CN1621148A - Methanation resisting active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity - Google Patents
Methanation resisting active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity Download PDFInfo
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- CN1621148A CN1621148A CNA2004100853301A CN200410085330A CN1621148A CN 1621148 A CN1621148 A CN 1621148A CN A2004100853301 A CNA2004100853301 A CN A2004100853301A CN 200410085330 A CN200410085330 A CN 200410085330A CN 1621148 A CN1621148 A CN 1621148A
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- catalyst
- active carbon
- ammonia synthesis
- high intensity
- methanation
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- 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
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Abstract
The present invention discloses one kind of ammonia-synthesizing Ru-carrying active carbon catalyst with high strength and high methanation resistance. The catalyst consists of Ru 3-12 (in weight of the active carbon, the same below); Ba+Ln 3-7 with Ln being RE metal La, Ce, Pr, Nd or Sm and Ba/Ln=1-25; and K 8-20. The catalyst is prepared through extruding the material with inorganic adhesive and is shaped in cylinder of 3-10 mm diameter and 3-20 mm length or ball. It has pressure strength higher than 50 N/cm (cylinder) or 30 N (ball), wear rate less than 0.6 % and methanation resistance 0.35-4 times that of Ru/AC ammonia-synthesizing catalyst.
Description
Technical field
The present invention relates to be used in the ammonia synthesizing industry new ammonia synthesis catalyst technology by hydrogen, nitrogen synthetic ammonia, specifically, is the preparation method of the active carbon ruthenium carrying catalyst for ammonia synthesis of a kind of methanation resisting, high mechanical properties.
Background technology
The application of traditional Fused-iron Catalyst for Ammonia Synthesis in ammonia synthesizing industry has the history of nine more than ten years.Advantages such as that though iron catalyst has is cheap, good stabilities, when being to use iron catalyst, ammonia synthesis reaction must carry out under high-temperature and high-pressure conditions, production process to equipment require harsh, investment is big, energy consumption is high.
Develop and used a kind of active carbon loading ruthenium ammonia synthesis catalyst in recent years abroad, can be with H under the temperature and pressure condition more much lower than the use iron catalyst
2, N
2Catalysis synthetic ammonia, thereby have considerable energy saving consumption reduction effect.But the absorbent charcoal carrier of active carbon loading ruthenium ammonia synthesis catalyst at the high temperature of synthetic ammonia, contain under the hydrogen condition easily by methanation, therefore very unstable; Simultaneously because the mechanical strength of active carbon own is relatively poor, for example the mean compressive strength of amorphous cocoanut active charcoal is about 40N, but rate of wear is up to more than 4%, risk that its industry is used as catalyst carrier is bigger. for improve active carbon at high temperature, contain the stability of methanation resisting under the hydrogen condition, people carry out common active carbon high temperature graphitization usually and handle.PCT patent WO03/048045 A2 disclose a kind of with the BET surface area handled through 2000 ℃ of high-temperature process and redox greater than 280m
2The graphite of/g is carrier, with Ba (NO
3)
2, CsOH+KOH is auxiliary agent, containing the ruthenium amount is 1～10wt% ammonia synthesis catalyst, it is that the catalyst of carrier is compared high about 20 times of its methanation resisting ability with the active carbon of only handling through 1500 ℃ and 425 ℃ of redox are handled.
Our practice shows, even use the active carbon of handling through 1900 ℃ of high temperature graphitizations as the prepared catalyst of ruthenium catalyst carrier, and at 15MPa, 450 ℃, 30000h
-1, hydrogen nitrogen is than being that methane content still can reach 0.0049% in the reactor outlet gas under 3 the condition, this will have a strong impact on the long-term use of catalyst.
Show from the interrelated data retrieval that comprises Chinese patent, have not yet to see the mechanical strength height, specific surface, pore structure suit, with ruthenium is main activating agent, with the oxide of alkali metal, rare earth metal and alkaline-earth metal or hydroxide is auxiliary agent, the relevant report of the prescription of the active carbon loading ruthenium ammonia synthesis catalyst of methanation resisting, high mechanical properties and Preparation of catalysts method.
Summary of the invention
The objective of the invention is to provide a kind of mechanical strength height, specific surface, pore structure suit, with ruthenium is main activating agent, with the oxide of alkali metal, rare earth metal and alkaline-earth metal or hydroxide is auxiliary agent, the preparation method of the active carbon loading ruthenium ammonia synthesis catalyst of methanation resisting, high mechanical properties.
The technical solution adopted for the present invention to solve the technical problems is: a kind of methanation resisting, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity, it is characterized in that: get the oven dry after diluted acid is handled and washed of unbodied common cocoanut active charcoal, after the oven dry that it is levigate to 200 orders, on mixer, mix after adding a kind of inorganic binder; Be φ 3～φ 10mm under 15～20MPa pressure material being squeezed into diameter on the banded extruder then, length is the cylindrical of 3～20mm or the sphere that is shaped as equivalent diameter; Again with the shaping thing 80～120 ℃ of oven dry, then under the protection of inert gas in 1700～1950 ℃ of high-temperature process, feed at last by oxygen, CO
2And/or the mist of steam and nitrogen and/or argon gas, be to carry out reaming under 250-485 ℃ to handle in temperature, promptly form targeted activity charcoal carrier; With Ba (NO
3)
2And Ln (NO
3)
3Mixture aqueous solution is controlled Ba/Ln=1～25 (w/w), described Ln (NO with infusion process modification activities charcoal carrier
3)
3In Ln be the single rare earth metal (La, Ce, Pr, Nd, Sm) or the two or more mixture of rare earth metal; ) plate RuCl with infusion process again after the drying
3With hydrogen or hydrogen nitrogen mixed gas at 120～450 ℃ RuCl
3After being reduced to metal Ru, plate KNO with infusion process again
3Or KOH makes auxiliary agent, promptly form compression strength 〉=50N/cm (cylindrical) or 〉=30N/ is spherical, rate of wear≤0.6%, the high strength that methanation resisting energy force rate tradition Ru/AC catalyst is high 0.35～4 times, the active carbon loading ruthenium ammonia synthesis catalyst of methanation resisting.Described diluted acid is hydrochloric acid or nitric acid, and wherein acid is 1: 1～20 (V/V) with the ratio of water; Described binding agent is the compound of iron, aluminium, calcium, silicon, they are nitrate, carbonate, silicate, hydroxide, the oxide of these elements, the mol ratio of each element is Fe: Al: Ca: Si=5: 4: 1: 21～50, and perhaps Fe: Si=1: 10～20, perhaps 100%Si; Described nitrate can be rare-earth metal La, Ce, Pr, Nd, the single metal nitrate of Sm or the nitrate of their mixtures, each rare earth metal can not to scale (NTS) mixes in mixture nitrate, with Ba (NO
3)
2Must control Ba/Ln=1～25 (w/w) during coupling; Described binding agent addition is a benchmark with active carbon weight, and the adding binder amount is 3～10Wt%.Weight with absorbent charcoal carrier is benchmark, the consisting of of catalyst of the present invention: Ru:3～12wt%; (Ba+Ln): 3～7wt%; K:8～20wt%; Ba/Ln=1～25 (wherein Ln refers to rare-earth metal La, Ce, and Pr, Nd, Sm).
The invention has the beneficial effects as follows: because catalyst of the present invention has adopted with ruthenium is main activating agent, the novel ammonia synthesis catalysis technique that is auxiliary agent with the oxide or the hydroxide of alkali metal, rare earth metal and alkaline-earth metal, make it have the mechanical strength height, the methanation resisting ability is strong, advantages such as the ammonia synthesis activity is suitable with similar catalyst. therefore, it is 5～30MPa that the present invention will be more suitable in reaction pressure, and reaction temperature is by the occasion of hydrogen, nitrogen synthetic ammonia under 230～475 ℃ the industrial condition.
The specific embodiment
Embodiment 1:
Getting 500 gram BET specific areas is 1050m
2The coconut husk charcoal of/g behind the HCl solution immersion 20h with 1: 20 (v/v), is told acid solution, and active carbon places scrubbing tower to be washed till pH value=7 with the pure water that flows; The active carbon that takes out at 120 ℃ of following dry 4h, places in the ball mill in drying oven then, is milled to whole powdered carbons and can passes through 280 mesh sieves.Above-mentioned powdered carbon is placed blender, and adding weight is about the inorganic binder of powdered carbon weight 5% and mixes.Inorganic binder is the compound of iron, aluminium, calcium, silicon, and the mol ratio of each component element is Fe: Al: Ca: Si=5: place banded extruder in 20MPa pressure under be extruded into diameter the material that be mixed at 4: 1: 21. and be the cylinder bar of about 4mm, be made into short cylindrical or φ 4 spheries that length is about 3～15mm again in trimmer.The shaping charcoal is inserted in the high temperature furnace after 80～120 ℃ of oven dry dewater, and handles 2h in 1800～1900 ℃ under inert gas shielding, reduce the temperature to room temperature after, take out and place the reaming stove, feed by oxygen, CO
2, nitrogen, water vapour gas composition gaseous mixture to reduce to room temperature after handling 16h at 460 ℃ stand-by.Resulting shaping charcoal compression strength 〉=50N/cm (cylindrical) or 〉=30N/ (sphere), rate of wear≤0.5%, the BET specific area is 950m
2/ g.
Get the above-mentioned cylindrical shaping charcoal of 100g, use Ba (NO respectively
3)
2And Nd
2(NO
3)
3The aqueous solution (also can simultaneously with two kinds of salt mixture aqueous solution) floods.With the charcoal vehicle weight is benchmark, and the control carrier contains the about 4wt% of Ba amount, contains the about 1wt% of Nd amount; Under infrared lamp, after about 80～110 ℃ of oven dry dewater, use RuCl
3Aqueous solution dipping has been used Ba (NO
3)
2And Nd
2(NO
3)
3The charcoal carrier of modified, with shaping charcoal weight be benchmark control catalyst to contain the Ru amount be about 5wt%; Plating RuCl
3After catalyst be placed in the reduction furnace through infrared lamp oven dry, under normal pressure in 120～450 ℃ RuCl
3Be reduced to metal Ru; After catalyst after the reduction is reduced to room temperature, flood it with the KOH aqueous solution, making the K content of catalyst is about 17wt% (is benchmark with the charcoal vehicle weight), and oven dry is finished product then.
Activity of such catalysts and methanation speed are tested with the high-pressure flow method.Catalyst powder is broken into the granule of granularity 1.0～1.6mm, accurately measures 2ml (through ram-jolt) and be contained in the isothermal region that internal diameter is the stainless steel high-pressure reactor of φ 12mm, use H at normal pressure with under 120 ℃, 200 ℃, 300 ℃, 400 ℃, 450 ℃, 500 ℃ temperature
2/ N
2(the control gas space velocity is 15000～30000h to=3/1 hydrogen nitrogen mixed gas
-1) difference reductase 12 h, conditioned reaction device pressure, temperature and air speed are also carried out activity of such catalysts mensuration behind the constant 3h for the test controlling value then.Catalyst activity represents that with the volumn concentration of ammonia in the reactor outlet gas this numerical value is demarcated with standard sulfuric acid titration.
The methanation speed of catalyst is tested with gas chromatography, and the instrumentation condition is as follows:
Detector: FID;
Pillar: 5A molecular sieve, 40-60 order, 3m * φ 4mm, stainless steel tube;
60 ℃ of temperature: COL, 100 ℃ of DET, 100 ℃ of INJ;
Carrier gas: Ar; Flow velocity: 40ml/min;
Combustion gas: H
2Flow velocity: 20ml/min;
Combustion-supporting gas: air; Flow velocity: 300ml/min;
Quantity tube: 2.00ml.
According under the situation that does not change operating condition, the content of material of the same race is directly proportional with its peak area.Therefore by the peak area of methane in the assaying reaction gas, then its peak area with calibrating gas is compared, can calculate the content of methane in the reaction gas.
Because there is more organic machine group in the catalyst carrier carbon surface, under the effect of high temperature, high pressure and reactive metal, they are at first with H
2Reaction generates methane.At 10MPa, 450 ℃, 10000h
-1Controlled condition through after nearly 20 hours reaction, is easily reacted completely by the material of methanation down basically, so the content of methane tends towards stability in working off one's feeling vent one's spleen.Therefore when the present invention investigates the methanation speed of catalyst, all stablize under these conditions after 20 h, adjustment is 475 ℃ carries out the methanation data determination again.
The compression strength of catalyst is measured on ZQJ-II type intelligence granule strength testing machine, and rate of wear is tested on the multi-functional abrasion machine of DGM type, instrument rotary drum rotating speed: 60r/min, wearing time: 15min.After the off-test, be that the sieve of 1.6mm (12 order) screens out the powder that grinds with mesh size, the percentage of weight ratio is as the rate of wear of catalyst before weight that is worn away with catalyst and the catalyst mill.
The mechanical strength of catalyst and ammonia synthesis activity and methanation data see Table 1.
Embodiment 2
Repeat the process of embodiment 1, just the shaping charcoal is changed into φ 4 spheries, Nd
2(NO
3)
3Make mixed rare earth nitrates into.In rare earth oxide, the content of each rare-earth oxide is La in this mishmetal
2O
3: 32.76%, CeO
2: 57.8%, Pr
6O
11: 1.37%, Nd
2O
3: 8.07%.With the charcoal vehicle weight is base, and the control carrier contains the about 4wt% of Ba amount, contains the about 0.5wt% of Ln amount.Catalyst activity and methanation resisting data see Table 1.
Embodiment 3
Repeat the process of embodiment 1, but carrier when being shaped binder component change Ludox into, and the content of each rare earth metal changes in the mixed rare earth nitrates.In rare earth oxide, the weight content of each rare-earth oxide is La in this mishmetal
2O
3: 90.6%, CeO
2: 9.23%, Pr
6O
11: 0.07%, Nd
2O
3: 0.09%, Sm
2O
3: 0.01%.With the charcoal vehicle weight is base, and the control carrier contains the about 3.5wt% of Ba amount, contains the about 3.0wt% of Ln amount.Catalyst activity and methanation resisting data see Table 1.
Embodiment 4
Repeat the process of embodiment 1, but carrier when being shaped binder component to change mol ratio into be Fe: Si=1: 10 Fe (NO
3)
2And SiO
2, and the content of each rare earth metal changes in the mixed rare earth nitrates.In rare earth oxide, the weight content of each rare-earth oxide is La in this mishmetal
2O
3: 91.3%, CeO
2: 6.25%, Nd
2O
3: 2.45%.With the charcoal vehicle weight is base, and the control carrier contains the about 4.5wt% of Ba amount, contains the about 0.3wt% of Ln amount, and the metal Ru content of catalyst is about 6wt%.Catalyst activity and methanation resisting data see Table 1.
Embodiment 5 (comparative example)
Get 100g equally through the amorphous coconut husk charcoal of example 1 described high temperature graphitization and reaming processing, use RuCl earlier
3Aqueous solution dipping plates Ba (NO with infusion process respectively after the oven dry again
3)
2And KOH.With the carried by active carbon body weight is benchmark, and the composition of catalyst is: Ru:5%, Ba:4%, K:17.The physical-chemical parameters assay method of catalyst and condition are with example 1.
As seen from Table 1, catalyst of the present invention has than higher mechanical strength and methanation resisting ability and the catalyst of its catalytic activity and conventional method preparation is suitable, thereby is applicable to that more the industrial production field boundary closes.
Table 1. activity of such catalysts, methanation resisting and mechanical strength
Catalyst n H
3% (v/v) CH
4% (v/v) compression strength rate of wear (%)
Example 1 18.00 0.0012 61.2N/cm 0.243
Example 2 (sphere) 18.15 0.0015 32.1N/ individual 0.462
Example 3 17.43 0.0011 52.9N/cm 0.502
Example 4 18.93 0.0018 55.4N/cm 0.384
(comparative example is 18.23 0.0073 39.8N/ individual 4.93 not for example 5
Contain rare earth) (granularity 2.2-3.3mm)
Annotate: 1. the active testing condition is: 10.0MPa, 400 ℃, 10000h
-1
2. methanation survey survey condition is: 10.0MPa, 475 ℃, 10000h
-1
Claims (12)
1, a kind of methanation resisting, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity, it is characterized in that: get the oven dry after diluted acid is handled and washed of unbodied common cocoanut active charcoal, after the oven dry that it is levigate to 200 orders, on mixer, mix after adding a kind of inorganic binder; Then on banded extruder, be squeezed into cylindrical or be shaped as the sphere of equivalent diameter; With the oven dry of shaping thing, under the protection of inert gas, carry out high-temperature process then again, feed at last by oxygen, CO
2And/or the mist of steam and nitrogen and/or argon gas, be to carry out reaming under 250-485 ℃ to handle in temperature, promptly form targeted activity charcoal carrier; With Ba (NO
3)
2And Ln (NO
3)
3Mixture aqueous solution is controlled suitable Ba/Ln value with infusion process modification activities charcoal carrier, plates RuCl with infusion process again after the drying
3With hydrogen or hydrogen nitrogen mixed gas at 120～450 ℃ RuCl
3After being reduced to metal Ru, plate KNO with infusion process again
3Or KOH makes the active carbon loading ruthenium ammonia synthesis catalyst of auxiliary agent.
2, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: described catalyst is consisting of of base: Ru:3～12wt% with the weight of absorbent charcoal carrier; Ba+Ln:3～7wt%; K:8～20wt%; Ba/Ln=1～25.
3, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: described diluted acid is hydrochloric acid or nitric acid, and wherein acid is 1: 1～20 (V/V) with the ratio of water.
4, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity, it is characterized in that: described inorganic binder is the compound of iron, aluminium, calcium, silicon, and they are nitrate, carbonate, silicate, hydroxide, the oxide of these elements; The mol ratio of described each element is Fe: Al: Ca: Si=5: 4: 1: 21～50, and perhaps Fe: Si=1: 10～20 or 100%Si.
5, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity, it is characterized in that: described nitrate can be rare-earth metal La, Ce, Pr, Nd, the single metal nitrate of Sm or the nitrate of their mixtures, each rare earth metal can not to scale (NTS) mixes in mixture nitrate, with Ba (NO
3)
2Must control Ba/Ln=1～25 (w/w) during coupling.
6, a kind of methanation resisting according to claim 1, high-intensity Ru/AC ammonia synthesis catalyst, it is characterized in that: described binding agent addition is a benchmark with active carbon weight, the adding binder amount is 3～10Wt%.
7, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: described high-temperature process under the protection of inert gas, its treatment temperature are 1700～1950 ℃.
8, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: material is φ 3～φ 10mm be squeezed into diameter on the banded extruder under 15～20MPa pressure, and length is the cylindrical of 3～20mm.
9, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: the shaping thing after the described extruding is 80～120 ℃ of oven dry.
10, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: described Ln (NO
3)
3In Ln be single rare earth metal La, Ce, Pr, Nd, Sm or their two or more mixture.
11, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: described shaped catalyst thing, its cylindrical compression strength 〉=50N/cm or 〉=sphere of 30N/, rate of wear≤0.6%.
12, a kind of methanation resisting according to claim 1, active carbon ruthenium carrying catalyst for ammonia synthesis with high intensity is characterized in that: the methanation resisting of described shaped catalyst thing can force rate tradition Ru/AC catalyst height be 0.35～4 times.
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| CN1299823C CN1299823C (en) | 2007-02-14 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807383A (en) * | 2017-02-10 | 2017-06-09 | 西北大学 | A kind of method for preparing catalyst of ammonia and preparation method thereof and the catalyst preparation ammonia |
| CN107413341A (en) * | 2017-06-09 | 2017-12-01 | 武汉大学 | A kind of ruthenium-based catalyst for being carried on SrNb2 O6 surface and its preparation method and application |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1133493C (en) * | 1999-04-14 | 2004-01-07 | 中国科学院大连化学物理研究所 | Efficient catalyst for synthesizing ammonia and its preparing process |
| CN1162219C (en) * | 2001-08-15 | 2004-08-18 | 中国石油化工股份有限公司 | Ammonia synthesis ruthenium based catalyst and preparing process thereof |
| CN1359868A (en) * | 2002-01-06 | 2002-07-24 | 大庆石油管理局 | Sintered product with high content of flyash |
| CN1128016C (en) * | 2002-03-01 | 2003-11-19 | 福州大学化肥催化剂国家工程研究中心 | Pore-enlarging process for activated carbonate as carrier of carried ruthenium catalyst |
| CN1133492C (en) * | 2002-06-03 | 2004-01-07 | 福州大学 | Process for preparing ammonia synthesis catalyst |
-
2004
- 2004-10-10 CN CNB2004100853301A patent/CN1299823C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106807383A (en) * | 2017-02-10 | 2017-06-09 | 西北大学 | A kind of method for preparing catalyst of ammonia and preparation method thereof and the catalyst preparation ammonia |
| CN106807383B (en) * | 2017-02-10 | 2019-03-22 | 西北大学 | A method of preparing catalyst of ammonia and preparation method thereof and the catalyst preparation ammonia |
| CN107413341A (en) * | 2017-06-09 | 2017-12-01 | 武汉大学 | A kind of ruthenium-based catalyst for being carried on SrNb2 O6 surface and its preparation method and application |
| CN107413341B (en) * | 2017-06-09 | 2019-08-20 | 武汉大学 | A kind of ruthenium-based catalyst and its preparation method and application being carried on SrNb2 O6 surface |
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Effective date of registration: 20151229 Address after: 350015, Fuzhou, Fujian province Mawei District, Mawei Town, Huli branch, No. 1, building 9 (main workshop), the whole block Patentee after: Fuzhou branch catalytic material Co., Ltd. Address before: 350015, Mawei hi tech park, 27, Fujian, Fuzhou Patentee before: Kesheng Catalytic Material Co., Ltd., Fuzhou Development Zone |
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Granted publication date: 20070214 Termination date: 20181010 |