CN101322947B - Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof - Google Patents
Active carbon supported ruthenium-based ammonia synthetic catalyst and preparation thereof Download PDFInfo
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- CN101322947B CN101322947B CN2008100715437A CN200810071543A CN101322947B CN 101322947 B CN101322947 B CN 101322947B CN 2008100715437 A CN2008100715437 A CN 2008100715437A CN 200810071543 A CN200810071543 A CN 200810071543A CN 101322947 B CN101322947 B CN 101322947B
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention provides an active carbon-supported ruthenium ammonia synthesis catalyst and a preparation method thereof. The catalyst takes active carbon as a carrier and takes ruthenium as an active component; the components of the catalyst are (CA+Ru)-Ba-K/AC and CA-Ru-Ba-K/AC, wherein, CA represents citric acid and AC represents the active carbon; in preparation of the catalyst, the citric acid is selected to carry out the pretreatment of the active carbon and ruthenium chloride; one or more of barium nitrate, potassium hydroxide or potassium nitrate is or are selected as an assistant; the equivalent-volumetric impregnation method is adopted in the preparation method for preparing the catalyst. Compared with the sol-gel method or the oxidation method in the prior art, the invention adopts the citric acid method and has the advantages of simple technique, high preparation efficiency, little energy consumption, cheap raw material and less material consumption, thus being beneficial to greatly lowering the production cost. The devices required by the invention are simple, are easy to be operated, do not need to change the original devices and are easy to realize mass production. The catalyst prepared by the invention has good performance and strong catalytic activity.
Description
Technical field
The invention belongs to the ammonia synthesis catalyst preparing technical field, more specifically relate to a kind of ruthenium-based ammonia synthetic catalyst and preparation method thereof
Background technology
Ammonia synthesis catalyst is a most important catalyst in the ammonia synthesizing industry.The 80s and 90s in last century, people just after deliberation the application of various oxides in ruthenium-based ammonia synthetic catalyst, some early stage documents have been introduced the achievement in research of this part: the main presoma of ruthenium catalyst is Ru
3(CO)
12, RuCl
3, Ru (acac)
2, RuNO (NO
3)
3, RuCl
3Deng, but hindering it, the input that noble metal is high in ruthenium catalyst uses widely.The presoma cost performance significant difference of various rutheniums, the presoma of low price has high cost performance.Generally speaking, adopt Ru in the ruthenium catalyst
3(CO)
12Or other no chlorine presoma rather than ruthenic chloride, because the existence of chlorine may significantly reduce the activity that ruthenium is an ammonia synthesis catalyst.At present, the cost performance of relatively cheap ruthenic chloride Yin Qigao and dechlorination development of technology are subjected to extensive concern.But, to do in the Ru/AC catalyst of presoma at ruthenic chloride, the decentralization of ruthenium is less, and particle size is inhomogeneous, the cost performance that is unfavorable for reducing the consumption of unit mass carrier ruthenium and improves catalyst.
At present, the relevant method that improves the decentralization of ruthenium mainly is to adopt RuCl
3Prereduction and the preliminary treatment of carrier.Some researcher adopts sol-gel process to prepare the ruthenium particle of high degree of dispersion, but present this method inevitably relates to the use of nonaqueous solvents, adverse effects such as the recovery of ruthenium and preparation time are long, hinder it and extensively adopt (W.F.Han, H.Z.Liu, H.Zhu, Catalysis Communications.8 (2007) 351-354; Q.C.Xu, J.D.Lin, X.-Z.Fu, D.W.Liao, CatalysisCommunications.9 (2008) 1214-1218; Shan Wu, Jixin Chen, Xingfang Zheng, Haisheng Zeng, C.Zheng, N.Guan, Chemical Communication. (2003) 2488-2489); Activated carbon oxidation process increases surperficial oxy radical, can improve decentralization (T.Kyotani, S.Nakazaki, W.-H.Xu, A.Tomita, Carbon.39 (2001) 782-785 of ruthenium to a certain extent; K.Hernadi, A.Siska, L.Thien-Nga, L.Forr, I.Kiricsi, Solid State Ionics.141-142 (2001) 203-209; A.N.A.El-Hendawy, Carbon.41 (2003) 713-722; A.H.El-Sheikh, Talanta.75 (2008) 127-134; V.Z.Radkevich, T.L.Senko, K.Wilson, L.M.Grishenko, A.N.Zaderko, V.Y.Diyuk, Applied Catalysis A:General.335 (2008) 241-251).But this method need be used HNO
3, H
2O
2Or O
3Deng handling active carbon, be a kind of consuming time, prepare the high method of expense, in catalyst, be difficult to extensive employing.Adopt citric acid to make auxiliary agent, improve the distribution of ruthenium on active carbon, improve the active sites number of unit mass ruthenium, thereby improve activity of such catalysts, reduce the use amount of unit mass ruthenium catalyst, further reduce the preparation expense of ruthenium catalyst by citric acid.It is that ammonia synthesis catalyst is not seen bibliographical information that citric acid method prepares ruthenium as auxiliary agent.
Summary of the invention
Purpose of the present invention provides a kind of activated carbon supported ruthenium-based ammonia synthetic catalyst and preparation method thereof; under lower ruthenium load capacity; the catalyst of this preparation method's preparation is compared not, and the catalyst activity of adding assistant citric acid has the lifting of increasing; and the raw material that needs is cheap; preparation flow is simple; help reducing cost, accomplish scale production.
Catalyst of the present invention is selected citric acid preliminary treatment active carbon and ruthenic chloride for use in preparation, selecting the barium auxiliary agent for use is barium nitrate, and potassium promoter is a kind of in potassium hydroxide or the potassium nitrate; Described catalyst is carrier with the active carbon, and metal Ru is an active component, catalyst consist of (CA+Ru)-Ba-K/AC, CA-Ru-Ba-K/AC; Wherein CA represents citric acid, and AC represents active carbon, and (CA+Ru) expression citric acid and ruthenic chloride hybrid infusion, CA-Ru represent that the dipping citric acid floods ruthenic chloride more earlier.
Method for preparing catalyst of the present invention is: adopt equi-volume impregnating to prepare catalyst: adopt citric acid ruthenic chloride hybrid infusion method or flood earlier and after heat treatment flood earlier ruthenic chloride again after citric acid floods ruthenic chloride or dipping citric acid again, reduction ruthenic chloride in oven dry back is again with incipient impregnation method dipping auxiliary agent.
The present invention compared with prior art has following remarkable advantage:
A) the present invention prepares ruthenium catalyst employing citric acid method, compare with prior art sol-gel process or oxidizing process, the present invention adopts citric acid significantly to improve the Size Distribution of ruthenium nano particle, make ruthenium particle size distribution interval mainly between 2-2.5nm, this technology is simple, the preparation efficiency height, less energy consumption.
B) it is ruthenic chloride that the present invention adopts the active component presoma, and solvent is a water, and auxiliary agent citric acid cost of material is cheap, and use amount seldom helps reducing production costs significantly.
C) equipment required for the present invention is simple, and operation is easily gone, and does not need to transform existing equipment, realizes large-scale production easily.
D) performance of the catalyst of the present invention's preparation is good, and catalytic activity is strong.
The specific embodiment
Adopt the preparation process of citric acid ruthenic chloride hybrid infusion method to be:
1) with citric acid ruthenic chloride mixed dissolution in water, the mass ratio of citric acid and ruthenic chloride is 1: 0.5～15 in the described mixed solution, the mass fraction of citric acid is 1%～30% in the described mixed solution, the mass fraction of ruthenium is 1.5%～2.5%, with mixed solution incipient impregnation active carbon; With the carried by active carbon body weight is benchmark, and ruthenium content is 3.5～8% of a carried by active carbon body weight in the described catalyst;
2) will heat-treat through the active carbon of dipping, described heat treatment temperature is 100～250 ℃;
3) reduction: the active carbon after Overheating Treatment is reduced, use hydrogen-nitrogen mixture as reducing gas, hydrogen wherein is reducing medium, 450 ℃ of reduction temperatures, 6 hours recovery times;
4) auxiliary agent load: according to the incipient impregnation compounding agent solution: will through the active carbon of reduction step earlier behind the dipping baric solution again dipping contain potassium solution; With the carried by active carbon body weight is benchmark, and the mass fraction of barium and potassium is respectively 2～8% and 0～12% of carried by active carbon body weight in the described catalyst; The mass fraction of barium is 0.5～4% in the described baric solution, and the described mass fraction that contains potassium in the potassium solution solution is 1%～8%;
5) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst.
Adopt the preparation process that elder generation's dipping citric acid floods ruthenic chloride again to be:
1) citric acid and ruthenic chloride are dissolved in the water respectively, the mass ratio of described citric acid and ruthenic chloride is 1: 0.5～15, the mass fraction of citric acid is 1%～30% in the described citric acid solution, the mass fraction of ruthenium is 1.5%～2.5% in the described ruthenic chloride solution, with active carbon earlier the dipping citric acid solution flood ruthenic chloride solution again;
2) will heat-treat through the active carbon of dipping ruthenic chloride solution, described heat treatment temperature is 100～250 ℃;
3) reduction: the active carbon after Overheating Treatment is reduced, use hydrogen-nitrogen mixture as reducing gas, wherein hydrogen is reducing medium, 450 ℃ of reduction temperatures, 6 hours recovery times;
4) auxiliary agent load: according to the incipient impregnation compounding agent solution: will through the active carbon of reduction step earlier behind the dipping baric solution again dipping contain potassium solution; With the carried by active carbon body weight is benchmark, and the mass fraction of barium and potassium is respectively 2～8% and 0～12% of carried by active carbon body weight in the described catalyst; The mass fraction of barium is 0.5～4% in the described baric solution, and the described mass fraction that contains potassium in the potassium solution solution is 1%～8%;
5) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst.
The preparation process of after heat treatment flooding earlier ruthenic chloride behind the employing dipping citric acid again is:
1) citric acid and ruthenic chloride are dissolved in the water respectively, the mass ratio of described citric acid and ruthenic chloride is 1: 0.5～15, the mass fraction of citric acid is 1%～30% in the described citric acid solution, the mass fraction of described ruthenic chloride solution ruthenium is 1.5%～2.5%, with active carbon dipping citric acid solution earlier;
2) will heat-treat through the active carbon of dipping citric acid solution, described heat treatment temperature is 100～250 ℃;
3) will be through heat treated active carbon dipping ruthenic chloride solution;
4) reduction: the active carbon after Overheating Treatment is reduced, use hydrogen-nitrogen mixture as reducing gas, wherein hydrogen is reducing medium, 450 ℃ of reduction temperatures, 6 hours recovery times;
5) auxiliary agent load: according to the incipient impregnation compounding agent solution: will through the active carbon of reduction step earlier behind the dipping baric solution again dipping contain potassium solution; With the carried by active carbon body weight is benchmark, and the mass fraction of barium is 0.5～4% in the described baric solution, and the described mass fraction that contains potassium in the potassium solution solution is 1%～8%;
6) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst.
Heat treatment method is a sintering, and described sintering temperature is 100～250 ℃; Described sintering time is: 3 hours～12 hours; Described sintering gas is an air atmosphere.
Described reduction gas is hydrogen-nitrogen mixture, and the volume ratio of described hydrogen and nitrogen is 3: 1.
Dry infrared lamp or the baking oven of adopting of product behind the described dipping dried.
Embodiment 1
Get 0.22g ruthenium trichloride and 0.08g citric acid and mix that water-soluble (with the carried by active carbon body weight is base, ruthenium and citric acid content be the carried by active carbon body weight 4%), behind citric acid and the ruthenic chloride incipient impregnation active carbon active carbon is dried under infrared lamp, be that 3: 1 mist is 450 ℃ of reduction with the volume ratio of hydrogen and nitrogen again, the equal-volume load auxiliary agent B a of active carbon elder generation after the reduction, equal-volume load K again, the weight content of barium and potassium is respectively 4% and 12% of a carried by active carbon body weight, and barium and potassium presoma are respectively barium nitrate and potassium hydroxide.The mass fraction of barium is 0.5%～4% in the described baric solution, and the described mass fraction that contains potassium in the potassium solution solution is 1%～8%.
Below also can 0.22g ruthenium trichloride and 0.08g citric acid is water-soluble respectively, prepare catalyst according to the preparation method of after heat treatment flooding earlier ruthenic chloride after the dipping citric acid floods ruthenic chloride again or adopts the dipping citric acid earlier again.
Change citric acid and ruthenic chloride interpolation order, the heat treatment mode that changes citric acid and content and change the content of barium potassium in catalyst, can make a series of catalyst.
Embodiment 2
The catalyst activity evaluation is carried out in high pressure active testing device.Reactor inside diameter is the fixed bed of 14mm.Catalyst granules is 12～16 orders, and the heap volume is 2ml, and catalyst is seated in the isothermal region of reactor.Reaction gas is nitrogen and hydrogen mixed gas, and hydrogen nitrogen ratio is 3: 1.Catalyst activity is represented with the volumn concentration of ammonia in the reactor outlet gas.
Embodiment 3
Repeating the process of embodiment 1, is 10000h in the reacting gas air speed
-1, reaction pressure is under the 10MPa condition, investigates the influence of citric acid consumption variation to catalyst activity.Wherein CA2+Ru4 represents that the citric acid consumption is 2%, metal Ru consumption 4%, and all the other implications are identical therewith.
Table 1 citric acid consumption is to the influence (vol%) of outlet ammonia concentration
Embodiment 4
Repeat the process of embodiment 1, the reacting gas air speed is 10000h
-1, reaction pressure is under the 10MPa condition, employing citric acid and the order that ruthenic chloride is mixed or priority adds are investigated the influence of citric acid load order to catalyst activity.
Table 2 citric acid load order is to the influence (vol%) of outlet ammonia concentration
Embodiment 5
Repeat the process of embodiment 1, the reacting gas air speed is 10000h
-1, reaction pressure is under the 10MPa condition, and the following 300 ℃ of heat treatments of first air atmosphere are after 2 hours after the load of investigation citric acid, and the load ruthenic chloride is investigated citric acid content to the influence to catalyst activity again.
Table 3 citric acid content is to the influence (vol%) of outlet ammonia concentration
Embodiment 6
Repeat the process of embodiment 1, the reacting gas air speed is 10000h
-1, reaction pressure is under the 10MPa condition, first load citric acid, and heat treatment is after 2 hours under air atmosphere, the load ruthenic chloride is investigated the influence of heat treatment temperature to the CA4-Ru4-Ba4-K10/AC catalyst activity again.
Table 4 heat treatment temperature is to the influence (vol%) of outlet ammonia concentration
Embodiment 7
Repeat the process of embodiment 1, the reacting gas air speed is 10000h
-1, reaction pressure is under the 10MPa condition, first load citric acid, and under 200 ℃, air atmosphere in heat treatment after 2 hours, the load ruthenic chloride is investigated the influence of different citric acid contents to the CA-Ru-Ba-K/AC catalyst activity again.
Table 5 citric acid content is to the influence (vol%) of outlet ammonia concentration
Embodiment 8
Repeat the process of embodiment 1, the reacting gas air speed is 10000h
-1, reaction pressure is under the 10MPa condition, investigate citric acid and ruthenic chloride elder generation back loading after, load ruthenic chloride again, the mass fraction of citric acid and ruthenium is 4wt%, investigates the influence of ruthenium content to catalyst activity.
Table 6 ruthenium content is to the influence (vol%) of outlet ammonia concentration
Claims (4)
1. the preparation method of an activated carbon supported ruthenium-based ammonia synthetic catalyst, it is characterized in that: described catalyst is selected citric acid preliminary treatment active carbon and ruthenic chloride for use in preparation, and selecting the barium auxiliary agent for use is barium nitrate, and potassium promoter is a kind of in potassium hydroxide or the potassium nitrate; Described catalyst is carrier with the active carbon, and metal Ru is an active component;
Method for preparing catalyst is: adopt equi-volume impregnating to prepare catalyst: adopt citric acid ruthenic chloride hybrid infusion method or flood earlier and after heat treatment flood earlier ruthenic chloride again after citric acid floods ruthenic chloride or dipping citric acid again;
The preparation process of described employing citric acid ruthenic chloride hybrid infusion method is:
1) with citric acid ruthenic chloride mixed dissolution in water, the mass ratio of citric acid and ruthenic chloride is 1: 0.5～15 in the described mixed solution, the mass fraction of citric acid is 1%～30% in the described mixed solution, the mass fraction of ruthenium is 1.5%～2.5%, with mixed solution incipient impregnation active carbon; With the carried by active carbon body weight is benchmark, and ruthenium content is 3.5～8% of a carried by active carbon body weight in the described catalyst;
2) will heat-treat through the active carbon of dipping, described heat treatment temperature is 100～250 ℃;
3) reduction: the active carbon after Overheating Treatment is reduced, use hydrogen-nitrogen mixture as reducing gas, hydrogen wherein is reducing medium, 450 ℃ of reduction temperatures, 6 hours recovery times;
4) auxiliary agent load: according to the incipient impregnation compounding agent solution: will through the active carbon of reduction step earlier behind the dipping baric solution again dipping contain potassium solution; With the carried by active carbon body weight is benchmark, and the mass fraction of barium and potassium is respectively 2～8% and 0～12% of carried by active carbon body weight in the described catalyst; The mass fraction of barium is 0.5～4% in the described baric solution, and the described mass fraction that contains potassium in the potassium solution solution is 1%～8%;
5) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst;
The preparation process that the first dipping of described employing citric acid floods ruthenic chloride again is:
1) citric acid and ruthenic chloride are dissolved in the water respectively, the mass ratio of described citric acid and ruthenic chloride is 1: 0.5～15, the mass fraction of citric acid is 1%～30% in the described citric acid solution, the mass fraction of ruthenium is 1.5%～2.5% in the described ruthenic chloride solution, with active carbon earlier the dipping citric acid solution flood ruthenic chloride solution again;
2) will heat-treat through the active carbon of dipping ruthenic chloride solution, described heat treatment temperature is 100～250 ℃;
3) reduction: the active carbon after Overheating Treatment is reduced, use hydrogen-nitrogen mixture as reducing gas, wherein hydrogen is reducing medium, 450 ℃ of reduction temperatures, 6 hours recovery times;
4) auxiliary agent load: according to the incipient impregnation compounding agent solution: will through the active carbon of reduction step earlier behind the dipping baric solution again dipping contain potassium solution; With the carried by active carbon body weight is benchmark, and the mass fraction of barium and potassium is respectively 2～8% and 0～12% of carried by active carbon body weight in the described catalyst; The mass fraction of barium is 0.5～4% in the described baric solution, and the described mass fraction that contains potassium in the potassium solution solution is 1%～8%;
5) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst;
The preparation process of after heat treatment flooding earlier ruthenic chloride behind the described employing dipping citric acid again is:
1) citric acid and ruthenic chloride are dissolved in the water respectively, the mass ratio of described citric acid and ruthenic chloride is 1: 0.5～15, the mass fraction of citric acid is 1%～30% in the described citric acid solution, the mass fraction of described ruthenic chloride solution ruthenium is 1.5%～2.5%, with active carbon dipping citric acid solution earlier;
2) will heat-treat through the active carbon of dipping citric acid solution, described heat treatment temperature is 100～250 ℃;
3) will be through heat treated active carbon dipping ruthenic chloride solution;
4) reduction: the active carbon after Overheating Treatment is reduced, use hydrogen-nitrogen mixture as reducing gas, wherein hydrogen is reducing medium, 450 ℃ of reduction temperatures, 6 hours recovery times;
5) auxiliary agent load: according to the incipient impregnation compounding agent solution: will through the active carbon of reduction step earlier behind the dipping baric solution again dipping contain potassium solution; With the carried by active carbon body weight is benchmark, and the mass fraction of barium is 0.5～4% in the described baric solution, and the described mass fraction that contains potassium in the potassium solution solution is 1%～8%;
6) drying: the product behind the dipping is dried down at 50-120 ℃ and is prepared into catalyst.
2. the preparation method of ruthenium-based ammonia synthetic catalyst according to claim 1, it is characterized in that: described heat treatment method is a sintering, described sintering temperature is 100～250 ℃; Described sintering time is: 3 hours～12 hours; Described sintering gas is an air atmosphere.
3. the preparation method of ruthenium-based ammonia synthetic catalyst according to claim 1, it is characterized in that: described reduction gas is hydrogen-nitrogen mixture, the volume ratio of described hydrogen and nitrogen is 3: 1.
4. the preparation method of ruthenium-based ammonia synthetic catalyst according to claim 1 is characterized in that: dry infrared lamp or the baking oven of adopting of the product behind the described dipping dried.
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| CN102380420B (en) * | 2011-09-02 | 2013-04-17 | 福州大学 | Ammonia synthesis catalyst and preparation method thereof |
| CN102580778B (en) * | 2012-02-06 | 2014-07-30 | 福州大学 | Ruthenium-based ammonia synthesis catalyst with polyhydroxy ruthenium complex as precursor |
| CN103285863B (en) * | 2012-02-28 | 2015-07-22 | 比亚迪股份有限公司 | Catalyst for preparing dichlorosilane, preparation method of catalyst and preparation method of dichlorosilane |
| CN105597760B (en) * | 2015-12-18 | 2018-03-16 | 福州大学 | It is a kind of to be used to synthesize Co catalysts of ammonia and preparation method thereof |
| CN105457643B (en) * | 2015-12-25 | 2017-12-05 | 湖北大学 | A kind of preparation method of activated carbon supported type catalyst for Electrocatalysis Degradation organic wastewater |
| US20170253492A1 (en) * | 2016-03-01 | 2017-09-07 | Joseph Beach | Electrically enhanced haber-bosch (eehb) anhydrous ammonia synthesis |
| CN108435166A (en) * | 2018-03-22 | 2018-08-24 | 福州大学 | A kind of preparation method of free from chloride active carbon loading ruthenium ammonia synthesis catalyst |
| CN108970610A (en) * | 2018-07-23 | 2018-12-11 | 福州大学 | A kind of preparation method of active carbon loading ruthenium ammonia synthesis catalyst |
| CN110975885A (en) * | 2019-12-25 | 2020-04-10 | 桂林电子科技大学 | Bimetallic oxide supported ruthenium catalytic material and preparation method and application thereof |
| CN114210351B (en) * | 2021-12-29 | 2023-06-30 | 重庆敏恒科技有限公司 | Catalyst for synthesizing vinyl sulfate and method for synthesizing vinyl sulfate |
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