CN106552678A - The quick method of reducing of Cu-contained catalyst - Google Patents
The quick method of reducing of Cu-contained catalyst Download PDFInfo
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- CN106552678A CN106552678A CN201510634416.3A CN201510634416A CN106552678A CN 106552678 A CN106552678 A CN 106552678A CN 201510634416 A CN201510634416 A CN 201510634416A CN 106552678 A CN106552678 A CN 106552678A
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Abstract
The present invention relates to a kind of method of reducing of catalyst, and in particular to a kind of quick method of reducing of Cu-contained catalyst.Methods described, first reduction raw material is added in raw material storage tank, heated subsequently into feed preheater, reactor bed entrance is rapidly heated to after 190 DEG C using the reduction raw material after preheating, speed adjust be will heat up for 1-2 DEG C/h, when reactor inlet reaches 200-205 DEG C, constant temperature 10-20h is kept to reduce catalyst；Gas-liquid separator is entered after cooler cooling through the reduction raw material of reactor bed, gas phase is vented or loops back reactor, and liquid is entered into raw material storage tank and circulated next time；Analysis reactor tail gas is constituted, CO in exit gas composition2When volume content is close to or smaller than 25%, reduction terminates；Wherein, reduce mixed solution of the raw material for first alcohol and water.Methods described is simple, and supplies consumption is few, and in reduction process, beds temperature rise is steady, and the recovery time is short.
Description
Technical field
The present invention relates to a kind of method of reducing of catalyst, and in particular to a kind of quick method of reducing of Cu-contained catalyst.
Background technology
In prior art, Cu-contained catalyst is often reduced using nitrogen, hydrogen atmosphere, and in reduction, thermal discharge is huge, if control is not
Strictly, easily there is larger temperature rise, cause copper excessive grain to be grown up, so that catalyst activity reduction or forfeiture.
In addition, the method for reducing of copper-based catalysts is carried out using nitrogen, hydrogen, in reduction process, gas consumption is big, Jing
Ji property is poor.
ZL 00110704.6 (Authorization Notice No. CN 1102451C) is selected there is provided a kind of method of reducing of Cu-contained catalyst
C1-C12Primary alconol or secondary alcohol as reduction raw material, in actual applications find reactor outlet can detect that impurity (as fusel,
Ketone, aldehyde etc.)；In addition with the appearance of these impurity, can be detected by Instrumental Analysis and have on catalyst slight carbon deposit, carbon deposit meeting
Significantly affect the performance of catalyst.
ZL 200610021008.1 (Authorization Notice No. CN 100420517C) is there is provided a kind of Methanol cluster hydrogen manufacturing copper
The method of reducing of base catalyst, including the reduction phase in catalyst water smoking, the initiating stage of catalyst reduction and catalyst,
Operating process is loaded down with trivial details, wayward.
CN201110327063.4 (Authorization Notice No. CN 102416327B) is there is provided a kind of Methanol cluster hydrogen manufacturing copper
The method of reducing of zinc catalyst, including the reduction of copper zinc catalyst water smoking, copper zinc catalyst reduction phase and copper zinc catalyst is by force
In the change stage, operating process is loaded down with trivial details；Particularly in the water hydrogen reduction stage, cupric oxide by hydrogen reducing into copper, under water vapour atmosphere,
Copper crystal grain is grown up rapidly, so as to reduce catalyst activity.
The content of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of quick method of reducing of Cu-contained catalyst, reduction process behaviour
Make simple, supplies consumption is few, the temperature rise of reduction process beds is steady, and the recovery time is short, reduction process free from admixture is produced
It is raw, be conducive to clean manufacturing.
The quick method of reducing of Cu-contained catalyst of the present invention, first, reduction raw material is added in raw material storage tank, then
Heated into feed preheater, reactor bed entrance be rapidly heated to after 190 DEG C using the reduction raw material after preheating,
Will heat up speed adjust is 1-2 DEG C/h, when reactor inlet reaches 200-205 DEG C, keeps constant temperature 10-20h to reduce catalyst；
Gas-liquid separator is entered after cooler cooling through the reduction raw material of reactor bed, gas phase is vented or loops back reactor,
Liquid is entered into raw material storage tank and is circulated next time；Analysis reactor tail gas is constituted, CO in exit gas composition2Volume content connects
Near or during less than 25%, reduction terminates；
Wherein, reduce mixed solution of the raw material for first alcohol and water.
When preferably reactor inlet is up to 200 DEG C, constant temperature 10-20h is kept to reduce catalyst.Higher than 210 DEG C, catalysis
Agent reduction rate is substantially fast, but the catalyst activity for restoring is slow decline, after higher than 230 DEG C, is restored
The ratio that catalyst activity is reduced is bigger；Less than 200 DEG C, reduction rate is very slow, and constant temperature time can exceed 24h, not be suitable for
Industrial production.
Before being warming up to 190 DEG C to beds entrance, the programming rate of beds can quickly, as long as less than anti-
Answer the license programming rate of equipment matter；In addition, the programming rate of beds and feed preheater are designed with great pass
Connection, the programming rate that usual feed preheater can be provided are 20～40 DEG C/h.
In the mixed solution of first alcohol and water, methyl alcohol is 1.5-2.5 with the volume ratio of water:97.5-98.5.Methods described utilizes Methanol Decomposition
The trace hydrogen that reaction is produced is reducing Cu-contained catalyst.Increase the methyl alcohol ratio regular meeting obvious shortening recovery time in the solution, but
It is also thus to bring the risk in industrial operation.Methanol decomposition reaction is exothermic reaction, when in mixed solution, methanol content is higher
When, it is easy to expect, the quantity of methyl alcohol decomposed in the unit interval is more, reaction bed temperature thus can be caused to occur more obvious
Rising.Temperature raises the generation that can promote methanol decomposition reaction, so as to accelerate catalyst reduction speed.Thus be likely to occur compared with
Bad situation, such as reaction bed temperature are out of hand, and serious meeting damages the performance of catalyst.The inventive method is preferably by gas
The gas phase emptying of liquid/gas separator, is also based on considerations above.
It is 0.5-2.0h that reduction raw material after preheating is passed through the liquid hourly space velocity (LHSV) of reactor-1。
When reducing to catalyst, reactor pressure is controlled in 0.1-1.5MPa, preferably 0.1-0.2MPa.Reaction system pressure
Power can substantially restrict the reduction rate of catalyst, and the copper content identical catalyst recovery time in atmospheric conditions is significantly shorter than and adds
Press strip part, methanol decomposition reaction are the reactions of volume increase, and it is unfavorable to methanol decomposition reaction to pressurize.
The principle of the quick method of reducing of described Cu-contained catalyst：
Unreduced Cu-contained catalyst, the form of its active ingredient copper are mainly CuO.When reaction bed temperature is suitable, first
Alcohol can occur faint methanol decomposition reaction (CH in catalyst activity metal oxide surface3OH=CO+2H2), so as to discharge
Go out extremely micro hydrogen, at a suitable temperature, CuO can be reduced to Cu by the extremely micro hydrogen in this part.By anti-
Retrial is issued after examination and approval now, and reaction bed temperature controls at 200 DEG C the lower limit for being preference temperature.During less than 200 DEG C, Methanol Decomposition amount
Seldom, catalyst reduction process is excessively very long, and such as bed temperature is controlled at 180 DEG C, the catalyst reduction time of copper content 40%
More than 100h；When reaction bed temperature is controlled at 200 DEG C, the catalyst reduction time of copper content 60% can be controlled in
10-15h.When bed temperature is more than 200 DEG C, the recovery time is shorter, and here does not just enumerate test data.By to containing
Multiple catalyst of amount of copper 40-60% are tested, and result of the test confirms：Using the method for the present invention, reduce at 200 DEG C
Catalyst, its activity have reached the performance requirement of normal production, it is not necessary to carry out the reduction of higher temperature to catalyst.
In sum, beneficial effects of the present invention are as follows：
(1) present invention provides a kind of quick method of reducing of Cu-contained catalyst, and operation is simple for reduction process, and supplies consumption is few,
Easily controllable reaction bed temperature, in reduction process, beds temperature rise is steady, and the recovery time is short.The methyl alcohol pair for being used
It is environmentally friendly, in reduction process, other impurities (such as fusel, ketone, aldehyde etc.) are not produced, is conducive to clean manufacturing.
(2) method of reducing is particularly well-suited to catalst for synthesis of methanol, methanol steam cracking hydrogen production catalyst and copper-based desulfurization and urges
The quick reduction of agent.
Specific embodiment
With reference to embodiment, the present invention will be further described.
The all raw materials used in embodiment unless otherwise specified, are commercial.
Embodiment 1
Copper-based catalysts, constitute CuO 60%, ZnO 35%, balance of Al2O3And auxiliary agent.
The liquid circulation of raw material storage tank-feed preheater-reactor-cooler-gas-liquid separator-raw material storage tank is set up first, using first
Alcohol and water mixed solution is rapidly heated reactor bed porch to after 190 DEG C, will heat up speed and is changed to 2 DEG C/h, works as catalyst
When 200 DEG C are reached at bed inlet, constant temperature is kept.
Contained by methyl alcohol and water mixed solution, methyl alcohol, the ratio of water are 1.5:98.5.The feeding control of mixed solution is in 0.5h-1。
During reduction, system pressure is controlled in normal pressure.
In reduction process, the gas of generation takes the mode of emptying.
During constant temperature, 1 secondary response device tail gas composition or raffinate methanol content are analyzed every 1h, result of the test is shown in Table 1.
1 embodiment of table, 1 activation of catalyst result of the test
According to experimental result, it is believed that the catalyst constant temperature time of CuO contents 60% can complete catalyst reduction in 15h.
Embodiment 2
Copper-based catalysts, constitute CuO 40%, ZnO 50%, balance of Al2O3And auxiliary agent.
The liquid circulation of raw material storage tank-feed preheater-reactor-cooler-gas-liquid separator-raw material storage tank is set up first, using first
Alcohol and water mixed solution is rapidly heated reactor bed porch to after 190 DEG C, will heat up speed and is changed to 1 DEG C/h, works as catalyst
When 200 DEG C are reached at bed inlet, constant temperature is kept.
Contained by methyl alcohol and water mixed solution, methyl alcohol, the ratio of water are 2.5:97.5.The feeding control of mixed solution is in 2h-1。
During reduction, system pressure is controlled in 0.2MPa.
In reduction process, the gas of generation takes the mode of circulation.
During constant temperature, 1 secondary response device tail gas composition or raffinate methanol content are analyzed every 1h, result of the test is shown in Table 2.
2 embodiment of table, 2 activation of catalyst result of the test
According to experimental result, it is believed that the catalyst constant temperature time of CuO contents 40% can complete catalyst reduction in 10h.
Embodiment 3
Using the copper-based catalysts of embodiment 2.
The liquid circulation of raw material storage tank-feed preheater-reactor-cooler-gas-liquid separator-raw material storage tank is set up first, using first
Alcohol and water mixed solution is rapidly heated reactor bed porch to after 190 DEG C, will heat up speed and is changed to 2 DEG C/h, works as catalyst
When 200 DEG C are reached at bed inlet, constant temperature is kept.
Contained by methyl alcohol and water mixed solution, methyl alcohol, the ratio of water are 2.5:97.5.The feeding control of mixed solution is in 2h-1。
During reduction, system pressure is controlled in 0.2MPa.
In reduction process, the gas of generation takes the mode of emptying.
During constant temperature, 1 secondary response device tail gas composition or raffinate methanol content are analyzed every 1h, result of the test is shown in Table 3.
3 embodiment of table, 3 activation of catalyst result of the test
According to experimental result, it is believed that the catalyst constant temperature time of CuO contents 40% can complete catalyst reduction in 14h.
Claims (6)
1. the quick method of reducing of a kind of Cu-contained catalyst, it is characterised in that：First, reduction raw material is added in raw material storage tank,
Heated subsequently into feed preheater, reactor bed entrance is rapidly heated to 190 DEG C using the reduction raw material after preheating
Afterwards, will heat up speed adjust is 1-2 DEG C/h, when reactor inlet reaches 200-205 DEG C, keeps constant temperature 10-20h to carry out catalyst
Reduction；Gas-liquid separator is entered after cooler cooling through the reduction raw material of reactor bed, gas phase is vented or loops back anti-
Device, liquid is answered to enter into raw material storage tank and circulate next time；Analysis reactor tail gas is constituted, CO in exit gas composition2Volume
When content is close to or smaller than 25%, reduction terminates；
Wherein, reduce mixed solution of the raw material for first alcohol and water.
2. the quick method of reducing of Cu-contained catalyst according to claim 1, it is characterised in that：The mixing of first alcohol and water is molten
In liquid, methyl alcohol is 1.5-2.5 with the volume ratio of water:97.5-98.5.
3. the quick method of reducing of Cu-contained catalyst according to claim 1, it is characterised in that：Reduction raw material after preheating
The liquid hourly space velocity (LHSV) for being passed through reactor is 0.5-2.0h-1。
4. the quick method of reducing of Cu-contained catalyst according to claim 1, it is characterised in that：Catalyst is reduced
When, reactor pressure is controlled in 0.1-1.5MPa.
5. the quick method of reducing of Cu-contained catalyst according to claim 4, it is characterised in that：Catalyst is reduced
When, reactor pressure is controlled in 0.1-0.2MPa.
6. the quick method of reducing of Cu-contained catalyst according to claim 1, it is characterised in that：Through reactor bed
Reduction raw material enters gas-liquid separator after cooler cooling, and gas phase emptying, liquid are entered into raw material storage tank and circulated next time.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620093A (en) * | 2018-05-15 | 2018-10-09 | 常州博能新能源有限公司 | A kind of hydrogen production from methanol-steam reforming copper-based catalysts activation method |
| CN111348987A (en) * | 2018-12-20 | 2020-06-30 | 上海华谊能源化工有限公司 | Reduction method of catalyst in preparation of ethylene glycol by dimethyl oxalate gas-phase hydrogenation |
| CN112916017A (en) * | 2021-01-29 | 2021-06-08 | 华东理工大学 | Raw material gas activation method for copper-based catalyst for hydrogen production by methanol steam reforming |
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| CN1102451C (en) * | 2000-07-24 | 2003-03-05 | 中国石油化工股份有限公司 | Reduction process of copper-containing catalyst |
| CN1850332A (en) * | 2006-05-26 | 2006-10-25 | 西南化工研究设计院 | Reduction method for copper-radic catalyst for reforming methanol vapour to produce hydrogen |
| EP2399671A1 (en) * | 2009-02-23 | 2011-12-28 | Mitsui Chemicals, Inc. | Copper-based catalyst manufacturing method, copper-based catalyst, and pretreatment method for same |
| CN102416327A (en) * | 2011-10-25 | 2012-04-18 | 江苏诺盟化工有限公司 | Reduction method of copper zinc catalyst for hydrogen production by methanol steam reforming |
-
2015
- 2015-09-30 CN CN201510634416.3A patent/CN106552678A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1102451C (en) * | 2000-07-24 | 2003-03-05 | 中国石油化工股份有限公司 | Reduction process of copper-containing catalyst |
| CN1850332A (en) * | 2006-05-26 | 2006-10-25 | 西南化工研究设计院 | Reduction method for copper-radic catalyst for reforming methanol vapour to produce hydrogen |
| EP2399671A1 (en) * | 2009-02-23 | 2011-12-28 | Mitsui Chemicals, Inc. | Copper-based catalyst manufacturing method, copper-based catalyst, and pretreatment method for same |
| CN102416327A (en) * | 2011-10-25 | 2012-04-18 | 江苏诺盟化工有限公司 | Reduction method of copper zinc catalyst for hydrogen production by methanol steam reforming |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620093A (en) * | 2018-05-15 | 2018-10-09 | 常州博能新能源有限公司 | A kind of hydrogen production from methanol-steam reforming copper-based catalysts activation method |
| CN111348987A (en) * | 2018-12-20 | 2020-06-30 | 上海华谊能源化工有限公司 | Reduction method of catalyst in preparation of ethylene glycol by dimethyl oxalate gas-phase hydrogenation |
| CN111348987B (en) * | 2018-12-20 | 2023-09-26 | 上海华谊能源化工有限公司 | Reduction method of catalyst in preparation of ethylene glycol by gas-phase hydrogenation of dimethyl oxalate |
| CN112916017A (en) * | 2021-01-29 | 2021-06-08 | 华东理工大学 | Raw material gas activation method for copper-based catalyst for hydrogen production by methanol steam reforming |
| CN112916017B (en) * | 2021-01-29 | 2022-05-06 | 华东理工大学 | Raw material gas activation method for copper-based catalyst for hydrogen production by methanol steam reforming |
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Application publication date: 20170405 |