CN107199054B - A kind of metal catalyst recovery method - Google Patents
A kind of metal catalyst recovery method Download PDFInfo
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- CN107199054B CN107199054B CN201610154938.8A CN201610154938A CN107199054B CN 107199054 B CN107199054 B CN 107199054B CN 201610154938 A CN201610154938 A CN 201610154938A CN 107199054 B CN107199054 B CN 107199054B
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- catalyst
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- regeneration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/90—Regeneration or reactivation
- B01J23/94—Regeneration or reactivation of catalysts comprising metals, oxides or hydroxides of the iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/08—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using ammonia or derivatives thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/64—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts
- B01J38/66—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using alkaline material; using salts using ammonia or derivatives thereof
Abstract
The method of the present invention belongs to catalyst preparation technical field, more particularly to a kind of metal catalyst recovery method, it is regenerated by following device, according to process, sequence successively includes vibration carbon dioxide cleaner (1) to the device from front to back, vibrating screen (2), metal redisperse device (3) and heating calciner (4).By the method for the invention, the metallic catalyst industrially inactivated can be regenerated, so as to extend the service life of catalyst.
Description
Technical field
The invention patent technology belongs to catalyst preparation technical field, and in particular to a kind of metal catalyst recovery method.
Background technique
Catalysis is one of most important subject in chemistry, and nearly all chemical reaction is all catalysis reaction.And industrially,
90% or more chemical industry production all be unable to do without catalyst.Industrially every year with the catalyst of millions of tons or so, these are urged
Agent value is up to ten million, and these catalyst can produce self-value hundred again to thousand times of chemical products.Catalyst inactivation
It will problems faced in almost all industrial catalyst use processes.Under normal circumstances, industrial catalyst once inactivates,
Catalyst can replace catalyst using producer, and decaying catalyst is abandoned, and deal with improperly to these solid waste
It also will cause the pollution to environment (soil, water etc.).The catalyst how these inactivated regenerates, to obtain
It re-uses, improves its use value, reducing to the pollution of environment is the project for being worth research.
Summary of the invention
The purpose of the invention patent is to be handled by the method for the invention patent decaying catalyst, thus significantly extensive
The catalytic performance of compound catalyst.
The present invention is mainly characterized by the processing of decaying catalyst by the method for the invention, carbon distribution can be made to be removed,
The metal of sintering is dispersed again, to restore the catalytic performance of decaying catalyst.
Main technical content of the present invention is as follows: the regeneration method of metallic catalyst, it is characterized in that being carried out by following device
Regeneration, according to process, sequence successively includes vibration carbon dioxide cleaner, vibrating screen, metal redisperse device and heating to the device from front to back
Calciner.
Generally, the vibration carbon dioxide cleaner bottom is to have uniform raised structures.
The metal redisperse device includes the catalyst regeneration room for filling water, and catalyst regeneration room enters equipped with ammonia
Mouth, auxiliary gas entrance, the lower part of catalyst regeneration room are cavity, and abscess and air inlet are made above cavity, and the lower part of cavity connects
Residual night circulation pipe, pump and bubbler are connect, bubbler protrudes into the top of catalyst regeneration room, and catalyst regeneration room top is connected to outlet
Mouth is through offgas outlet to tail gas absorber.
The regeneration method, be the catalyst that will industrially inactivate be placed in vibration carbon dioxide cleaner in, vibration except carbon move back to
Vibrating screen, vibration are moved back into the catalyst regeneration room for filling water of metal dispersion device, adjust the temperature in catalyst regeneration room
Degree, is passed through metal dispersion device by ammonia entrance for ammonia;After closing ammonia, air is passed through metal dispersion by auxiliary gas entrance
Device, while the temperature in catalyst regeneration room is adjusted, the residual night in cavity is delivered to spray by raffinate circulation pipe by starting pump
In liquid device, and on the catalyst being ejected into catalyst regeneration room, after the liquid in catalyst regeneration room and cavity is dried,
Catalyst is moved into heating calciner, roasting obtains regenerated catalyst in inert gas.
The vibration carbon dioxide cleaner vibration frequency is 100 ~ 300min-1, the shaker vibration frequency is 80 ~
200min-1。
The auxiliary gas inlet induction includes one of air, nitrogen, helium, argon gas and carbon dioxide gas.
Described makes size of the abscess-size less than loaded catalyst in catalyst regeneration room.
The gas outlet and offgas outlet is equal sized, and the size of both greater than air inlet.
What is contained in the tail gas absorber is aqueous solution.
Atmosphere in the heating calciner is the inert atmosphere of flowing, is one of nitrogen, helium and argon gas.
The regeneration method of metallic catalyst of the present invention can be such that the Industrial Metal catalyst catalytic performance of inactivation obtains extensive
It is multiple, to substantially prolong the service life of catalyst.
Detailed description of the invention
Fig. 1 is the attachment structure schematic diagram of present invention method.
Fig. 2 is the structural schematic diagram of metal redisperse device in embodiment.
In figure, 1: vibration carbon dioxide cleaner, 2: vibrating screen, 3: metal redisperse device, 4: heating calciner, 6: ammonia enters
Mouthful, 7: auxiliary gas entrance, 8: catalyst regeneration room, 9: making abscess, 10: air inlet, 11: cavity, 12: gas outlet, 13: tail gas goes out
Mouthful, 14: tail gas absorber, 15: raffinate circulation pipe, 16: pump, 17: bubbler.
Specific embodiment
The method of the present invention is described in detail below by way of attached drawing, embodiment and comparative example.
As shown in figure 1 and 2, according to process, sequence successively includes that vibration removes to the device of embodiment regeneration method from front to back
Carbon device (1), vibrating screen (2), metal redisperse device (3) and heating calciner (4).The vibration carbon dioxide cleaner vibration frequency
For 100 ~ 300min-1, shaker vibration frequency is 80 ~ 200min-1.The vibration carbon dioxide cleaner bottom is to have uniform protrusion knot
Structure.The metal redisperse device group becomes ammonia entrance (6), assists gas entrance (7), fills the catalyst regeneration room of water
(8), it makes abscess (9), air inlet (10), cavity (11), gas outlet (12), offgas outlet (13), tail gas absorber (14), residual night
Circulation pipe (15) pumps (16), bubbler (17).Described auxiliary gas entrance (7) air inlet include air, nitrogen, helium, argon gas and
One of carbon dioxide gas.Described makes size of abscess (9) size less than loaded catalyst in catalyst regeneration room.
The gas outlet (12) and offgas outlet (13) is equal sized, and the size of both greater than air inlet (10).The tail gas
What is contained in absorber (14) is aqueous solution.Atmosphere in the heating calciner (4) is the inert atmosphere of flowing, is nitrogen
One of gas, helium and argon gas.
Embodiment
The copper-zinc-aluminium methanol synthetic catalyst industrially inactivated (φ 5mm × 5mm) D is placed in vibration carbon dioxide cleaner, is adjusted
Vibration frequency is 100min-1;After vibrating 30min, catalyst is moved into vibrating screen, adjusting vibration frequency is 80min-1;Vibration
After 20min, catalyst is moved in the catalyst regeneration room for filling water of metal dispersion device, by the temperature in catalyst regeneration room
Degree is adjusted to 50 DEG C, and the ammonia of 100mL/min is passed through metal dispersion device by ammonia entrance;After 20min, ammonia is closed, it will
The air of 200mL/min is passed through metal dispersion device by auxiliary gas entrance, while adjusting the temperature in catalyst regeneration room is 80
DEG C, the residual night in cavity is delivered in bubbler, and be ejected into catalyst regeneration room by starting pump by raffinate circulation pipe
On catalyst, after the liquid in catalyst regeneration room and cavity is dried, continuation purges 4h at 80 DEG C;Then by catalyst
It moves in heating calciner, in 200mL/min nitrogen stream, roasts 2h at 300 DEG C, obtain regenerated catalyst R.
By the catalyst D inactivated in industrial fresh methanol synthesis catalyst F and embodiment and through the invention
The regenerated catalyst R of patented technology is reacted for synthesising gas systeming carbinol, is reacted enterprising in former two pipe fixed-bed reactor of granularity
Row.Reaction condition are as follows: weigh original catalyst particle size (φ 5mm × 5mm) each 100mL and be placed in reactor constant temperature zone, first lead to 2000h-1
5% H2/N2, activation of catalyst is carried out under the conditions of normal pressure, 200 DEG C, after 10h, by H2/N2Autogenous cutting is changed to 10000h-1Original
Expect gas, it is CO/CO that unstripped gas, which forms volume,2/H2/N2=20/5/70/5, by temperature rise to 230 DEG C, pressure rise to 5MPa, react
After 2h, tail gas chromatography is carried out, the results are shown in Table 1 for analysis.
Catalytic performance of 1 catalyst of table in synthesising gas systeming carbinol reaction
Catalyst | CO conversion ratio (%) | Methanol selectivity (%) |
D | 10.3 | 79.4 |
F | 69.7 | 97.6 |
R | 68.5 | 98.1 |
Table 1 statistics indicate that, the catalyst recovery process of patent, can restore the catalytic of decaying catalyst through the invention
Energy.
Claims (8)
1. a kind of regeneration method of metallic catalyst, it is characterized in that regenerated by following device, the device according to process from
Sequence successively includes vibration carbon dioxide cleaner, vibrating screen, metal redisperse device and heating calciner front to back;The metal is again
Dispersal device includes the catalyst regeneration room for filling water, and catalyst regeneration room is equipped with ammonia entrance, auxiliary gas entrance, and catalyst is again
The lower part of raw room is cavity, and abscess and air inlet, lower part connection raffinate circulation pipe, pump and the hydrojet of cavity are made above cavity
Device, bubbler protrude into the top of catalyst regeneration room, and catalyst regeneration room top is connected to gas outlet and inhales through offgas outlet to tail gas
Receive device;
The regeneration method is that the catalyst that will industrially inactivate is placed in vibration carbon dioxide cleaner, and vibration is moved back except carbon to vibration
Sieve, vibration are moved back into the catalyst regeneration room for filling water of metal dispersion device, adjust the temperature in catalyst regeneration room, will
Ammonia is passed through metal dispersion device by ammonia entrance;After closing ammonia, air is passed through metal dispersion device by auxiliary gas entrance,
The temperature in catalyst regeneration room is adjusted simultaneously, and the raffinate in cavity is delivered to bubbler by raffinate circulation pipe by starting pump
In, and on the catalyst being ejected into catalyst regeneration room, after the liquid in catalyst regeneration room and cavity is dried, it will urge
Agent moves to heating calciner, and roasting obtains regenerated catalyst in inert gas.
2. regeneration method according to claim 1, it is characterised in that the vibration carbon dioxide cleaner bottom is to have uniform protrusion
Structure.
3. regeneration method according to claim 1, it is characterised in that the vibration carbon dioxide cleaner vibration frequency be 100 ~
300min-1, the shaker vibration frequency is 80 ~ 200min-1。
4. regeneration method according to claim 1, it is characterised in that the auxiliary gas inlet induction includes air, nitrogen
One of gas, helium, argon gas and carbon dioxide gas.
5. regeneration method according to claim 1, it is characterised in that described makes abscess-size less than catalyst regeneration room
The size of middle loaded catalyst.
6. regeneration method according to claim 1, it is characterised in that the gas outlet and offgas outlet is equal sized, and
And the size of both greater than air inlet.
7. regeneration method according to claim 1, it is characterised in that is contained in the tail gas absorber is aqueous solution.
8. regeneration method according to claim 1, it is characterised in that the atmosphere in the heating calciner is flowing
Inert atmosphere, be one of nitrogen, helium and argon gas.
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CN201610154938.8A CN107199054B (en) | 2016-03-18 | 2016-03-18 | A kind of metal catalyst recovery method |
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CN201610154938.8A CN107199054B (en) | 2016-03-18 | 2016-03-18 | A kind of metal catalyst recovery method |
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CN107199054A CN107199054A (en) | 2017-09-26 |
CN107199054B true CN107199054B (en) | 2019-09-17 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102744103A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Regeneration method of zeolite molecular sieve catalyst |
CN104226377A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Regeneration method of inactivated hydrogenation catalyst |
CN104588094A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Regeneration method for deactivated catalyst |
CN105618161A (en) * | 2016-01-16 | 2016-06-01 | 中国科学院福建物质结构研究所 | Method for activating and regenerating catalyst for dehydrogenizing CO raw gas |
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2016
- 2016-03-18 CN CN201610154938.8A patent/CN107199054B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102744103A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Regeneration method of zeolite molecular sieve catalyst |
CN104226377A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Regeneration method of inactivated hydrogenation catalyst |
CN104588094A (en) * | 2013-11-03 | 2015-05-06 | 中国石油化工股份有限公司 | Regeneration method for deactivated catalyst |
CN105618161A (en) * | 2016-01-16 | 2016-06-01 | 中国科学院福建物质结构研究所 | Method for activating and regenerating catalyst for dehydrogenizing CO raw gas |
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Address after: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee after: China Petroleum & Chemical Corp. Patentee after: SINOPEC NANJING CHEMICAL RESEARCH INSTITUTE Co.,Ltd. Address before: Liuhe District of Nanjing City, Jiangsu province 210048 geguan Road No. 699 Patentee before: China Petroleum & Chemical Corp. Patentee before: Nanhua Group Research Institute |
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