CN101342488A - Catalyst for steam reformation hydrogen production with by-product glycerol of biological diesel oil and preparation method thereof - Google Patents
Catalyst for steam reformation hydrogen production with by-product glycerol of biological diesel oil and preparation method thereof Download PDFInfo
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- CN101342488A CN101342488A CNA2008100395477A CN200810039547A CN101342488A CN 101342488 A CN101342488 A CN 101342488A CN A2008100395477 A CNA2008100395477 A CN A2008100395477A CN 200810039547 A CN200810039547 A CN 200810039547A CN 101342488 A CN101342488 A CN 101342488A
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Abstract
The invention discloses a catalyst for preparing hydrogen by reforming the by-product glycerine vapour of biological diesel oil and a preparation method thereof. The ingredients of the catalyst include 30-70 weight percent of bentonite, 5-20 weight percent of NiO and 5-15 weight percent of CuO. The catalyst prepared by such method has the advantages of that the reaction activity of preparation of hydrogen by glycerine vapour reforming is relatively high, the activity grows following the increase of temperature, the yield of hydrogen and carbon dioxide is increased and the quantity of carbon accumulation is lowered. The raw materials are mainly minerals and compounds which are cheap and abundant; the preparation process is simple, and the cost is low. In addition, the long-term storage or direct abandonment of the catalyst does not incur secondary pollution, therefore, the catalyst is environment-friendly.
Description
Technical field
The present invention relates to a kind ofly be used for the catalyst of steam reformation hydrogen production with by-product glycerol of biological diesel oil and utilize the double base oxide and bentonite is the method for this catalyst of feedstock production.
Background technology
Utilize grease crop or waste edible oil and methyl alcohol (or ethanol) to carry out transesterification, can produce products such as fatty acid methyl ester (or ethyl ester) and glycerine, after separation of glycerin, can produce and the general suitable biodiesel of diesel quality.Along with the increase of global yield of biodiesel, seek the new approach that utilizes for the accessory substance one-glycerine of biodiesel and caused common concern.Wherein the glycerin vapor reformation hydrogen production is that the more promising by-product glycerol that utilizes carries out one of energy transformed technology approach, and the key of this technology is to obtain high performance catalyst.At present, the catalyst that glycerin vapor reformation hydrogen production research institute selects for use focuses mostly on aspect the catalyst of methane, methanol vapor reformation to produce hydrogen, and these catalyst prices all compare expensive.And, owing to contain many impurity in the by-product glycerin of biodiesel, oxygen content height in the glycerol molecule, the chemical process that glycerin vapor is reformed is very complicated, therefore, developing the cheap catalyst that is specifically designed to the glycerin vapor reformation hydrogen production is that present by-product glycerol of biological diesel oil utilizes the problem that presses for solution in the technology.
Summary of the invention
Technical problem to be solved by this invention provides a kind of Catalysts and its preparation method that is specifically designed to steam reformation hydrogen production with by-product glycerol of biological diesel oil of cheapness.
The technical solution used in the present invention: a kind of catalyst that is used for steam reformation hydrogen production with by-product glycerol of biological diesel oil, form by following component: the NiO of the bentonite of 30～70 parts by weight, 5～20 parts by weight and the CuO of 5～15 parts by weight.
The method of above-mentioned glycerin vapor reforming hydrogen-production catalyst comprises the following steps:
A. the bentonite water of getting purification fully soaks into, to wherein adding softex kw, the molal quantity of softex kw is 3～10 times of bentonite molal quantity, through abundant stirring reaction after 12～24 hours, adding molal quantity in reaction system again is the lauryl amine of 5～10 times of bentonite molal quantitys, abundant stirring reaction is 3～12 hours under 60～80 ℃ of temperature, and then the interpolation molal quantity is the nickel nitrate and the copper nitrate mixture of 0.2～0.8 times of bentonite molal quantity, the mol ratio of nickel nitrate and copper nitrate is controlled at 0.5～2.0: 1, in reaction system, add excess of ammonia water at last and react the product Separation of Solid and Liquid, washing;
B. the product that step a is made is dried under 60～100 ℃ of temperature, 500 ℃ roasting temperature 2～4 hours, makes described catalyst again.
Beneficial effect of the present invention: the present invention is based on the compound double base oxide of nanometer layer structure of natural montmorillonite, make the catalyst porous and reach cheap large-scale industrial application aims.The present invention is with combination of oxides NiO-CuO and bentonite, carry out reaction in-situ and make the catalyst of high specific surface area, made full use of the interaction between NiO-CuO and the bentonite structure, catalyst surface is formed fully expose, be easy to approaching catalytic reaction activity center, catalyst is when having higher stability, bring into play the synergy at surperficial different activities center, had efficient catalytic glycerin vapor reformation hydrogen production performance.Catalyst of the present invention carbon deposition quantity in reforming process is little, simultaneously product CO
2Can absorption or chemical reaction take place with bentonite, the steam reformation chemical balance is moved towards the direction that helps the hydrogen generation, play the purpose of strengthening hydrogen manufacturing.The used primary raw material of the present invention is cheapness and abundant mineral and compound, and preparation process is simple, controlled, does not relate to complex apparatus and operation, and cost is low.Even secondary pollution can not take place in catalyst long-term storage of the present invention or directly abandon yet, and is environmentally friendly.
The specific embodiment
Below by drawings and Examples the present invention is described in further detail, a kind of catalyst that is used for steam reformation hydrogen production with by-product glycerol of biological diesel oil is made up of following component: the NiO of the bentonite of 30～70 parts by weight, 5～20 parts by weight and the CuO of 5～15 parts by weight.Described Preparation of catalysts method, comprise the following steps: that the bentonite water that a. gets purification fully soaks into, to wherein adding softex kw, the molal quantity of softex kw is 3～10 times of bentonite molal quantity, through abundant stirring reaction after 12～24 hours, adding molal quantity in reaction system again is the lauryl amine of 5～10 times of bentonite molal quantitys, abundant stirring reaction is 3～12 hours under 60～80 ℃ of temperature, and then the interpolation molal quantity is the nickel nitrate and the copper nitrate mixture of 0.2～0.8 times of bentonite molal quantity, the mol ratio of nickel nitrate and copper nitrate is controlled at 0.5～2.0: 1, in reaction system, add excess of ammonia water at last and react the product Separation of Solid and Liquid, washing; B. the product that step a is made is dried under 60～100 ℃ of temperature, 500 ℃ roasting temperature 2～4 hours, makes described catalyst again.The catalyst of described invention adopts Japanese D/Max-2500VB2+/PC X-ray diffractometer of science to analyze (XRD) and studies its structure, and interlamellar spacing is asked for by Bragg formula λ=2dsin θ.Adopt U.S. ASAP 2405 absorption instrument (BET method) to measure the specific area of catalyst.The reformation hydrogen production performance test of the catalyst of described invention is to be to carry out in the 10mm fixed bed reactors at internal diameter, the reactor inlet mist adopts nitrogen as carrier gas, keeping the mol ratio of import water vapour and glycerine is 6: 1, the gas mixture volume fraction of glycerine and water vapour remains 1-2% in the inlet gas, and the test volume air speed is 1000hr
-1The particle of catalyst is 0.30-0.60mm in the fixed bed reactors, the quality of catalyst is 5g, to in fixed bed reactors, establish the steel wire of 1～2 layer of aperture during the catalyst filling less than catalyst particle size, online face laying depth is that 200mm, granularity are the porcelain ball of about 10mm, beds should load smooth even as far as possible, atmospheric operation.
Description of drawings
Fig. 1 is embodiment 1 hydrogen yield, yield of carbon dioxide and the carbon deposition quantity graph of a relation with temperature;
Fig. 2 is embodiment 2 hydrogen yields, yield of carbon dioxide and the carbon deposition quantity graph of a relation with temperature;
Fig. 3 is embodiment 3 hydrogen yields, yield of carbon dioxide and the carbon deposition quantity graph of a relation with temperature.
Embodiment 1
At first get the bentonite of purification, water fully infiltrates, to wherein adding the cetyl trimethyl bromine Change ammonium, the molal quantity of softex kw is 10 times of bentonite molal quantity, through abundant Stirring reaction 12 hours, adding molal quantity is the lauryl amine of 10 times of bentonite molal quantitys again, 60～Under 80 ℃ of temperature, fully stirring reaction is after 12 hours, and adding then molal quantity is the bentonite molal quantity 0.8 nickel nitrate doubly and copper nitrate mixture, the mol ratio of nickel nitrate and copper nitrate are controlled at 2.0 ratios In the example scope, react again Separation of Solid and Liquid, washing with excess of ammonia water; What will make at last is mixed Compound is dried under 60～100 ℃ of temperature, 500 ℃ roasting temperature 4 hours, namely makes again Described catalyst. Namely make described catalyst, its component is the bentonite of 60wt%; 20wt%'s NiO; The CuO of 13wt%. The interlamellar spacing of XRD determining is 2.59nm, and the specific area that BET measures is 108m2/ g, the glycerol liquor steam reformation hydrogen production result of the test of measuring by fixed bed reactors is seen shown in Figure 1, and along with the rising of temperature, hydrogen and yield of carbon dioxide raise, and carbon deposition quantity reduces, and hydrogen yield can reach 18mol/m in the time of 600 ℃3，CO
2Productive rate is 5mol/m3, carbon deposition quantity is that 10mg/100mg urges Change agent.
At first get the bentonite of purification, water fully soaks into, to wherein adding softex kw, the molal quantity of softex kw is 5 times of bentonite molal quantity, the abundant stirring reaction of warp 24 hours, adding molal quantity again is the lauryl amine of 10 times of bentonite molal quantitys, under 60～80 ℃ of temperature, fully stirring reaction is after 6 hours, adding molal quantity then is the nickel nitrate and the copper nitrate mixture of 0.5 times of bentonite molal quantity, the mol ratio of nickel nitrate and copper nitrate is controlled in 0.5 proportion, reacts Separation of Solid and Liquid with excess of ammonia water again, washing; At last the mixture that makes is dried under 60～100 ℃ of temperature, 500 ℃ roasting temperature 3 hours, promptly make described catalyst again.Promptly make described catalyst, its composition is the bentonite of 75wt%; The NiO of 8wt%; The CuO of 12wt%.The interlamellar spacing of XRD determining is 2.89nm, and the specific area that BET measures is 88m
2/ g, the glycerol liquor steam reformation hydrogen production result of the test of measuring by fixed bed reactors is seen shown in Figure 2, and along with the rising of temperature, hydrogen and yield of carbon dioxide raise, and carbon deposition quantity reduces, and hydrogen yield can reach 13mol/m in the time of 600 ℃
3, CO
2Productive rate is 5mol/m
3, carbon deposition quantity is the 13mg/100mg catalyst.
Embodiment 3
At first get the bentonite of purification, water fully soaks into, to wherein adding softex kw, the molal quantity of softex kw is 10 times of bentonite molal quantity, the abundant stirring reaction of warp 12 hours, adding molal quantity again is the lauryl amine of 10 times of bentonite molal quantitys, under 60～80 ℃ of temperature, fully stirring reaction is after 12 hours, adding molal quantity then is the nickel nitrate and the copper nitrate mixture of 0.8 times of bentonite molal quantity, the mol ratio of nickel nitrate and copper nitrate is controlled in 2.0 proportions, reacts Separation of Solid and Liquid with excess of ammonia water again, washing; At last the mixture that makes is dried under 60～100 ℃ of temperature, 500 ℃ roasting temperature 4 hours, promptly make described catalyst again.Promptly make described catalyst, its composition is the bentonite of 70wt%; The NiO of 18wt%; The CuO of 10wt%.The interlamellar spacing of XRD determining is 2.60nm, and the specific area that BET measures is 102m
2/ g, the glycerol liquor steam reformation hydrogen production result of the test of measuring by fixed bed reactors is seen shown in Figure 3, and along with the rising of temperature, hydrogen and yield of carbon dioxide raise, and carbon deposition quantity reduces, and hydrogen yield can reach 16mol/m in the time of 600 ℃
3, CO
2Productive rate is 3.5mol/m
3, carbon deposition quantity is the 11mg/100mg catalyst.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (2)
1. a catalyst that is used for steam reformation hydrogen production with by-product glycerol of biological diesel oil is made up of following component: the NiO of the bentonite of 30～70 parts by weight, 5～20 parts by weight and the CuO of 5～15 parts by weight.
2. prepare the method for the described steam reformation hydrogen production with by-product glycerol of biological diesel oil catalyst of claim 1, comprise the following steps:
A. the bentonite water of getting purification fully soaks into, to wherein adding softex kw, the molal quantity of softex kw is 3～10 times of bentonite molal quantity, through abundant stirring reaction after 12～24 hours, adding molal quantity in reaction system again is the lauryl amine of 5～10 times of bentonite molal quantitys, abundant stirring reaction is 3～12 hours under 60～80 ℃ of temperature, and then the interpolation molal quantity is the nickel nitrate and the copper nitrate mixture of 0.2～0.8 times of bentonite molal quantity, the mol ratio of nickel nitrate and copper nitrate is controlled at 0.5～2.0: 1, in reaction system, add excess of ammonia water at last and react the product Separation of Solid and Liquid, washing;
B. the product that step a is made is dried under 60～100 ℃ of temperature, 500 ℃ roasting temperature 2～4 hours, makes described catalyst again.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105396588A (en) * | 2015-12-16 | 2016-03-16 | 钟俊超 | Preparation method and application of antiwear microspherical CuO/SiO2 catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105396588A (en) * | 2015-12-16 | 2016-03-16 | 钟俊超 | Preparation method and application of antiwear microspherical CuO/SiO2 catalyst |
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Open date: 20090114 |