CN102744089B - High stability Ni-based phosphide catalyst and its preparation method - Google Patents
High stability Ni-based phosphide catalyst and its preparation method Download PDFInfo
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- CN102744089B CN102744089B CN201110100043.3A CN201110100043A CN102744089B CN 102744089 B CN102744089 B CN 102744089B CN 201110100043 A CN201110100043 A CN 201110100043A CN 102744089 B CN102744089 B CN 102744089B
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Abstract
The invention relates to a high stability Ni-based phosphide catalyst and its preparation method, and aims to mainly solve the problem of poor stability of existing acetone hydrogenation catalysts. The invention adopts a high stability Ni-based phosphide catalyst, which comprises the following components by weight percent: a) 5.0-15.0% of NiO; b) 5.0-25.0% of MoOx; c) 5.0-15.0% of POx; d) 45.0-75.0% of Al2O3; and E) 5-15% of at least one of MgO, BaO or CaO. The catalyst and the technical scheme of its preparation method of the invention well solve the problem, and can be used in the industrial production of isopropanol through acetone hydrogenation.
Description
Technical field
The present invention relates to a kind of high stability Ni base phosphide catalyst and preparation method thereof.
Technical background
Transition metal phosphide is the compound that a class has metal and characteristic of semiconductor, at electricity, mechanics, the aspect such as anticorrosive, there is notable feature, they are again heat and electric good conductor simultaneously, have higher heat endurance and chemical stability, thereby cause people's extensive concern.Since the method that adopts temperature programmed reduction for 1998 is prepared and is had compared with bigger serface and good catalytic activity metal phosphide, people have carried out a series of new explorations as new catalyst to the synthetic and catalytic performance of phosphide, and phosphide is all obtained good catalytic applications at aspects such as hydrodesulfurization, hydrodenitrogeneration, hydrofinishing, hydrazine decomposition.
Acetone hydrogenation can adopt the catalyst such as precious metals pd, Pt, Ru, Ru, carry out, but these catalyst prices is very expensive on fixed bed reactors.
Yue Hong, Wu wait (Shenyang Institute of Chemical Technology journal quietly, 2008,22 (3): 208-210.) adopt Ni-B amorphous alloy catalyst for the research of normal pressure acetone gas phase hydrogenation, as (n) Ni: (n) B=1: 2.5, the catalyst that Ni concentration forms while being 0.6mol/L has good non crystalline structure and high active of hydrogenation catalysis, this catalyst is adapted at batch reactor to carry out, and poor stability is difficult to realize serialization and produces.
Wang Yaobin, Yang Rongbin (Shanghai University Of Engineering Science's journal, 1994,8 (1): 42-47) adopt deposition-precipitation method to prepare Ni/Al
2o
3catalyst, is studied the dynamics of acetone gas phase hydrogenation reaction, does not study the stability of this catalyst.
In sum, catalyst prepared by prior art, is applied in preparing isopropyl alcohol by acetone hydrogenation process, has because using noble metal to cause catalyst expensive the problem of existing nickel-base catalyst poor stability.
Summary of the invention
One of technical problem to be solved by this invention is the catalyst based problem that is applied to exist in preparing isopropyl alcohol by acetone hydrogenation process catalyst valency poor stability of Ni prepared by prior art, and a kind of new high stability Ni base phosphide catalyst is provided.This catalyst has advantages of good stability for preparing isopropyl alcohol by acetone hydrogenation.Two of the technical problem to be solved in the present invention provides a kind of preparation method of the catalyst corresponding with technical solution problem one.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of high stability Ni base phosphide catalyst, comprises following component by weight percentage:
a)5.0～15.0％NiO；
b)5.0～25.0％MoOx；
c)5.0～15.0％POx；
d)45.0～75.0％Al
2O
3；
E) 5.0～15.0% be selected from least one in MgO, BaO or CaO.
In technique scheme, by weight percentage, the preferable range of NiO consumption is that the preferable range of 8.0～15.0%, MoOx consumption is that the preferable range of 10.0～20.0%, POx consumption is 6.0～12.0%, Al
2o
3the preferable range of consumption is 50.0～70.0%, and at least one the amount ranges being selected from MgO, CaO or BaO is 5.0～10.0%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of high stability Ni base phosphide catalyst, comprises the following steps:
1) with HNO
3, H
3pO
4for binding agent, take boehmite as Al source, introduce water and the Mg of aequum
2+, Ba
2+or Ca
2+in at least one, extruded moulding, after wet bar is dry, at 400～1100 ℃, roasting obtains catalyst carrier;
2) take aequum Ni (NO
3)
26H
2o and (NH
4)
6mo
7o
244H
2o is soluble in water, then adds aequum (NH
4)
2hPO
4, add wherein HNO
3to precipitate dissolving, and adjust pH value between 3.0～7.0, form solution I;
3) in solution I, add aequum citric acid, form solution II;
4) solution II is heated to 70～90 ℃, is impregnated into while hot Al
2o
3on carrier;
5) sample after dipping, roasting at 400～800 ℃ after oven dry.
In technique scheme, it is 3.5～5.0 that solution I forms pH value, and in solution II, citric acid concentration is 3.0～5.0%, and dry roasting temperature is 500～650 ℃.Catalyst reduction temperature is 550～650 ℃.
The high stability Ni base phosphide catalyst the present invention relates to, by introducing at least wherein a kind of to Al of MgO, CaO, BaO
2o
3carrier is modified, and has reduced the acidity of carrier, effectively reduces the possibility of acetone and isopropanol reaction.The stable compound forming by optimization of catalysts preparation technology Mo, P species and Ni, the existence of this compound has strengthened the interaction force of Ni and carrier, has improved the stability of Ni, has effectively extended the service life of this catalyst.Use catalyst of the present invention, at 150 ℃ of reaction temperatures, reaction pressure 3.0MPa, raw material (25% acetone, 75% isopropyl alcohol by weight percentage) cumulative volume air speed is 2.0h
-1, preparing isopropyl alcohol by acetone hydrogenation under the reaction condition that the mol ratio of hydrogen and acetone is 8.0, after reaction 72h, acetone conversion can reach 100%, generates isopropyl alcohol and selectively can reach 99.8%, and catalyst stability is good, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
Take commercially available boehmite as Al source, by weight percentage with 3%HNO
3the aqueous solution is binding agent, introduces appropriate Mg
2+extruded moulding is by 120 ℃ of oven dry, and 600 ℃ of roastings, obtain consisting of 5%MgO-95%Al
2o
3carrier.
Take 6.7g Ni (NO
3)
26H
2o and 2.4g (NH
4)
6mo
7o
246H
2o4H
2o is dissolved in 10.0g distilled water, adds a certain amount of 1.7g NH
4h
2pO
4or 2.4g (NH
4)
2h
2pO
4, drip wherein dense HNO
3to precipitate dissolving, and adjust pH value between 4～5, form solution I; In solution I, add 3.5g citric acid, form solution II; Solution II is heated to 70 ℃, is added drop-wise to while hot on 10.0g carrier, roasting 8 hours at 550 ℃ after drying at 120 ℃.Catalyst is used front at H
2under in 650 ℃ reduction 12 hours.Catalyst consists of: 12%NiO-10MoOx-5%POx-3.6%MgO-69.4%Al
2o
3.This catalyst is at 150 ℃, and reaction pressure 3.0MPa, total liquid volume air speed are 2.0h
-1, under the reaction condition that the mol ratio of hydrogen and acetone is 4.0, by weight percentage, 25% acetone-75% isopropyl alcohol is that raw material carries out hydrogenation reaction, reaction result is in Table 1.
[embodiment 2]
Take commercially available boehmite as Al source, by weight percentage with 1.5%HNO
3and 1.5%H
3pO
4solution is binding agent, introduces appropriate Mg
2+extruded moulding is by 120 ℃ of oven dry, and 600 ℃ of roastings obtain consisting of 5%MgO-95%Al
2o
3carrier.Method for preparing catalyst and appreciation condition are with embodiment 1, and reaction result is in Table 1.
[embodiment 3]
The roasting at 600 ℃ of commercially available boehmite powder is obtained to δ-Al for 4 hours
2o
3, get equivalent δ-Al
2o
3with boehmite be Al source, in weight ratio with 1.5%HNO
3and 1.5%H
3pO
4solution is binding agent, introduces appropriate Mg
2+, Ca
2+extruded moulding is by 120 ℃ of oven dry, and 600 ℃ of roastings obtain consisting of 5%MgO-5%CaO-90%Al
2o
3carrier.Method for preparing catalyst is with embodiment 1.Method for preparing catalyst and evaluation method are with embodiment 1, and reaction result is in Table 1.
[embodiment 4]
The roasting at 900 ℃ of commercially available boehmite powder is obtained to γ-Al for 4 hours
2o
3, get equivalent γ-Al
2o
3with boehmite be Al source, in weight ratio with 1.5%HNO
3and 15%H
3pO
4solution is binding agent, introduces appropriate Mg
2+, Ca
2+extruded moulding is by 120 ℃ of oven dry, and 600 ℃ of roastings obtain consisting of 5%MgO-5%CaO-90%Al
2o
3carrier.Method for preparing catalyst and appreciation condition are with embodiment 1, and reaction result is in Table 1.
[embodiment 5]
The roasting at 600 ℃ of commercially available boehmite powder is obtained to δ-Al for 4 hours
2o
3, get equivalent γ-Al
2o
3with boehmite be Al source, in weight ratio with 1.5%HNO
3and 2.5%H
3pO
4solution is binding agent, introduces appropriate Ba
2+extruded moulding is by 120 ℃ of oven dry, and 600 ℃ of roastings obtain consisting of 5%CaO-95%Al
2o
3carrier.Method for preparing catalyst and appreciation condition are with embodiment 1.Reaction result is in Table 1.
[embodiment 6]
The roasting at 1100 ℃ of commercially available boehmite Al powder is obtained to α-Al for 4 hours
2o
3, with this α-Al
2o
3for Al powder, in weight ratio with 1.5%HNO
3and 2.5%H
3pO
4for binding agent, introduce appropriate Ba
2+extruded moulding is by 120 ℃ of oven dry, and 600 ℃ of roastings obtain consisting of 5%BaO-95%Al
2o
3carrier.Method for preparing catalyst and evaluation method are with embodiment 1.Reaction result is in Table 1.
The acetone hydrogenation reactivity worth of table 1 catalyst 1～6
As can be seen from Table 1, under identical reaction condition, catalyst 4,5,6 have good stability and selective.
[embodiment 7～13]
According to the preparation method of embodiment 5, the composition that just changes catalyst is prepared catalyst 7～13, and it forms in Table 2.
[comparative example 1]
According to Chinese patent CN1255482A, adopting the 30%CuO-70%ZnO mixture of compression molding is catalyst.
The composition of table 2 catalyst and preparation condition
The acetone hydrogenation performance of catalyst 7～13 and comparative example catalyst is in Table 3, and comparative example catalyst adopts and counts 5%H with percent by volume
2-95%N
2gaseous mixture at 230 ℃, reduce after 12 hours for hydrogenation reaction.
The acetone hydrogenation reactivity worth of table 3 different catalysts
As can be seen from Table 3, this catalyst is applied to preparing isopropyl alcohol by acetone hydrogenation and has obtained good reaction result, in reaction temperature, is that 150 ℃, reaction pressure 3.0Mpa, raw material volume space velocity are 2.0h
-1, hydrogen and the mol ratio of acetone are 8.0 to react after 72h, and acetone conversion can reach 100%, generates isopropyl alcohol and selectively can reach 99.8%, and this catalyst price is low simultaneously, and reaction condition is gentle.
Claims (1)
1. a high stability Ni base phosphide catalyst, its preparation process is:
Take commercially available boehmite as Al source, by weight percentage with 3%HNO
3the aqueous solution is binding agent, introduces appropriate Mg
2+extruded moulding is by 120 ℃ of oven dry, and 600 ℃ of roastings, obtain consisting of 5%MgO-95%Al
2o
3carrier;
Take 6.7g Ni (NO
3)
26H
2o and 2.4g (NH
4)
6mo
7o
244H
2o is dissolved in 10.0g distilled water, adds a certain amount of 1.7g NH
4h
2pO
4or 2.4g (NH
4)
2h
2pO
4, drip wherein dense HNO
3to precipitate dissolving, and adjust pH value between 4～5, form solution I; In solution I, add 3.5g citric acid, form solution II; Solution II is heated to 70 ℃, is added drop-wise to while hot on 10.0g carrier, roasting 8 hours at 550 ℃ after drying at 120 ℃; Catalyst is used front at H
2under in 650 ℃ reduction 12 hours; Catalyst consists of: 12%NiO-10%MoOx-5%POx-3.6%MgO-69.4%Al
2o
3; This catalyst is at 150 ℃, and reaction pressure 3.0MPa, total liquid volume air speed are 2.0h
-1the mol ratio of hydrogen and acetone is under 4.0 reaction condition, by weight percentage, 25% acetone-75% isopropyl alcohol is that raw material carries out in hydrogenation reaction, reaction result is: within 24 hours, acetone conversion is 100.0%, 24 hours isopropyl alcohols are selectively that 92.6%, 72 hour acetone conversion is that 95.0%, 72 hour isopropyl alcohol is selectively 93.6%.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191078A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Nickel catalyst with composite pore structure used for selective hydrogenation |
| CN101491760A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Nickle base catalyst for producing butane-1 by hydro-isomerization of butane-2 |
| CN101940928A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel-based catalyst for hydroisomerization of n-butene for preparing butene-2 or butene-1 |
-
2011
- 2011-04-20 CN CN201110100043.3A patent/CN102744089B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101191078A (en) * | 2006-11-21 | 2008-06-04 | 中国石油化工股份有限公司 | Nickel catalyst with composite pore structure used for selective hydrogenation |
| CN101491760A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Nickle base catalyst for producing butane-1 by hydro-isomerization of butane-2 |
| CN101940928A (en) * | 2009-07-06 | 2011-01-12 | 中国石油化工股份有限公司上海石油化工研究院 | Nickel-based catalyst for hydroisomerization of n-butene for preparing butene-2 or butene-1 |
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