catalysts.Since reports such as Haruta in 1987 had good low-temperature oxidation activity with the high-dispersion load Au catalyst of methods such as co-precipitation preparation to CO, Au catalyst began to be subjected to certain concern.
CN1579621A discloses a kind of elimination CO catalyst, and its active component is the gold of 0.1%-5%, the hydroxide of catalyst carrier chosen from Fe, nickel, zinc or manganese.Use this catalyst can be used for eliminating the carbon monoxide of air, aerobic and hydrogen mixed gas.
CN1508233A discloses catalyst for selectivity oxidizing carbon monoxide under a kind of rich hydrogen condition, and it is to be the Al that matrix is loaded with metal oxide containing precious metals with porous honeycomb ceramic, metal alloy honeycomb substrate or other metal plate-like body
2O
3Coating constitutes, at described Al
2O
3Contain the auxiliary agent of metal oxide as catalyst in the coating, and load has minute amount of noble metal, catalyst consists of and contains coating ingredients weight 40-150 gram in every liter; Auxiliary agent metal oxides is CeO
2, MgO, K
2O, ZrO
2, La
2O
3In two or more, account for the 5-30% of coating weight; Noble metal is one or more in rhodium, platinum, ruthenium, the gold, accounts for the 1.0-5.0% of coating weight.This catalyst is suitable for rich H
2In at a lower temperature CO selective oxidation, used honeycomb ceramic integral carrier is applicable to big air speed operation, operating temperature can make CO concentration be reduced to below the 50ppm at 120-200 ℃, even less than 10ppm.Obviously, this catalyst and be not suitable for removing of trace amounts of CO in the olefin stream (less than 5ppm).
WO2005061080, WO2002114746, WO2005089937, patents such as JP2005052718 disclose also that some are differently formed, the Au catalyst of different carriers, but whether all do not mention described Au catalyst is applicable to that CO removes technology in the olefin stream.
Therefore, seek a kind of low temperature that is applicable to and remove the catalyst of CO, be applied to that CO removes in the olefin stream, and alkene is not depleted, and is very necessary.
Summary of the invention
The inventor explores through long term studies, and developing a kind of is the catalyst system of main active component with Precious Metals-Gold, uses catalyst of the present invention at room temperature can remove trace impurity CO in the olefinic monomer logistics.
One object of the present invention is to provide a kind of catalyst that removes the trace amounts of CO in alkene and/or the saturated hydrocarbons logistics.
Before trace amounts of CO removes Catalysts and its preparation method in disclosure and description alkene of the present invention and/or saturated hydrocarbons logistics, it may be noted that the restriction that the invention is not restricted to feature structure described herein, method step and material.
The catalyst that removes CO from alkene and/or saturated hydrocarbons logistics of the present invention is made up of with at least a active component that helps that is selected among cerium Ce, tungsten W and the magnesium Mg with the main active component gold Au that is carried on the described carrier porous inorganic carrier,
Wherein in metallic element weight, the weight content of main active component gold Au is 0.001～4%, is preferably 0.1～3%;
It is described that to help the weight content of active component be 8～15%;
Described weight content is with the total restatement of catalyst;
Described porous inorganic carrier is La
2O
3-Al
2O
3Compound and/or La
2O
3-TiO
2-Al
2O
3Compound.
Described La
2O
3-Al
2O
3La in the complexes carrier
2O
3Weight content be 0.1～15%; Described La
2O
3-TiO
2-Al
2O
3La in the compound
2O
3Weight content be 0.1～15%, TiO
2Weight content be 1～20%; Described weight content is with the total restatement of compound.
More preferably described carrier is La
2O
3-TiO
2-Al
2O
3Compound, wherein TiO
2Weight content be 4～12%, La
2O
3Weight content be 0.1～6%.
In concrete enforcement of the present invention, that the shape of described carrier can be selected from is granular, spherical, profile of tooth, column, strip, is preferably dentation or/and spherical; Its specific surface is 1～200m
2/ g is preferably 60～150m
2/ g.It needs to be noted and in the commercial Application of catalyst of the present invention, preferably use the dentation carrier.This is owing to the increase along with the selective oxidation reaction velocity, and the beds pressure drop increases, to the certain influence of normal running meeting generation of downstream section.When air speed increases, select the dentation carrier for use and select for use the bed pressure drop of the prepared catalyst of spheroid carrier all can increase to some extent, but the spheroid carrier bed pressure drop is faster than gathering way of dentation carrier bed pressure drop.Because dentation is similar to spherical shapes, and the contact external surface area of dentation is more much bigger than spherical, can more help improving the usable floor area of catalyst like this, when the catalyst that uses with volume, the dentation catalyst consumption can reduce significantly and utilization rate increases substantially.Therefore select for use the catalyst of dentation preparing carriers to be better than selecting for use spheroid carrier.
Second purpose of the present invention provides above-mentioned Preparation of catalysts method.
Catalyst of the present invention can adopt the general Preparation of catalysts method preparation in this area, as infusion process, spraying process, coprecipitation etc.; Preferred use infusion process such as equi-volume impregnating or supersaturation infusion process, or spraying method, with described active constituent loading on carrier.
In concrete preparation process, the load of described active component can be carried out step by step, also can carry out synchronously; Preferred Preparation of catalysts method of the present invention may further comprise the steps:
(1) with behind the described described carrier of salt solution impregnation that helps active component, drying, calcination process, standby;
(2) flood the carrier that helps active component with what the salt solution impregnation step (1) of described main active component gold obtained, drying or calcination process obtain described catalyst.
In described step (1), preferred described to help the salting liquid of active component be nitrate, carbonate or muriatic solution, as using cerous nitrate, the aqueous solution of cerous sulfate, the ammonia spirit of wolframic acid etc.; Sintering temperature is 200～800 ℃, is preferably 360～600 ℃.
In described step (2), the metal salt solution of golden Au can use nitrate, carbonate or muriatic solution, is preferably the chloride solution of Au such as gold chloride, four chloraurides, more preferably adopts gold chloride; Preferred activation temperature is 90～600 ℃, is preferably 110～400 ℃.
What specify is: when the solution of each component of preparation, all according to the good reagent of percentage by weight weighing, the maximum water absorption rate with carrier is mixed with an amount of solution with agent dissolves again, then the solution one or many is immersed on the carrier.Should be noted that, preferably when the time with the salt solution impregnated carrier of active component, with carrier the solution of absorbent maximum flood.
In catalyst of the present invention, the lanthanum-titanium of use-aluminium complexes carrier can adopt precipitate gel mixing method preparation, disclosedly in the prior art prepares the compound that titanium-aluminium compound, the method for lanthanum-aluminium compound obtain and may be used to catalyst of the present invention.
Preferred complexes carrier of the present invention is to be raw material with sodium metaaluminate, metatitanic acid and/or lanthanum carbonate, obtain titanium aluminium hydroxide, lanthanum aluminium hydroxide or lanthanum titanium aluminium hydroxide at CO as neutralization under the precipitating reagent, obtain through kneading, method dry, that roasting obtains lanthanum-titanium-aluminium compound again.Concrete preparation process is as follows:
At first,, be added in the finite concentration sodium hydroxide solution, under 120-130 ℃, stirring, make complete reaction, make sodium aluminate solution the powdery aluminium hydroxide of weighing;
Then, as the pure CO that will measure
2Be passed in the sodium aluminate solution when carrying out precipitation reaction with gaseous form with sodium aluminate solution, control pH value≤10, precipitation is neutralized into gel aluminum hydroxide under 55 ℃ of left and right sides conditions of control reaction temperature; When neutralization precipitates near terminal point, under powerful high-speed stirred state, respectively with metatitanic acid and/or lanthanum carbonate solution according to being metered in the sediment, itself and sediment are fully mixed, again through washing, dry, pulverizing, be shaped to strip, spherical and/or dentation particle, after roasting promptly obtains described titanium-aluminium compound, lanthanum-aluminium compound or titanium-lanthanum-aluminium compound.Preferred sintering temperature is 400～1200 ℃, more preferably 600-1000 ℃.
Using the lanthanum-titanium-aluminium complexes carrier of method for preparing is with La
2O
3-TiO
2-Al
2O
3Composite form exists, it and pure Al
2O
3The carrier ratio has the moulding of being easy to, and the stable characteristics of rerum natura.As: because TiO
2And La
2O
3Existence, can make Al
2O
3Heat temperature transition reduces about about 160 ℃, and the heat-resistant stability of carrier has been improved; Can make that also the decentralization of Au is more even.
The 3rd purpose of the present invention provides and a kind of above-mentioned catalyst is applied to alkene, particularly C
2-C
4Remove the method for trace impurity CO in alkene and/or the saturated hydrocarbons.
In the method that removes trace impurity CO of the present invention, the condition that removes trace impurity CO from alkene and/or saturated hydrocarbons logistics comprises: in room temperature～70 ℃, under preferred 10～50 ℃ reaction temperature, pressure is 0.2～3MPa, and air speed is 10～4000hr
-1, the time, the olefin stream that contains CO is contacted with catalyst of the present invention with gaseous state or liquid state, make the selected Catalytic Oxygen of CO wherein change into CO
2, and olefin stream is not oxidized.
The catalyst that removes trace amounts of CO of the present invention in alkene and/or saturated hydrocarbons logistics purification process, has good low temperature active and stability to removing trace impurity CO, and this is that copper-based catalysts can not be compared.
Of the present invention is that the catalyst of main active component is compared with existing copper-based catalysts with noble metal, has following characteristics:
1. catalyst of the present invention is to trace amounts of CO selective oxidation low temperature active height, under normal temperature-50 ℃, only trace amounts of CO is had the catalytic selective oxidation activity, and alkene is not oxidized.
2. catalyst tolerates wet performance of the present invention is good, has the effects such as (as sulfide) of antitoxin thing.
3. catalyst preparation process mild condition of the present invention, method is easy, and handling safety is easy to implement.
4. catalyst of the present invention adds Al with La element and/or titanium element
2O
3In, improved Al
2O
3Heat endurance, and improved the decentralization of noble metal component gold on carrier, it is more evenly distributed.
5. short, the easy operating of the commercial Application cell arrangement flow process of catalyst of the present invention.During in particular for the removing of trace amounts of CO in the liquid phase stream, need not increase phase change device equipment, therefore, catalyst of the present invention has broad prospects for commercial application.
The specific embodiment
Below, further describe the present invention with limiting examples, any improvement or modification that this area insider has done according to above-mentioned spirit, only otherwise leave spirit of the present invention, all within the scope of the present invention and the claim that proposed.
The preparation method of the complexes carrier that the present invention uses is as follows:
With the powdery aluminium hydroxide of weighing, be added in the finite concentration sodium hydroxide solution, under 115 ℃ of stirrings, make complete reaction, make sodium aluminate solution; As the pure CO that will measure
2Be passed in the sodium aluminate solution when carrying out precipitation reaction with gaseous form with sodium aluminate solution, control PH≤10, precipitation is neutralized into gel aluminum hydroxide under 55 ℃ of left and right sides conditions of control reaction temperature; When neutralization precipitates near terminal point, under powerful high-speed stirred state, respectively with metatitanic acid or lanthanum carbonate solution according to being metered in the sediment, itself and sediment are fully mixed, dry through washing, about 120 ℃ then, pulverize, be shaped to strip or dentation particle, promptly get titanium dioxide-aluminum oxide carrier, lanthana-alumina support or the lanthana-titanium dioxide-aluminum oxide carrier of required weight content again through 600～1000 ℃ of roastings.
Preparation of catalysts process in the embodiments of the invention is as described below:
(1) at first accurately weighing 40 restrains described carrier, with the described nitrate that helps active component of the accurate weighing of percentage by weight, add water/or ammonia solvent, make liquor capacity equal the maximum that carrier absorbs, this solution impregnation that will prepare under the room temperature is to carrier, and drying, roasting are standby.
(2) calculate the consumption of gold chloride with the percentage by weight of required Au in the catalyst, accurately the weighing gold chloride adds dissolving with hydrochloric acid, uses aqueous slkali Na
2CO
3And/or KOH transfers the aqueous solution of chloraurate pH value in 6.9～8 scopes, make overall solution volume equal the absorbent maximum of carrier, under the room temperature solution impregnation for preparing is arrived carrier, with the deionized water washing, be catalyst of the present invention in 8 hours about 12 hours and/or through 180～400 ℃ of roastings again through 80～120 ℃ of dryings.
Embodiment 1
At first prepare the lanthanum titanium aluminium composite oxides strip carrier, the concrete operations step is as follows:
1) preparation NaAlO
2Solution: weighing sodium hydroxide 171.25 grams, add water 237.5ml dissolving, under 115 ℃ of stirrings, add 192.5 gram aluminium hydroxides, behind the sufficient reacting, being diluted to concentration is 20wt%, elimination impurity is NaAlO
2Solution.
2) use steel cylinder CO
2As precipitating reagent, at CO
2Slowly be passed into NaAlO under the dividing potential drop 0.13MPa
2In the solution, 55 ℃ of reaction temperatures, neutralization reaches terminal point during PH9.6.Add meta-titanium acid solution 120ml (TiO this moment
2Concentration: 10 grams/100ml), lanthanum carbonate solution 60ml (La
2O
3Concentration: 10 grams/100ml).Fully stirred 40 minutes, slurries after filtration, 120 ℃ of dryings are 6 hours in baking oven, are ground into 200-300 purpose lanthanum-titanium-aluminium hydroxide powder.
3) get above-mentioned powder 100 grams, adding concentration and be 2% aqueous solution of nitric acid fully mediates, be shaped to cylindrical strip or the dentation particle of Φ 2mm with banded extruder, the 950 ℃ of roastings 4 hours in Muffle furnace of dry back, obtain titania weight content and be 8%, the lanthana weight content is lanthana-titanium dioxide-aluminum oxide complexes carrier of 4%, and is standby.
Record the specific surface 126m of above-mentioned carrier with nitrogen absorption (BET) method
2/ g; Mechanical strength is 76.4N/.
Then, after transferring the chlorauric acid solution pH value to be 7.2 with potassium hydroxide solution, under the room temperature chlorauric acid solution 30ml (is 0.0204g/ml in Au concentration) for preparing is immersed on the 40 gram lanthana-titanium dioxide-aluminum oxide compound strip carriers that obtain, through 110 ℃ of dryings 8 hours, promptly obtained the catalyst of weight content in 8 hours through 360 ℃ of roastings, it is referred to as catalyst A for gold 1.53%.
The drying of catalyst in following examples, method of roasting and dipping solution consumption calculate all according to this that example is a benchmark, no longer one by one detailed description.
Embodiment 2
Use the contain TiO identical with embodiment 1
2(8wt%), La
2O
3Lanthana (4wt%)-titanium dioxide-aluminum oxide compound strip carrier 40 grams,
Use the method identical with embodiment 1 that chlorauric acid solution is impregnated on the carrier again, drying promptly gets the catalyst of active component weight content for gold 2.49%, and it is referred to as catalyst B.
Embodiment 3
Use the TiO that contains that the method identical with embodiment 1 prepare
2(8wt%), La
2O
3Lanthana (4wt%)-titanium dioxide-aluminum oxide compound strip carrier 40 grams, under the room temperature with the cerous nitrate solution 30ml for preparing (Ce wherein
2O
3Content 0.133g/ml) be impregnated on the carrier, through 120 ℃ of dryings after 9 hours, 600 ℃ of roastings 8 hours are standby in groom's stove again;
Other condition is identical with embodiment 1, obtains consisting of the catalyst of gold 1.2%, cerium 10%, and it is referred to as catalyst C.
Embodiment 4
Use lanthana-titanium dioxide-aluminum oxide composite oxides strip carrier 40 grams identical, use condition and the preparation method identical, obtain consisting of catalyst golden 2.49%, cerium 10%, it is referred to as catalyst D with embodiment 3 with embodiment 1.
Embodiment 5
Use the lanthana-titanium dioxide-aluminum oxide composite oxides strip carrier 40 identical to restrain with embodiment 1, under the room temperature with the wolframic acid ammonia spirit 30ml for preparing (WO wherein
3Content 0.067g/ml) be impregnated on the carrier, through 120 ℃ of dryings after 9 hours, 600 ℃ of roastings 8 hours in groom's stove again, standby;
Other condition is identical with embodiment 1, obtains consisting of the catalyst of gold 1.175%, tungsten 5%, and it is referred to as catalyst E.
Embodiment 6
Use the lanthana-titanium dioxide-aluminum oxide composite oxides strip carrier identical, obtain consisting of catalyst golden 2.35%, tungsten 5% with the method for embodiment 5 again, it is referred to as catalyst F with embodiment 1.
Embodiment 7
Prepare TiO with the method identical with embodiment 1
2Content is 8% titanium dioxide-aluminum oxide compound dentation carrier.With embodiment 3 method identical with 5, wolframic acid solution is flooded after the cerous nitrate solution for preparing is impregnated into carrier again in elder generation, and is standby after the roasting.
Method with embodiment 1 is impregnated into chlorauric acid solution on the carrier again, must consist of the catalyst of gold 1.21%, cerium 10%, tungsten 5%, and it is referred to as catalyst G.
Embodiment 8
With the TiO identical with embodiment 7
2Content is 8% titanium dioxide-aluminum oxide compound dentation carrier, is cut into 1/2, and other condition is identical with embodiment 1, obtains consisting of the catalyst of gold 2.35%, cerium 10%, tungsten 5%, and it is referred to as catalyst H.
Embodiment 9
With preparing TiO with embodiment 1 identical method
2Content is 5% titanium dioxide-aluminum oxide compound strip carrier, with the identical methods dipping lanthanum nitrate hexahydrate 30ml of embodiment 3 (La wherein
2O
3Content 0.033g/ml) be impregnated on the above-mentioned carrier, through 120 ℃ of dryings after 9 hours, 600 ℃ of roastings 8 hours are standby in Muffle furnace again; Method with embodiment 1 is impregnated into chlorauric acid solution on the carrier again, obtains consisting of the catalyst of gold 1.18%, lanthanum 2.5%, and it is referred to as catalyst I.
Embodiment 10
With preparing TiO with embodiment 1 identical method
2Content is 8% titanium dioxide-aluminum oxide compound dentation carrier.Use condition and the preparation method identical, obtain consisting of the catalyst of gold 1.19%, cerium 9.99%, lanthanum 2.5%, it is referred to as catalyst J with embodiment 3 and 9.
Embodiment 11
With preparing TiO with embodiment 1 identical method
2Content is 5% titanium dioxide-aluminum oxide compound strip carrier, uses condition and the preparation method identical with embodiment 9,5 and 3, obtains consisting of the catalyst of golden 2.5%, lanthanum 2.49%, tungsten 4.38%, cerium 9.99%, and it is referred to as catalyst K.
Comparative Examples (copper-based catalysts)
The CuO/ZnO copper-based catalysts that adopts the preparation of CN1044599C disclosed method as a comparison case, the weight ratio of CuO and ZnO is 30: 70 in the described catalyst.Under identical experimental condition, carry out the catalytic performance examination.The carbon monoxide removal rate the results are shown in Table 1 and table 2.
Embodiment 12
Catalyst A～K, A-0 to A-3 are carried out the catalyst performance examination in liquid phase stream, activity of such catalysts is represented with the CO elimination factor.
The CO elimination factor is calculated as follows: X (%)=[(C1-C2)/C1] * 100
In the formula: X (%)---CO elimination factor;
C1---reactor inlet CO content (ppm);
C2-reactor outlet CO content (ppm).
The performance certification test of catalyst carries out in fixed bed reactors, loaded catalyst 2ml, catalyst grain size 1.5～3mm.Unstripped gas consists of: CO content is 2.45～3.62ppm, and all the other are polymerization-grade propylene.Reaction temperature is at 35～45 ℃, reaction pressure 3.5MPa, liquid hourly space velocity 40hr
-1The elimination effect of carbon monoxide sees Table 1.
Find out by data: when contain＜the liquid propylene material of 4ppmCO is with 40h
-1Flow shows different results when by load on the lanthanum titanium aluminium complexes carrier catalyst that gold and/or cerium tungsten makes being arranged, the Catalyst for CO elimination factor of a load one-component gold is about 86% when 35 ℃ of maximum temperature, the Catalyst for CO elimination factor that contains golden cerium can reach about 94%, tungsten in the load again on this basis, reaction temperature is brought up to 45 ℃, and the CO elimination factor reaches about 99%.
The adding mode of lanthanum has certain influence to catalyst performance, for example: at TiO
2-Al
2O
3Flood catalytic effect that lanthanum makes on the carrier not as with La
2O
3-TiO
2-Al
2O
3The excellent catalytic effect of complexes carrier preparation.So this patent is preferably used La
2O
3-TiO
2-Al
2O
3Compound is a carrier, and last tungsten of dipping and cerium are made Au catalyst respectively again, and the oxidation susceptibility of CO is more satisfactory at low temperatures.
By Comparative Examples as can be seen, copper-based catalysts is not suitable for carbon monoxide oxidation reaction at low temperatures.
The elimination effect of carbon monoxide in table 1 liquid phase stream
Embodiment 13
Catalyst A～K, A-0 to A-3 are carried out the performance examination of catalyst in gaseous stream, activity of such catalysts is represented with the CO elimination factor.CO elimination factor calculating formula is with shown in the embodiment 12.
The performance certification test of catalyst carries out in fixed bed reactors, loaded catalyst 2ml, catalyst grain size 1.5～3mm.Unstripped gas consists of CO content, and all the other are polymer grade ethylene or propylene, and the examination condition is 40 ± 5 ℃ of reaction temperatures, reaction pressure normal pressure, gaseous state air speed 3000hr
-1The elimination effect of carbon monoxide sees Table 2.
The elimination effect of carbon monoxide in table 2 gaseous phase materials
Find out by data in the table 2: when CO content is at 3.26～3.79ppm in the material, at air speed 3000h
-1, reaction temperature is lower than under 50 ℃ the condition, carbon monoxide elimination factor and effect basically identical in liquid phase.Along with the adding of auxiliary agent cerium and tungsten, the carbon monoxide elimination factor improves.This explanation auxiliary agent has played and has disperseed gold, prevents the agglomeration that the one-component gold may take place, and has improved the performance of catalyst.Help the introducing of active component cerium and tungsten, the stability of catalyst is significantly improved.So, the multicomponent catalyst of the low gold content of selection, the adding of cerium and tungsten is effective.
Embodiment 14
Make the pure alumina gel with the method for embodiment 1, drying is shaped to strip carrier, and carrier is through roasting, and gold on the dipping obtains gold content and be 1.2% catalyst after the drying, it is referred to as catalyst A-0.
Embodiment 15
Prepare the titanium dioxide-aluminum oxide compound strip carrier of content of titanium dioxide 5% with the method for embodiment 1, the dipping gold obtains gold content and is 1.18% catalyst, and it is referred to as catalyst A-1.
Embodiment 16
Prepare the lanthana-aluminium oxide strip carrier of lanthanum sesquioxide content 5% with the method for embodiment 1, the dipping gold obtains gold content and is 1.19% catalyst, and it is referred to as catalyst A-2.
Embodiment 17
Prepare the La of content of titanium dioxide 5%, lanthanum sesquioxide content 5% with embodiment 1 same procedure
2O
3-TiO
2-Al
2O
3Strip carrier, the dipping gold, obtaining gold content is 1.21% catalyst, and it is referred to as catalyst A-3.
With the catalyst that hydrogen adsorption-desorption method test implementation example 14-17 obtains, the decentralization of main active component A u, and react in liquid phase stream, the removal efficiency of CO the results are shown in Table 3.
Table 3Ti, La element are to the influence of golden decentralization
| The catalyst numbering | A-0 | A-1 | A-2 | A-3 |
| Gold decentralization % | 50.209 | 69.583 | 72.846 | 120.38 |
| The specific surface m of gold 2/g | 199.04 | 223.72 | 243.49 | 487.36 |
| Jin Jing's granularity nm | 2.68 | 2.063 | 1.549 | 1.138 |
| The removal efficiency of CO | 58.16 | 66.86 | 79.37 | 87.57 |
Find out at La thus
2O
3-TiO
2-Al
2O
3The decentralization of gold is than only using Al on the carrier
2O
3, TiO
2-Al
2O
3Or La
2O
3-Al
2O
3Nearly one times of the decentralization height of gold on the carrier, and the grain size of gold diminishes, the removal efficiency of CO also improves thereupon.Therefore, the decentralization of gold on carrier is very favorable for improving catalyst activity.
Embodiment 18
With the method for embodiment 12 and 13 catalyst A-0, A-1, A-2, A-3 are carried out the performance examination of catalyst in the liquid and gas logistics, the elimination effect of carbon monoxide sees Table 1 and table 2.
CO content is in 3.37～3.62 scopes, at liquid phase material flow 40h in the control material
-1, reaction pressure 3.5MPa, reaction temperature are less than under 45 ± 0.3 ℃ the operating condition, and the elimination factor increase trend of CO is A-0＜A-1＜A-2＜A-3.This decentralization that shows gold on the carrier is high more, and catalytic activity is high more, and therefore, the reactivity worth of catalyst improves.Reaction result in gaseous stream and liquid phase be basically identical as a result.
Claims (9)
1. CO removes catalyst in alkene and/or the saturated hydrocarbons logistics, and it is by porous inorganic carrier and be carried on the main active component gold Au on the described carrier and at least a active component that helps that is selected among cerium Ce, tungsten W, the magnesium Mg is formed,
Wherein in metallic element weight, the weight content of main active component gold Au is 0.001～4%,
It is described that to help the weight content of active component be 8～15%,
Described weight content is with the total restatement of catalyst;
Described porous inorganic carrier is La
2O
3-Al
2O
3Compound and/or La
2O
3-TiO
2-Al
2O
3Compound.
2. CO according to claim 1 removes catalyst, it is characterized in that the weight content of described main active component gold Au is 0.1～3%.
3. remove catalyst according to the described CO of one of claim 1～2, it is characterized in that described carrier is La
2O
3-Al
2O
3Compound and/or La
2O
3-TiO
2-Al
2O
3Compound, wherein,
Described La
2O
3-Al
2O
3La in the complexes carrier
2O
3Weight content be 0.1～15%;
Described La
2O
3-TiO
2-Al
2O
3La in the compound
2O
3Weight content be 0.1～15%, TiO
2Weight content be 1～20%;
Described weight content is with the total restatement of compound.
4. CO according to claim 3 removes catalyst, it is characterized in that described carrier is La
2O
3-TiO
2-Al
2O
3Compound, wherein TiO
2Weight content be 4～12%, La
2O
3Weight content be 0.1～6%.
5. CO according to claim 1 removes catalyst, and the specific surface that it is characterized in that described carrier is 1～200m
2/ g; That its shape is selected from is granular, spherical, in column, strip and the tusk one or more.
6. CO according to claim 5 removes catalyst, and the specific surface that it is characterized in that described carrier is 60～150m
2/ g; It is shaped as dentation or/and spherical.
7. the described CO of one of claim 1～6 removes the Preparation of catalysts method, and it may further comprise the steps:
(1) with behind the described described carrier of salt solution impregnation that helps active component, drying, calcination process, standby;
(2) flood the carrier that helps active component with what the salt solution impregnation step (1) of described main active component gold obtained, drying or calcination process obtain described catalyst.
8. method that removes trace amounts of CO in alkene and/or the saturated hydrocarbons logistics is characterized in that: under the reaction temperature of room temperature～70 ℃, pressure is 0.2～3.0MPa, and air speed is 10～4000hr
-1The time, make the logistics that contains CO remove catalyst and contact with the described CO of one of claim 1～7, make the selected Catalytic Oxygen of CO wherein change into CO
2
9. method according to claim 8 is characterized in that described alkene and/or saturated hydrocarbons logistics are C
2-C
4Alkene and/or saturated hydrocarbons, and the content of the trace amounts of CO in the described logistics is less than 5ppm.
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| CN101371984B true CN101371984B (en) | 2011-08-03 |
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| CN108620059B (en) * | 2018-04-24 | 2020-09-22 | 东营海瑞宝新材料有限公司 | Catalyst for synthesizing alumina matrix by using diethyl toluene diamine loaded with active metal component and application thereof |
| CN109517414B (en) * | 2018-11-23 | 2021-06-29 | 郑州艾比利特节能科技有限公司 | Inorganic antibacterial coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049561A (en) * | 2007-04-29 | 2007-10-10 | 厦门大学 | Gold catalyst of catalytic oxidation of carbon monoxide under low temperature, and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101049561A (en) * | 2007-04-29 | 2007-10-10 | 厦门大学 | Gold catalyst of catalytic oxidation of carbon monoxide under low temperature, and preparation method |
Non-Patent Citations (5)
| Title |
|---|
| Donghui Wang,et al,.,Influence of pretreatment conditions on low-temperatureCOoxidaiton over Au/MOx/Al2O3 catalysts,.Journal of Molecular Catalysis A:Chemical200.2003,200230,232. * |
| J.A.Moma,et al,.Effects of incorporation of ions intoAu/TiO2catalystsforcarbon monoxide oxidation.Topics in catalysis,44 1-2.2007,44(1-2),168. |
| J.A.Moma,et al,.Effects of incorporation of ions intoAu/TiO2catalystsforcarbon monoxide oxidation.Topics in catalysis,44 1-2.2007,44(1-2),168. * |
| Laurent Delannoy,et al,.Preparation of supported gold nanoparticles byamodifiedincipient wetness impregnation method.J.Phys.Chem.B,110.2006,11022471. * |
| Zhen Ma,et al,.Au/MxOy/TiO2 catalysts for CO oxidaiton:promotionaleffectofmain-group,transition,and rare-earth metaloxideadditives.Journal of Molecular Catalysis A:Chemical,273.2007,273189,191. * |
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