CN104084206A - Aromatic amine hydrogenation catalyst recycling method - Google Patents
Aromatic amine hydrogenation catalyst recycling method Download PDFInfo
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- CN104084206A CN104084206A CN201410265355.3A CN201410265355A CN104084206A CN 104084206 A CN104084206 A CN 104084206A CN 201410265355 A CN201410265355 A CN 201410265355A CN 104084206 A CN104084206 A CN 104084206A
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- catalyst
- hydrogenation
- aromatic amine
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- sedimentation separation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 34
- 150000004982 aromatic amines Chemical class 0.000 title claims abstract description 22
- 238000004064 recycling Methods 0.000 title abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 62
- 238000004062 sedimentation Methods 0.000 claims abstract description 51
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 239000007788 liquid Substances 0.000 claims abstract description 21
- 230000000694 effects Effects 0.000 claims abstract 3
- 238000007599 discharging Methods 0.000 claims description 25
- 239000012530 fluid Substances 0.000 claims description 20
- 230000000149 penetrating effect Effects 0.000 claims description 20
- 238000005374 membrane filtration Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- -1 aromatic nitro compound Chemical class 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract 5
- 239000006228 supernatant Substances 0.000 abstract 3
- 239000000463 material Substances 0.000 abstract 2
- 238000012545 processing Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LZVRUDMTJCUUNP-UHFFFAOYSA-N [N+](=O)([O-])C1=C(OC)C=CC(C1)(N)C(C)=O Chemical compound [N+](=O)([O-])C1=C(OC)C=CC(C1)(N)C(C)=O LZVRUDMTJCUUNP-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DADSZOFTIIETSV-UHFFFAOYSA-N n,n-dichloroaniline Chemical compound ClN(Cl)C1=CC=CC=C1 DADSZOFTIIETSV-UHFFFAOYSA-N 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007616 round robin method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to an aromatic amine hydrogenation catalyst recycling method. The method comprises the following steps: (1) membrane-filtering and sedimentation separation are carried out, wherein hydrogenation feed liquid from a hydrogenation reaction kettle is delivered into a first-stage membrane filter; through membrane filtering separation, a permeated liquid discharged material enters a subsequent process, and concentrated liquid is subjected to sedimentation separation in a first-stage sedimentation tank; according to detected activity effect, a catalyst separated from the bottom of the first-stage sedimentation tank is delivered back to the hydrogenation reaction kettle and is reused, or is recovered as a waste catalyst; a supernatant is discharged into a next-stage membrane filter; the above membrane-filtering and sedimentation separation operations are repeated, and a supernatant from the final N-stage sedimentation tank is discharged into a last-stage membrane filter, wherein N is no less than 2; and (2) last-stage membrane filtering separation is carried out, wherein the supernatant from the N-stage sedimentation tank enters the last-stage membrane filter; after membrane filtering separation, a permeated liquid discharged material enters a subsequent process, and concentrated liquid is delivered back into the N-stage sedimentation tank; and the catalyst is separated from the bottom.
Description
(1) technical field
The present invention relates to a kind of recoverying and utilizing method of hydrogenation catalyst, say that more specifically the on-line continuous of aromatic amine hydrogenation catalyst separates the method for recycling.
(2) background technology
Aromatic amine compounds is very important Organic Ingredients, is widely used in the production fields such as dyestuff, medicine, agricultural chemicals.Most aromatic amine compounds are to be made by reducing by fragrant nitro compound, and hydrogenating reduction method becomes the main stream approach of current industrial reduction nitro with advantages such as its technique is clean, reduction efficiency is high, good product qualities.
In hydrogenating reduction process, conventionally need to use catalyst and promote the carrying out reacting.In hydrogenation process, catalyst being pulverized in the process of vigorous stirring in reactor together with reaction mixture, and the catalyst that particle diameter is less is easily brought into subsequent handling by logistics, causes resultant metal content overproof and equipment fault.
Patent CN02112764.6, has disclosed a kind of method of inorganic membrane filtration separating catalyst, and it adopts hydrogenation to generate Matter Transfer repeatedly by inorganic filter film, and liquid-phase product is collected after seeing through fenestra, and solid-phase catalyst is stayed the method for reactor recycling.But this technique is intermittently carried out, and affects production efficiency, the catalyst fully recovering simultaneously separating, fails to separate the catalyst of inactivation, and to follow-up hydrogenation, reaction impacts.
Patent CN200710163811.3, introduce a kind of continuous separate of toluenediamine hydrogenation catalyst from round-robin method and equipment thereof, its adopt a kind of inclined plate separator continuous separate from and recycle the catalyst in crude cresylic acid diamines, charging catalyst concn 0.5-3.0wt%, after this device separates, in clear liquid, catalyst concn is controlled at 200-600ppm.
Patent CN201210026615.2, a kind of recoverying and utilizing method and device of toluenediamine hydrogenation catalyst particulate are disclosed, it adopts settling tank gravitational settling, the micro-swirl concentrator of one-level and the micro-cyclone clarificator processing of one-level, be not more than in 5wt% situation at import catalyst content, device outlet catalyst content is not more than 0.05wt%.In existing industrial production, though disclose aromatic amine hydrogenation catalyst continuous separate from the method reclaiming, in the feed liquid after separating, catalyst content is higher, unfavorable to following process process and product quality; Tradition hydrogenation technique, because the loss of catalyst is larger, needs to supplement and adds normally carrying out of new catalyst maintenance hydrogenation reaction, and integral membrane filtered and recycled technology is not distinguished utilization to the catalyst reclaiming.Therefore, separate in the urgent need to developing a kind of efficient on-line continuous the method for recycling catalyst.
(3) summary of the invention
The object of the invention is to provide a kind of efficient on-line continuous to separate the method for recycling aromatic amine hydrogenation catalyst, does not distinguish the higher problem that affects following process of catalyst content in the feed liquid that separation is reclaimed and separation obtains to solve aromatic amine hydrogenation dead catalyst in existing industrial production.
For realizing the object of the invention, the technical scheme adopting is as follows:
A recoverying and utilizing method for aromatic amine hydrogenation catalyst, comprises the following steps:
(1) membrane filtration-sedimentation separation: the hydrogenation feed liquid that comes from hydrogenation reaction kettle enters one-level film filter continuously, separate by membrane filtration, penetrating fluid discharging enters subsequent handling (being the postprocessing working procedures of aromatic amine product), concentrate enters first grade subsides groove and carries out sedimentation separation, the catalyst that first grade subsides trench bottom is separated returns to hydrogenation reaction kettle to be continued use or reclaim as dead catalyst, upper clear supernate discharging is to next stage film filter, repeat above-mentioned membrane filtration-sedimentation separation operation, the upper clear supernate discharging of last N level subsider is to final stage film filter, wherein N >=bis-, in described hydrogenation reaction kettle, carry out the reaction that aromatic nitro compound catalytic hydrogenation is prepared aromatic amine,
(2) final stage membrane filtration separates: the upper clear supernate that comes from N level subsider enters final stage film filter, separate by membrane filtration, penetrating fluid discharging enters subsequent handling, and concentrate returns and enters N level subsider, from bottom separating catalyst, generally as waste catalyst recovery.
Further, described aromatic amine hydrogenation catalyst is particle or the fine catalyst of nickeliferous, palladium, platinum, rhodium or iridium isoreactivity component.
Further, the described hydrogenation feed liquid that comes from hydrogenation reaction kettle is before carrying out membrane filtration-sedimentation separation, first carry out sedimentation separation: make to enter continuously subsider from the hydrogenation feed liquid of hydrogenation reaction kettle and carry out sedimentation separation, the concentrated slurry of the isolated catalyst in bottom returns to hydrogenation reaction kettle to be continued to use, and upper clear supernate discharging enters follow-up one-level film filter.
Further, described sedimentation separation also can adopt multistage operations, preferably 2～3 grades of sedimentations, i.e. the first discharging of the upper clear supernate of subsider is carried out sedimentation separation to next subsider, and after what sedimentation separation, the upper clear supernate of last subsider enters one-level membrane separator again.
Further, described membrane filtration-sedimentation separation preferably adopts 2-6 level operation (being that N is selected from two～six), more preferably adopts 2-3 level operation (being that N is two or three).
Further, enter the catalyst concn that the penetrating fluid of subsequent handling contains and be less than 40ppm.
In the present invention, the inoranic membrane that described film filter can adopt pottery, metal or other composite to form, the average pore size of film is at 1nm～1um, and filtered version can adopt cross-flow or and the mode of stream.General raw material enters film filter and is divided into both sides: seepage side and circulation side.The clean liquid (penetrating fluid) of seepage side enters following process operation, and the dope (concentrate) of circulation side enters subsider.
Compared with prior art, advantage of the present invention is by continuous feed, continuous sedimentation separation, continuous membrane filter-sedimentation separation, solve the problem that in catalytic hydrogenation industrial production, the continuous ON-LINE SEPARATION of catalyst reclaims, membrane filtration pattern and gravitational settling mode cooperate optimization, the separative efficiency of hydrogenation liquid catalyst is highly improved, significantly reduce the amount of feed liquid entrained catalyst, make catalyst obtain difference simultaneously and reclaim.
(4) brief description of the drawings
Fig. 1 is the schematic diagram of a kind of embodiment of technological process of the present invention.
(5) detailed description of the invention
With specific embodiment, technical scheme of the present invention is described further below, but protection scope of the present invention is not limited to this:
Embodiment 1
2-nitro-4-acetyl-anisidine, methyl alcohol, nickel aluminium powder catalyst and hydrogen enter by a certain percentage hydrogenation reaction kettle and carry out hydrogenation reaction, and wherein nickel aluminium powder catalyst content is 3.5%, and catalyst particle size is at 100-500 order.2-amino-4-acetyl-anisidine hydrogenation feed liquid that hydrogenation produces, enters subsider and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom returns to hydrogenation system and uses, and upper clear supernate catalyst concn is about 0.20%, is pumped to subsequent film filter.Subsequent film filter adopts titanium metal film, and film mean pore size is 50nm.
The upper clear supernate of sedimentation separation enters after the separation of one-level film filter, and the penetrating fluid catalyst content obtaining is 20ppm, and discharging is to subsequent processing; The dope catalyst content obtaining is 6000ppm, enters first grade subsides groove and carries out sedimentation separation.The isolated catalyst slurry in subsider bottom returns to hydrogenation still and uses, and upper clear supernate is pumped to secondary film filter.
The upper clear supernate that first grade subsides separates enters after the separation of secondary film filter, and the penetrating fluid catalyst content obtaining is 20ppm, and directly discharging is to subsequent processing; The dope catalyst content obtaining is 6000ppm, enters secondary subsider and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom is recycled by manufacturer as discarded catalyst, and upper clear supernate is pumped to three grades of film filters.
The upper clear supernate of secondary sedimentation separation enters after three grades of film filters separation, and the penetrating fluid catalyst content obtaining is for being 20ppm, and directly discharging is to subsequent processing; The dope obtaining returns and enters secondary subsider.
Embodiment 2
Mix dinitrobenzene, methyl alcohol, nickel aluminium powder catalyst and hydrogen enter by a certain percentage hydrogenation reaction kettle and react, and wherein nickel aluminium powder catalyst content is 5.1%, and catalyst particle size is at 100-500 order.The mixed diamines hydrogenation feed liquid that hydrogenation produces, enters subsider and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom returns to hydrogenation system and uses, and upper clear supernate catalyst concn is about 0.31%, is pumped to subsequent film filter.Subsequent film filter adopts ceramic membrane, and film mean pore size is 45nm.
The upper clear supernate of sedimentation separation enters after the separation of one-level film filter, and the penetrating fluid catalyst content obtaining is 27ppm, and discharging is to subsequent processing; The dope catalyst content obtaining is 9000ppm, enters first grade subsides groove and carries out sedimentation separation.The isolated catalyst in subsider bottom, its hydrogen-absorption speed is less than 50% theoretical hydrogen-absorption speed, can not return and continue to use, and is recycled by manufacturer as dead catalyst; Upper clear supernate is pumped to secondary film filter.
The upper clear supernate that first grade subsides separates enters after the separation of secondary film filter, and the penetrating fluid catalyst content obtaining is 27ppm, and directly discharging is to subsequent processing; The dope catalyst content obtaining is 9000ppm, enters secondary subsider and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom is recycled by manufacturer as discarded catalyst, and upper clear supernate is pumped to three grades of film filters.
The upper clear supernate of secondary sedimentation separation enters after three grades of film filters separation, and the penetrating fluid catalyst content obtaining is 27ppm, and directly discharging is to subsequent processing; The dope catalyst content obtaining is 13500ppm, enters three grades of subsiders and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom is recycled by manufacturer as discarded catalyst, and upper clear supernate is pumped to level Four film filter.
The upper clear supernate of three grades of sedimentation separations enters after the separation of level Four film filter, and the penetrating fluid catalyst content obtaining is for being 27ppm, and directly discharging is to subsequent processing; The dope obtaining returns and enters three grades of subsiders.
Embodiment 3
Nitrotoleune, methyl alcohol, nickel aluminium powder catalyst and hydrogen enter hydrogenation reaction kettle reaction according to a certain percentage, and wherein nickel aluminium powder catalyst content is 4.5%, and catalyst particle size is at 100-500 order.The methylaniline hydrogenation feed liquid that reaction obtains, enters subsider and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom returns to hydrogenation system and uses, and upper clear supernate catalyst concn is about 0.27%, is pumped to subsequent film filter.Subsequent film filter adopts titanium-aluminium alloy metal film, and film mean pore size is 100nm.
The upper clear supernate of sedimentation separation enters after the separation of one-level film filter, and the penetrating fluid catalyst content obtaining is 25ppm, and discharging is to subsequent processing; The dope catalyst content obtaining is 8000ppm, enters first grade subsides groove and carries out sedimentation separation.The isolated catalyst slurry in subsider bottom returns to hydrogenation still and uses, and upper clear supernate is pumped to secondary film filter.
The upper clear supernate that first grade subsides separates enters after the separation of secondary film filter, and the penetrating fluid catalyst content obtaining is 25ppm, and directly discharging is to subsequent processing; The dope catalyst content obtaining is 8000ppm, enters secondary subsider and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom is recycled by manufacturer as discarded catalyst, and upper clear supernate is pumped to three grades of film filters.
The upper clear supernate of secondary sedimentation separation enters after three grades of film filters separation, and the penetrating fluid catalyst content obtaining is for being 25ppm, and directly discharging is to subsequent processing; The dope obtaining returns and enters secondary subsider.
Embodiment 4
3,4-dichloronitrobenzene, methyl alcohol, nickel aluminium powder catalyst and hydrogen enter hydrogenation reaction kettle and react, and wherein nickel aluminium powder catalyst content is 0.71%, and catalyst particle size is at 100-500 order.3, the 4 dichloroaniline hydrogenation feed liquids that reaction obtains, enter one-level film filter and separate, and the penetrating fluid catalyst content obtaining is 35ppm, and discharging is to subsequent processing; The dope catalyst content obtaining is 15000ppm, enters first grade subsides groove and carries out sedimentation separation.The isolated catalyst slurry in subsider bottom returns to hydrogenation still and uses, and upper clear supernate is pumped to secondary film filter.
The upper clear supernate that first grade subsides separates enters after the separation of secondary film filter, and the penetrating fluid catalyst content obtaining is 35ppm, and directly discharging is to subsequent processing; The dope catalyst content obtaining is 15000ppm, enters secondary subsider and carries out sedimentation separation.The isolated catalyst pulp in subsider bottom is recycled by manufacturer as discarded catalyst, and upper clear supernate is pumped to three grades of film filters.Subsequent film filter adopts ceramic membrane, and film mean pore size is 200nm.
The upper clear supernate of secondary sedimentation separation enters after three grades of film filters separation, and the penetrating fluid catalyst content obtaining is for being 35ppm, and directly discharging is to subsequent processing; The dope obtaining returns and enters secondary subsider.
Claims (9)
1. a recoverying and utilizing method for aromatic amine hydrogenation catalyst, comprises the following steps:
(1) membrane filtration-sedimentation separation: the hydrogenation feed liquid from hydrogenation reaction kettle enters one-level film filter, separate by membrane filtration, penetrating fluid discharging enters subsequent handling, concentrate enters first grade subsides groove and carries out sedimentation separation, the catalyst that first grade subsides trench bottom is separated is according to the active effect detecting, returning to hydrogenation reaction kettle continues use or reclaim as dead catalyst, upper clear supernate discharging is to next stage film filter, repeat above-mentioned membrane filtration-sedimentation separation operation, the upper clear supernate discharging of last N level subsider is to final stage film filter, wherein N >=bis-, in described hydrogenation reaction kettle, carry out the reaction that aromatic nitro compound catalytic hydrogenation is prepared aromatic amine,
(2) final stage membrane filtration separates: the upper clear supernate that comes from N level subsider enters final stage film filter, separates by membrane filtration, and penetrating fluid discharging enters subsequent handling, and concentrate returns and enters N level subsider, from bottom separating catalyst.
2. the recoverying and utilizing method of aromatic amine hydrogenation catalyst as claimed in claim 1, it is characterized in that: the described hydrogenation feed liquid that comes from hydrogenation reaction kettle is before carrying out membrane filtration-sedimentation separation, first carry out sedimentation separation: make to enter continuously subsider from the hydrogenation feed liquid of hydrogenation reaction kettle and carry out sedimentation separation, the concentrated slurry of the isolated catalyst in bottom returns to hydrogenation reaction kettle to be continued to use, and upper clear supernate discharging enters follow-up one-level film filter.
3. the recoverying and utilizing method of aromatic amine hydrogenation catalyst as claimed in claim 2, it is characterized in that: described sedimentation separation adopts Multistage settling operation, the first discharging of upper clear supernate of subsider is carried out sedimentation separation to next subsider, and after Multistage settling separates, the upper clear supernate of last subsider enters one-level membrane separator again.
4. the recoverying and utilizing method of aromatic amine hydrogenation catalyst as claimed in claim 3, is characterized in that: described sedimentation separation adopts 2～3 grades of sedimentation operations.
5. the recoverying and utilizing method of the aromatic amine hydrogenation catalyst as described in one of claim 1～4, is characterized in that: described aromatic amine hydrogenation catalyst is particle or the fine catalyst of nickeliferous, palladium, platinum, rhodium or iridium active component.
6. the recoverying and utilizing method of the aromatic amine hydrogenation catalyst as described in one of claim 1～4, is characterized in that: enter the catalyst concn that the penetrating fluid of subsequent handling contains and be less than 40ppm.
7. the recoverying and utilizing method of the aromatic amine hydrogenation catalyst as described in one of claim 1～4, is characterized in that: in step (1), N is selected from two～six.
8. the recoverying and utilizing method of aromatic amine hydrogenation catalyst as claimed in claim 7, is characterized in that: in step (2), N is two or three.
9. the recoverying and utilizing method of the aromatic amine hydrogenation catalyst as described in one of claim 1～4, is characterized in that: the inoranic membrane that described film filter adopts pottery or metal to form, the average pore size of film is at 1nm～1 μ m.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047096A (en) * | 2017-12-29 | 2018-05-18 | 烟台安诺其精细化工有限公司 | The preparation method of 1-naphthylamine-5-sulfonic acid |
| CN114308141A (en) * | 2021-12-15 | 2022-04-12 | 安徽华尔泰化工股份有限公司 | Separation process and separation system for phenylenediamine hydrogenation reduction liquid catalyst |
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| CN1377875A (en) * | 2002-03-15 | 2002-11-06 | 南京工业大学 | Production process of p-aminophenol |
| US20060144787A1 (en) * | 2005-01-06 | 2006-07-06 | Eet Corporation | Integrated electro-pressure membrane deionization system |
| CN103846008A (en) * | 2012-12-04 | 2014-06-11 | 厦门市天泉鑫膜科技股份有限公司 | Device for continuously concentrating and separating substance by membrane and separation method |
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- 2014-06-13 CN CN201410265355.3A patent/CN104084206B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1377875A (en) * | 2002-03-15 | 2002-11-06 | 南京工业大学 | Production process of p-aminophenol |
| US20060144787A1 (en) * | 2005-01-06 | 2006-07-06 | Eet Corporation | Integrated electro-pressure membrane deionization system |
| CN103846008A (en) * | 2012-12-04 | 2014-06-11 | 厦门市天泉鑫膜科技股份有限公司 | Device for continuously concentrating and separating substance by membrane and separation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047096A (en) * | 2017-12-29 | 2018-05-18 | 烟台安诺其精细化工有限公司 | The preparation method of 1-naphthylamine-5-sulfonic acid |
| CN114308141A (en) * | 2021-12-15 | 2022-04-12 | 安徽华尔泰化工股份有限公司 | Separation process and separation system for phenylenediamine hydrogenation reduction liquid catalyst |
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| CN104084206B (en) | 2017-01-11 |
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Inventor after: He Xubin Inventor after: Wang Xinwu Inventor after: Yang Risheng Inventor after: Yuan Wenbing Inventor after: Ruan Liangfeng Inventor after: Zhu Jingxin Inventor after: Tao Jianguo Inventor after: Meng Ming Inventor before: He Xubin Inventor before: Wang Xinwu Inventor before: Yang Risheng Inventor before: Yuan Wenbing Inventor before: Ruan Liangfeng Inventor before: Zhu Jingxin Inventor before: Tao Jianguo Inventor before: Meng Ming |
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