CN103908967A - Catalyst for hydrogen production by reforming by carbon monoxide steam as well as preparation method thereof - Google Patents

Catalyst for hydrogen production by reforming by carbon monoxide steam as well as preparation method thereof Download PDF

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CN103908967A
CN103908967A CN201410127860.1A CN201410127860A CN103908967A CN 103908967 A CN103908967 A CN 103908967A CN 201410127860 A CN201410127860 A CN 201410127860A CN 103908967 A CN103908967 A CN 103908967A
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catalyst
nitrate
sediment
mixed solution
carbon monoxide
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CN103908967B (en
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吴洪达
刘天时
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Guangxi University of Science and Technology
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Guangxi University of Science and Technology
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract

The invention discloses a catalyst for hydrogen production by reforming by carbon monoxide steam as well as a preparation method thereof. The catalyst consists of oxides of cerium, zirconium, copper and ferrum, and the chemical formula is CumFenCepZrqOx. The method comprises the following steps: A. preparing a catalyst carrier: dissolving zirconium nitrate and cerous nitrate into water so as to form a metal nitrate mixed solution, mixing and reacting the metal nitrate mixed solution and a precipitator so as to generate initial sediment, filtering, washing, refiltering, drying and roasting the acquired initial sediment so as to form the catalyst carrier consisting of a cerium zirconium oxide; B. loading cupric nitrate and ferric nitrate: loading cupric nitrate and ferric nitrate for the catalyst carrier by an impregnation method so as to prepare medium-term precipitate; C. dispersing and filtering; D. drying; and E. roasting. The catalyst provided by the invention has favorable low-temperature high activity and stability, also has high selectivity, and is low in cost, and the preparation method is simple.

Description

For the Catalysts and its preparation method of carbon monoxide aqueous vapor reformation hydrogen production
Technical field
The present invention relates to a kind of Catalysts and its preparation method, particularly a kind of Catalysts and its preparation method for carbon monoxide aqueous vapor reformation hydrogen production.
Background technology
Carbon monoxide and aqueous vapor reforming reaction can produce hydrogen and carbon dioxide, are the important reactions of obtaining hydrogen feed in ammonia synthesizing industry; In the hydrocarbon and aqueous vapor reforming reaction hydrogen production process of broad research, also relate to carbon monoxide and aqueous vapor reforming reaction recently; Particularly, in the time that hydrogen is used for hydrogen fuel cell, the carbon monoxide in hydrogen is easy to make electrode poisoning, thereby requires to remove as far as possible the carbon monoxide in raw hydrogen.From thermodynamics, the equilibrium constant that carbon monoxide reacts with aqueous vapor is very large, but is also an exothermic reaction, and therefore, when rising temperature, the equilibrium constant that carbon monoxide reacts with aqueous vapor can reduce.This just requires to look for the catalyst of low temperature high activity high selectivity.Traditional siderochrome oxide catalyst just has activity to carbon monoxide aqueous vapor reforming reaction under higher temperature, and therefore, while reaction on siderochrome oxide catalyst, the conversion ratio of carbon monoxide is not high enough.In addition, easy sintering deactivation when siderochrome oxide catalyst at high temperature uses, stability is bad.In recent years, the catalyst that also to have developed by noble metals such as platinum, rhodium, gold be active constituent, demonstrates good low-temperature catalytic activity.But the cost of noble metal catalyst series is high, limit its application prospect.
Summary of the invention
The technical problem to be solved in the present invention is: a kind of Catalysts and its preparation method for carbon monoxide aqueous vapor reformation hydrogen production is provided, to improve activity and the stability of catalyst, reduces the production cost of catalyst.
The technical scheme solving the problems of the technologies described above is: a kind of catalyst for carbon monoxide aqueous vapor reformation hydrogen production, and this catalyst is made up of the oxide of cerium, zirconium, copper, iron, and the chemical formula of catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.1～1.25.
Another kind of technical scheme of the present invention is: a kind of preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production, and the method comprises the following steps:
A. Kaolinite Preparation of Catalyst carrier:
The metal nitrate mixed solution of zirconium nitrate, the water-soluble formation of cerous nitrate is reacted with precipitant mix and generates precipitation, the amount of substance=Zr of described precipitating reagent 4+amount × (2.1～the 2.3)+Ce of ionic species 3+amount × (1.575～1.725) of ionic species, unit: mole; Filter, the initial stage sediment of acquisition passes through and washs, refilters, is dried, roasting, forms the catalyst carrier being made up of cerium Zirconium oxide;
B. load copper nitrate and ferric nitrate:
Catalyst carrier, through infusion process load copper nitrate and ferric nitrate, is made to sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
D. dry:
Sediment in mid-term after disperseing and filtering carry out bake drying;
E. roasting:
By sediment in mid-term roasting in air after drying, the final solid of gained is the catalyst that can be used for carbon monoxide aqueous vapor reformation hydrogen production being made up of the oxide of cerium, zirconium, copper, iron, and the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.1～1.25.
Further technical scheme of the present invention is: described steps A comprises following operation:
A1. prepare metal nitrate mixed solution:
By zirconium nitrate, the water-soluble formation metal nitrate of cerous nitrate mixed solution, in this metal nitrate mixed solution, zirconium, ce metal total ion concentration are 0.1mol/L～1mol/L;
A2. prepare precipitating reagent:
Ammonium carbonate solution using water-soluble ammonium carbonate formation as precipitating reagent, in this ammonium carbonate solution, ammonium carbonate concentration is 0.1mol/L～2mol/L;
A3. hybrid reaction:
Metal nitrate mixed solution is reacted with precipitant mix and generate precipitation, the amount of substance=Zr of described precipitating reagent 4+amount × the 2.2+Ce of ionic species 3+amount × 1.65 of ionic species, unit: mole;
A4. filter for the first time:
The precipitation generating after reaction is filtered for the first time, obtain initial stage sediment;
A5. washing:
Add washing agent to carry out supersound washing the initial stage sediment after filtering for the first time;
A6. filter for the second time:
Initial stage sediment after washing is filtered for the second time;
A7. dry:
Initial stage sediment after filtering is for the second time carried out to bake drying;
A8. roasting:
Initial stage sediment is after drying carried out to roasting in air, form the catalyst carrier being formed by cerium Zirconium oxide.
Further technical scheme of the present invention is: in the hybrid reaction of described steps A 3, will to be added drop-wise in metal nitrate mixed solution as the ammonium carbonate solution of precipitating reagent under the temperature of 20 DEG C～40 DEG C and stirring, dripping off rear continuation stirs 1～2 hour, after hybrid reaction completes, ageing 8～12 hours.
Further technical scheme of the present invention is: in described steps A 5, washing agent used is absolute ethyl alcohol; In sedimentary process of washing initial stage, ultrasonic 5～20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 100W～500W.
Further technical scheme of the present invention is: described step B. load copper nitrate and ferric nitrate comprise following operation:
B1. prepare iron, copper nitrate mixed solution:
By ferric nitrate, the water-soluble formation iron of copper nitrate, copper nitrate mixed solution, in this iron, copper nitrate mixed solution, iron, copper ion total concentration are 0.1mol/L～1mol/L;
B2. add catalyst carrier and carry out hybrid reaction:
Catalyst carrier is added in iron, copper nitrate mixed solution, keep amount of substance ratio to be: (m+n)/(p+q)=0.1～1.25, m, n, p, q are followed successively by the atomic ratio coefficient of Cu in catalyst, Fe, Ce, Zr element; Hybrid reaction is carried out in stirring, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture solvent evaporated that under agitation progressively heats up, make sediment in mid-term.
Further technical scheme of the present invention is: in step B2, the time of described hybrid reaction is 1～2 hour, and temperature is 20 DEG C～80 DEG C.
In the dispersion filtration of step C, described dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 5～20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 100W～500W.
Baking temperature in described steps A and step D is 60 DEG C～100 DEG C, and the time is 4～8 hours; Roasting in described steps A and step e is all first roastings 2～4 hours in 400 DEG C～500 DEG C air, then roasting 2～4 hours in 650 DEG C～700 DEG C air.
In described metal nitrate mixed solution and precipitating reagent, all contain softex kw, chemical formula is C 19h 42nBr, and the concentration of softex kw in each solution is 0.1%～1% by mass percent.
Owing to adopting technique scheme, the present invention's the Catalysts and its preparation method for carbon monoxide aqueous vapor reformation hydrogen production compared with prior art, has following beneficial effect:
1. catalyst has good low temperature high activity:
Catalyst of the present invention is carried out to catalyst activity evaluation in normal pressure continuous flowing type micro fixed-bed reactor, loaded catalyst 500 mg, first use reducing gases activation processing fresh catalyst, then, maintain uniform temperature, pass into carbon monoxide and water vapor mixture (volume ratio: carbon monoxide/aqueous vapor=1/5; Air speed: 7200h -1) entering continuously catalyst bed, the carbon monoxide conversion ratio (%) of realizing in six typical catalyst sees the following form:
Reaction temperature (DEG C) Catalyst 1 Catalyst 2 Catalyst 3 Catalyst 4 Catalyst 5 Catalyst 6
300 41.90 67.93 70.66 53.10 71.79 55.36
350 74.72 78.52 81.36 86.73 78.01 73.15
400 83.61 85.04 89.99 94.58 91.46 74.56
450 86.14 85.37 90.62 94.67 92.04 92.70
500 92.22 86.85 95.14 87.30 88.72 93.27
550 79.99 79.31 92.41 89.80 86.73 86.42
Visible, catalyst of the present invention has good low temperature high activity.
2. there is higher stability:
As seen from the above table, by carbon monoxide and water vapor mixture by catalyst of the present invention, air speed 7200h -1, 400 DEG C time, carbon monoxide conversion ratio, up to 94%, shows good low temperature active and higher stability.
3. there is high selectivity:
The product that uses catalyst of the present invention to carry out carbon monoxide aqueous vapor reforming reaction only has hydrogen and carbon dioxide, and therefore, catalyst of the present invention has high selectivity.
4. cost is low:
Because catalyst of the present invention is made up of the oxide of cerium, zirconium, copper, iron, the price of various metals is lower, and or not containing noble metal, therefore its price is not lower.
5. preparation method is simple:
In the present invention, what catalyst preparation was used is soft chemical technology, and capital equipment is industrial conventional reactor, centrifuge, drying box and high temperature furnace, and operation is simple, and suitability for industrialized production very easily realizes.
Below, the technical characterictic of the Catalysts and its preparation method for carbon monoxide aqueous vapor reformation hydrogen production to the present invention is further described in conjunction with the embodiments.
Detailed description of the invention
For a catalyst for carbon monoxide aqueous vapor reformation hydrogen production, this catalyst is made up of the oxide of cerium, zirconium, copper, iron, and the chemical formula of catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.1～1.25.
The preparation method of the above-mentioned catalyst for carbon monoxide aqueous vapor reformation hydrogen production, the method comprises the following steps:
A. Kaolinite Preparation of Catalyst carrier:
The metal nitrate mixed solution of zirconium nitrate, the water-soluble formation of cerous nitrate is reacted with precipitant mix and generates precipitation, the amount of substance=Zr of described precipitating reagent 4+amount × (2.1～the 2.3)+Ce of ionic species 3+amount × (1.575～1.725) of ionic species, unit: mole; Filter, the initial stage sediment of acquisition passes through and washs, refilters, is dried, roasting, forms the catalyst carrier being made up of cerium Zirconium oxide; This step comprises following operation:
A1. prepare metal nitrate mixed solution:
By zirconium nitrate, the water-soluble formation metal nitrate of cerous nitrate mixed solution, in this metal nitrate mixed solution, zirconium, ce metal total ion concentration are 0.1mol/L～1mol/L;
A2. prepare precipitating reagent:
Ammonium carbonate solution using water-soluble ammonium carbonate formation as precipitating reagent, in this ammonium carbonate solution, ammonium carbonate concentration is 0.1mol/L～2mol/L;
A3. hybrid reaction:
At the temperature of 20 DEG C～40 DEG C, metal nitrate mixed solution is reacted with precipitant mix and generate precipitation; Amount of substance=the Zr of described precipitating reagent 4+amount × (2.1～the 2.3)+Ce of ionic species 3+amount × (1.575～1.725) of ionic species, unit: mole; In this hybrid reaction, be will to be added drop-wise in metal nitrate mixed solution as the ammonium carbonate solution of precipitating reagent under stirring, drip off rear continuation and stir 1～2 hour, after hybrid reaction completes, ageing 8～12 hours;
A4. filter for the first time:
The precipitation generating after reaction is filtered for the first time, obtain initial stage sediment;
A5. washing:
Add washing agent to carry out supersound washing the initial stage sediment after filtering for the first time; Washing agent used is absolute ethyl alcohol; In sedimentary process of washing initial stage, ultrasonic 5～20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 100W～500W;
A6. filter for the second time:
Initial stage sediment after washing is filtered for the second time;
A7. dry:
Initial stage sediment after filtering is for the second time carried out to bake drying;
A8. roasting:
Initial stage sediment is after drying carried out to roasting in air, form the catalyst carrier being formed by cerium Zirconium oxide.
B. load copper nitrate and ferric nitrate:
Catalyst carrier, through infusion process load copper nitrate and ferric nitrate, is made to sediment in mid-term; This step B comprises following operation:
B1. prepare iron, copper nitrate mixed solution:
By ferric nitrate, the water-soluble formation iron of copper nitrate, copper nitrate mixed solution, in this iron, copper nitrate mixed solution, iron, copper ion total concentration are 0.1mol/L～1mol/L;
B2. add catalyst carrier and carry out hybrid reaction:
Catalyst carrier is added in iron, copper nitrate mixed solution, keep amount of substance ratio to be: (m+n)/(p+q)=0.1～1.25, m, n, p, q are followed successively by the atomic ratio coefficient of Cu in catalyst, Fe, Ce, Zr element, hybrid reaction is carried out in stirring, the time of hybrid reaction is 1～2 hour, temperature is 20 DEG C～80 DEG C, obtains reactant mixture;
B3. solvent evaporated heats up:
By the solvent evaporated that progressively heats up under reactant mixture stirring, make sediment in mid-term.
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration; Dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 5～20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 100W～500W;
D. dry:
Sediment in mid-term after disperseing and filtering carry out bake drying;
E. roasting:
By sediment in mid-term roasting in air after drying, the final sediment of gained is the catalyst for carbon monoxide aqueous vapor reformation hydrogen production being made up of the oxide of cerium, zirconium, copper, iron, and the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.1～1.25.
Baking temperature in described described steps A and step D is 60 DEG C～100 DEG C, and the time is 4～8 hours; Roasting in described steps A and step e is all first roastings 2～4 hours in 400 DEG C～500 DEG C air, then roasting 2～4 hours in 650 DEG C～700 DEG C air.
In described metal nitrate mixed solution and precipitating reagent, all contain softex kw, chemical formula is C 19h 42nBr, and the concentration of softex kw in each solution is 0.1%～1% by mass percent.
Below the concrete embodiment mono-to embodiment six implementing:
embodiment mono-:
For a preparation method for the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the method comprises the following steps:
A. Kaolinite Preparation of Catalyst carrier:
A1. prepare metal nitrate mixed solution:
Take 222.7147 grams of six water cerous nitrates, 50.4330 grams of nitrate trihydrate zirconiums, add 1300 milliliters of distilled water, stirring and dissolving, then add 4.5 grams of softex kws, the chemical formula of softex kw is C 19h 42nBr, stirring and dissolving, obtains metal nitrate mixed solution.
A2. prepare precipitating reagent:
Take 103.52 grams of ammonium carbonates, be dissolved in 2300 ml distilled waters, then add 12 grams of softex kws, stirring and dissolving, obtains the ammonium carbonate solution as precipitating reagent.
A3. hybrid reaction:
Under 20 DEG C of stirrings, the metal nitrate mixed solution making is reacted to generation initial stage sediment with precipitant mix; Metal salt solution is added drop-wise in sal volatile, and with the pH value of ammoniacal liquor control reactant liquor be 10.In this hybrid reaction, be will to be added drop-wise in metal nitrate mixed solution as the ammonium carbonate solution of precipitating reagent under stirring, drip off rear continuation and stir 2 hours, after hybrid reaction completes, ageing 8 hours;
A4. filter for the first time:
The precipitation generating after reaction is filtered for the first time, obtain initial stage sediment;
A5. washing:
Add washing agent absolute ethyl alcohol to carry out supersound washing the initial stage sediment after filtering for the first time; Washing agent used is absolute ethyl alcohol; In sedimentary process of washing initial stage, ultrasonic 20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 100W;
A6. filter for the second time:
Initial stage sediment after washing is filtered for the second time;
A7. dry:
Respectively at 60 DEG C by through for the second time filter after the each bake drying 8h of initial stage sediment;
A8. roasting:
By initial stage sediment after drying at 400 DEG C, 650 DEG C in air each roasting 4h, form 90.5 grams of the catalyst carriers that formed by cerium Zirconium oxide;
B. load copper nitrate and ferric nitrate:
B1. prepare iron, copper nitrate mixed solution:
Take 9.7159 grams of nine water ferric nitrates, 13.5567 grams of nitrate trihydrate copper, add 80 milliliters of distilled water, and stirring and dissolving obtains iron, copper nitrate mixed solution.
B2. add catalyst carrier and carry out hybrid reaction:
Take 10 grams of catalyst carriers and be added in iron, copper nitrate mixed solution, stir and carry out hybrid reaction 2h, temperature is 20 DEG C, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture evaporate to dryness moisture content that progressively heats up, make sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
In step C. disperses and filters, described dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 100W;
D. dry:
Sediment in mid-term after disperseing and filtering is carried out to bake drying 8h at 60 DEG C;
E. roasting:
By after drying mid-term sediment at 400 DEG C, 650 DEG C in air each roasting 4h, the final sediment of gained be formed by the oxide of cerium, zirconium, copper, iron for 16.15 grams of the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=1.25.
embodiment bis-:
For a preparation method for the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the method comprises the following steps:
A. Kaolinite Preparation of Catalyst carrier:
A1. prepare metal nitrate mixed solution:
Take 44.5429 grams of six water cerous nitrates, 10.0866 grams of nitrate trihydrate zirconiums, add 1260 milliliters of distilled water, stirring and dissolving, then add 1.32 grams of softex kws, the chemical formula of softex kw is C 19h 42nBr, stirring and dissolving, obtains metal nitrate mixed solution.
A2. prepare precipitating reagent:
Take 22.67 grams of ammonium carbonates, be dissolved in 210 ml distilled waters, then add 2.32 grams of softex kws, stirring and dissolving, obtains the ammonium carbonate solution as precipitating reagent.
A3. hybrid reaction:
Under 40 DEG C of stirrings, the metal nitrate mixed solution making is reacted to generation initial stage sediment with precipitant mix; Metal salt solution is added drop-wise in sal volatile, and with the pH value of ammoniacal liquor control reactant liquor be 9.In this hybrid reaction, be will to be added drop-wise in metal nitrate mixed solution as the ammonium carbonate solution of precipitating reagent under stirring, drip off rear continuation and stir 1 hour, after hybrid reaction completes, ageing 12 hours;
A4. filter for the first time:
The precipitation generating after reaction is filtered for the first time, obtain initial stage sediment;
A5. washing:
Add washing agent absolute ethyl alcohol to carry out supersound washing the initial stage sediment after filtering for the first time; Washing agent used is absolute ethyl alcohol; In sedimentary process of washing initial stage, ultrasonic 15 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 250W;
A6. filter for the second time:
Initial stage sediment after washing is filtered for the second time;
A7. dry:
Respectively at 100 DEG C by through for the second time filter after the each bake drying 4h of initial stage sediment;
A8. roasting:
By initial stage sediment after drying at 400 DEG C, 650 DEG C in air each roasting 3h, form 17.51 grams of the catalyst carriers that formed by cerium Zirconium oxide;
B. load copper nitrate and ferric nitrate:
B1. prepare iron, copper nitrate mixed solution:
Take 7.7727 grams of nine water ferric nitrates, 10.8454 grams of nitrate trihydrate copper, add 80 milliliters of distilled water, and stirring and dissolving obtains iron, copper nitrate mixed solution.
B2. add catalyst carrier and carry out hybrid reaction:
Take 10 grams of catalyst carriers and be added in iron, copper nitrate mixed solution, stir and carry out hybrid reaction 2h, temperature is 80 DEG C, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture evaporate to dryness moisture content that progressively heats up, make sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
In step C. disperses and filters, described dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 15 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 250W;
D. dry:
Sediment in mid-term after disperseing and filtering is carried out to bake drying 4h at 100 DEG C;
E. roasting:
By after drying mid-term sediment at 450 DEG C, 650 DEG C in air each roasting 3h, the final sediment of gained be formed by the oxide of cerium, zirconium, copper, iron for 15.05 grams of the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=1.
embodiment tri-:
For a preparation method for the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the method comprises the following steps:
A. Kaolinite Preparation of Catalyst carrier:
A1. prepare metal nitrate mixed solution:
Take 44.5429 grams of six water cerous nitrates, 10.0866 grams of nitrate trihydrate zirconiums, add 126 milliliters of distilled water, stirring and dissolving, then add 1.81 grams of softex kws, the chemical formula of softex kw is C 19h 42nBr, stirring and dissolving, obtains metal nitrate mixed solution.
A2. prepare precipitating reagent:
Take 21.6 grams of ammonium carbonates, be dissolved in 2235 ml distilled waters, then add 2.26 grams of softex kws, stirring and dissolving, obtains the ammonium carbonate solution as precipitating reagent.
A3. hybrid reaction:
Under 30 DEG C of stirrings, the metal nitrate mixed solution making is reacted to generation initial stage sediment with precipitant mix; Metal salt solution is added drop-wise in sal volatile, and with the pH value of ammoniacal liquor control reactant liquor be 9.5.In this hybrid reaction, be will to be added drop-wise in metal nitrate mixed solution as the ammonium carbonate solution of precipitating reagent under stirring, drip off rear continuation and stir 1.5 hours, after hybrid reaction completes, ageing 9 hours;
A4. filter for the first time:
The precipitation generating after reaction is filtered for the first time, obtain initial stage sediment;
A5. washing:
Add washing agent absolute ethyl alcohol to carry out supersound washing the initial stage sediment after filtering for the first time; Washing agent used is absolute ethyl alcohol; In sedimentary process of washing initial stage, ultrasonic 10 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 400W;
A6. filter for the second time:
Initial stage sediment after washing is filtered for the second time;
A7. dry:
Respectively at 70 DEG C by through for the second time filter after the each bake drying 7h of initial stage sediment;
A8. roasting:
By initial stage sediment after drying at 450 DEG C, 700 DEG C in air each roasting 2h, form 16.94 grams of the catalyst carriers that formed by cerium Zirconium oxide;
B. load copper nitrate and ferric nitrate:
B1. prepare iron, copper nitrate mixed solution:
Take 3.8864 grams of nine water ferric nitrates, 5.4227 grams of nitrate trihydrate copper, add 50 milliliters of distilled water, and stirring and dissolving obtains iron, copper nitrate mixed solution.
B2. add catalyst carrier and carry out hybrid reaction:
Take 10 grams of catalyst carriers and be added in iron, copper nitrate mixed solution, stir and carry out hybrid reaction 2h, temperature is 60 DEG C, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture evaporate to dryness moisture content that progressively heats up, make sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
In step C. disperses and filters, described dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 10 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 400W;
D. dry:
Sediment in mid-term after disperseing and filtering is carried out to bake drying 7h at 70 DEG C;
E. roasting:
By after drying mid-term sediment at 500 DEG C, 700 DEG C in air each roasting 2h, the final sediment of gained be formed by the oxide of cerium, zirconium, copper, iron for 12.30 grams of the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.5.
embodiment tetra-:
For a preparation method for the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the method comprises the following steps:
A. Kaolinite Preparation of Catalyst carrier:
A1. prepare metal nitrate mixed solution:
Take 55.6787 grams of six water cerous nitrates, 12.6083 grams of nitrate trihydrate zirconiums, add 750 milliliters of distilled water, stirring and dissolving, then add 1.65 grams of softex kws, the chemical formula of softex kw is C 19h 42nBr, stirring and dissolving, obtains metal nitrate mixed solution.
A2. prepare precipitating reagent:
Take 27.0 grams of ammonium carbonates, be dissolved in 122 ml distilled waters, then add 1.2 grams of softex kws, stirring and dissolving, obtains the ammonium carbonate solution as precipitating reagent.
A3. hybrid reaction:
Under 30 DEG C of stirrings, the metal nitrate mixed solution making is reacted to generation initial stage sediment with precipitant mix; Metal salt solution is added drop-wise in sal volatile, and with the pH value of ammoniacal liquor control reactant liquor be 10.In this hybrid reaction, be will to be added drop-wise in metal nitrate mixed solution as the ammonium carbonate solution of precipitating reagent under stirring, drip off rear continuation and stir 2 hours, after hybrid reaction completes, ageing 10 hours;
A4. filter for the first time:
The precipitation generating after reaction is filtered for the first time, obtain initial stage sediment;
A5. washing:
Add washing agent absolute ethyl alcohol to carry out supersound washing the initial stage sediment after filtering for the first time; Washing agent used is absolute ethyl alcohol; In sedimentary process of washing initial stage, ultrasonic 5 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 500W;
A6. filter for the second time:
Initial stage sediment after washing is filtered for the second time;
A7. dry:
Respectively at 80 DEG C by through for the second time filter after the each bake drying 6h of initial stage sediment;
A8. roasting:
By initial stage sediment after drying at 400 DEG C, 700 DEG C in air each roasting 4h, form 22.23 grams of the catalyst carriers that formed by cerium Zirconium oxide;
B. load copper nitrate and ferric nitrate:
B1. prepare iron, copper nitrate mixed solution:
Take 1.9432 grams of nine water ferric nitrates, 2.7113 grams of nitrate trihydrate copper, add 45 milliliters of distilled water, and stirring and dissolving obtains iron, copper nitrate mixed solution.
B2. add catalyst carrier and carry out hybrid reaction:
Take 10 grams of catalyst carriers and be added in iron, copper nitrate mixed solution, stir and carry out hybrid reaction 2h, temperature is 50 DEG C, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture evaporate to dryness moisture content that progressively heats up, make sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
In step C. disperses and filters, described dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 5～20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 200W;
D. dry:
Sediment in mid-term after disperseing and filtering is carried out to bake drying 6h at 80 DEG C;
E. roasting:
By after drying mid-term sediment at 400 DEG C, 600 DEG C in air each roasting 4h, the final sediment of gained be formed by the oxide of cerium, zirconium, copper, iron for 11.00 grams of the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.25.
embodiment five:
For a preparation method for the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the step of the method is with embodiment mono-, not part be: the parameter of step B～step e is different:
B. load copper nitrate and ferric nitrate:
B1. prepare iron, copper nitrate mixed solution:
Take 1.2955 grams of nine water ferric nitrates, 1.8076 grams of nitrate trihydrate copper, add 50 milliliters of distilled water, and stirring and dissolving obtains iron, copper nitrate mixed solution.
B2. add catalyst carrier and carry out hybrid reaction:
Take 10 grams of catalyst carriers and be added in iron, copper nitrate mixed solution, stir and carry out hybrid reaction 2h, temperature is 40 DEG C, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture evaporate to dryness moisture content that progressively heats up, make sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
In step C. disperses and filters, described dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 15 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 350W;
D. dry:
Sediment in mid-term after disperseing and filtering is carried out to bake drying 5h at 90 DEG C;
E. roasting:
By after drying mid-term sediment at 500 DEG C, 750 DEG C in air each roasting 4h, the final sediment of gained be formed by the oxide of cerium, zirconium, copper, iron for 10.60 grams of the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.17.
embodiment six:
For a preparation method for the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the step of the method is with embodiment mono-, not part be: the parameter of step B～step e is different:
B. load copper nitrate and ferric nitrate:
B1. prepare iron, copper nitrate mixed solution:
Take 0.7773 gram of nine water ferric nitrate, 1.0845 grams of nitrate trihydrate copper, add 60 milliliters of distilled water, and stirring and dissolving obtains iron, copper nitrate mixed solution.
B2. add catalyst carrier and carry out hybrid reaction:
Take 10 grams of catalyst carriers and be added in iron, copper nitrate mixed solution, stir and carry out hybrid reaction 2h, temperature is 30 DEG C, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture evaporate to dryness moisture content that progressively heats up, make sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
In step C. disperses and filters, described dispersant is absolute ethyl alcohol, and in ultrasonic wave dispersion process, ultrasonic 20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 150W;
D. dry:
Sediment in mid-term after disperseing and filtering is carried out to bake drying 4h at 100 DEG C;
E. roasting:
By after drying mid-term sediment at 400 DEG C, 650 DEG C in air each roasting 4h, the final sediment of gained be formed by the oxide of cerium, zirconium, copper, iron for 10.20 grams of the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.1.

Claims (10)

1. for a catalyst for carbon monoxide aqueous vapor reformation hydrogen production, it is characterized in that: this catalyst is made up of the oxide of cerium, zirconium, copper, iron, the chemical formula of catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.1～1.25.
2. for a preparation method for the catalyst of carbon monoxide aqueous vapor reformation hydrogen production, it is characterized in that: the method comprises the following steps:
A. Kaolinite Preparation of Catalyst carrier:
The metal nitrate mixed solution of zirconium nitrate, the water-soluble formation of cerous nitrate is reacted with precipitant mix and generates precipitation, the amount of substance=Zr of described precipitating reagent 4+amount × (2.1～the 2.3)+Ce of ionic species 3+amount × (1.575～1.725) of ionic species, unit: mole; Filter, the initial stage sediment of acquisition passes through and washs, refilters, is dried, roasting, forms the catalyst carrier being made up of cerium Zirconium oxide;
B. load copper nitrate and ferric nitrate:
Catalyst carrier, through infusion process load copper nitrate and ferric nitrate, is made to sediment in mid-term;
C. disperse and filter:
In sediment, add dispersant to carry out ultrasonic wave dispersion in mid-term, and after filtration;
D. dry:
Sediment in mid-term after disperseing and filtering carry out bake drying;
E. roasting:
By sediment in mid-term roasting in air after drying, the final solid of gained is the catalyst that can be used for carbon monoxide aqueous vapor reformation hydrogen production being made up of the oxide of cerium, zirconium, copper, iron, and the chemical formula of this catalyst is Cu mfe nce pzr qo x, wherein, m, n, p, q, x are the atomic ratio coefficient of each element in catalyst, x=m+1.5n+1.5p+2q; Each atomic ratio is m/n=7/3, p/q=8/2, (m+n)/(p+q)=0.1～1.25.
3. the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production according to claim 2, is characterized in that: described steps A comprises following operation:
A1. prepare metal nitrate mixed solution:
By zirconium nitrate, the water-soluble formation metal nitrate of cerous nitrate mixed solution, in this metal nitrate mixed solution, zirconium, ce metal total ion concentration are 0.1mol/L～1mol/L;
A2. prepare precipitating reagent:
Ammonium carbonate solution using water-soluble ammonium carbonate formation as precipitating reagent, in this ammonium carbonate solution, ammonium carbonate concentration is 0.1mol/L～2mol/L;
A3. hybrid reaction:
Metal nitrate mixed solution is reacted with precipitant mix and generate precipitation, the amount of substance=Zr of described precipitating reagent 4+amount × (2.1～the 2.3)+Ce of ionic species 3+amount × (1.575～1.725) of ionic species, unit: mole;
A4. filter for the first time:
The precipitation generating after reaction is filtered for the first time, obtain initial stage sediment;
A5. washing:
Add washing agent to carry out supersound washing the initial stage sediment after filtering for the first time;
A6. filter for the second time:
Initial stage sediment after washing is filtered for the second time;
A7. dry:
Initial stage sediment after filtering is for the second time carried out to bake drying;
A8. roasting:
Initial stage sediment is after drying carried out to roasting in air, form the catalyst carrier being formed by cerium Zirconium oxide.
4. the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production according to claim 3, it is characterized in that: in the hybrid reaction of described steps A 3, will to be added drop-wise in metal nitrate mixed solution as the ammonium carbonate solution of precipitating reagent under the temperature of 20 DEG C～40 DEG C and stirring, dripping off rear continuation stirs 1～2 hour, after hybrid reaction completes, ageing 8～12 hours.
5. the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production according to claim 3, is characterized in that: in described steps A 5, washing agent used is absolute ethyl alcohol; In sedimentary process of washing initial stage, ultrasonic 5～20 minutes, ultrasonic frequency was 40KHz, and ultrasonic power is 100W～500W.
6. the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production according to claim 2, is characterized in that: described step B. load copper nitrate and ferric nitrate comprise following operation:
B1. prepare iron, copper nitrate mixed solution:
By ferric nitrate, the water-soluble formation iron of copper nitrate, copper nitrate mixed solution, in this iron, copper nitrate mixed solution, iron, copper ion total concentration are 0.1mol/L～1mol/L;
B2. add catalyst carrier and carry out hybrid reaction:
Catalyst carrier is added in iron, copper nitrate mixed solution, keep amount of substance ratio to be: (m+n)/(p+q)=0.1～1.25, m, n, p, q are followed successively by the atomic ratio coefficient of Cu in catalyst, Fe, Ce, Zr element; Hybrid reaction is carried out in stirring, obtains reactant mixture;
B3. solvent evaporated heats up:
By the reactant mixture solvent evaporated that under agitation progressively heats up, make sediment in mid-term.
7. the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production according to claim 6, is characterized in that: in step B2, the time of described hybrid reaction is 1～2 hour, and temperature is 20 DEG C～80 DEG C.
8. the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production according to claim 2, it is characterized in that: in the dispersion filtration of step C, described dispersant is absolute ethyl alcohol, in ultrasonic wave dispersion process, ultrasonic 5～20 minutes, ultrasonic frequency is 40KHz, and ultrasonic power is 100W～500W.
9. the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production according to claim 2, is characterized in that: the baking temperature in described steps A and step D is 60 DEG C～100 DEG C, and the time is 4～8 hours; Roasting in described steps A and step e is all first roastings 2～4 hours in 400 DEG C～500 DEG C air, then roasting 2～4 hours in 650 DEG C～700 DEG C air.
10. according to the preparation method of the catalyst for carbon monoxide aqueous vapor reformation hydrogen production described in the arbitrary claim of claim 2～9, it is characterized in that: in described metal nitrate mixed solution and precipitating reagent, all contain softex kw, chemical formula is C 19h 42nBr, and the concentration of softex kw in each solution is 0.1%～1% by mass percent.
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