CN105618081A - Rare earth metal La doped copper manganese catalyst and experiment method thereof - Google Patents
Rare earth metal La doped copper manganese catalyst and experiment method thereof Download PDFInfo
- Publication number
- CN105618081A CN105618081A CN201610072689.8A CN201610072689A CN105618081A CN 105618081 A CN105618081 A CN 105618081A CN 201610072689 A CN201610072689 A CN 201610072689A CN 105618081 A CN105618081 A CN 105618081A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- sample
- copper
- gas
- tpr
- 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.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
- C01B3/16—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide using catalysts
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
-
- 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 invention discloses a rare earth metal La doped copper manganese catalyst and an experiment method thereof. XRD, TPR/s-TPR, CO2-TPD are utilized to represent a prepared catalyst sample. When comparing a catalyst prepared with 0.5% of La doping quantity with a pure Cu-Mn sample, dispersity of surface copper can be improved effectively to obviously improve low-temperature transformation reaction catalysis performance. In a catalyst sample with the La doping quantity greatly than or equal to 3.0%, crystalline phase of Cu1.5Mn1.5O4 exists, CuO crystalline phase appears obviously, and amplitude of increase in surface basic sites along with increase in La doping quantity is reduced; when the La doping quantity is high, part of active sites are covered by La gathering, and manganese cannot effectively inhibit growing of copper crystalline grains, so that dispersity of the surface copper is lowered, which leads to water gas transformation reaction activity is lowered obviously.
Description
Technical field
The invention belongs to catalyst technical field, relate to a kind of rare-earth metal doped La copper Mn catalyst and experimental technique thereof.
Background technology
CO conversion is synthesis gas manufacture, C/Hratio adjustment and purifies the removing indispensable course of reaction of CO. Along with transformationreation potential using value in a fuel cell, the development work of novel transformation catalyst at home and abroad obtains very big attention. At more than 10 year of the past, the research of transformation catalyst was concentrated mainly on noble metal carrier catalyst, as water gas shift reaction is shown good low temperature active by carried noble metal Au, Pt catalyst. But due to the price that noble metal is expensive, the research emphasis of novel transformation catalyst is more to be had shifted towards on transition-metal catalyst, copper Mn catalyst is to study more a kind of transformation catalyst except industrialization, and correlational study is primarily directed to the factors such as preparation method, proportioning raw materials, solution concentration, charging rate, temperature and pH value of solution to carry out. As Tanaka etc. has investigated the impact on copper Mn catalyst transformationreation catalytic performance of preparation method, auxiliary agent kind, Cu/Mn and sintering temperature, finding that coprecipitation Cu/Mn is 1: 2, sintering temperature is that the catalyst prepared at 900 DEG C has preferably transformationreation catalytic performance; Citric acid method can prepare highly active copper Mn catalyst, and the part replacement of Mn is conducive to improving its catalytic performance by Fe or Al. Recently, T.Tabakova etc. think, the raising of catalyst activity can be realized by new preparation method and the suitable carrier of interpolation, and he adopts urea nitrate combustion method to be prepared for copper manganese transformation catalyst, and contrast with coprecipitation, it has been found that catalyst activity prepared by this method is better. Due to the difference of preparation method and condition, cause that its composition, structure and catalytic performance there will be very big difference. Although through years of researches, the properties of copper Mn catalyst is greatly improved, but distance practical application still has bigger gap, and mainly its low temperature active is poor, and thermostability also needs to be improved further.
For the problem of copper manganese transformation catalyst low temperature active and poor stability, mainly through adding the third component wherein to improve its low-temperature catalyzed performance. Lanthanum element stores oxygen ability because it is excellent, can be effectively improved electric transmission and the transfer ability of catalyst after interpolation. Based on the electronic structure of its uniqueness, good electron transfer orbital, many with it for additive, the catalyst that transition metal, noble metal etc. are active component all demonstrates good catalytic performance. The research of La doped Modified Cu manganese water gas converting catalyst is rarely reported, and the report of other system of adulterating is more. Prior art report La copper doped cerium catalyst, it was shown that the oxidation selectivity of copper cerium catalyst is had certain facilitation by the doping of La. RothmanKamD etc. have studied the impact on Cu/ZnO catalyst of the La doping, show that the Cu/ZnO catalyst that doping is 2.3wt% of La shows good catalysis activity and heat stability under 300 DEG C of heat-resisting 25h, catalysis activity relatively Cu/ZnO catalyst is high by about 20%, and simultaneous reactions activation energy reduces. Andreeva etc. adopt deposition-precipitation method to be prepared for the rare earth doped Au/CeO such as La, Sm, Gd, Yb2Catalyst, it has been found that the sample adding Yb and Sm has good WGS reactivity. Herunxia etc. report the copper Mn catalyst of doped with rare-earth oxide, it has been found that La2O3Doping can significantly improve the reducing property of sample, improve the dispersibility of its surface copper, be effectively improved activity and the stability of copper manganese system water gas shift reaction.
The present invention is on the basis of previous research work, copper manganese water gas converting catalyst is prepared for raw material with copper mn sulphate and lanthanum nitrate, to utilizing lanthanum element distinctive physico-chemical property that copper Mn catalyst is modified research, to improve its low temperature shift reaction activity.
Summary of the invention
It is an object of the invention to the defect overcoming above-mentioned technology to exist, a kind of rare-earth metal doped La copper Mn catalyst and experimental technique thereof are provided, with copper sulfate, manganese sulfate and lanthanum nitrate crystal for raw material, sodium hydroxide solution is precipitant, adopts coprecipitation to prepare the copper Mn catalyst of 1.2 times of lower 5 kinds of Doping with Rare Earth Lanthanum amounts of alkali number. Respectively these 5 kinds of samples are carried out active testing, XRD, TPR/s-TPR and CO2The means such as-TPD characterize, and investigate the impact on copper manganese-based catalyst structure and performance of the precipitation system middle rare earth La doping.
Its concrete technical scheme is:
A kind of rare-earth metal doped La copper Mn catalyst, adulterate 0.5% rare earth element.
The experimental technique of a kind of rare-earth metal doped La copper Mn catalyst, comprises the following steps:
Step 1: the preparation of doped with rare-earth elements La copper Mn catalyst
1.1) dosing
By CuSO4��5H2O��MnSO4.H2O and La (NO3)3��6H2O is configured to the mixed liquor that concentration is 0.225mol/L by a certain percentage;
1.2) constant temperature dissolves
Being placed in by mixed liquor in the thermostat water bath of 45 DEG C, stir speed (S.S.) is maintained at 300rad/min, and constant temperature makes it fully dissolve in 10 minutes, and remains that in titration process this is temperature-resistant;
1.3) neutralize
The NaOH solution that mixed liquor concentration is 4mol/L after dissolving is neutralized and is precipitated thing, neutral temperature 45 DEG C, neutralize endpoint pH 11.5, neutralizer titration speed 10.5rad/min, be kept stirring for speed 300rad/min;
1.4) over-cookeding of heat
The precipitate obtained being carried out heat boil, temperature when heat is boiled is 45 DEG C, and the heat time of boiling is 30min;
1.5) washing
Wash through the overheated precipitate boiled so that it is pH to 7:
1.6) dry
Carry out at 80 DEG C, dry 4 hours;
1.7) roasting
Roasting medium is air, sintering temperature 550 DEG C, heating rate 5 DEG C/min, roasting time 4h.
Step 2: catalyst activity is tested
The active testing experiment of catalyst completes on fixed bed coal burning-gasification reactor apparatus. fixed bed coal burning-gasification reactor apparatus belongs to fixed bed adiabatic formula integral reactor, tube inner diameter is 6mm, active testing process is: first through molecular sieve, the unstripped gas from steel cylinder is removed impurity molecule therein, trace oxygen is removed subsequently into deoxidation pipe, measure then through spinner flowmeter, enter reaction tube from top to bottom catalyst is reduced, the reacted reducing gases of catalyzed oxidant layer is then through condensation, Silicagel dehydration finally empties, after having reduced, unstripped gas is removed through molecular sieve and after impurity molecule therein, enter deoxidation pipe elimination trace oxygen, then after spinner flowmeter measures, the reaction gas with certain WGR is become through saturated steam pipe humidification, reaction gas enters reaction tube from top to bottom and carries out the transformationreation of CO, the reacted conversion gas of catalyzed oxidant layer is then through condensation, sample after Silicagel dehydration, use gas chromatograph on-line analysis, Thermal Conductivity goes out the composition of the gas after transformationreation.
Step 3:XRD/TPR/s-TPR/TPD tests
XRD crystal phase analysis carries out on Germany's BrukerD8advanceX ray powder diffractometer, Cu target, and Ni filters, Si-Li detector, 40KV �� 40mA, sweep limits 20 ��-80 ��, 2 ��/min of scanning speed.
TPR test is to carry out in the U-shaped quartz tube reactor of normal pressure, with 8.9%H2It is reducing gases that/Ar (V/V) mixes gas, reducing gases flow velocity: 30mL/min, sample dosage: 20mg, granularity: 40-80 order, before catalyst carries out TPR test, first carrying out pretreatment, pretreatment condition is that in room temperature, catalyst is raised to 120 DEG C under Ar gas atmosphere, drop to 40 DEG C again after purging 30min, then switch to 8.9%H2/ Ar (V/V) mixes gas, after baseline is walked and put down, with the speed of 10 DEG C/min from room temperature to 600 DEG C.
S-TPR test is that sample completes as above to be cooled to 40 DEG C after TPR step, sweeps 30 minutes to system stability with Ar air-blowing, passes into the N that flow is 30mL/min2O gas carries out surface oxidation 30 minutes to system stability, then passes into the 8.9%H that flow is 50mL/min2/ Ar (V/V) gaseous mixture, is raised to 600 DEG C with the speed of 10 DEG C/min.
CO2-TPD test is that sample completes as above to be cooled to 40 DEG C after TPR step, then heats to 200 DEG C, passes into CO2Gas, constant temperature 2h carries out chemisorbed. It is cooled to 40 DEG C under an ar atmosphere, with the rate program desorption by heating of 10 DEG C/min to 600 DEG C.
Compared with prior art, the invention have the benefit that
In the copper manganese-based catalyst of 5 kinds of different Doping with Rare Earth Lanthanum amounts that present invention experiment is done, La doping is the low temperature active of the catalyst of 0.5% is best.
Accompanying drawing explanation
Fig. 1 is the CO conversion ratio of La Modified Cu Mn catalyst, and wherein, Fig. 1 a is 450 DEG C of resistance to thermal processs (350min); Fig. 1 b is temperature-fall period after 450 DEG C of heat-resisting 350min;
Fig. 2 is the XRD figure of La Modified Cu Mn catalyst, and wherein, Fig. 2 a is catalyst sample; Fig. 2 b is sample after transformationreation;
Fig. 3 is the TPR figure of La Modified Cu Mn catalyst;
Fig. 4 is the s-TPR figure of La Modified Cu Mn catalyst, and wherein, Fig. 4 a is CuMn catalyst sample; Fig. 4 b is CuMn/La-0.5 catalyst sample; Fig. 4 c is CuMn/La-3.0 catalyst sample; Fig. 4 d is CuMn/La-5.0 catalyst sample; Fig. 4 e is CuMn/La-10.0 catalyst sample;
Fig. 5 is the CO of La Modified Cu Mn catalyst2-TPD schemes.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, technical scheme is described in more detail.
The preparation of the rare-earth metal doped La copper Mn catalyst of embodiment 1
Agents useful for same and medicine are in Table 1.
Chemical reagent used tested by table 1
Experimental design
Its preparation process is summarized as follows: by CuSO4.5H2O��MnSO4.H2O and La (NO3)3��6H2O is dissolved in a certain amount of distilled water in designed ratio and is configured to the mixed liquor that concentration is 0.225mol/L, is then neutralized by the NaOH solution that concentration is 4mol/L, generates precipitate. Obtained mixture is scrubbed, sucking filtration, obtain catalyst sample after dry, roasting. The preparation technology conceptual design of doped with rare-earth elements La copper Mn catalyst
(1) dosing
In order to obtain copper, manganese, catalyst that lanthanum ratio is substantially certain, when joining mixed solution, need to weigh the CuSO of specified quantitative4��5H2O��MnSO4.H2O and La (ON3)3��6H2O, simultaneously in order to ensure the concentration of mixed liquor, also to add a certain amount of water in the mixture, and after mixture adds water, stirring becomes the solution that mix homogeneously is consistent in 10 minutes.
Dosing process computation is as follows:
Assume precipitation only Cu (OH)2��Mn(OH)2With Mn (OH)3, precipitation be decomposed into CuO, Mn3O4. Make the mol ratio n of copper and manganese in catalystcuo: nMn3O4=1: 1, to prepare 5 grams of catalyst for benchmark, for the 0.5%La that adulterates:
Then Cu: Mn: La=49.75%: 49.75%: 0.5%=1: 1: 0.01005
If Cu2+Molal quantity be x, then (Mn2++Mn3+) for x, La3+For 0.01005x
Then CuOMn3O4La2O3
X1/3x0.01005x/2=0.005025x
M79.55228.84325.81
Then 79.55x+228.84 �� 1/3x+325.81 �� 0.005025x=5
Obtain x=0.032mol
m(CuSO4��5H2O)=0.032 �� 249.68 �� 99%=8.071g
m(MnSO4��H2O)=0.032 �� 169.02 �� 99%=5.463g
m(La(NO3)3.6H2O)=0.032 �� 0.01005 �� 433.01 �� 99%=0.141g
If CuSO4The concentration of solution is 0.225mol/L, then MnSO4The concentration of solution is also 0.225mol/L,
Then 0.225v=0.032, v=0.1422L=142.2mL
It can thus be appreciated that: in the process dissolving medicine, the required distilled water added is 142.2mL
Cu2+��2OH-Mn2+��2OH-La3+��3OH-
0.0320.0640.0320.0640.01005��0.0323��0.01005��0.032
The concentration of NaOH solution used in experimentation is 4mol/L, the alkali number of 1.2 times.
Then, n (OH-)=0.064+0.064+3 �� 0.01005 �� 0.032=0.1290mol
V (NaOH)=0.1290 �� 1.2 �� 4=38.7mL
So the volume adding NaOH solution is 38.7mL.
(2) constant temperature dissolves
Neutralize reaction for making mixed liquor and alkali liquor can occur under steady temperature (45 DEG C), mixed liquor need to be heated to and within 10 minutes, make it dissolve to constant temperature after fixed temperature, and in titration process, remain that this is temperature-resistant.
(3) neutralize
N-process is the process that copper sulfate, manganese sulfate and Lanthanum (III) nitrate and alkali liquor react generation BS. Cu in N-process2+With OH-Reaction generates Cu azury (OH)2Precipitation, Mn2+With OH-First reaction obtains the Mn (OH) of white2Precipitation, Mn (OH)2Quickly oxidized in atmosphere, generate brown Mn2O3And MnO2Hydrate. About Mn (OH)2The concrete oxidizing process of precipitation is not also fully aware of, and the reaction equation of its supposition is as follows:
Cu2++OH-��Cu(OH)2(s)
Mn2++OH-��Mn(OH)2(s)
La3++OH-��La(OH)3(s)
Cu(OH)2(s)��CuO.aH2O(s)
La(OH)3(s)��La2O3.bH2O(s)
Mn(OH)2(s)+O2(g)��Mn2O3.cH2O(s)
Mn2O3.xH2O(s)+O2(g)��MnO2.dH2O(s)
In the preparation process of catalyst, when catalyst forms a timing, catalyst performance is had material impact by the condition of N-process. In N-process, in the factor such as neutral temperature, mixed liquid concentration, concentration of lye, charging rate, pH value, stir speed (S.S.), the performance of final catalyst all may be impacted by the variation of one of them condition. The concrete technology condition of this experiment is as shown in table 2.
With process conditions and parameter in table 2
(4) over-cookeding of heat
This process is to make it keep sedimentary ageing process under uniform temperature after titration terminates, and heat is boiled and can be improved sedimentary crystal formation, and growing up of crystal grain is also played an important role. Temperature when heat is boiled is 45 DEG C, and the heat time of boiling is 30 minutes.
(5) washing
In catalyst preparation process, it is necessary to precipitate is washed so that it is pH to 7. Washing catalyst is partly in order to remove the SO being mingled with in catalyst4 2-With other foreign ion. If washing is not thorough, in dry run, impurity is likely to vaporization decomposition of being heated, and so can destroy the crystal structure of catalyst, make catalyst structure become loose, decrease in strength. On the other hand, catalyst body sulfur content thoroughly can not be caused high if not washing or washing, affect the activity of catalyst. It addition, washing process can make sedimentary crystal formation more perfect.
(6) dry
The dehydration of dry mainly solid material, generally carries out, dry 4 hours at 80 DEG C. Moisture in solid matter has three kinds: 1. chemical bonding water; 2. adsorb water, be the water of absorption in the surface of solids or pore; 3. free water, is in the water between material particles, and dry run mainly removes latter two water. The dry general chemical constitution on catalyst affects little, but the physical arrangement of double finished catalyst has impact.
Baking temperature, drying means, dry rate, dry medium difference, all by the pore size to catalyst, specific surface area, mechanical strength affect to some extent. It addition, baking temperature is too high or the time is oversize, moisture loss in catalyst being made excessive, catalyst particle is tightly combined, and pore structure changes, and affects the performance of catalyst.
(7) roasting
Roasting is an important heat treatment process in catalyst preparation process, is that hydroxide decomposes the process generating oxide. Sintering temperature, roasting time difference the aspects such as the activity of catalyst, heat stability, mechanical strength can be had a significant impact. Roasting process can remove a part of water in catalyst, makes catalyst volume shrink, and improves the mechanical strength of catalyst. Table 3 is roasting technique condition and the parameter of catalyst.
Table 3 roasting technique condition and parameter
The active testing of embodiment 2 doped with rare-earth elements La copper Mn catalyst and characterization result
Fig. 1 is the CO transformationreation active testing result of prepared catalyst. Fig. 1 a is the CO conversion ratio in 450 DEG C of heat-resisting 350min processes, and Fig. 1 b is the CO conversion ratio of temperature-fall period after 450 DEG C of heat-resisting 350min. Being schemed by Fig. 1 a it can be seen that mix the sample that La amount is 0.5%, in resistance to thermal process, CO conversion ratio remains at more than 95%, and mix the sample that La amount is 10.0%, when heat-resistant time is less than 280min, CO conversion ratio is maintained at about 93%, after 280min, CO conversion ratio is decreased obviously. Schemed from Fig. 1 b, the sample of different La dopings difference in whole active testing warm area is bigger, between 350 DEG C-450 DEG C, mix the La amount sample less than 5.0%, CO conversion ratio varies less, mixing the La amount CuMn/La-10.0 sample more than 5.0%, CO conversion ratio declines with the reduction of temperature. Between 200 DEG C-350 DEG C, mix the La amount sample less than or equal to 3.0%, CO conversion ratio is all big compared with CuMn, especially the most obvious with CuMn/La-0.5 sample, when 250 DEG C, CO conversion ratio reaches 87%, reaches 38%, and do not mix the CuMn sample of La when 200 DEG C, when 250 DEG C, CO conversion ratio only has 40%, when 200 DEG C 8.0%. Mixing the La amount sample more than 3.0%, in whole test warm area, CO conversion ratio is all relatively low, particularly CuMn/La-10.0 sample, and less than 300 DEG C substantially inactivate, illustrate that La doping is bigger to the activity influence of catalyst.
Fig. 2 is the XRD figure spectrum of sample after prepared catalyst and transformationreation, and its structural parameters are in Table 4. From Fig. 2 a, the principal crystalline phase of each sample is the Cu of spinel structure1.5Mn1.5O4(JCPDS35-1172), it does not have the characteristic peak of independent lanthanum compounds occur, illustrating that La is likely to is that dispersity is present in catalyst grain surface or enters Cu1.5Mn1.5O4Lattice. But data show in table 4, the sample interplanar distance of doping La all increases, and part La has been described3+Enter Cu1.5Mn1.5O4Lattice, this is due to La3+Radius (0.1106nm) be significantly greater than Cu+��Cu2+��Mn3+And Mn4+Radius (0.096,0.072,0.062 and 0.054nm). The doping of La directly affects interplanar distance and the grain size of sample, and CuMn/La-0.5 sample is less due to the La amount of doping, and the amplitude that interplanar distance increases is less, and grain size is little compared to CuMn change. When La doping >=3.0%, and CuMn/La-m (m=3.0,5.0,10.0) interplanar distance of sample is more or less the same, but it is all higher than CuMn/La-0.5 sample, illustrates that the La amount entering in lattice has certain limit, and crystallite dimension is little with the increase change mixing La amount. The sample of La doping >=3.0% all finds have comparatively significantly Cu oxide crystalline phase, part Cu has been described2+Do not enter into spinelle Cu1.5Mn1.5O4In lattice, it may be possible to the La entered in lattice prevents Cu2+Entrance. After transformed reaction (Fig. 2 b), the Cu of spinel structure1.5Mn1.5O4Metal solid solution is all reduced and is decomposed into Cu (JCPDS04-0836) and MnO (JCPDS07-0230), and high temperature sintering Cu crystal grain is all grown up. The amplitude mixing the La less sample Cu grain growth of amount is less, especially the most obvious with CuMn/La-0.5 sample, mix the sintering of Cu after the La more transformed reaction of sample of amount more serious, especially the most obvious with CuMn/La-10.0 sample, the amplitude that unadulterated CuMn sample simple substance Cu sintering is grown up is little compared with CuMn/La-10.0, but much larger than CuMn/La-0.5 sample. Illustrate in transformationreation process, mixing of a small amount of La can make copper manganese component be uniformly dispersed, manganese can effectively suppress the sintering of copper to grow up, mix (characteristic diffraction peak that CuMn/La-10.0 sample has simple substance La at 29.4 DEG C) of more La disturbs the manganese cooperative effect to copper, makes copper can not get effectively isolating and agglomeration. In addition CuMn and CuMn/La-0.5 sample has MnCO at 31.5 ��3(JCPDS44-1472) characteristic peak.
The structural parameters of table 4La Modified Cu Mn catalyst
Fig. 3 is the H of prepared catalyst2-TPR spectrogram. In conjunction with prior art and experimental analysis it can be seen that the reduction main peak temperature of each sample all between 250-350 DEG C (�� peak), it is believed that be copper galaxite phase Cu1.5Mn1.5O4Reduction, compared to prior art report Mn2O3Reduction want easily, this phenomenon may be interpreted as the copper also original facilitation to manganese. Morales etc. think, there is the Mn of the fault of construction relevant to Lacking oxygen and high dispersive in copper manganese mixed phase2O3It is easier to reduction. In addition, acromion (�� peak) has been it was additionally observed that between 100-250 DEG C, think the reduction of copper oxide, when La doping is less than 3.0%, copper oxide is that high degree of dispersion state is present in sample the existence of CuO (XRD be not detected by), and this result means all to have in all samples a small amount of Cu2+Do not enter in spinel crystal lattice, Cu2+At copper galaxite Cu1.5Mn1.5O4Middle ratio is more difficult to reduction in CuO, and this part CuO is easy to be reduced (when La doping is less than 3.0%, it is easier to reduction), and in reduction reaction process, because not having the synergism of manganese, the copper crystal grain of generation is easy to caking and becomes big. As shown in Figure 3, La doping is the CuMn/La-0.5 sample of 0.5%, reduction temperature reduces, its main peak is reduced to 273 DEG C by 285 DEG C of CuMn sample, and mixes La amount CuMn/La-m (m=5.0, the 10.0) sample more than 3.0%, reduction main peak temperature all relatively CuMn sample is high, the same chemical environment site made it possible to hydrogen reaction of mixing being likely to be due to more La is wrapped, and hydrogen is in body middle mass transfer difficulty mutually, and therefore reduction temperature all increases.
The s-TPR curve of Fig. 4 and Biao 5 respectively catalyst and parameter result of calculation. As shown in Figure 4, the secondary reduction peak summit temperature of an each sample all relatively reduction peak shifts to an earlier date more than 70 DEG C, and what H2 secondary reduction was described is copper oxide surface. Twice reduction temperature of CuMn/La-10.0 sample is all the highest (especially the reduction temperature of surface copper), show its difficult reduction, although the overall reduction temperature of CuMn sample is not high, but the reduction temperature of surface copper is higher, twice reduction temperature of CuMn/La-0.5 sample is all relatively low, illustrate that this sample is easier to reduction, consistent with H2-TPR characterization result. As can be seen from Table 5, each sample has different surface copper dispersion (SAcu(m2g-1)), CuMn/La-0.5 sample has the highest surface copper dispersion (35.96m2g-1), its surface copper species chemism is high, the surface copper dispersion (17.58m of CuMn/La-10.0 sample2g-1) minimum, the amplitude that reason is the Cu grain growth that CuMn/La-0.5 sample obtains owing to the cooperative effect between copper manganese is good in reduction reaction process is less, be conducive to Cu crystal grain in the dispersion of catalyst surface, and CuMn/La-10.0 sample Cu in course of reaction is grained sintered seriously, it is impossible to effectively disperse on its surface.
The s-TPR of table 5La Modified Cu Mn catalyst calculates parameter
Fig. 5 is the CO of prepared catalyst sample2-TPD spectrogram. As seen from Figure 5, the sample CO after La is mixed2Desorption peaks is bimodal, illustrates there is two distinct types of chemisorbed position on sample surfaces, and inhomogeneous adsorption potential is to CO2Adsorption strength is different with adsorbance, and the adsorption strength of primary adsorption position weakens with the increase of La doping, and the adsorption strength of secondary adsorption position strengthens with the increase of La doping, and namely too much the doping of La adds CO2Desorption difficulty. With the increase of La doping, CO2Adsorbance increases, when La doping is more than 3.0%, and CO2The amplitude that adsorbance increases reduces. La doped samples is to CO2Adsorption desorption is it is shown that La is doped with helping increase the surface basic site of this catalyst, but when La doping exceedes certain proportion, then the amplitude that its surface basic site increases reduces. The size of different types of two kinds of basic sites adsorption strengths and adsorbance difference, it was shown that the scattered uniformity coefficient of copper manganese component in catalyst, increases with the increase of La doping, the adsorption strength of two kinds of basic sites and adsorbance difference. CuMn/La-0.5 sample is less due to the difference of two kinds of basic sites, to CO2Adsorbance moderate, therefore show good catalysis activity, and the adsorption strength of two kinds of basic sites of CuMn/La-m (5.0,10.0) sample and adsorbance difference be relatively big, to CO2Absorption relatively strong, adsorbance is relatively big, covers amount of activated position, and the activity therefore shown is poor, and CuMn sample is to CO2Absorption very little, relatively CuMn/La-0.5 sample is poor for the activity shown.
The present invention have studied the impact on water gas shift reaction catalytic performance of the Cu-Mn catalyst of different La doping, utilizes XRD, TPR/s-TPR, CO2Prepared catalyst sample has been characterized by-TPD etc. Result shows, La doping is that 0.5% (mol) catalyst prepared is compared with pure Cu-Mn sample, due to copper manganese uniform component distribution, intermetallic cooperative effect is good, can effectively increase the dispersibility of surface copper and make low temperature shift reaction catalytic performance significantly improve. Except there being Cu in the catalyst sample of La doping >=3.0%1.5Mn1.5O4Outside crystalline phase, also have comparatively significantly CuO crystalline phase, and the amplitude that surface basic site increases with the increase of La doping reduces, higher La doping covers amount of activated position due to the gathering of La, manganese can not effectively suppress growing up of copper crystal grain, makes the dispersion of surface copper decline and cause that water gas shift reaction activity substantially reduces.
The above; it is only the present invention preferably detailed description of the invention; protection scope of the present invention is not limited to this; any those familiar with the art is in the technical scope of present disclosure, and the simple change of the technical scheme that can become apparent to or equivalence are replaced and each fallen within protection scope of the present invention.
Claims (2)
1. a rare-earth metal doped La copper Mn catalyst, it is characterised in that adulterate 0.5% rare earth element.
2. the experimental technique of rare-earth metal doped La copper Mn catalyst described in a claim 1, it is characterised in that comprise the following steps:
Step 1: the preparation of doped with rare-earth elements La copper Mn catalyst
1.1) dosing
By CuSO4��5H2O��MnSO4��H2O and La (NO3)3��6H2O is configured to the mixed liquor that concentration is 0.225mol/L by a certain percentage;
1.2) constant temperature dissolves
Being placed in by mixed liquor in the thermostat water bath of 45 DEG C, stir speed (S.S.) is maintained at 300rad/min, and constant temperature makes it fully dissolve in 10 minutes, and remains that in titration process this is temperature-resistant;
1.3) neutralize
The NaOH solution that mixed liquor concentration is 4mol/L after dissolving is neutralized and is precipitated thing, neutral temperature 45 DEG C, neutralize endpoint pH 11.5, neutralizer titration speed 10.5rad/min, be kept stirring for speed 300rad/min;
1.4) over-cookeding of heat
The precipitate obtained being carried out heat boil, temperature when heat is boiled is 45 DEG C, and the heat time of boiling is 30min;
1.5) washing
Wash through the overheated precipitate boiled so that it is pH to 7;
1.6) dry
Carry out at 80 DEG C, dry 4 hours;
1.7) roasting
Roasting medium is air, sintering temperature 550 DEG C, heating rate 5 DEG C/min, roasting time 4h;
Step 2: catalyst activity is tested
The active testing experiment of catalyst completes on fixed bed coal burning-gasification reactor apparatus, fixed bed coal burning-gasification reactor apparatus belongs to fixed bed adiabatic formula integral reactor, tube inner diameter is 6mm, active testing process is: first through molecular sieve, the unstripped gas from steel cylinder is removed impurity molecule therein, trace oxygen is removed subsequently into deoxidation pipe, measure then through spinner flowmeter, enter reaction tube from top to bottom catalyst is reduced, the reacted reducing gases of catalyzed oxidant layer is then through condensation, Silicagel dehydration finally empties, after having reduced, unstripped gas is removed through molecular sieve and after impurity molecule therein, enter deoxidation pipe elimination trace oxygen, then after spinner flowmeter measures, the reaction gas with certain WGR is become through saturated steam pipe humidification, reaction gas enters reaction tube from top to bottom and carries out the transformationreation of CO, the reacted conversion gas of catalyzed oxidant layer is then through condensation, sample after Silicagel dehydration, use gas chromatograph on-line analysis, Thermal Conductivity goes out the composition of the gas after transformationreation,
Step 3:XRD/TPR/s-TPR/TPD tests
XRD crystal phase analysis carries out on Germany's BrukerD8advanceX ray powder diffractometer, Cu target, and Ni filters, Si-Li detector, 40KV �� 40mA, sweep limits 20 ��-80 ��, 2 ��/min of scanning speed;
TPR test is to carry out in the U-shaped quartz tube reactor of normal pressure, with 8.9%H2/ Ar mixing gas is reducing gases, reducing gases flow velocity: 30mL/min, sample dosage: 20mg, granularity: 40-80 order, before catalyst carries out TPR test, first carrying out pretreatment, pretreatment condition is that in room temperature, catalyst is raised to 120 DEG C under Ar gas atmosphere, drop to 40 DEG C again after purging 30min, then switch to 8.9%H2/ Ar mixing gas, after baseline is walked and put down, with the speed of 10 DEG C/min from room temperature to 600 DEG C;
S-TPR test is that sample completes as above to be cooled to 40 DEG C after TPR step, sweeps 30 minutes to system stability with Ar air-blowing, passes into the N that flow is 30mL/min2O gas carries out surface oxidation 30 minutes to system stability, then passes into the 8.9%H that flow is 50mL/min2/ Ar gaseous mixture, is raised to 600 DEG C with the speed of 10 DEG C/min;
CO2-TPD test is that sample completes as above to be cooled to 40 DEG C after TPR step, then heats to 200 DEG C, passes into CO2Gas, constant temperature 2h carries out chemisorbed, is cooled to 40 DEG C under an ar atmosphere, with the rate program desorption by heating of 10 DEG C/min to 600 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610072689.8A CN105618081A (en) | 2016-01-31 | 2016-01-31 | Rare earth metal La doped copper manganese catalyst and experiment method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610072689.8A CN105618081A (en) | 2016-01-31 | 2016-01-31 | Rare earth metal La doped copper manganese catalyst and experiment method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105618081A true CN105618081A (en) | 2016-06-01 |
Family
ID=56033654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610072689.8A Pending CN105618081A (en) | 2016-01-31 | 2016-01-31 | Rare earth metal La doped copper manganese catalyst and experiment method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105618081A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603842A (en) * | 2018-12-03 | 2019-04-12 | 四川大学 | Cu-Mn complex oxide catalyst of La doped and preparation method thereof |
| CN110280266A (en) * | 2019-07-23 | 2019-09-27 | 福建龙新三维阵列科技有限公司 | Metal oxide catalyst and its preparation with high stability energy |
| CN110793855A (en) * | 2019-11-13 | 2020-02-14 | 北京理工大学 | Evaluation method for intercrystalline stress of polycrystalline alloy with cubic structure |
| CN111644182A (en) * | 2020-03-05 | 2020-09-11 | 王金波 | Honeycomb ceramic monolithic catalyst for rapidly catalyzing and oxidizing CO under high airspeed condition and preparation method thereof |
| CN112828279A (en) * | 2020-12-31 | 2021-05-25 | 昆明理工大学 | Metal powder gas phase deoxidation method |
| CN113401946A (en) * | 2021-07-16 | 2021-09-17 | 中国科学院兰州化学物理研究所 | Light absorption material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006239557A (en) * | 2005-03-03 | 2006-09-14 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift reaction |
| CN101607201A (en) * | 2009-07-16 | 2009-12-23 | 复旦大学 | Be difficult for water gas converting catalyst of spontaneous combustion and its production and application |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
| CN105797741A (en) * | 2016-01-19 | 2016-07-27 | 宁波钛安新材料科技有限公司 | Copper-doped manganese dioxide catalyst and preparation method therefor |
-
2016
- 2016-01-31 CN CN201610072689.8A patent/CN105618081A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006239557A (en) * | 2005-03-03 | 2006-09-14 | National Institute Of Advanced Industrial & Technology | Catalyst for water gas shift reaction |
| CN101607201A (en) * | 2009-07-16 | 2009-12-23 | 复旦大学 | Be difficult for water gas converting catalyst of spontaneous combustion and its production and application |
| CN102451701A (en) * | 2010-10-22 | 2012-05-16 | 中国石油化工股份有限公司 | High-concentration CO synthesis gas sulfur tolerance conversion pre-conversion treatment method |
| CN105797741A (en) * | 2016-01-19 | 2016-07-27 | 宁波钛安新材料科技有限公司 | Copper-doped manganese dioxide catalyst and preparation method therefor |
Non-Patent Citations (2)
| Title |
|---|
| HE RUNXIA ET AL.: "Effect of doping rare earth oxide on performance of copper-manganese catalysts for water-gas shift reaction", 《JOURNAL OF RARE EARTHS》 * |
| 姜浩强: "稀土掺杂对铜锰催化剂织构和水煤气变换反应催化性能的影响", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603842A (en) * | 2018-12-03 | 2019-04-12 | 四川大学 | Cu-Mn complex oxide catalyst of La doped and preparation method thereof |
| CN109603842B (en) * | 2018-12-03 | 2022-03-29 | 四川大学 | Lanthanum-doped copper-manganese composite oxide catalyst and preparation method thereof |
| CN110280266A (en) * | 2019-07-23 | 2019-09-27 | 福建龙新三维阵列科技有限公司 | Metal oxide catalyst and its preparation with high stability energy |
| CN110793855A (en) * | 2019-11-13 | 2020-02-14 | 北京理工大学 | Evaluation method for intercrystalline stress of polycrystalline alloy with cubic structure |
| CN110793855B (en) * | 2019-11-13 | 2021-03-02 | 北京理工大学 | Evaluation method for intercrystalline stress of polycrystalline alloy with cubic structure |
| CN111644182A (en) * | 2020-03-05 | 2020-09-11 | 王金波 | Honeycomb ceramic monolithic catalyst for rapidly catalyzing and oxidizing CO under high airspeed condition and preparation method thereof |
| CN112828279A (en) * | 2020-12-31 | 2021-05-25 | 昆明理工大学 | Metal powder gas phase deoxidation method |
| CN112828279B (en) * | 2020-12-31 | 2022-08-12 | 昆明理工大学 | Metal powder gas phase deoxidation method |
| CN113401946A (en) * | 2021-07-16 | 2021-09-17 | 中国科学院兰州化学物理研究所 | Light absorption material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105618081A (en) | Rare earth metal La doped copper manganese catalyst and experiment method thereof | |
| Lai et al. | Oxygen vacancy engineering in spinel-structured nanosheet wrapped hollow polyhedra for electrochemical nitrogen fixation under ambient conditions | |
| CN107930672B (en) | Metal-nitrogen-carbon material with metal in atomic-level dispersion, preparation method and application thereof | |
| CN101829579B (en) | Preparation method and application of cerium-zirconium composite oxide catalyst loaded with copper oxide | |
| CN103480375A (en) | Carbon monoxide methanating catalyst and preparation method thereof | |
| CN104399491B (en) | A kind of high temperature resistant methanation catalyst and preparation method thereof | |
| CN101564690A (en) | Preparation method of perovskite-like La*NiO* and applications | |
| CN107570162B (en) | Nickel-based catalyst for reverse water gas shift reaction and preparation method thereof | |
| CN108043406B (en) | A kind of derivative cobalt-base catalyst of auxiliary agent promotion hydrotalcite of acetic acid self-heating reforming hydrogen manufacturing | |
| CN107042111A (en) | The laminated perovskite type catalyst and preparation method of a kind of acetic acid self-heating reforming hydrogen manufacturing | |
| CN106311269B (en) | Ferrum-based catalyst, preparation method and the application of sol-gel combustion method preparation | |
| Zeng et al. | Promotional effect of preparation methods on catalytic reduction of NO by CO over CoCeO x catalysts | |
| CN108993530A (en) | A kind of preparation method and application of hydrotalcite NiMnTi catalyst | |
| CN112473678B (en) | Catalyst for wet quenching coke steam mixed reforming of methane and preparation method thereof | |
| CN102091617A (en) | Cu-based low-temperature water gas conversion catalyst under hydrogen rich reformed gas and preparation method thereof | |
| Xu et al. | Enhancement low-temperature NH3-SCR activity of the Fe-Mn-Mo/TiO2 catalyst and its DFT calculations and kinetics | |
| CN110075889B (en) | Catalyst for hydrogen production by methanol reforming and preparation method thereof | |
| CN102864008B (en) | Composite oxide oxygen carrier and preparation method and application thereof | |
| Su et al. | The Template‐Free Synthesis of CuO@ CeO2 Nanospheres: Facile Strategy, Structure Optimization, and Enhanced Catalytic Activity toward CO Oxidation | |
| Liu et al. | Catalytic combustion of toluene over Cu–Mn mixed oxide catalyst | |
| CN102862960A (en) | Application and preparation of high-activity composite oxide oxygen carrier in chemical link circulation hydrogen production | |
| CN105032437B (en) | Perovskite type composite oxide catalyst and its preparation method and application | |
| Yi et al. | Green and facile synthesis of nanostructured Co3O4/CeO2 catalysts via a glucose-urea method for NO oxidation | |
| CN111450840B (en) | Cobalt-cerium-manganese composite oxide catalyst for autothermal reforming of acetic acid to produce hydrogen | |
| Tian et al. | Preparation and characterization of Cu-doped mesoporous CeO2 for CO oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160601 |