CN101623632A - Catalyst for removing hydrocarbon impurities in carbon dioxide, preparation method and application - Google Patents
Catalyst for removing hydrocarbon impurities in carbon dioxide, preparation method and application Download PDFInfo
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- CN101623632A CN101623632A CN200810116293A CN200810116293A CN101623632A CN 101623632 A CN101623632 A CN 101623632A CN 200810116293 A CN200810116293 A CN 200810116293A CN 200810116293 A CN200810116293 A CN 200810116293A CN 101623632 A CN101623632 A CN 101623632A
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Abstract
The invention discloses a catalyst for removing hydrocarbon impurities in carbon dioxide waste gas discharged by an industrial device, which mainly takes theta, delta-mixed crystal alumina as a carrier, comprises 0.01 to 3.0 percent of active component and 0.10 to 20 percent of assist agent Sn based on 100 percent by weight of the catalyst, and has the specific surface area between 60 and 140m<2>/g and the pore volume between 0.50 and 0.70ml/g. The invention provides a preparation method for the catalyst. The catalyst has high oxidant activity on carbon oxide and hydrocarbon, can purify the hydrocarbon of 6,000 ppm (methane of 4,500 ppm) in the carbon dioxide to lower than 10 ppm at an air speed of 10,000h<-1> and a reaction temperature below 420 DEG C, and has the residual oxygen between 0.2 and 0.3 percent.
Description
The application is that last the applying date is on October 25th, 2005, and application number is 200510114256.6, and denomination of invention is divided an application for " being used for removing catalyst, preparation method and the application of carbon dioxide hydrocarbon impurities " patent application.
Technical field
The present invention relates to a kind of Catalysts and its preparation method, application that is used for removing the carbon dioxide hydrocarbon impurities, this catalyst is specially adapted to remove hydro carbons and carbon monoxide in the industrial carbon dioxide waste gas, thereby obtains food-grade carbon-dioxide.This catalyst also can be used for the purified treatment of other organic exhaust gas.
Background technology
The carbon dioxide that contains a large amount of high concentrations in some process units exhaust gas discharged, as oil plant device for producing hydrogen, synthetic ammonia installation, glycol unit, coal gas, sweat etc., the gas concentration lwevel of some device discharging wherein contains flammable impurity such as a small amount of hydro carbons, carbon monoxide more than 95%, these impurity can be removed by the method for catalytic combustion, obtain the high-pureness carbon dioxide of hydrocarbonaceous, remove other impurity through purification again, obtain food-grade carbon-dioxide less than 10ppm.This is an environmental benefit type technology.
China's carbon dioxide aboundresources, but have only the small part carbon dioxide to obtain recycling, a large amount of high concentration carbon dioxides directly enter in the atmosphere, and promptly contaminated environment causes the waste of resource again.
Carbon dioxide is mainly used in industries such as welding, fire-fighting, environmental protection, food product refrigeration and storage, soda, beer.In recent years, China's carbon dioxide demand is in continuous growth, and wherein the food-grade carbon-dioxide demand increases very fast.Adopt the method for catalytic combustion to remove impurity such as micro-hydrocarbon and carbon monoxide in the carbon dioxide, have the purifying rate height, combustion reaction temperature is low, does not produce characteristics such as secondary pollution.It is the effective means of producing food-grade carbon-dioxide.
Common in the thick carbon dioxide have a CH
4, C
2H
6, C
2H
4, C
3H
8, C
3H
6Reach impurity such as small amount of carbon fourth class hydrocarbon component and carbon monoxide, sulphur, phosphorus, water, each is variant for different source of the gas impurities kinds and quantity.The most dysoxidizable in the contained hydrocarbon component of thick carbon dioxide is CH
4It is active component that hydrocarbon oxidation is generally selected noble metals such as Pt, Pd for use.Because active high, the life-span is long, has stronger practicality.
Carbon dioxide de hydrocarbon catalyst bibliographical information few, " low temperature and special gas " 1999,4, " research of high-purity carbon dioxide preparation " has reported that a kind of Production by Catalytic Combustion Process removes the method for trace methane in the carbon dioxide, ethane, this method employing γ-Al
2O
3Carried noble metal is at air speed 1400h
-1, contain methane 3000ppm in the raw material, ethane 300ppm, purify to the reaction temperature of 1ppm be 380 ℃ in methane, 331 ℃ in ethane.
The practical both at home and abroad at present catalyst that removes micro-hydrocarbon in the carbon dioxide mostly is Pd/Al greatly
2O
3Catalyst, active component are single palladium, and support shapes is granular as sphere or column.Though this type of catalyst is active good, is not suitable for higher air speed, the beds resistance drop is bigger under high-speed.
For obtaining higher activity, on catalyst appearance, also have and adopt hollow cylinder, trilobal and corrugated cylinder, to increase the voidage between carrier, improve the utilization rate of outer surface.As United States Patent (USP) 4,441,990,3,966,644, CN85 1 08965.
In addition, the introducing of Sn can improve catalyst performance, and Sn generally is used for reforming and certain embodiments, also be used in recent years in the combustion catalyst research, as United States Patent (USP) 5302365, the compound that Sn and Nd, Gd, Mn form has good heat-resistant and activity for methane oxidation.
Summary of the invention
Catalyst of the present invention consists of: in total catalyst weight is 100%, contain active component Pd or and Pt 0.01～3.0%, auxiliary agent Sn 0.10～20%, specific area 60～140m
2/ g, pore volume 0.50～0.70ml/g; Wherein active component Pd or and Pt content is preferably 0.1～1.0%, Sn is preferably 1.0～10%; Active component is palladium or platinum, palladium bi-component; Catalyst carrier is Al
2O
3, also contain the rare earth oxide that accounts for total weight of carrier 0.2～10.0% in the carrier.Platinum and palladium are preferably between 0～5.0 by atomic ratio in the catalyst activity component.Sn preferably adds with water-soluble Sn salt form, can select SnCl
22H
2O, SnCl
45H
2O, SnSO
4In a kind of, particularly add during carrier in preparation.This catalyst outward appearance is Φ 2.0～Φ 4.0 trilobal strips, tooth sphere preferably.
The present invention also provides a kind of this Preparation of catalysts method, adopt infusion process, the preparation palladium or and platinum solution, carrier is immersed, and dip time is 15～60 minutes, and drying, activation make catalyst, wherein the catalyst baking temperature is 90～120 ℃, be 3～20 hours drying time, 400～600 ℃ of activation temperatures, and soak time is 3～6 hours.When containing palladium and platinum simultaneously, Preparation of Catalyst also can adopt step impregnation method, first platinum-impregnated, and after drying, the roasting, palladium-impregnated again.Or first palladium-impregnated, after drying, the roasting, platinum-impregnated again.
Aluminium oxide is preferably with θ, δ-Al in the catalyst carrier
2O
3It is main mixing crystal formation, and bulk density is 0.60～0.80g/cm
3, specific area 80～120m
2/ g, pore volume 0.50～0.70ml/g, auxiliary agent Sn preferably add when the preparation carrier.
The preparation method of catalyst carrier can adopt universal method, and the method for optimizing that the present invention recommends is at Al
2O
3Add peptizing agent in the dry glue powder, extrusion aid and water are pinched into plasticity material group in kneader, through extrusion modling, can be tooth spherical, also can be the trilobal strip, drying, roasting make this catalyst carrier.
Peptizing agent mainly provides an acid environment, aluminium hydroxide is reacted with it generate aluminium colloidal sol, improves the caking property of storeroom, improves support strength, therefore has acid getting final product.Peptizing agent can be selected one or more in inorganic acid, organic acid, the polyacid for use, and as being general nitric acid, phosphoric acid, acetic acid, citric acid etc., addition is generally 1～10% of total weight of carrier.Recommend among the present invention to contain nitric acid and acetic acid in the carrier peptizing agent.
Adding extrusion aid can make material group extrude smooth surface easily.Extrusion aid can be selected general sesbania powder, starch, methylcellulose, carbon dust, citric acid etc. for use, also can be wherein two kinds of uses simultaneously.The effect that has pore-creating and peptization is simultaneously also arranged, as citric acid in the extrusion aid.Addition is generally 1～10% of total weight of carrier.
The carrier roasting can make carrier remove volatile components by thermal decomposition, forms stable pore structure, specific surface, crystal formation and mechanical strength.900～1100 ℃ of this catalyst carrier sintering temperatures of the present invention, preferably 950～1050 ℃, roasting time is 3～10 hours, is preferably 3～6 hours.In the catalyst carrier, also added rare earth oxide, as the oxide of lanthanum or cerium, preferably addition is for accounting for total weight of carrier 0.2～10.0%, to improve catalyst performance.
Catalyst of the present invention is not specially limited the shape of carrier, is preferably the tooth sphere of φ 2～φ 4, and the hole of φ 0.3～0.5 is particularly arranged in the middle of the tooth ball, and the number of teeth is 4～8 better; Also can be trilobal strip, column, adopt the extrusion moulding preparation.Catalyst carrier shape of the present invention is preferably the tooth sphere of hollow, compares with traditional sphere or cylindrical catalyst, and external surface area is big, active high, the beds pressure drop is low, can be fit to higher air speed, when effectively reducing the beds resistance drop, improved catalyst activity.
Catalyst of the present invention mixes Sn in the carrier, compares with single Pd catalyst, and is higher for the hydrocarbon oxidation activity, exists the concerted catalysis effect between Pd in the catalyst and the Sn.Sn is good cocatalyst component.This catalyst is under 0.2～0.3% the condition, effectively to remove methane, ethane, propane, ethene, propylene and carbon monoxide in the carbon dioxide at residual oxygen.Controlling residual oxygen is 0.2～0.4%, the too high energy consumption that can increase after-treatment system of residual oxygen concentration.
Catalyst of the present invention, the carrier rerum natura is stable, the intensity height, active component is evenly distributed, and is eggshell shape and distributes, and is active high, has practicality.The present invention also provides a kind of this catalyst application process, and its service condition is: air speed 3000～10000h
-1, reaction temperature is below 420 ℃, unstripped gas total hydrocarbon content 3000～10000ppm (with methanometer), residual oxygen are 0.2～0.4%.Be used for removing micro-hydro carbons of industrial carbon dioxide and carbon monoxide, reaction temperature is low, and is active high, the purifying rate height.This catalyst also can be used for purifying industrial organic waste gas.
The specific embodiment
Use raw material source and specification:
Al
2O
3Dry glue powder: the dry glue powder that adopts petrochemical industry Xiang prosperous company in Lanzhou to produce, wherein boehmite accounts for more than 80% of raw material weight, specific area 200m
2More than/the g, impurity natrium content is less than 0.2%.
Total hydrocarbon mole number in conversion ratio=(total hydrocarbon mole number in total hydrocarbon mole number in the waste gas-purification back waste gas) * 100%/waste gas
Total hydrocarbon content: the total amount of hydrocarbon in the waste gas (amounting to into methane), gas chromatography determination, quantitative with methane standard gas external standard method.
Embodiment 1:
Take by weighing 200g Al
2O
3Dry glue powder mixes with 8g sesbania powder, pours in the kneader and mixes 5 minutes.With deionized water dissolving 10g SnCl
45H
2O and 5g citric acid, and add 1.5ml nitric acid.To contain Sn solution and join Al
2O
3In the batch mixing, with Al
2O
3Powder was mediated about 15 minutes, and extrusion modling is φ 4 tooth balls, and the number of teeth is 6, and 0.5 hole is arranged in the middle of the tooth ball.100～120 ℃ of forced air dryings 5 hours, carrier was made in 980～990 ℃ of roastings in 4 hours.
Take by weighing carrier that 100g makes and immerse and contain in the Pd 0.32g solution, take out after 30 minutes, drain away the water, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst of the present invention.In this catalyst, Pd accounts for 0.3% of catalyst weight, and Sn accounts for 2.3% of catalyst weight, and carrier is θ, δ-Al
2O
3Mix crystal formation.Catalyst specific surface 103m
2/ g, pore volume 0.63cm
3/ g.
The gained catalyst is estimated with fixed-bed reactor.Loaded catalyst 50ml, total hydrocarbon content adopt the on-line analysis of HP-5890 gas chromatograph, and oxygen content adopts the GC-14C gas chromatograph on-line analysis of Tianjin, island.
Test is with certain industry CO of factory
2Be unstripped gas, CO
2Purity 98.2%, total hydrocarbon content are 6000ppm (with methanometer), and the hydrocarbon component has CH
4, C
2H
6, C
2H
4, C
3H
8, wherein containing the about 4500ppm of methane, control purifies in the gas of back oxygen content at 0.2～0.3% (vol) in the test.At air speed 10000h
-1Under the condition, the reaction temperature under the differentiated yields is: T
10=262 ℃ of T
30=313 ℃ of T
50=335 ℃ of T
70=348 ℃ of T
90=364 ℃ of T
99=398 ℃ of T
99.9=415 ℃
Embodiment 2:
Take by weighing 200g Al
2O
3Dry glue powder mixes with 10g starch, pours in the kneader and mixes 5 minutes.With deionized water dissolving 12g SnCl
45H
2O, and add 2.0ml acetic acid and 15ml 25% Ludox.To contain Sn solution and join Al
2O
3In the batch mixing, with Al
2O
3Powder was mediated about 15 minutes, and extrusion modling is φ 4 tooth balls, and the number of teeth is 6, and 0.5 hole is arranged in the middle of the tooth ball.100～120 ℃ of forced air dryings 5 hours, carrier was made in 1000～1010 ℃ of roastings in 4 hours.
Take by weighing carrier that 100g makes and immerse and contain in the aqueous solution of palladium bichloride, take out after 30 minutes, drain away the water, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.The carrier that will soak palladium immerses in the aqueous solution that contains chloroplatinic acid again, take out after 20 minutes, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace, make catalyst of the present invention.In this catalyst, Pd accounts for 0.15% of catalyst weight, and Pt accounts for 0.15% of catalyst weight, and Sn accounts for 2.4% of catalyst weight, and carrier is θ, δ-Al
2O
3Mix crystal formation, catalyst specific surface 98m
2/ g, pore volume 0.60cm
3/ g contains SiO in the carrier
23.2%.
The gained catalyst adopts with embodiment 1 same procedure and estimates on fixed-bed reactor.Loaded catalyst 50ml.
Test is identical with embodiment 1 with process conditions with unstripped gas, and the reaction temperature under the differentiated yields is: T
10=249 ℃ of T
30=303 ℃ of T
50=310 ℃ of T
70=337 ℃ of T
90=341 ℃ of T
99=379 ℃ of T
99.9=406 ℃
Embodiment 3:
Take by weighing 200g Al
2O
3Dry glue powder mixes with 8g sesbania powder, mixes 5 minutes in kneader.With deionized water dissolving 12g SnCl
45H
2O and 5g La (NO
3)
3NH
2O, and add 2.0ml acetic acid.With Al
2O
3Powder was mediated about 15 minutes, and extrusion modling is φ 3.2 trilobal cross strips.100～120 ℃ of forced air dryings 5 hours, carrier was made in 1000～1010 ℃ of roastings in 4 hours.
Take by weighing the carrier that 100g makes with said method, immerse and to contain in the mixed solution of Pd, Pt, take out after 40 minutes, drain away the water, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst of the present invention.In this catalyst, Pd accounts for 0.15% of catalyst weight, and Pt accounts for 0.15% of catalyst weight, and Sn accounts for 2.4% of catalyst weight, and carrier is θ, δ-Al
2O
3Mix crystal formation, catalyst specific surface 110m
2/ g, pore volume 0.62cm
3/ g.Carrier contains lanthana 1.5%.
The gained catalyst adopts with embodiment 1 the same terms and estimates down, and the reaction temperature under the differentiated yields is: T
10=255 ℃ of T
30=308 ℃ of T
50=316 ℃ of T
70=342 ℃ of T
90=347 ℃ of T
99=382 ℃ of T
99.9=413 ℃.
Embodiment 4:
Take by weighing 200g Al
2O
3Dry glue powder mixes with 8g sesbania powder, pours in the kneader and mixes 5 minutes.Get 4ml acetic acid, 5g citric acid dissolving back adding 7.0g SnCl
22H
2O is made into the certain density Sn of containing solution, joins Al
2O
3In the batch mixing, with Al
2O
3Powder was mediated about 15 minutes, and extrusion modling is φ 3.2 trilobal cross strips.100～120 ℃ of forced air dryings 12 hours, 980～990 ℃ of roastings 4 hours.
Take by weighing carrier that 100g makes and immerse and contain in the aqueous solution of palladium bichloride, take out after 30 minutes, drain away the water, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.The carrier that will soak palladium immerses in the aqueous solution that contains chloroplatinic acid again, take out after 20 minutes, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace, make catalyst of the present invention.In this catalyst, Pd accounts for 0.15% of catalyst weight, and Pt accounts for 0.15% of catalyst weight, and Sn accounts for 2.5% of catalyst weight, and carrier is θ, δ-Al
2O
3Mix crystal formation, catalyst specific surface 93m
2/ g, pore volume 0.56cm
3/ g.
The gained catalyst adopts with embodiment 1 the same terms and estimates down, and the reaction temperature under the differentiated yields is: T
10=258 ℃ of T
30=314 ℃ of T
50=321 ℃ of T
70=354 ℃ of T
90=362 ℃ of T
99=390 ℃ of T
99.9=422 ℃.
Embodiment 5:
Take by weighing 200g Al
2O
3Dry glue powder mixes with 8g sesbania powder and 16g cerium hydroxide, mixes 5 minutes in kneader.With deionized water dissolving 6g citric acid, and add 1.5ml nitric acid.With Al
2O
3Powder was mediated about 15 minutes, and extrusion modling is a φ 3.2mm trilobal cross strip, 100～120 ℃ of forced air dryings 12 hours, and 990～1000 ℃ of roastings 4 hours.
Take by weighing carrier that 100g makes and immerse and contain in the solution of Sn 1.0%, 100～110 ℃ dry 5 hours down, 600 ℃ of following roastings are 3 hours in muffle furnace.The Sn catalyst of making that contains immerses and contains among the Pd solution 0.32g, takes out after 30 minutes, drain away the water, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst of the present invention.This catalyst contains Pd, and 0.3%, contain Sn 0.3%, catalyst specific surface 96m
2/ g, pore volume 0.58cm
3/ g.Carrier oxidation-containing cerium 7.0%.
The gained catalyst is estimated on fixed-bed reactor.Loaded catalyst 50ml.
Test is methane and air and nitrogen with raw material, and oxygen content is at 0.2～0.3% (vol) in the gas of control purification back.At air speed 6000h
-1Under the condition, the reaction temperature under the differentiated yields is: T
10=286 ℃ of T
30=319 ℃ of T
50=337 ℃ of T
70=363 ℃ of T
90=385 ℃ of T
99=410 ℃ of T
99.9=436 ℃
Comparative example 1:
Take by weighing 200g Al
2O
3Dry glue powder mixes with 8g sesbania powder, pours in the kneader and mixes 5 minutes.With deionized water dissolving 5g citric acid.And add 1.5ml nitric acid, with Al
2O
3Powder was mediated about 15 minutes, and extrusion modling is φ 4 tooth balls, and the number of teeth is 6, and 0.5 hole is arranged in the middle of the tooth ball.100～120 ℃ of forced air dryings 12 hours, 980～990 ℃ of roastings 4 hours.Carrier is θ, δ-Al
2O
3Mix crystal formation.
Take by weighing carrier that 100g makes and immerse and contain among the Pd solution 0.32g, take out after 30 minutes, drain away the water, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst of the present invention.This catalyst contains Pd 0.3%, and catalyst does not contain Sn.The catalyst specific surface 108m that makes
2/ g, pore volume 0.62cm
3/ g.
The gained catalyst adopts with embodiment 1 the same terms and estimates down, and the reaction temperature under the differentiated yields is: T
10=287 ℃ of T
30=309 ℃ of T
50=327 ℃ of T
70=338 ℃ of T
90=370 ℃ of T
99=437 ℃ of T
99.9=467 ℃
Claims (5)
1. a catalyst that is used for removing the carbon dioxide hydrocarbon impurities is characterized in that in total catalyst weight be 100%, contain active component Pd or and Pt 0.01～3.0%, auxiliary agent Sn 0.10～20%, specific area 60～140m
2/ g, pore volume 0.50～0.70ml/g; Wherein active component Pd or and Pt content is 0.1～1.0%, Sn is 1.0～10%; Active component is palladium or platinum, palladium bi-component; Catalyst carrier is Al
2O
3, also contain the rare earth oxide that accounts for total weight of carrier 0.2～10.0% in the carrier.
2. catalyst according to claim 1, it is characterized in that platinum and palladium in the catalyst activity component by atomic ratio between 0～5.0.
3. catalyst according to claim 1 is characterized in that active component content is 0.1～1.0%, and Sn content is 1.0～10%.
4. described Preparation of catalysts method of claim 1, it is characterized in that catalyst adopts immersion process for preparing, preparation palladium or palladium and platinum solution immerse carrier, dip time is 15～60 minutes, drying, activation make catalyst, and wherein the catalyst baking temperature is 90～120 ℃, and be 3～20 hours drying time, 400～600 ℃ of activation temperatures, soak time is 3～6 hours, and wherein, Sn adds when the preparation carrier.
5. the described Application of Catalyst method of claim 1 is characterized in that its service condition is: air speed 3000～10000h
-1, reaction temperature is below 420 ℃, with methanometer, unstripped gas total hydrocarbon content 3000～10000ppm, residual oxygen are 0.2～0.4%.
Priority Applications (1)
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|---|---|---|---|
| CN200810116293A CN101623632A (en) | 2008-07-08 | 2008-07-08 | Catalyst for removing hydrocarbon impurities in carbon dioxide, preparation method and application |
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|---|---|---|---|
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| CN101623632A true CN101623632A (en) | 2010-01-13 |
Family
ID=41519713
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106853368A (en) * | 2015-12-03 | 2017-06-16 | 中国石油化工股份有限公司 | The dehydrogenation of CO unstripped gas refined catalyst, Preparation method and use |
| CN109911851A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of ultra-pure hydrogen purification process |
-
2008
- 2008-07-08 CN CN200810116293A patent/CN101623632A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106853368A (en) * | 2015-12-03 | 2017-06-16 | 中国石油化工股份有限公司 | The dehydrogenation of CO unstripped gas refined catalyst, Preparation method and use |
| CN106853368B (en) * | 2015-12-03 | 2019-09-06 | 中国石油化工股份有限公司 | Catalyst, the Preparation method and use of CO unstripped gas dehydrogenation purification |
| CN109911851A (en) * | 2017-12-12 | 2019-06-21 | 中国科学院大连化学物理研究所 | A kind of ultra-pure hydrogen purification process |
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