CN108686671A - A kind of preparation of low-temp methanol decomposition catalyst - Google Patents
A kind of preparation of low-temp methanol decomposition catalyst Download PDFInfo
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- CN108686671A CN108686671A CN201810592702.1A CN201810592702A CN108686671A CN 108686671 A CN108686671 A CN 108686671A CN 201810592702 A CN201810592702 A CN 201810592702A CN 108686671 A CN108686671 A CN 108686671A
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- 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
- B01J23/835—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 germanium, tin or lead
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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
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- 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
- C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses a kind of high activities to decompose methanol CO and H under the conditions of low-temp reaction2Catalyst and preparation method thereof, catalyst used is the ferrum-based catalyst being modified with tin-oxide, cerium oxide, lanthanum-oxides and gallium oxide, and the molar ratio of each metal is Fe:Sn:Ce:La:Ga=100:0.5~10:0.1~1:0.1~1:0.1~1.Method for preparing catalyst uses coprecipitation.The reaction absolute pressure 0.05-0.1MPa, GHSV are 5000-9000 h-1, reaction temperature is under 80-150 DEG C of reaction condition, methanol conversion reaches as high as 73.2%, to CO selectively close to 100%.The catalyst can be in low temperature(80-150℃)Under the conditions of close to the prior art(200 DEG C or more)Conversion ratio, reduce the operation cost, improve catalytic efficiency.
Description
Technical field
The invention belongs to chemical catalyst preparation method fields, specifically, being related to a kind of catalysis that low-temperature methanol decomposes
Agent and preparation method thereof.
Background technology
With the fast development of science and technology, using quickly growing, each advanced country will also fire energy conversion from fossil
Material gradually transfers to utilize sustainable development, the free of contamination non-fossil energy.Compared with existing gaseous fuel, methanol derives from a wealth of sources,
It is common industrial chemicals, easily stored and transport, is H2With the good carriers of CO.But methanol directly burns and pays no attention to as fuel
Think, the calorific value of unit volume is relatively low, and the latent heat of vaporization is larger.Such as methanol is catalytically decomposed to obtain H2And CO, and due to H2
It is the highest gas of calorific value, therefore methanol is considered as a kind of hydrogen storage material of safe ready, is H2With the good carriers of CO.Methanol
Catalytic pyrolysis H2It can occur under normal pressure with CO, theoretically there is 30% or so conversion ratio at 100 DEG C, since temperature occurs
It is relatively low, it can be reacted using the waste heat of combustion engine, and single raw material is also one of its advantage.Therefore, methanol
Catalytic pyrolysis H2There is good application prospect with CO.
In recent ten years, the catalyst that the catalysis methanol of many types decomposes is developed.It is wherein representative
Mainly copper-based, Ni-based and noble metal carrier catalyst.R. Nickolov etc. (Fuel, 2002,81:203-209) open
The copper-based catalysts of Cu (4.1 wt.%)/oxidized AC are sent out.The catalyst is 1.6 vol.% in methanol content(Carrier gas is
He gas, similarly hereinafter), WHSV is 1.5 h-1, selectively it is 100% (210 DEG C) -78% to CO(310 ℃), non-CO objects system is formic acid
Methyl esters;T. (the Journal of Molecular Catalysis A such as Tsoncheva: Chemical, 2005, 225:
245-251) Cu (the 5wt.%)/AC catalyst developed is 1.6 vol.% in methanol content, and WHSV is 0.63 h-1, temperature is
350 DEG C, to CO selectivity more than 90%, non-CO objects system be methyl formate and methane, but its conversion ratio can within 1 h from
100% drops to 30%, inactivates quickly;(the Applied Catalysis B such as Gregorio Marb á n: Environmental,
2010, 99:257-264) the U-350-35 catalyst developed, pre-processes 1 h using high-purity He at 350 DEG C, contains in methanol
Amount is 10 vol.%, and WHSV is 4.2 h-1, selectively it is 92% (225 DEG C) -100 (275 DEG C) to CO, non-CO objects system is first
Sour methyl esters, can be in 7 h of steady operation under condition of different temperatures.
Y. (the Journal of Molecular Catalysis A such as Matsumura: Chemical, 2000, 152:
157-165) develop nickel-base catalyst.They are by Ni (40 wt.%)/SiO of synthesis2Catalyst 17% hydrogen 500
It is 25 vol.% in methanol content, WHSV is 4.0 h after pre-processing 1h at DEG C-1, reaction temperature is to carry out methanol at 250 DEG C to urge
Change decomposition reaction, it is 91% to find CO selectively.But nickel-base catalyst can generate methane CH during the reaction4, so for H2
It is not high with the selectivity of CO.
M.P. (the Journal of Molecular Catalysis A such as Kapoor: Chemical, 2003, 198:
303-308) developing group becomes Pd (3 wt.%)/TiO2Noble metal carrier catalyst.H of the catalyst 20%2300
It is 20 vol.% in methanol content, WHSV is 6.39 h after pre-processing 1 h at DEG C-1, run under non-constant temperature, CO selected
Selecting property is 100%;K. (the Applied Catalysis A such as Sun: General, 2004, 268:107-113) the Pd developed
(2 wt.%)/La/CeO2, use 10% H21h, pure methanol feeding are pre-processed at 400 DEG C, WHSV is 0.95 h-1, CO is selected
Selecting property is down to the 92% of 290 DEG C from the 99% of 220 DEG C, and by-product is mainly CO2And CH4。
In conclusion the catalyst activity of copper-based catalysts is relatively low, and can be generated in methanol oxidation decomposable process more
Byproduct formic acid methyl esters.Nickel-base catalyst can generate methane during the reaction, so for H2It is not high with the selectivity of CO.
Your gold support type metal catalyst(Such as Pt, Pd)Although decomposing H processed to methanol oxidation2There is higher catalytic activity with CO,
But its catalytic performance is also influenced by carrier.Also, copper-based, Ni-based and noble metal support type the Methanol Decomposition studied at present is urged
The reaction temperature of agent rarely has 100 DEG C or so of methanol oxidation to decompose research, reaction velocity is small to be also at 220 DEG C or more
Its very important problem.In order to save the cost of catalyst preparation, reaction temperature and the reduction of Methanol Decomposition is greatly lowered
Energy consumption needed for reaction, in order to using the waste heat of alcohol-ether fuel vehicle, be by the larger Methanol Decomposition of the latent heat of vaporization preferably
The H of high heating value2And CO, it would be highly desirable to develop a kind of low temperature, high activity and long-life carbinol resolving catalyst.
Invention content
The purpose of the present invention is intended to provide a kind of under cryogenic conditions(80-150 ℃)Catalysis methanol decomposes the system of CO processed
Preparation Method is doped on ferrum-based catalyst using cerium oxide and lanthanum-oxides and is modified to it, wherein iron is as activearm
Point, for tin as co-catalyst, the modification of lanthanum cerium can inhibit the generation of by-product dimethyl ether, gallium that can greatly improve low temperature active
And stability, solve the conversion ratio of current Methanol Decomposition under cryogenic it is low, to CO and H2Poor selectivity, service life are shorter
Deng and the shortcomings of involve great expense.The preparation method of the catalyst includes the following steps:
1)It is according to component proportion, the presoma of tin-oxide, cerium oxide, lanthanum-oxides, gallium oxide and ferriferous oxide is molten
Liquid dissolves in deionized water, and it is 0.1-2.0 molL to be configured to total concentration-1Solution, to described under the conditions of 60 DEG C
Precipitating reagent is added in solution to be titrated, until pH value is 4-11, the aging at 25-65 DEG C under stirring condition;
2)1) solution obtained is obtained into sediment after suction filtration, after washing removes nitrate ion for several times, at 40-150 DEG C
Lower drying 12-48 h calcine 1-12 h in 300-700 DEG C, obtain blocks of solid.
The presoma of tin-oxide includes one or both of stannic chloride and stannous chloride.
The presoma of cerium oxide includes one or more in cerous nitrate, cerous acetate and cerium oxalate.
The presoma of lanthanum-oxides includes one or more in lanthanum nitrate, lanthanum acetate and lanthanum oxalate.
The presoma of gallium oxide includes the one or two of gallium nitrate, acetic acid gallium.
The presoma of ferriferous oxide includes the one or more of ferric nitrate, iron chloride, ferric acetate and ferric oxalate.
Precipitating reagent is the one or more of urea, ammonium hydroxide, sodium hydroxide and potassium hydroxide.
The metal oxide catalyst decomposed for low-temperature methanol prepared by the precipitation method, which is characterized in that the catalysis
The atomic molar ratio of each metal of agent is Fe:Sn:Ce:La:Ga=100:0.5~10:0.1~1:0.1~1:0.1~1.
The reaction temperature that low-temperature methanol decomposes is 80-150 DEG C;Reaction absolute pressure is 0.05-0.1 MPa;Reactant
GHSV is 5000-9000 h-1。
The present invention compared with the existing technology, under the conditions of the active testing, has reaction temperature relatively low(80-150
℃), the high conversion rate of methanol(Up to 73.2%), CO high selectivities(Close to 100% or more)The advantages of.
Specific implementation mode
The catalyst of high activity methanol low-temperature decomposition of the present invention is described further below by specific example.
Embodiment 1:It is raw material to choose ferric nitrate, stannic chloride, cerous nitrate, lanthanum nitrate and gallium nitrate, accurately prepares each pivot
Molar ratio is Fe:Sn:Ce:La:Ga=100:2:0.1:0.1:0.1, total concentration is 1 molL-1Solution;It takes out above-mentioned molten
Liquid pours into large beaker, it is put into thermostatical water bath, and using mechanical stirring device, rotating speed is controlled in 300 r/min, temperature
PH electrodes are inserted into the solution configured by control at 60 DEG C or so, after solution temperature and pH registrations are stablized, prepare 1:1
Above-mentioned solution is added dropwise in ammonia spirit by ammonia spirit, be titrated to pH value be 7 until, in 60 DEG C of agings 6 after the completion of titration
h;Sediment is filtered using Buchner funnel, the precipitation filtered out makes to be washed with deionized for several times, it is to be removed it is extra from
After son, sediment is put into togerther in porcelain boat together with filter paper and is sent into dry in baking oven, drying temperature is 100 DEG C, and drying time is
24 h;Precipitation after drying, which is put into mortar, to be ground to without apparent granular sensation(Below 100 mesh)And it is 4.5 to be shaped to radius
Mm, the highly cylinder for 6 mm;Then sample calcines 3 h in 500 DEG C of Muffle furnace, is crushed, takes out after being taken out after calcining
Sample between 30-50 mesh is the catalyst that the low-temperature methanol that can be used for testing decomposes.It is at one to be catalyzed reaction evaluating
It is carried out in the fixed bed reactors that caliber is 15 mm, takes the above-mentioned catalyst of 1 L to be fitted into reactor, the reaction absolute pressure
0.05 MPa, reaction velocity GHSV are 7000 h-1, reaction absolute pressure is 0.08 MPa, and bed temperature is 150 DEG C.Reaction knot
Fruit is as shown in table 1.
Embodiment 2:Catalyst preparation step is with embodiment 1, particularly, chooses ferric acetate, stannic chloride, cerous acetate, acetic acid
Lanthanum and acetic acid gallium are raw material, and it is Fe accurately to prepare each pivot molar ratio:Sn:Ce:La:Ga=100:3:0.2:0.2:0.1, it is overall
A concentration of 1 molL-1Solution, solution be titrated to pH value be 9 until, filtration cakes torrefaction condition be 80 DEG C, 24 h.Catalysis is anti-
Same embodiment 1 should be evaluated, particularly, reaction velocity GHSV is 5000 h-1, reaction absolute pressure is 0.1 MPa, and bed temperature is
120 ℃.The results are shown in Table 1.
Embodiment 3:Catalyst preparation step is with embodiment 1, particularly, chooses ferric nitrate, stannic chloride, cerous nitrate and nitric acid
Lanthanum is raw material, and it is Fe accurately to prepare each pivot molar ratio:Sn:Ce:La:Ga=100:3:0.2:0.2:0.2, total concentration 0.7
The solution of molL-1, solution be titrated to pH value be 9 until, filtration cakes torrefaction condition be 110 DEG C, 24 h, calcination condition 550
DEG C, 3 h.Reaction evaluating is catalyzed with embodiment 1, particularly, reaction absolute pressure is 0.08 MPa, and reaction velocity GHSV is 8000
h-1, bed temperature is 100 DEG C.Reaction result is as shown in table 1.
Embodiment 4:Catalyst preparation step is with embodiment 1, particularly, chooses ferric nitrate, stannous chloride, cerous nitrate, nitre
Sour lanthanum and acetic acid gallium are raw material, and it is Fe accurately to prepare each pivot molar ratio:Sn:Ce:La:Ga=100:4:0.1:0.1:0.1, always
Bulk concentration is 0.5 molL-1Solution, solution be titrated to pH value be 8 until, filtration cakes torrefaction condition be 110 DEG C, 24 h.It urges
Change reaction evaluating with embodiment 1, particularly, reaction absolute pressure is 0.05 MPa, and reaction velocity GHSV is 5000 h-1, bed
Temperature is 80 DEG C.Reaction result is as shown in table 1.
Embodiment 5:Catalyst preparation step is with embodiment 1, particularly, chooses ferric nitrate, stannic chloride, cerous nitrate, nitric acid
Lanthanum and gallium nitrate are raw material, and it is Fe accurately to prepare each pivot molar ratio:Sn:Ce:La:Ga=100:4:0.1:0.1:0.2, it is overall
A concentration of 0.5 molL-1Solution, solution is titrated to until pH value is 9, and in 50 DEG C of 6 h of aging after the completion of titration, filter cake is dry
Dry condition is 150 DEG C, 24 h, and sample calcination condition is 550 DEG C, 5 h.Reaction evaluating is catalyzed with embodiment 1, particularly, is reacted
Absolute pressure is 0.1 MPa.Reaction result is as shown in table 1.
Comparative example illustrates the catalyst of distinct methods synthesis on the active influence of Methanol Decomposition.
Comparative example 1:
This comparative example illustrates according to (the Journal of Molecular Catalysis A such as Y. Matsumura:
Chemical, 2000, 152:Method synthesis 157-165) proposed.
Under room temperature, 20.833 g tetraethyl orthosilicates of precise, 4.6 g ethyl alcohol, 12 g water after mixing,
Add 0.3 mL nitric acid acidifications and the nickel nitrate solution of a concentration of 1 mol/L, object to be mixed that hydrolysis occurs and gathers dropwise again
Cooperation with after 2 h, under the conditions of 120 DEG C by drying be solid, solid is roasted into 5 h to remove extra nitre at 400 DEG C
Acid ion and remaining organic component.After pre-processing 1 h at 17% 500 DEG C of atmosphere of hydrogen, Ni/SiO is obtained2Catalyst.
Reaction evaluating condition is catalyzed with example 1, particularly, bed temperature is 150 DEG C, and reaction absolute pressure is 0.1 MPa, catalysis point
It is as shown in table 1 to solve reaction result.
Comparative example 2
This comparative example illustrates according to (the Applied Catalysis A such as K. Sun: General, 2004, 268:107-113)
The method synthesis of proposition.
Under room temperature, 0.177 g PdCl of precise2With 0.433 g La (NO3)3·6H2O is dissolved in 500 mL's
In deionized water, 8.85 g CeO are added2Powder carries out solution using mechanical agitation paddle to continue stirring, stir speed (S.S.) 800
r·min-1, then use 0.25 molL-1Nac2CO3It is added dropwise in mixed solution, until pH is 10, will precipitate
It is filtered, precipitation is washed using distilled water when filtering, to remove extra chlorion, is deposited at 120 DEG C dry
4 h obtain 2wt.%PdLa/CeO after finally calcining 3 h at 400 DEG C2.It is catalyzed reaction evaluating condition with example 1, especially
Ground, bed temperature are 120 DEG C, and reaction absolute pressure is 0.1 MPa, and the results are shown in Table 1 for cartalytic decomposition effect.
The low-temperature methanol degrading activity table of 1 catalyst of table
| Embodiment | Methanol conversion, % | CO selectivity, % |
| 1 | 73.2 | 99.7 |
| 2 | 42.8 | 73.2 |
| 3 | 35.4 | 70.2 |
| 4 | 16.6 | 86.7 |
| 5 | 69.8 | 96.8 |
| Comparative example 1 | 8.6 | 70.6 |
| Comparative example 2 | 10.7 | 65.4 |
Above-described embodiment illustrates that Fe-series catalyst of the invention is controlled in reaction temperature at 80-150 DEG C;React absolute pressure
Power is 0.05-0.1 MPa;The GHSV of reaction mass is 5000 ~ 9000 h-1.The conversion ratio of best methanol is up to 73.2%, CO
Selectivity is a kind of catalyst that excellent low-temperature methanol decomposes up to 99.7%.
Claims (5)
1. the metal oxide catalyst decomposed for low-temperature methanol prepared by a kind of precipitation method, which is characterized in that the catalysis
The atomic molar ratio of each metal of agent is Fe:Sn:Ce:La:Ga=100:0.5~10:0.1~1:0.1~1:0.1~1.
2. the catalyst that low-temperature methanol according to claim 1 decomposes, which is characterized in that the methanol decomposition reaction
Condition is absolute pressure 0.05-0.1 MPa, and GHSV is 5000-9000 h-1, reaction temperature is 80-150 DEG C.
3. the preparation method for the catalyst that low-temperature methanol decomposes according to claim 1, it is characterised in that include the following steps:
1)It is according to component proportion, the presoma of tin-oxide, cerium oxide, lanthanum-oxides, gallium oxide and ferriferous oxide is molten
Liquid dissolves in deionized water, and it is 0.1-2.0 molL to be configured to total concentration-1Solution, to the solution at 60 DEG C
Middle addition precipitating reagent is titrated, until pH value is 4-11, the aging at 25-65 DEG C under stirring condition;
2)By 1)In solution obtain sediment after suction filtration, after washing removes excess ions for several times, dried at 40-150 DEG C
Dry 12-48 h calcine 1-12 h in 300-700 DEG C, obtain blocks of solid catalyst.
4. the preparation method of the catalyst according to claim 3 decomposed for low-temperature methanol, it is characterised in that step 1)
In, the presoma of tin-oxide includes the one or two of stannic chloride and stannous chloride, and the presoma of cerium oxide includes nitric acid
One or more in cerium, cerous acetate and cerium oxalate, the presoma of lanthanum-oxides includes in lanthanum nitrate, lanthanum acetate and lanthanum oxalate
One or more, the presoma of gallium oxide includes the presoma packet of gallium nitrate, the one or two of acetic acid gallium and ferriferous oxide
Include the one or more of ferric nitrate, iron chloride, ferric acetate and ferric oxalate.
5. the preparation method of the catalyst according to claim 3 decomposed for low-temperature methanol, it is characterised in that step 1)
In, precipitating reagent is the one or more of urea, ammonium hydroxide, sodium hydroxide and potassium hydroxide.
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Application publication date: 20181023 |