CN116393152B - Preparation method of catalyst for removing organic chlorine in garbage pyrolysis and gasification - Google Patents
Preparation method of catalyst for removing organic chlorine in garbage pyrolysis and gasification Download PDFInfo
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- CN116393152B CN116393152B CN202310394057.3A CN202310394057A CN116393152B CN 116393152 B CN116393152 B CN 116393152B CN 202310394057 A CN202310394057 A CN 202310394057A CN 116393152 B CN116393152 B CN 116393152B
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- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
本发明公开了一种用于垃圾热解气化中有机氯脱除的催化剂的制备方法，涉及催化剂的制备技术领域。其包括：以天然白云石作为原料，对其进行改性处理制备得到具有层状结构的水滑石，再利用次磷酸盐歧化法合成磷化镍并加入磷化钼将其负载到水滑石上。通过将白云石改性为层状双氢氧化物即水滑石，有利于捕获有酸性性质的气体HCl；通过分离镍源和次磷酸盐源，在次磷酸盐歧化过程中形成的磷酸盐保留在第一含磷容器中，不会污染金属磷化物产物和堵塞载体的孔。通过本发明利用气化燃气富含H2的特点，在高温条件下将有机氯定向转化为HCl并原位吸附脱除，可高效脱除有机氯。
The invention discloses a method for preparing a catalyst for removing organic chlorine in garbage pyrolysis and gasification, and relates to the technical field of catalyst preparation. The method comprises: using natural dolomite as a raw material, modifying it to prepare a hydrotalcite with a layered structure, synthesizing nickel phosphide by a hypophosphite disproportionation method, and adding molybdenum phosphide to load it on the hydrotalcite. By modifying dolomite into a layered double hydroxide, i.e., hydrotalcite, it is beneficial to capture acidic gas HCl; by separating the nickel source and the hypophosphite source, the phosphate formed in the hypophosphite disproportionation process is retained in the first phosphorus-containing container, and will not pollute the metal phosphide product and block the pores of the carrier. By utilizing the characteristics of gasification fuel gas rich in H2 , the present invention can directionally convert organic chlorine into HCl under high temperature conditions and remove it by in-situ adsorption, so that organic chlorine can be removed efficiently.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a catalyst for removing organic chlorine in pyrolysis gasification of garbage.
Background
In recent years, with the continuous improvement of the economic and social development level, the annual output of organic solid waste in China exceeds billions of tons, and the problems of environmental pollution and resource waste are increasingly serious, so that development of a large amount of resource utilization technology is urgently needed. The organic solid waste classification pyrolysis gasification technology taking the fuel gas as a target product has the advantages of small occupied area, high reduction degree, high gasification combined power generation efficiency and the like, and becomes one of main ways for clean and efficient utilization of the organic solid waste. The chlorine element content in the organic solid waste is higher, and the organic solid waste can enter fuel gas in the forms of HCl, organic chlorine and the like in the gasification process, so that corrosion of downstream equipment pipelines is accelerated, and serious harm is caused to the environment. The gasified fuel gas contains a large amount of chlorine-containing compounds such as chlorobenzene and the like, and has large dioxin toxicity equivalent. In view of the fact that the C-Cl bond is an important precursor for generating dioxin, efficient removal of organic chlorine in organic solid waste gasification gas has become a technical problem to be broken through.
Application number 202211574414.6 discloses an adsorbent for removing organic chlorine, a preparation method and application thereof, wherein the adsorbent takes a composite metal oxide of a minor group element as an active component, takes a silica-based material with a high surface and rich mesoporous structure as a carrier, and adds a small amount of rare earth metal element as an accelerator. The adsorbent utilizes the active composition and rich oxygen vacancy defects generated by the accelerator to form chemical adsorption with chlorine atoms in the organic chloride, so as to realize the removal of chloride impurities. The adsorbent not only realizes high dispersion of active components by virtue of the characteristics of high surface area of the silicon oxide carrier and rich mesoporous channel structure, but also improves the mass transfer efficiency of macromolecular organic chlorine impurities in the adsorbent.
The above prior art removes the organic chlorine by adsorption, and is applied to removing the organic chlorine in the oil products, however, for the garbage pyrolysis gas, the adsorption method is not suitable for the high temperature condition existing in the pyrolysis process, if the high temperature environment (600-800 ℃) generated by the pyrolysis of the garbage pyrolysis gas is combined, the research on a catalyst suitable for removing the organic chlorine in the environment is the main direction of the research of the technicians in the field.
Disclosure of Invention
The invention aims to provide a preparation method of a catalyst for removing organic chlorine in pyrolysis gasification of garbage, which utilizes the characteristic that gasification gas of the pyrolysis gas of the garbage is rich in H 2, directionally converts the organic chlorine into HCl under high temperature (600-800 ℃) and adsorbs and removes the HCl in situ, can cut off a dioxin generation path from the source, and simultaneously avoids the problem of equipment corrosion caused by the HCl.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage comprises the following steps:
firstly, natural dolomite and Al (OH) 3 are taken as raw materials, and are mixed and ground; calcining the powder obtained by grinding in a muffle furnace, and cooling to room temperature; dispersing the cooled product, regulating the pH value of the cooled product, filtering, collecting precipitate, washing the precipitate, and freeze-drying to obtain hydrotalcite with a layered structure;
Step two, preparing metal nickel phosphide
Drying Ni (CH 3COO)2·4H2 O to obtain nickel acetate, namely a nickel source, putting nickel acetate and hypophosphorous acid into a tubular reactor, introducing nitrogen into the tubular reactor, controlling the temperature to be 120-300 ℃ for reaction, cooling after the reaction is finished, stopping introducing nitrogen, and passivating the obtained nickel phosphide;
and thirdly, placing the hydrotalcite prepared in the first step into the nickel phosphide prepared in the second step, adding molybdenum phosphide for impregnation, loading nickel and molybdenum on the hydrotalcite at the impregnation temperature of 50-70 ℃, and drying, granulating, crushing and screening to obtain the catalyst.
The technical scheme directly brings the following beneficial technical effects:
The hydrotalcite with the layered structure is obtained by modifying natural dolomite serving as a raw material and is used as a carrier of a garbage pyrolysis gasification catalyst, and the hydrotalcite with the layered structure has large specific surface area and alkaline sites, so that the hydrotalcite is beneficial to capturing gas HCl with acidic properties; in addition, by loading nickel phosphide and molybdenum phosphide on the carrier, phosphate formed in the process of disproportionation of hypophosphite remains in the first phosphorus-containing container, so that metal phosphide products are not polluted and holes of the carrier are not blocked; by utilizing the characteristic that the garbage pyrolysis gasification gas is rich in H 2, organic chlorine is directionally converted into HCl and is adsorbed and removed in situ under the high temperature condition, so that the organic chlorine can be obviously removed, and the service life of the catalyst is effectively prolonged.
The preparation method of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage comprises the step of preparing the catalyst, wherein the total loading amount of nickel and molybdenum is 5-15%.
In the preparation method of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage, in the first step, the molar ratio of magnesium to aluminum is 2.0, and the calcination temperature in a muffle furnace is 800-1000 ℃.
In the first step, nitric acid is added to adjust the pH to 10.0+/-0.2.
In the second step, nickel acetate is placed in a separate ceramic container in a tubular reactor, and when nitrogen flows through the tubular reactor, a container for placing a phosphorus source is positioned upstream of the container for placing the nickel source.
In the second step, the temperature of the tubular reactor is kept at 120 ℃ for 0.5-1.5 h, then the tubular reactor is further heated to 300 ℃ in -1 min at 2 ℃ and kept at 300 ℃ for 0.5-1.5 h.
In the third step, the drying temperature is 110-130 ℃ and the drying time is 10-14 h.
In the third step, the catalyst with the particle size of 20-40 meshes is crushed and sieved.
The preparation method of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage comprises the steps of (1) in nickel phosphide, according to a molar ratio, ni/P=2; in MoP, P/mo=1 in terms of molar ratio.
The mechanism of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage is as follows:
CxHyClz+zH2→CxHy+z+zHCl
and under the high-temperature condition, the H atoms are utilized to attack the C-Cl bond and combine with the Cl atoms to form a stable H-Cl bond, and meanwhile, the H atoms fill the vacancies left by the Cl atoms and combine with the C atoms to form a relatively stable C-H bond.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention solves the technical problem of low chlorine poisoning resistance of the catalyst in the prior art, and the invention is helpful for the activity of the catalyst to show the chlorine poisoning resistance of nickel phosphide due to the electronic defect of nickel and rich hydrogen species (especially those overflowed hydrogen species).
The method removes HCl and organic chlorine in the gas at a high temperature stage (600-800 ℃) after gasification of the organic solid waste, can effectively avoid the problem of high-temperature corrosion caused by HCl, and can cut off a chlorine source for synthesizing dioxin from the source.
The catalyst of the invention has good catalytic activity and stability in the directional catalytic conversion reaction of organochlorine hydrogenation, which can not be achieved by the existing catalyst.
The support in the process of the invention is modified from dolomite, which has been proposed as a more efficient sorbent alternative than limestone, since the uniform distribution in the inert MgO dolomite-based sorbent effectively prevents sintering of CaO crystallites, which stands out in terms of cost effectiveness and natural abundance.
The hydrodechlorination technology disclosed by the invention is wide in application range and excellent in pollutant removal efficiency. The beneficial technical effects of the invention can be further embodied by specific embodiments.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 is a flow chart of the preparation of the catalyst of the present invention.
Detailed Description
The invention discloses a preparation method of a catalyst for removing organic chlorine in pyrolysis gasification of garbage, and in order to make the advantages and the technical scheme of the catalyst clearer and more definite, the invention is further described below by combining specific embodiments.
The raw materials required by the invention can be purchased through commercial sources.
The method for removing the organic chlorine by the catalyst prepared in the invention comprises the following steps:
Because the garbage gasification fuel gas is rich in H 2, the active components of nickel phosphide and added molybdenum phosphide in the catalyst prepared by the invention have good hydrodechlorination effect, chlorine in organic chlorine is replaced by hydrogen at high temperature, and HCl converted after dechlorination is adsorbed by carrier hydrotalcite in situ, so that good hydrodechlorination effect is achieved.
The components and contents of the pyrolysis gasification of the kitchen waste are shown in table 1:
TABLE 1
| Project | Composition of the components | Mass fraction/% |
| 1 | Moisture content | 13.1 |
| 2 | Volatile matters | 53.1 |
| 3 | Fixed carbon | 11.1 |
| 4 | Ash content | 35.3 |
| 5 | C | 31 |
| 6 | H | 3.84 |
| 7 | O | 15.1 |
| 8 | N | 16.4 |
| 9 | S | 0.17 |
| 10 | Cl | 0.15 |
Example 1:
the preparation method of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage specifically comprises the following steps:
Firstly, weighing natural dolomite and Al (OH) 3, giving a Mg/Al molar ratio of 2.0, physically mixing, and grinding in a mortar; the milled powder was then heated to 900 ℃ in muffle TME 2200 at a rate of 10 ℃/min, maintained at 900 ℃ for 3 hours, and allowed to stand to cool to room temperature; subsequently, the product was dispersed in 100mL of 0.25M Na 2CO 3 for 3 hours under stirring; adding the obtained product into 1M HNO 3 solution, and regulating the pH value of the solution to 9.8; filtering, collecting precipitate, washing with deionized water, and freeze drying overnight; obtaining layered hydrotalcite.
Step two, P source i.e. hypophosphorous acid (H 3PO2, 50wt.% aqueous solution) and Ni source i.e. nickel acetate obtained by drying Ni (CH 3COO)2·4H2 O over 12H at 120 ℃, put into a separate ceramic vessel in a tubular reactor in a furnace, N 2 flowing through the reactor and the vessel with P source being located upstream of the vessel with Ni source, heating the vessel in a 10ml·min -1N2 flow from room temperature to 120 ℃ at 2 ℃ min -1, holding for 1H at 120 ℃ to dehydrate the metal salts, further heating to 300 ℃ at 2 ℃ min -1, and holding for 1H at 300 ℃, after cooling to below 35 ℃, terminating the N 2 flow and passivating the nickel phosphide in H 2 (flowing in 10mL min -1) containing 10vol% H 2 S for 1H;
And step three, loading, namely, impregnating hydrotalcite (LDH) with nickel phosphide and MoP obtained in the step two at 60 ℃ so that the Ni and Mo loading of 10 weight percent can be achieved through one impregnation step. After dipping, the samples were left overnight in air and dried at 120 ℃ for 12h. The dried samples were granulated, crushed and sieved to 20 mesh size. Placing the resulting granules in a ceramic vessel, placing the P source in another vessel, and placing both vessels in a furnace as described above;
the PH 3 in the outlet gas is directed through an absorber bottle (first MnO 2, then NaOH solution) where it reacts to a solution of sodium phosphate and phosphite.
Example 2:
The difference from example 1 is that:
in the third step, the total loading of Ni and Mo is 15%.
Example 3:
The difference from example 1 is that:
In the third step, the total loading of Ni and Mo is 5%.
Example 4:
the preparation method of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage specifically comprises the following steps:
Firstly, weighing natural dolomite and Al (OH) 3, giving a Mg/Al molar ratio of 2.0, physically mixing, and grinding in a mortar; the milled powder was then heated to 800 ℃ in muffle TME 2200 at a rate of 10 ℃/min, maintained at 800 ℃ for 3 hours, and allowed to stand to cool to room temperature; subsequently, the product was dispersed in 100mL of 0.25M Na 2CO 3 for 3 hours under stirring; adding the obtained product into 1M HNO 3 solution, and regulating the pH value of the solution to 10.2; filtering, collecting precipitate, washing with deionized water, and freeze drying overnight; obtaining layered hydrotalcite.
Step two, P source i.e. hypophosphorous acid (H 3PO2, 50wt.% aqueous solution) and Ni source i.e. nickel acetate obtained by drying Ni (CH 3COO)2·4H2 O over 12H at 120 ℃, put into a separate ceramic vessel in a tubular reactor in a furnace, N 2 flowing through the reactor and the vessel with P source being located upstream of the vessel with Ni source, heating the vessel in a 10ml·min -1N2 flow from room temperature to 120 ℃ at 2 ℃ min -1, holding for 1H at 120 ℃ to dehydrate the metal salts, further heating to 300 ℃ at 2 ℃ min -1, and holding for 1H at 300 ℃, after cooling to below 35 ℃, terminating the N 2 flow and passivating the nickel phosphide in H 2 (flowing in 10mL min -1) containing 10vol% H 2 S for 1H;
and step three, loading, namely, impregnating hydrotalcite (LDH) with nickel phosphide and MoP obtained in the step two at 50 ℃ so that the Ni and Mo loading of 10 weight percent can be achieved through one impregnation step. After dipping, the samples were left overnight in air and dried at 110 ℃ for 12h. The dried samples were granulated, crushed and sieved to 20 mesh size. Placing the resulting granules in a ceramic vessel, placing the P source in another vessel, and placing both vessels in a furnace as described above;
the PH 3 in the outlet gas is directed through an absorber bottle (first MnO 2, then NaOH solution) where it reacts to a solution of sodium phosphate and phosphite.
Example 5:
the preparation method of the catalyst for removing the organic chlorine in the pyrolysis gasification of the garbage specifically comprises the following steps:
Firstly, weighing natural dolomite and Al (OH) 3, giving a Mg/Al molar ratio of 2.0, physically mixing, and grinding in a mortar; the milled powder was then heated to 1000 ℃ in muffle TME 2200 at a rate of 10 ℃/min, maintained at 1000 ℃ for 3 hours, and allowed to stand to cool to room temperature; subsequently, the product was dispersed in 100mL of 0.25M Na 2CO 3 for 3 hours under stirring; adding the obtained product into 1M HNO 3 solution, and regulating the pH value of the solution to 10; filtering, collecting precipitate, washing with deionized water, and freeze drying overnight; obtaining layered hydrotalcite.
Step two, P source i.e. hypophosphorous acid (H 3PO2, 50wt.% aqueous solution) and Ni source i.e. nickel acetate obtained by drying Ni (CH 3COO)2·4H2 O over 12H at 120 ℃, put into a separate ceramic vessel in a tubular reactor in a furnace, N 2 flowing through the reactor and the vessel with P source being located upstream of the vessel with Ni source, heating the vessel in a 10ml·min -1N2 flow from room temperature to 120 ℃ at 2 ℃ min -1, holding for 1H at 120 ℃ to dehydrate the metal salts, further heating to 300 ℃ at 2 ℃ min -1, and holding for 1H at 300 ℃, after cooling to below 35 ℃, terminating the N 2 flow and passivating the nickel phosphide in H 2 (flowing in 10mL min -1) containing 10vol% H 2 S for 1H;
and step three, loading, namely, impregnating hydrotalcite (LDH) with nickel phosphide and MoP obtained in the step two at 70 ℃ so that the Ni and Mo loading of 10 weight percent can be achieved through one impregnation step. After dipping, the samples were left overnight in air and dried at 130 ℃ for 12h. The dried samples were granulated, crushed and sieved to 20 mesh size. Placing the resulting granules in a ceramic vessel, placing the P source in another vessel, and placing both vessels in a furnace as described above;
the PH 3 in the outlet gas is directed through an absorber bottle (first MnO 2, then NaOH solution) where it reacts to a solution of sodium phosphate and phosphite.
Comparative example 1:
The difference from example 1 is that:
Directly adopting dolomite as a carrier; the remaining steps are the same.
Comparative example 2:
The difference from example 1 is that:
only nickel phosphide is loaded;
Firstly, weighing natural dolomite and Al (OH) 3, giving a Mg/Al molar ratio of 2.0, physically mixing, and grinding in a mortar; the milled powder was then heated to 1000 ℃ in muffle TME 2200 at a rate of 10 ℃/min, maintained at 1000 ℃ for 3 hours, and allowed to stand to cool to room temperature; subsequently, the product was dispersed in 100mL of 0.25M Na 2CO 3 for 3 hours under stirring; adding the obtained product into 1M HNO 3 solution, and regulating the pH value of the solution to 10; filtering, collecting precipitate, washing with deionized water, and freeze drying overnight; obtaining layered hydrotalcite.
Step two, P source i.e. hypophosphorous acid (H 3PO2, 50wt.% aqueous solution) and Ni source i.e. nickel acetate obtained by drying Ni (CH 3COO)2·4H2 O over 12H at 120 ℃, put into a separate ceramic vessel in a tubular reactor in a furnace, N 2 flowing through the reactor and the vessel with P source being located upstream of the vessel with Ni source, heating the vessel in a 10ml·min -1N2 flow from room temperature to 120 ℃ at 2 ℃ min -1, holding for 1H at 120 ℃ to dehydrate the metal salts, further heating to 300 ℃ at 2 ℃ min -1, and holding for 1H at 300 ℃, after cooling to below 35 ℃, terminating the N 2 flow and passivating the nickel phosphide in H 2 (flowing in 10mL min -1) containing 10vol% H 2 S for 1H;
and step three, loading, namely, carrying out the nickel phosphide-impregnated hydrotalcite (LDH) obtained in the step two at 70 ℃ so as to achieve the Ni loading of 10 weight percent through one impregnation step. After dipping, the samples were left overnight in air and dried at 130 ℃ for 12h. The dried samples were granulated, crushed and sieved to 20 mesh size. Placing the resulting granules in a ceramic vessel, placing the P source in another vessel, and placing both vessels in a furnace as described above;
the PH 3 in the outlet gas is directed through an absorber bottle (first MnO 2, then NaOH solution) where it reacts to a solution of sodium phosphate and phosphite.
Comparative example 3:
The difference from example 1 is that:
Only molybdenum phosphide is loaded;
Firstly, weighing natural dolomite and Al (OH) 3, giving a Mg/Al molar ratio of 2.0, physically mixing, and grinding in a mortar; the milled powder was then heated to 1000 ℃ in muffle TME 2200 at a rate of 10 ℃/min, maintained at 1000 ℃ for 3 hours, and allowed to stand to cool to room temperature; subsequently, the product was dispersed in 100mL of 0.25MNa 2CO3 for 3 hours under stirring; adding the obtained product into 1M HNO 3 solution, and regulating the pH value of the solution to 10; filtering, collecting precipitate, washing with deionized water, and freeze drying overnight; obtaining layered hydrotalcite.
Step two, loading, impregnation of hydrotalcite (LDH) with MoP is performed at 70 ℃ so that Mo loading of 10wt% can be achieved by one impregnation step. After dipping, the samples were left overnight in air and dried at 130 ℃ for 12h. The dried samples were granulated, crushed and sieved to 20 mesh size.
Comparative example 4:
The difference from example 1 is that:
Nickel phosphide and cobalt phosphide are loaded;
Firstly, weighing natural dolomite and Al (OH) 3, giving a Mg/Al molar ratio of 2.0, physically mixing, and grinding in a mortar; the milled powder was then heated to 1000 ℃ in muffle TME 2200 at a rate of 10 ℃/min, maintained at 1000 ℃ for 3 hours, and allowed to stand to cool to room temperature; subsequently, the product was dispersed in 100mL of 0.25M Na 2CO3 for 3 hours under stirring; adding the obtained product into 1M HNO 3 solution, and regulating the pH value of the solution to 10; filtering, collecting precipitate, washing with deionized water, and freeze drying overnight; obtaining layered hydrotalcite.
Step two, P source i.e. hypophosphorous acid (H 3PO2, 50wt.% aqueous solution) and Ni source i.e. nickel acetate obtained by drying Ni (CH 3COO)2·4H2 O over 12H at 120 ℃, put into a separate ceramic vessel in a tubular reactor in a furnace, N 2 flowing through the reactor and the vessel with P source being located upstream of the vessel with Ni source, heating the vessel in a 10ml·min -1N2 flow from room temperature to 120 ℃ at 2 ℃ min -1, holding for 1H at 120 ℃ to dehydrate the metal salts, further heating to 300 ℃ at 2 ℃ min -1, and holding for 1H at 300 ℃, after cooling to below 35 ℃, terminating the N 2 flow and passivating the nickel phosphide in H 2 (flowing in 10mL min -1) containing 10vol% H 2 S for 1H;
And step three, loading, namely, impregnating hydrotalcite (LDH) with nickel phosphide and CoP obtained in the step two at 70 ℃ so that the Ni and Co loading of 10 weight percent can be achieved through one impregnation step. After dipping, the samples were left overnight in air and dried at 130 ℃ for 12h. The dried samples were granulated, crushed and sieved to 20 mesh size. Placing the resulting granules in a ceramic vessel, placing the P source in another vessel, and placing both vessels in a furnace as described above;
the PH 3 in the outlet gas is directed through an absorber bottle (first MnO 2, then NaOH solution) where it reacts to a solution of sodium phosphate and phosphite.
The catalysts prepared in the above examples 1 to 5, comparative examples 1 to 4 were tested and applied to the removal of organic chlorine in pyrolysis gasification of garbage, and the removal efficiency thereof is shown in table 2.
TABLE 2
| Project | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 |
| Removal efficiency/% | 95 | 90 | 88 | 92 | 91 | 82 | 90 | 70 | 72 |
It will be appreciated by persons skilled in the art that the above embodiments have been provided for the purpose of illustrating the application and are not to be construed as limiting the application, and that suitable modifications and variations of the above embodiments are within the scope of the application as claimed.
Claims (7)
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| CN103157497A (en) * | 2013-04-08 | 2013-06-19 | 南开大学 | Preparation method of thermometal phosphide hydrofining catalyst |
| CN104258895A (en) * | 2014-07-24 | 2015-01-07 | 中国石油大学(华东) | Hydrogenation catalyst taking transition metal phosphide as aid |
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| CN105344368B (en) * | 2015-09-28 | 2018-03-13 | 东南大学 | A kind of preparation method and application of transition metal phosphide for hydrogenation-dechlorination reaction |
| CN108620117B (en) * | 2018-05-03 | 2020-12-11 | 常州大学 | A method for preparing highly dispersed supported Ni2P catalyst by low temperature reduction |
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