CN1481933A - Ammonia synthetic catalyst and method for making the same - Google Patents

Ammonia synthetic catalyst and method for making the same Download PDF

Info

Publication number
CN1481933A
CN1481933A CNA02142327XA CN02142327A CN1481933A CN 1481933 A CN1481933 A CN 1481933A CN A02142327X A CNA02142327X A CN A02142327XA CN 02142327 A CN02142327 A CN 02142327A CN 1481933 A CN1481933 A CN 1481933A
Authority
CN
China
Prior art keywords
mgo
ammonia synthesis
catalyst
synthesis catalyst
alkaline
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA02142327XA
Other languages
Chinese (zh)
Other versions
CN1193825C (en
Inventor
廖代伟
林敬东
王欣莹
陈鸿博
蔡启瑞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen University
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CNB02142327XA priority Critical patent/CN1193825C/en
Publication of CN1481933A publication Critical patent/CN1481933A/en
Application granted granted Critical
Publication of CN1193825C publication Critical patent/CN1193825C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The present invention relates to catalyst, and is especially new ammonia synthesizing catalyst, which has noble metal Ru as active component, fluoride of alkali metal or alkali earth metal as assistant and magnesia as carrier and has high activity, and its preparation process. The catalyst has Ru/MgO ratio of 3-8 % and molar Ru/MFx of 0.5-8, the solvent adopted is water or organic solvent capable of dissolving RuCl3.nH2O or carbonyl ruthenium. The catalyst is prepared via soaking process or mechanically mixing, calcination and soaking process. It is used mainly in catalyzing the synthesis of ammonia with nitrogen and hydrogen. The greater electronegativity of F in fluoride may accelerate the hydrogenation of N to synthesize ammonia, and the catalyst has activity 1-3 times that of catalyst with oxide rather than fluoride and has the lower use temperature and pressure of ammonia synthesizing Ru catalyst maintained.

Description

Ammonia synthesis catalyst and preparation method thereof
(1) technical field
The present invention relates to a kind of ammonia synthesis catalyst, especially is activeconstituents with the noble ruthenium, and the fluorochemical of basic metal or alkaline-earth metal is an auxiliary agent, is high reactivity new ammonia synthesis catalyst of carrier and preparation method thereof with magnesium oxide etc.
(2) background technology
Ammonia synthesis catalyst is a most important catalyzer in the ammonia synthesizing industry, and it directly affects the economic benefit of synthetic ammonia and the production technique of synthetic ammonia.Traditional ammonia synthesis catalyst is a molten iron type catalyzer, and it is technical ripe, but working pressure and temperature are higher, and it is not only to the equipment requirements height, and process energy consumption height.Therefore seek the direction and goal that the highly active ammonia synthesis catalyst of a kind of low-temp low-pressure has become people to make great efforts.At beginning of the seventies late 1960s, it is activeconstituents that Japanese scientist finds with the noble ruthenium, and potassium is auxiliary agent, is the highly active advantage of low-temp low-pressure that the ammonia synthesis catalyst of carrier has traditional molten iron type catalyzer not have with gac etc.Nineteen ninety, first adopted the commercialization ammonia synthesis technology KAAP (Kellogg Advanced Ammonia Process) of non-iron (ruthenium base) ammonia synthesis catalyst to be born.It is activeconstituents with the ruthenium that Chinese patent CN 1270081A discloses a kind of, is carrier with the gac, is the ammonia synthesis catalyst of auxiliary agent with alkaline-earth metal, rare earth etc.The ruthenium charge capacity is 0.1%～16%wt, and the mol ratio of ruthenium and auxiliary agent is 0.01～10.It adopts immersion process for preparing.But most ruthenium-based ammonia synthetic catalyst all is carrier with carbon, and it relates to catalyzer problems such as stability in process of production.It is a focus of research that a kind of ammonia synthesis catalyst that low-temp low-pressure high reactivity characteristics are more arranged is provided always.
(3) summary of the invention
The object of the present invention is to provide a kind of novel ruthenium-based ammonia synthetic catalyst, this catalyzer has the ability than the nitrogen hydrogen ammonification that uses the conventional adjuvants catalyzer to come highly.
The said catalyzer of the present invention is noble ruthenium (Ru) and a kind of alkaline metal fluoride cpd or the Ru-MF that forms of the alkaline-earth metal fluoride except that the beryllium metal except that the lithium metal that loads on the magnesium oxide (MgO) x/ MgO system, said catalyzer is an active ingredient with Ru, is carrier with MgO, with alkaline metal fluoride cpd or alkaline-earth metal fluoride MF xBe auxiliary agent, the charge capacity Ru/MgO of Ru is 3%～8%, Ru and MF xMol ratio be 0.5～8, used solvent is water or solubilized RuCl 3NH 2The organic solvent of O or ruthenium etc., MF xSubscript represent the number of fluorine in the molecule, wherein for alkaline metal fluoride cpd, X=1, for alkaline-earth metal fluoride, X=2.
The charge capacity of Ru is preferably 3%～6%, Ru and MF xMol ratio be preferably 1～5.Ru can be from RuCl 3NH 2O or ruthenium etc.Used organic solvent can be selected acetone or tetrahydrofuran (THF) etc.
Auxiliary agent is that the preparation method of the ammonia synthesis catalyst of alkaline metal fluoride cpd is:
1) the soluble alkali metal fluorochemical MF lead compound of metering is dissolved in H 2Among the O;
2) again with the MgO dipping, dry behind the evaporation deionized water, get MF/MgO;
3) use MF x/ MgO floods RuCl 3Acetone soln, revaporization removes acetone, oven dry promptly gets catalyzer.
Above-mentionedly flood 1h at least with MgO, after evaporation is anhydrated, 110～140 ℃ of oven dry down in air;
Auxiliary agent is that the preparation method of the ammonia synthesis catalyst of alkaline-earth metal fluoride is:
1) the MF of metering 2Even with the MgO mechanically mixing, transfer to pasty state and calcining with deionized water, get MF 2/ MgO;
2) use MF 2/ MgO floods RuCl 3Acetone soln, revaporization removes acetone, oven dry promptly gets catalyzer.
The above-mentioned incinerating time is 1h at least, and the incinerating temperature is about 900 ℃ in air, uses MF 2/ MgO floods RuCl 3The time 1h at least of acetone soln.The temperature of drying in air is 110～140 ℃.
Use preceding through reduction (granularity 35～60 orders).
Catalyzer of the present invention is mainly used in nitrogen hydrogen mixed gas catalysis synthetic ammonia.
The advantage of this catalyzer is to utilize fluorine is big in the fluorochemical electronegativity to have to help the characteristic of the hydrogenation ammonification of assisting nitrogen, make that the catalysis ammonia synthesis activity of catalyzer of the present invention is to use 1 to 3 times of the promoted catalyzer of the same type of oxide compound usually, kept ruthenium-based ammonia synthetic catalyst use temperature, characteristics that pressure is low simultaneously.
(4) embodiment
Following examples will the present invention is further illustrated.Example 1.
KFH with 1.0450g 2O is dissolved in and adopts pickling process that above-mentioned solution is immersed 5h among the 5.6142gMgO in the proper amount of deionized water, and rotary evaporation anhydrates, and through 120 ℃ of oven dry 12h, gets KF/MgO in air.The RuCl that 0.2942g is contained Ru37% 3NH 2O is dissolved in an amount of acetone, immerses KF/MgO 3.2370g6h as above, makes Ru/MgO=4/100 (weight ratio), Ru/KF=1/5 (mol ratio), and rotary evaporation removes acetone, obtains the Ru-KF/MgO ammonia synthesis catalyst through 120 ℃ of oven dry 12h in air.This catalyzer 0.5g is at H 2Switch synthetic gas behind the following 425 ℃ of reductase 12 4h of air-flow, synthetic gas consists of N 2/ H 2=1/3, flow velocity is 1800ml/h.Under pressure 1MPa, measure its catalytic activity.Reference catalyst Ru-KO 1/2/ MgO also prepares under the same conditions and estimates.The result shows, adopt alkaline metal fluoride cpd be auxiliary agent than with the alkalimetal oxide be auxiliary agent ammonia synthesis catalyst activity high, see Table 1.
Table 1. catalyzer Ru-KF/MgO and reference catalyst Ru-KO 1/2/ MgO specific activity is (mL NH 3/ hrg-cat)
Temperature of reaction ??653K ??673K ??693K ??713K ??733K
?Ru-KF/MgO ??11.85 ??22.44 ??42.82 ??49.44 ??31.92
?Ru-KO 1/2/MgO ??7.33 ??11.99 ??15.63 ??12.52 ??7.72
Example 2
By the Ru-KF/MgO catalyzer of the different ruthenium charge capacity of example 1 preparation, catalyst levels 0.5g, at 1MPa, temperature of reaction 673K, synthetic gas consists of N 2/ H 2=1/3, flow velocity is to estimate its ammonia synthesis activity under the condition of 1800ml/h.The result is as shown in table 2.The result shows that when the charge capacity of ruthenium was 4%, catalytic activity was the highest.
The different ruthenium charge capacity of table 2. are to the influence of catalyst activity
Ruthenium charge capacity (wt%) ????3 ????4 ????5 ????6 ????8
Active (mL NH 3/hr·g-cat) ??19.63 ??22.44 ??20.25 ??18.12 ??15.34
Example 3
By the Ru-KF/MgO catalyzer of the different Ru/KF mol ratios of example 1 preparation, the ruthenium charge capacity is 4%wt, catalyst levels 0.5g, and at 1MPa, temperature of reaction 673K, synthetic gas consists of N 2/ H 2=1/3, flow velocity is to estimate its ammonia synthesis activity under the condition of 1800ml/h.The result is as shown in table 3.The result shows that when the Ru/KF mol ratio was 3, catalytic activity was the highest.
Table 3. auxiliary agent content is to the influence of catalyst activity
The Ru/KF mol ratio ????1 ????3 ????5 ????8
Active (mL NH 3/hr·g-cat) ????20.54 ????37.33 ????22.44 ????18.56
Example 4
BaF with 0.7287g 2Mix with the MgO of 4.1710g, transfer to pasty state with deionized water, 600 ℃ of calcining 6h get BaF in air 2/ MgO contains 0.1756g the RuCl of Ru37% 3NH 2O is dissolved in an amount of acetone, immerses BaF as above 2/ MgO 1.9087g6h makes Ru/MgO=4/100 (weight ratio), Ru/BaF 2=1/2.5 (mol ratio), rotary evaporation removes acetone, obtains Ru-BaF through 120 ℃ of oven dry 12h in air 2/ MgO ammonia synthesis catalyst.This catalyzer is at H 2Switch synthetic gas behind the following 425 ℃ of reductase 12 4h of air-flow, synthetic gas consists of N 2/ H 2=1/3, flow velocity is 1800ml/h.Under 1MPa, measure its catalytic activity.Reference catalyst Ru-BaO/MgO also prepares under the same conditions and evaluation sees Table 4, and the result shows, adopt alkaline-earth metal fluoride be auxiliary agent than with the alkaline earth metal oxide be auxiliary agent ammonia synthesis catalyst activity high.
Table 4. catalyzer Ru-BaF 2/ MgO and reference catalyst Ru-BaO/MgO specific activity be (mL NH 3/ hrg-cat)
Temperature of reaction ??673K ??693K ??713K ??733K ??753K ??773K
?Ru-BaF 2/MgO ??30.12 ??39.56 ??48.25 ??53.96 ??51.85 ??47.63
?Ru-BaO/MgO ??16.48 ??24.75 ??29.96 ??35.09 ??36.68 ??31.96

Claims (9)

1, a kind of ammonia synthesis catalyst is an active ingredient with Ru, it is characterized in that with MgO being carrier, with alkaline metal fluoride cpd except that the lithium metal or the alkaline-earth metal fluoride MF except that the beryllium metal xBe auxiliary agent, the charge capacity Ru/MgO of Ru is 3%～8%, Ru and MF xMol ratio be 0.5～8, used solvent is water or solubilized RuCl 3NH 2The organic solvent of O or ruthenium, MF xSubscript represent the number of fluorine in the molecule, wherein for alkaline metal fluoride cpd, X=1, for alkaline-earth metal fluoride, X=2.
2, ammonia synthesis catalyst as claimed in claim 1 is characterized in that the charge capacity of Ru elects 3%～6% as.
3, ammonia synthesis catalyst as claimed in claim 1 is characterized in that Ru and MF xMol ratio elect 1～5 as.
4, ammonia synthesis catalyst as claimed in claim 1 is characterized in that used organic solvent selection acetone or tetrahydrofuran (THF).
5, auxiliary agent is that the preparation method of the ammonia synthesis catalyst of alkaline metal fluoride cpd is:
1) the soluble alkali metal fluorochemical MF lead compound of metering is dissolved in H 2Among the O;
2) again with the MgO dipping, dry behind the evaporation deionized water, get MF/MgO;
3) use MF x/ MgO floods RuCl 3Acetone soln, revaporization removes acetone, oven dry promptly gets catalyzer.
6, the preparation method of ammonia synthesis catalyst as claimed in claim 5 is characterized in that flooding 1h at least with MgO, after evaporation is anhydrated, and 110～140 ℃ of oven dry down in air;
7, auxiliary agent is that the preparation method of the ammonia synthesis catalyst of alkaline-earth metal fluoride is:
1) the MF of metering 2Even with the MgO mechanically mixing, transfer to pasty state and calcining with deionized water, get MF 2/ MgO;
2) use MF 2/ MgO floods RuCl 3Acetone soln, revaporization removes acetone, oven dry promptly gets catalyzer.
8, the preparation method of ammonia synthesis catalyst as claimed in claim 7 is characterized in that 1h at least of said incinerating time, and the incinerating temperature is 900 ℃ in air.
9, the preparation method of ammonia synthesis catalyst as claimed in claim 7 is characterized in that using MF 2/ MgO floods RuCl 3The time 1h at least of acetone soln, the temperature of drying in air is 110～140 ℃.
CNB02142327XA 2002-09-12 2002-09-12 Ammonia synthetic catalyst and method for making the same Expired - Fee Related CN1193825C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB02142327XA CN1193825C (en) 2002-09-12 2002-09-12 Ammonia synthetic catalyst and method for making the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB02142327XA CN1193825C (en) 2002-09-12 2002-09-12 Ammonia synthetic catalyst and method for making the same

Publications (2)

Publication Number Publication Date
CN1481933A true CN1481933A (en) 2004-03-17
CN1193825C CN1193825C (en) 2005-03-23

Family

ID=34148012

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB02142327XA Expired - Fee Related CN1193825C (en) 2002-09-12 2002-09-12 Ammonia synthetic catalyst and method for making the same

Country Status (1)

Country Link
CN (1) CN1193825C (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100421788C (en) * 2006-03-03 2008-10-01 厦门大学 Mixed ruthenium base amino synthetic catalyst and its preparing method
CN100551523C (en) * 2005-10-28 2009-10-21 厦门大学 A kind of metal oxide supported Nobel-metal catalyst preparation method
CN102029199A (en) * 2010-11-15 2011-04-27 大连理工大学 Method for preparing load-type noble metal nanometer catalyst by solvent-free microwave-assisted pyrolysis method
CN103464151A (en) * 2013-09-29 2013-12-25 福州大学 Composite oxide load ruthenium ammonia synthesis catalyst and preparing method thereof
CN104713968A (en) * 2013-12-13 2015-06-17 中国科学院大连化学物理研究所 Online analysis system and method for continuous monitoring of catalysis of ammonia synthesis reaction

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100493700C (en) * 2005-10-28 2009-06-03 厦门大学 Preparation method of ruthenium-base ammonia synthetic catalyst

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100551523C (en) * 2005-10-28 2009-10-21 厦门大学 A kind of metal oxide supported Nobel-metal catalyst preparation method
CN100421788C (en) * 2006-03-03 2008-10-01 厦门大学 Mixed ruthenium base amino synthetic catalyst and its preparing method
CN102029199A (en) * 2010-11-15 2011-04-27 大连理工大学 Method for preparing load-type noble metal nanometer catalyst by solvent-free microwave-assisted pyrolysis method
CN103464151A (en) * 2013-09-29 2013-12-25 福州大学 Composite oxide load ruthenium ammonia synthesis catalyst and preparing method thereof
CN103464151B (en) * 2013-09-29 2016-01-20 福州大学 A kind of composite oxide supported ruthenium ammonia synthesis catalyst and preparation method thereof
CN104713968A (en) * 2013-12-13 2015-06-17 中国科学院大连化学物理研究所 Online analysis system and method for continuous monitoring of catalysis of ammonia synthesis reaction

Also Published As

Publication number Publication date
CN1193825C (en) 2005-03-23

Similar Documents

Publication Publication Date Title
CN107365287B (en) A method of synthesis 2,5- furandicarboxylic acid
Collin et al. Electrocatalytic properties of (tetraazacyclotetradecane) nickel (2+) and Ni2 (biscyclam) 4+ with respect to carbon dioxide and water reduction
PT800508E (en) PROCESS FOR THE PRODUCTION OF ALPHA, OMEGA-AMINONITRILLOS ALIFATICOS
CN1193825C (en) Ammonia synthetic catalyst and method for making the same
CN101811056A (en) Method for preparing Cu-CeO2 catalyst
CN112871188B (en) Preparation method of copper-based catalyst and application of copper-based catalyst in acetylene hydration reaction
CN113634257A (en) Application of bifunctional catalyst to CO in flue gas2Integration of capture and methanation
JP2015523694A (en) Carbendazim-based catalytic agent
CN112547093A (en) Hydrodechlorination catalyst, and preparation method and application thereof
CN101992086B (en) Catalyst for producing alpha, alpha-dimethyl benzyl alcohol by hydrogenation of cumene hydroperoxide and preparation method thereof
JP3552766B2 (en) Ammonia synthesis catalyst and its preparation method
CN1351903A (en) Catalystic hydrogenation and dechlorination catalyst for preparing trifluorochloroethylene and trichloroethylene
CN113862723B (en) Surface phase engineering modified carbon-coated nickel-iron nitride nanosphere and preparation method and application thereof
CN109718763B (en) Carrier, supported catalyst, preparation method and application of supported catalyst, and method for preparing synthesis gas by dry reforming of methane
CN1954910A (en) Preparation method of ruthenium-base ammonia synthetic catalyst
CN1207264C (en) Nitrobenzene hydrogenation catalyst with high aniline yield rate
EP2749351B1 (en) A catalyst for reductive amination-reaction and uses thereof
JP3773293B2 (en) Method for producing ammonia synthesis catalyst
CN1428293A (en) Catalyst for low-temp. selective oxidation of CO in hydrogen gas and its preparation method
CN1088402C (en) Dicarbonic oxygen-contained compound catalyst such as alcohols, acetic acid, acetaldehyde etc. made from synthetic gas and process thereof
CN106807422B (en) For the catalyst of modulation synthesis gas higher alcohol performance and its preparation and application
JP3672367B2 (en) Ammonia synthesis catalyst and production method thereof
CN1309811C (en) Carbon mono oxide combustion improver and preparation method and use
CN86108869A (en) Iso-butylene-formaldehyde vapour phase condensation preparing isoprene catalyzer
CN1048423C (en) Catalyst for hydrogenation of acetone to synthesize methyl-isobutyl ketone, and its prepn. method

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee