CN103752354A - Regeneration method and device used for deactivation catalyst layer of membrane ozone catalytic reactor - Google Patents
Regeneration method and device used for deactivation catalyst layer of membrane ozone catalytic reactor Download PDFInfo
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- CN103752354A CN103752354A CN201410011432.2A CN201410011432A CN103752354A CN 103752354 A CN103752354 A CN 103752354A CN 201410011432 A CN201410011432 A CN 201410011432A CN 103752354 A CN103752354 A CN 103752354A
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Abstract
The invention relates to a regeneration method and a device used for a membrane module deactivation catalyst layer in a membrane ozone catalytic reactor. The regeneration method comprises the steps of firstly, introducing air, heating and roasting to remove residual organic pollutants in a membrane module; then carrying out hot dissolution for 5-20 minutes by adopting mixed liquor of nitric acid and hydrochloric acid, and removing metal oxide attached to a membrane catalytic layer; after atomizing 5%-30% modified Mn-Si-Ti catalyst suspension, sucking under negative pressure to enable the modified Mn-Si-Ti catalyst suspension to enter a membrane supporting body, and loading the inner surfaces of holes of the suspension; and finally removing a modified Mn-Si-Ti catalyst adsorbed on the surface of a membrane separation layer by spraying and washing, and after immersing the outer surface of the membrane module into 15%-25% modified Ni-Co catalyst suspension for 5-10 minutes, drying the obtained sample at 80-150 DEG C to obtain the regenerative catalytic membrane module. By utilizing the regeneration method and the device for the deactivation catalyst provided by the invention, the deactivation catalyst can be effectively regenerated, the service life is prolonged, and the operating cost is reduced.
Description
Technical field
The invention belongs to environmental protection
technologyfield, relates to a kind of renovation process and device for film ozone catalytic reactor membrane module inactivation Catalytic Layer is provided, and this reactor is mainly processed organic wastewater with difficult degradation thereby.
Background technology
High concentration hard-degraded organic waste water is mainly the waste water producing in the production processes such as dyestuff, agricultural chemicals, medicine, chemical industry, coking, contaminated wastewater substrate concentration is high, toxicity large, salt is more high-leveled and difficult in biodegradation, therefore must adopt preconditioning technique and method, can effectively process.Several typical high concentrated organic wastewaters, as coking chemical waste water, pharmacy waste water, weaving/, dyeing waste water, oil/wastewater from chemical industry etc., mainly the effluent COD concentration of production workshop section is general all more than 3000～5000mg/ L for it, the water outlet of some workshop sections even exceedes 10000 mg/ L, even the mixing water of each workshop section, generally also all more than 2000 mg/ L.At present, process this class waste water, adopt biological treatment more, and take the modified of aerobic method or aerobic method (as A/ O technique etc.) as main, the also employing anaerobic bio-treated having.From these techniques practice situation at home and abroad, the problem such as mainly have that technological process is long, the large and expense of additional thing (as additional carbon thing, regulate pH medicament etc.) amount is high, thus cause that unit water yield cost and unit water yield cost are all higher on the whole.More external companies do not consider processing cost especially as the first factor.
Membrane catalytic reaction technology is the new technology that development in recent years is got up, and has started at hydrogen manufacturing, methyl alcohol, acetaldehyde, propane, NH
3in the courses of reaction such as oxidation, apply, can effectively change organic structure and state, but in the processing that contains gas chromatography waste water, not yet find so far to use.It is blank with application in the technology of water treatment field that film ozone catalytic reactor can be filled up, organic wastewater is efficiently processed, its core component is mainly membrane module, ozone catalytic reaction can be coupled with film separation function, by the surface at inoranic membrane and supporter supported catalyst, catalytic oxidation two process integration separation with film are carried out in a unit.But after the long-term use of above-mentioned membrane module, there is the problem of catalysqt deactivation.Therefore, need to, to the processing of regenerating of the decaying catalyst of membrane module load, to realize the recycling of membrane module, reduce costs, improve the treatment effect of waste water.But, at present for also not relevant research report of the renovation process of catalyst in film ozone catalytic deactivation assembly.
Summary of the invention
The invention discloses a kind of renovation process for film ozone catalytic reactor inactivation catalytic membrane assembly, it is characterized in that being undertaken by following step:
(1) first pass into air roasting at 600～850 ℃ remove remain in membrane module in organic pollution;
(2) then use mixed liquor heat of solution 5～20min at 75～160 ℃ of concentration 66% nitric acid and concentration 37% hydrochloric acid, remove the metal oxide being attached in film Catalytic Layer; The wherein mol ratio 1:3 of nitric acid and hydrochloric acid.
(3) by mass concentration, be 5%～30%(w/w again) the atomization of modification Mn-Si-Ti catalyst suspension after, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by spray irrigation, remove the modification Mn-Si-Ti catalyst that is adsorbed on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is modification Ni-Co catalyst suspension 5～10min of 15%～25%;
(5) by 80～150 ℃ after dry 4～12 hours again, the sample obtaining, obtain the catalytic membrane assembly of regeneration.
Renovation process for film ozone catalytic reactor inactivation catalytic membrane assembly of the present invention, wherein concentration of nitric acid is 66%, concentration of hydrochloric acid is 37%, the mol ratio 1:3 of nitric acid and hydrochloric acid.
Renovation process for film ozone catalytic reactor inactivation catalytic membrane assembly of the present invention, the preparation method of wherein said modification Mn-Si-Ti catalyst is as follows:
1. with SiO 2 molecular sieve, average grain diameter 3
by being uniformly mixed, form suspension with deionized water;
2. slowly add the Mn (Ac) of 0.5 mole
2solution 100mL, and lasting stirring makes Mn
2+with H
+exchange swap time: 36～100 hours, obtained mixed liquor is repeatedly filtered, washed 5 times, by the Mn on absorption molecular sieve surface
2+remove;
3. the sample that obtains of filter is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and finally dried sample is calcined at 600 ℃ 3 hours in Muffle furnace, obtains Mn-Si catalyst intermediate;
4. by Mn-Si catalyst intermediate and TiO
2powder 3:1 by ratio of weight and the number of copies～5:1 adds deionized water mix and blend after mixing, and then sample is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and obtains modification Mn-Si-Ti catalyst.
Renovation process for film ozone catalytic reactor inactivation catalytic membrane assembly of the present invention, the preparation method of wherein said modification Ni-Co catalyst is as follows:
1. with
-Al
2o
3average grain diameter 30
micro mist, NiO and Co
3o
4al:Ni:Co=1:2:3 in molar ratio～1:2:5 configuration, and by volume 1:2～1:5 with deionized water by being uniformly mixed, formation suspension;
2. put into baking oven in 100 ~ 120 ℃ of dry 4h, then immersed the Na of 3wt%
2cO
3solution, after 100-120 ℃ of dry 4h, washs with distilled water after taking-up;
3. the sample obtaining is put at 100 ℃ of thermostatic drying chambers and dried 8h, obtain modification Ni-Co catalyst.
Device for film ozone catalytic reactor inactivation catalytic membrane assembly of the present invention, is characterized in that comprising inactivation membrane module organic residue removal device, inactivation membrane module regeneration recovery device; Wherein
Inactivation membrane module organic residue removal device: mainly formed by air compressor, temp controlling heater and roasting case, temp controlling heater with being connected of roasting case is: temp controlling heater regulates and controls the heating electrode of its inside by the temperature sensor in roasting case, so that temperature wherein reaches setting value; Air compressor is connected with air inlet in roasting case by wireway, air is entered in roasting case, for oxidation provides oxygen source, by inactivation membrane module is put into airtight device, control temperature and time roasting in roasting case, the organic pollution that makes to remain in membrane module is oxidized to carbon dioxide;
Inactivation membrane module regeneration recovery device: mainly comprise that main reactor 1, catalysis system 2, purging system 3, robot control system(RCS) 4, temperature control heating system 5 and water tank 6 form, wherein catalysis system 2 is connected with main reactor by measuring pump and corrosion-resistant pvc pipe with purging system 3; Robot control system(RCS) is controlled measuring pump in the motor in rotary separator in main reactor, spray and atomising device and negative pressure suction pump and catalysis system by PLC etc.; Temperature control heating system regulates and controls the heating electrode of its inside by the temperature sensor in main body reactor, so that temperature wherein reaches setting value.
Rotary separator 1a, spray and atomising device 1b, negative pressure suction 1c, waste liquid storage tank 1d are installed in described main body reactor 1;
Described catalysis system 2 comprises supporter catalyst 2a, the allotment of film top layer catalyst and storage system 2b, clarifier 2c; Wherein supporter catalyst 2a is connected with main reactor with atomising device 1b by spray; The catalyst allotment of film top layer is connected with main body reactor by measuring pump and pipeline with clarifier 2c with storage system 2b;
Supporter catalyst suspension is forming water smoke 1b by pressure type rotary atomizer in main body reactor 1, by form negative pressure suction 1c at film core inner, catalyst water smoke is entered and is attached to the top layer of supporter internal voids by film surface; The suspension of film top layer catalyst enters the rear employing submergence of main reactor 1 mode, make catalysis medicament be adsorbed on membrane module top layer, and after immersion processes finishes, 2c reclaims medicament by clarifier, and is stored in 2b in the catalyst regulating tank of film top layer;
Purging system (3): comprise (3a) cleaning agent storage bin, (3b): clean waste liquid and reclaim and store basin; Clear water spray and catalysis atomization are actual is to share a system (spray and atomising device), in the time of catalysis, and opening pressure formula rotary atomizer; When clear water sprays, close atomizer, open shower nozzle; To the allotment of cleaning fluid, be wherein to after hydrochloric acid and nitric acid component proportion, by stirring, realize evenly and mixing; The mol ratio of described hydrochloric acid and nitric acid component is 3:1.
Robot control system(RCS) 4: robot control system(RCS) mainly realizes assembly cleaning in main reactor, the absorption of catalysis liquid and centrifugal process control;
Temperature control heating system 5: be mainly inorganic acid cleaning fluid in inactivation membrane module to be carried out to heating for dissolving be attached to the metal oxide in film Catalytic Layer, and realization is dried the membrane module of adsorption catalyst;
Water tank 6: be mainly that clear water in water tank is passed through to spray and atomising device 1b, realize spray and flushing to membrane module in main body reactor.
Device for film ozone catalytic reactor inactivation catalytic membrane assembly of the present invention, wherein the rotary separator material in inactivation membrane module regeneration recovery device is polytetrafluoroethylene (PTFE).
The present invention has developed the complexes for regeneration membrane assembly catalytic performance, mainly inactivation membrane module organic residue removal device (as Fig. 1) and two parts of inactivation membrane module regeneration recovery device, consists of.Its concrete structure and composed as follows:
(1) inactivation membrane module organic residue removal device
This device major function be remove that conventional means is difficult to wash remain in the organic pollution in membrane module.This device is mainly comprised of air compressor, temperature control heating device and roasting case.By membrane module being put into airtight device, pass into air, roasting at 600～700 ℃, makes to remain in that organic pollution in membrane module is oxidized to carbon dioxide and the object that reaches removal.
(2) inactivation membrane module regeneration recovery device
This device major function is the regeneration realizing decaying catalyst in membrane module mesexine and supporter.This device mainly consists of five parts such as main body reactor, catalysis system, purging system, robot control system(RCS) and temperature control heating systems.Specific as follows:
1. main body reactor
Main body reactor is the agent set of realizing the regeneration of inactivation membrane module catalytic, it is mainly by rotary separator (material is polytetrafluoroethylene (PTFE), for the centrifugation of the liquids such as cleaning agent, catalyst and membrane module), spray and atomising device (can realize respectively clear water spray washing to membrane module and the atomization of catalysis medicament), negative suction system and waste liquid storage tank composition.
2. catalysis system
Catalysis system mainly comprises supporter catalysis and the two-part storage of film top layer catalysis, catalysis and recovery.Wherein supporter catalyst suspension is forming water smoke by pressure type rotary atomizer in main body reactor, by form negative pressure suction at film core inner, catalyst water smoke is entered and is attached to the top layer of supporter internal voids by film surface; The suspension of film top layer catalyst enters after main reactor, adopts submergence mode, makes catalysis medicament be adsorbed on membrane module top layer, and after immersion processes finishes, by clarifier, medicament is reclaimed, and be stored in the catalyst regulating tank of film top layer.
3. purging system
Purging system mainly comprises allotment, the cleaning of membrane module and the recovery of tail washings and the storage to cleaning fluid.To the allotment of cleaning fluid, be wherein to after the component proportions such as hydrochloric acid and nitric acid, by stirring, realize evenly and mixing.
4. robot control system(RCS)
Robot control system(RCS) mainly realize to assembly in main reactor clean, catalysis liquid absorption and the process control such as centrifugal.
5. temperature control heating system
Temperature control heating system is mainly inorganic acid cleaning fluid in inactivation membrane module to be carried out to heating for dissolving be attached to the metal oxide in film Catalytic Layer, and realization is dried the membrane module of adsorption catalyst.
6. water tank
Clear water in water tank, by atomizing sprayer, is rinsed to removal and is adsorbed on supporter catalyst on film top layer.
The present invention has carried out following research to inactivation catalytic membrane assembly renovation process:
(1) inventive principle
The present invention is in order to solve the problems of the prior art, set up renovation process and the device of a set of film ozone catalytic reactor membrane module inactivation catalytic for treatment of Organic Wastewater, object is to fill up the blank of the regeneration of membrane module inactivation catalytic in existing water treatment field and regenerating unit.
(2) method step
For realizing the regeneration of above-mentioned membrane module catalytic performance, mainly by following steps, realize:
(1) first pass into air roasting at 600～850 ℃ remove remain in membrane module in organic pollution;
(2) then use the nitric acid of 15-55% and the mixed liquor of hydrochloric acid heat of solution 5～20min at 75～160 ℃, remove the metal oxide being attached in film Catalytic Layer;
(3), after the modification Mn-Si-Ti catalyst suspension atomization that is 5%～30% by mass concentration again, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by spray irrigation, remove the modification Mn-Si-Ti catalyst that is adsorbed on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is modification Ni-Co catalyst suspension 5～10min of 15%～25%;
(5) by 80～150 ℃ after dry 4～12 hours, to obtain the catalytic membrane assembly of regeneration again, the sample obtaining.
For realizing said method, developed the complexes for regeneration membrane assembly catalytic performance, mainly by inactivation membrane module organic residue removal device (as Fig. 1) and two parts of inactivation membrane module regeneration recovery device, formed.Its concrete structure and composed as follows:
(1) inactivation membrane module organic residue removal device
This device major function be remove that conventional means is difficult to wash remain in the organic pollution in membrane module.This device is mainly comprised of air compressor, temperature control heating device and roasting case.By membrane module being put into airtight device, pass into air, roasting at 600～700 ℃, makes to remain in that organic pollution in membrane module is oxidized to carbon dioxide and the object that reaches removal.
(2) inactivation membrane module regeneration recovery device
This device major function is the regeneration realizing decaying catalyst in membrane module mesexine and supporter.This device mainly consists of five parts such as main body reactor, catalysis system, purging system, robot control system(RCS) and temperature control heating systems.
Specific as follows:
1. main body reactor
Main body reactor is the agent set of realizing the regeneration of inactivation membrane module catalytic, and its inside mainly contains rotary separator, and material is polytetrafluoroethylene (PTFE), for the centrifugation of the liquids such as cleaning agent, catalyst and membrane module.
2. catalysis system
Catalysis system mainly comprises supporter catalysis and the two-part storage of film top layer catalysis, catalysis and recovery.Wherein supporter catalyst suspension is forming water smoke by pressure type rotary atomizer in main body reactor, by form negative pressure suction at film core inner, catalyst water smoke is entered and is attached to the top layer of supporter internal voids by film surface; The suspension of film top layer catalyst enters after main reactor, adopts submergence mode, makes catalysis medicament be adsorbed on membrane module top layer, and after immersion processes finishes, by clarifier, medicament is reclaimed, and be stored in the catalyst regulating tank of film top layer.
3. purging system
Purging system mainly comprises allotment, the cleaning of membrane module and the recovery of tail washings and the storage to cleaning fluid.To the allotment of cleaning fluid, be wherein to after the component proportions such as hydrochloric acid and nitric acid, by stirring, realize evenly and mixing.
4. robot control system(RCS)
Robot control system(RCS) mainly realize to assembly in main reactor clean, catalysis liquid absorption and the process control such as centrifugal.
5. temperature control heating system
Temperature control heating system is mainly inorganic acid cleaning fluid in inactivation membrane module to be carried out to heating for dissolving be attached to the metal oxide in film Catalytic Layer, and realization is dried the membrane module of adsorption catalyst.
(3) scope of application
The present invention is mainly used in inactivation catalytic membrane assembly in film ozone catalytic reactor, can realize the regeneration that causes the ozone film catalytic module of inactivation because processing various organic wastewater.
(4) technical characterstic of the present invention and effect
Utilize renovation process and the device of decaying catalyst of the present invention, can effectively make decaying catalyst regeneration, thereby can successfully obtain the regeneration catalytic ozonation membrane module of activation recovering, increase the service life, reduce processing cost.
Accompanying drawing explanation:
Fig. 1 is inactivation membrane module organic residue removal device; Wherein
1: main reactor 2: catalysis system 3: purging system
4: robot control system(RCS) 5: temperature control heating system 6: water tank.
The specific embodiment
Below in conjunction with embodiment, the present invention is described, the scheme of embodiment described here, do not limit the present invention, one of skill in the art can make improvements and change according to spirit of the present invention, these described improvement and variation all should be considered as within the scope of the invention, and scope of the present invention and essence are limited by claim.Various raw material used all has commercially available.
embodiment 1
For a renovation process for film ozone catalytic reactor inactivation catalytic membrane assembly, comprising:
(1) first pass into air roasting at 600 ℃ remove remain in membrane module in organic pollution;
(2) then use mixed liquor heat of solution 5min at 100 ℃ of concentration 66% nitric acid and concentration 37% hydrochloric acid, remove the metal oxide being attached in film Catalytic Layer; The wherein mol ratio 1:3 of nitric acid and hydrochloric acid;
(3) by mass concentration, be 10%(w/w again) the atomization of modification Mn-Si-Ti catalyst suspension after, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by spray irrigation, remove the modification Mn-Si-Ti catalyst that is adsorbed on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is 15%% modification Ni-Co catalyst suspension 5min;
(5) by 100 ℃ after dry 6 hours again, the sample obtaining, obtain the catalytic membrane assembly of regeneration.
The preparation method of wherein said modification Mn-Si-Ti catalyst is as follows:
1. with SiO 2 molecular sieve, average grain diameter 3
by being uniformly mixed, form suspension with deionized water;
2. slowly add the Mn (Ac) of 0.5 mole
2solution 100mL, and lasting stirring makes Mn
2+with H
+exchange swap time: 36 hours, obtained mixed liquor is repeatedly filtered, washed 5 times, by the Mn on absorption molecular sieve surface
2+remove;
3. the sample that obtains of filter is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and finally dried sample is calcined at 600 ℃ 3 hours in Muffle furnace, obtains Mn-Si catalyst intermediate;
4. by Mn-Si catalyst intermediate and TiO
2powder after 3:1 mixes by ratio of weight and the number of copies, adds deionized water mix and blend, then sample is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and obtains modification Mn-Si-Ti catalyst.
The preparation method of wherein said modification Ni-Co catalyst is as follows:
1. with
-Al
2o
3average grain diameter 30
micro mist, NiO and Co
3o
4al:Ni:Co=1:2:3 configuration in molar ratio, and by volume 1:2 with deionized water by being uniformly mixed, formation suspension;
2. put into baking oven in 100 ℃ of dry 4h, then immersed the Na of 3wt%
2cO
3solution, after 100 ℃ of dry 4h, washs with distilled water after taking-up;
3. the sample obtaining is put at 100 ℃ of thermostatic drying chambers and dried 8h, obtain modification Ni-Co catalyst.
Embodiment 2
For a renovation process for film ozone catalytic reactor inactivation catalytic membrane assembly, comprising:
(1) first pass into air roasting at 850 ℃ remove remain in membrane module in organic pollution;
(2) then use mixed liquor heat of solution 5～20min at 160 ℃ of 66% nitric acid and 37% hydrochloric acid, remove the metal oxide being attached in film Catalytic Layer; The wherein mol ratio 3:1 of nitric acid and hydrochloric acid
(3) by mass concentration, be 30%(w/w again) the atomization of modification Mn-Si-Ti catalyst suspension after, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by spray irrigation, remove the modification Mn-Si-Ti catalyst that is adsorbed on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is 25% modification Ni-Co catalyst suspension 10min;
(5) by 150 ℃ after dry 4～12 hours again, the sample obtaining, obtain the catalytic membrane assembly of regeneration.
The preparation method of described modification Mn-Si-Ti catalyst is as follows:
1. with SiO 2 molecular sieve, average grain diameter 3
by being uniformly mixed, form suspension with deionized water;
2. slowly add the Mn (Ac) of 0.5 mole
2solution 100mL, and lasting stirring makes Mn
2+with H
+exchange swap time: 36～100 hours, obtained mixed liquor is repeatedly filtered, washed 5 times, by the Mn on absorption molecular sieve surface
2+remove;
3. the sample that obtains of filter is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and finally dried sample is calcined at 600 ℃ 3 hours in Muffle furnace, obtains Mn-Si catalyst intermediate;
4. by Mn-Si catalyst intermediate and TiO
2powder after 5:1 mixes by ratio of weight and the number of copies, adds deionized water mix and blend, then sample is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and obtains modification Mn-Si-Ti catalyst.
The preparation method of described modification Ni-Co catalyst is as follows:
1. with
-Al
2o
3average grain diameter 30
micro mist, NiO and Co
3o
4al:Ni:Co=1:2:5 configuration in molar ratio, and by volume 1:5 with deionized water by being uniformly mixed, formation suspension;
2. put into baking oven in 120 ℃ of dry 4h, then immersed the Na of 3wt%
2cO
3solution, after 120 ℃ of dry 4h, washs with distilled water after taking-up;
3. the sample obtaining is put at 100 ℃ of thermostatic drying chambers and dried 8h, obtain modification Ni-Co catalyst.
Embodiment 3
For the device (see figure 1) of film ozone catalytic reactor inactivation catalytic membrane assembly, comprise inactivation membrane module organic residue removal device, inactivation membrane module regeneration recovery device; Wherein
Inactivation membrane module organic residue removal device: mainly formed by air compressor, temp controlling heater and roasting case, temp controlling heater with being connected of roasting case is: temp controlling heater regulates and controls the heating electrode of its inside by the temperature sensor in roasting case, so that temperature wherein reaches setting value; Air compressor is connected with air inlet in roasting case by wireway, air is entered in roasting case, for oxidation provides oxygen source, by inactivation membrane module is put into airtight device, control temperature and time roasting in roasting case, the organic pollution that makes to remain in membrane module is oxidized to carbon dioxide;
Inactivation membrane module regeneration recovery device: mainly comprise that main reactor 1, catalysis system 2, purging system 3, robot control system(RCS) 4, temperature control heating system 5 and water tank 6 form, wherein catalysis system 2 is connected with main reactor by measuring pump and corrosion-resistant pvc pipe with purging system 3; Robot control system(RCS) is controlled measuring pump in the motor in rotary separator in main reactor, spray and atomising device and negative pressure suction pump and catalysis system by PLC etc.; Temperature control heating system regulates and controls the heating electrode of its inside by the temperature sensor in main body reactor, so that temperature wherein reaches setting value.
Rotary separator 1a, spray and atomising device 1b, negative pressure suction 1c, waste liquid storage tank 1d are installed in described main body reactor 1;
Described catalysis system 2 comprises supporter catalyst 2a, the allotment of film top layer catalyst and storage system 2b, clarifier 2c; Wherein supporter catalyst 2a is connected with main reactor with atomising device 1b by spray; The catalyst allotment of film top layer is connected with main body reactor by measuring pump and pipeline with clarifier 2c with storage system 2b;
Supporter catalyst suspension is forming water smoke 1b by pressure type rotary atomizer in main body reactor 1, by form negative pressure suction 1c at film core inner, catalyst water smoke is entered and is attached to the top layer of supporter internal voids by film surface; The suspension of film top layer catalyst enters the rear employing submergence of main reactor 1 mode, make catalysis medicament be adsorbed on membrane module top layer, and after immersion processes finishes, 2c reclaims medicament by clarifier, and is stored in 2b in the catalyst regulating tank of film top layer;
Purging system (3): comprise 3a cleaning agent storage bin, 3b: clean waste liquid and reclaim and store basin; Clear water spray and catalysis atomization are actual is to share a system (spray and atomising device), in the time of catalysis, and opening pressure formula rotary atomizer; When clear water sprays, close atomizer, open shower nozzle; To the allotment of cleaning fluid, be wherein to after hydrochloric acid and nitric acid component proportion, by stirring, realize evenly and mixing; The mol ratio of described hydrochloric acid and nitric acid component is 3:1.
Robot control system(RCS) (4): robot control system(RCS) mainly realizes assembly cleaning in main reactor, the absorption of catalysis liquid and centrifugal process control;
Temperature control heating system (5): be mainly inorganic acid cleaning fluid in inactivation membrane module to be carried out to heating for dissolving be attached to the metal oxide in film Catalytic Layer, and realization is dried the membrane module of adsorption catalyst;
Water tank (6): be mainly that clear water in water tank is passed through to spray and atomising device (1b), realize spray and flushing to membrane module in main body reactor.Rotary separator material in described inactivation membrane module regeneration recovery device is polytetrafluoroethylene (PTFE)
Application Example 1
Manifold type film ozone catalytic reaction technology is for the treatment and reuse of Rubber Industrial Wastewater
One, concrete background
Craft in Chemical Industrial Area, huge port, Tianjin oil rubber Co., Ltd, this enterprise is to produce butadiene-styrene rubber as major product, and first stage of the project year is produced 100,000 tons, butadiene-styrene rubber, daily output wastewater flow rate 3600m
3.Because butadiene-styrene rubber need add a large amount of flocculation aids, diffusant, conditioning agent and polymerization inhibitor etc. when producing, cause the organic matter that contains higher concentration and utmost point difficult degradation in its waste water, these organic matters mostly are low molecular weight polycaprolactone and close structure or circulus, conventional method is difficult to obtain promising result, not only be difficult to up to standard, and advanced treating and reuse difficulty very large.Test water water quality is as shown in table 1, and organic pollutants composition is analyzed through gas chromatography-mass spectrum (GC/MS), as shown in table 2.
table 1 test water water quality
table 2 wastewater through organic matter qualitative results
two, the preparation of membrane module
(1) preparation of supporter modified catalyst
The element of modified catalyst is mainly: Si, Mn and Ti.Preparation process is as follows:
1. with SiO 2 molecular sieve (average grain diameter 3
) with deionized water by being uniformly mixed, form suspension;
2. slowly add the Mn (Ac) of 0.5 mole
2solution 100mL, and lasting stirring makes Mn
2+with H
+exchange (swap time: 36 hours), obtained mixed liquor is repeatedly filtered, washed 5 times, by the Mn on absorption molecular sieve surface
2+remove;
3. the sample that obtains of filter is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and finally dried sample is calcined at 600 ℃ 3 hours in Muffle furnace, obtains Mn-Si catalyst intermediate;
4. by Mn-Si catalyst intermediate and TiO
2powder after 3:1 mixes in mass ratio, adds deionized water mix and blend, then sample is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and has prepared supporter modification Mn-Si-Ti catalyst.
(2) selection of aggregate and additive and proportioning
Aggregate is:
-Al
2o
3(average grain diameter 30
), bentonite; Pore former is: camwood knag; Additive is: modification Mn-Si-Ti catalyst, copper nitrate; Dispersant is: lecithin; Above-mentioned each component is mixed with certain proportion, and each component quality proportioning is in Table 3.
Table 3: film support component proportion list
(3) mix
After the composition of above-mentioned film support is mixed, 1:2 adds a certain amount of water and at ball mill, grinds the regular hour (45min) and obtain stable suspension by volume, adds a small amount of flower bulb alkali to regulate the pH value of suspension to increase the stability of suspension in 10.5 left and right in ball milling.The stable suspension that ball milling is obtained with
-Al
2o
3powder and fully ground scattered carbon dust and mix by a certain percentage.Control liquid slowly and add speed, inhomogeneous to prevent from mixing, avoid supporter to produce defect.And utilize mixer fully to stir, obtain uniform pug.
(4) mud refining
Adopt vacuum mud refining mode, the pug mixing stirring mud refining 2 hours in vacuum pugmill." mud refining-ageing " process of repetition is more than three times.Moisture in pug and additive are mixed more even with powder, remove the bubble in pug simultaneously, obtain the plasticity meeting the demands.
(5) ageing
By through the pug of mud refining in uniform temperature (26 ℃) and humidity (relative humidity: 20%) place 36 hours in environmental condition, improve its performance.
(6) moulding
Adopt extrusion moulding.Extrusion pressure is: 1.2 atmospheric pressure; Rate of extrusion is: 30mm/min; The plastic mud material having refined is added in screw extruder, under the effect of pressure, extrude the tubular support of 19 passages.
(7) body drying
By the base substrate of extrusion molding, at certain ambient humidity, (relative humidity: (26 ℃) are dried the moisture removing in base substrate 15%) and under baking temperature guarantees that base substrate is indeformable in the middle of dry run, does not ftracture.
(8) sintering
Dried supporter green compact are put into program control temp .-elevating electric furnace, according to the sintering schedule of 4 ℃/min, be warmed up to 1500 ℃, then constant temperature 3 hours.Naturally after cooling, come out of the stove.Then after polishing and detection, obtain qualified supporter.
2, the preparation of film separating layer
(1) preparation of film separating layer modified catalyst
The essential element of modified catalyst is: NiO and Co
3o
4.Preparation process is as follows:
1. with
-Al
2o
3(average grain diameter 30
) micro mist, NiO and Co
3o
4al:Ni:Co=1:2:3 configuration in molar ratio, and by volume 1:2 with deionized water by being uniformly mixed, formation suspension;
2. put into baking oven in 100 ℃ of dry 4h, then immersed the Na of 3w t%
2cO
3solution, after 100 ℃ of dry 4h, washs with distilled water after taking-up;
3. the sample obtaining is put at 100 ℃ of thermostatic drying chambers and dried 8h, finally prepared the Ni-Co catalyst for the modification of film separating layer.
(2) preparation of coating liquid
Will
-Al
2o
3(average grain diameter 30
) micro mist, bentonite and camwood knag grind 30 minutes at ball mill, and put into a certain amount of dispersant and water (by 1:3.5) obtains stable suspension, and suitably regulate after its viscosity, make the preparation liquid that film is used.
Table 4: film separating layer component proportion list
(3) film
Adopt infusion process film forming, will clean in advance, be dried porous Al after treatment
2o
3the outer surface of ceramic supporting body seals with Polypropylence Sheet, then immerses in coating liquid and from coating liquid, takes out after 36 h; Then the supporter after film is dry, put into baking oven in 100 ~ 120 ℃ of dry 4h; Finally be placed in temp .-elevating electric furnace, according to the sintering schedule of 5 ℃/min, be warmed up to 1600 ℃, and constant temperature 3 hours, come out of the stove after naturally cooling, obtain the membrane module of modification separating layer and modification supporter.
three, the cleaning agent of concrete film:
By following component, mixed by mass percentage: 8% methylol benzylcellulose, 40% hydroxy ethylidene-diphosphate, 5% EDTA, 20% polyacrylic acid, 9% neopelex, 5% natrium citricum, 7% sodium polyphosphate and 6% sodium carbonate.Said components is according to the condition of water quality of film ozone catalytic reactor for treatment, with pure water by volume 1:5 proportioning go out cleaning fluid.
Result:
Rubber Industrial Wastewater after manifold type film ozone catalytic cell processing, water outlet COD
crscope is 33.6-101.1mg/L, average 51.9mg/L, and average removal rate is 97.1%.Due to factory's production line maintenance Replacement procedure, cause mid-June influent COD to raise suddenly, the corresponding rising of water outlet, but water outlet COD is still stabilized in low concentration level, and clearance can reach 80%.Along with waste water quality tends towards stability, water outlet COD returns to processing horizontal in early stage, and COD goes out water concentration can be reduced to 40-55 mg/L.Visible the present invention technique used has good impact resistance to Rubber Industrial Wastewater.
Four, the regenerative process method of the inactivation catalytic membrane assembly described in the embodiment of the present invention is as follows:
(1) first inactivation membrane module is put into inactivation membrane module organic residue removal device, passed into air, adjust the temperature at 600 ℃ roasting and remove and remain in organic pollution in membrane module;
(2), after then membrane module is cooling, put into inactivation membrane module regeneration recovery device, the nitric acid with 25% and the mixed liquor of hydrochloric acid heat of solution 10min at 100 ℃, removal is attached to the metal oxide in film Catalytic Layer;
(3), after the modification Mn-Si-Ti catalyst suspension atomization that is 10% by mass concentration again, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by clear water spray irrigation, remove and be adsorbed on the modification Mn-Si-Ti catalyst on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is 15% modification Ni-Co catalyst suspension 7min;
(5) by the sample obtaining after 100 ℃ of dry 5h, obtain regeneration catalytic membrane assembly.
Above-mentioned formula can be used as for this type of water quality optimization technique formula.Effect after catalytic regeneration is as shown in the table.
(mg/L) of sewage disposal plant effluent water-quality ratio before and after the regeneration of inactivation membrane module
As seen from the above table, the performance of inactivation membrane module has obtained good recovery.
Embodiment 2
Manifold type film ozone catalytic reaction technology is for the upgrading of certain comprehensive chemical wastewater treatment in chemical industrial park
Certain Craft in Chemical Industrial Area composite wastewater treatment plant, actual treatment water yield 2000m
3/ d, first stage of the project after building up in June, 2009, but in operation process, find actual influent quality and design water quality have relatively big difference.According to actual tracking and testing result SS, TN, NH3-N, all compare former design influent quality and improve a lot, all have raising in various degree.Former design effluent quality is secondary discharge standard when not reuse, < < urban wastewater treatment firm pollutant emission standard > > (GB18918-2002) the one-level B standard of carrying out after transformation, concrete water quality index is in Table 5.
Table 5 sewage treatment plant inflow water-quality ratio is (mg/L)
| Project | COD | BOD5 | SS | TN | NH3-N | TP | Oils |
| Former design load | 1000 | 300 | 300 | 50 | 35 | 10 | ? |
| Actual detected value | 700～1400 | 160~300 | 200~400 | 60~80 | 50~70 | 6~12 | 100 |
| New water outlet requirement | ≤60 | ≤20 | ≤20 | ≤20 | ≤8（15） | ≤1 | ≤3 |
According to the influent quality of this garden sewage treatment plant and effluent quality requirement, in conjunction with sewage treatment plant's scale and key technology preferred result, on the basis of original common process flow process, strengthened the improvement and design of pretreatment unit, biological reinforced unit and advanced treatment unit.
Treatment effect: before and after transformation, sewage disposal plant effluent water quality as shown.
(mg/L) of sewage disposal plant effluent water-quality ratio before and after table 6 transformation
As seen from the above table, adopt the present invention to carry out after upgrading, effluent index meets designing requirement completely, obtains good treatment effect.
two, the preparation of membrane module
(1) preparation of supporter modified catalyst
The element of modified catalyst is mainly: Si, Mn and Ti.Preparation process is as follows:
1. with SiO 2 molecular sieve (average grain diameter 3
) with deionized water by being uniformly mixed, form suspension;
2. slowly add the Mn (Ac) of 0.5 mole
2solution 100mL, and lasting stirring makes Mn
2+with H
+exchange (swap time: 48 hours), obtained mixed liquor is repeatedly filtered, washed 5 times, by the Mn on absorption molecular sieve surface
2+remove;
3. the sample that obtains of filter is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and finally dried sample is calcined at 600 ℃ 3 hours in Muffle furnace, obtains Mn-Si catalyst intermediate;
4. by Mn-Si catalyst intermediate and TiO
2powder after 3:1 mixes in mass ratio, adds deionized water mix and blend, then sample is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and has prepared supporter modification Mn-Si-Ti catalyst.
(2) selection of aggregate and additive and proportioning
Aggregate is:
-Al
2o
3(average grain diameter 30
), bentonite; Pore former is: camwood knag; Additive is: modification Mn-Si-Ti catalyst, copper nitrate; Dispersant is: lecithin; Above-mentioned each component is mixed with certain proportion, and each component quality proportioning is in Table 3.
Table 3: film support component proportion list
(3) mix
After the composition of above-mentioned film support is mixed, 1:2 adds a certain amount of water and at ball mill, grinds the regular hour (45min) and obtain stable suspension by volume, adds a small amount of flower bulb alkali to regulate the pH value of suspension to increase the stability of suspension in 10.5 left and right in ball milling.The stable suspension that ball milling is obtained with
-Al
2o
3powder and fully ground scattered carbon dust and mix by a certain percentage.Control liquid slowly and add speed, inhomogeneous to prevent from mixing, avoid supporter to produce defect.And utilize mixer fully to stir, obtain uniform pug.
(4) mud refining
Adopt vacuum mud refining mode, the pug mixing stirring mud refining 2 hours in vacuum pugmill." mud refining-ageing " process of repetition is more than three times.Moisture in pug and additive are mixed more even with powder, remove the bubble in pug simultaneously, obtain the plasticity meeting the demands.
(5) ageing
By through the pug of mud refining in uniform temperature (26 ℃) and humidity (relative humidity: 20%) place 36 hours in environmental condition, improve its performance.
(6) moulding
Adopt extrusion moulding.Extrusion pressure is: 1.2 atmospheric pressure; Rate of extrusion is: 30mm/min; The plastic mud material having refined is added in screw extruder, under the effect of pressure, extrude the tubular support of 19 passages.
(7) body drying
By the base substrate of extrusion molding, at certain ambient humidity, (relative humidity: (26 ℃) are dried the moisture removing in base substrate 15%) and under baking temperature guarantees that base substrate is indeformable in the middle of dry run, does not ftracture.
(8) sintering
Dried supporter green compact are put into program control temp .-elevating electric furnace, according to the sintering schedule of 4 ℃/min, be warmed up to 1500 ℃, then constant temperature 3 hours.Naturally after cooling, come out of the stove.Then after polishing and detection, obtain qualified supporter.
2, the preparation of film separating layer
(1) preparation of film separating layer modified catalyst
The essential element of modified catalyst is: NiO and Co
3o
4.Preparation process is as follows:
1. with
-Al
2o
3(average grain diameter 30
) micro mist, NiO and Co
3o
4al:Ni:Co=1:2:4 configuration in molar ratio, and by volume 1:3 with deionized water by being uniformly mixed, formation suspension;
2. put into baking oven in 120 ℃ of dry 4h, then immersed the Na of 3w t%
2cO
3solution, after 120 ℃ of dry 4h, washs with distilled water after taking-up;
3. the sample obtaining is put at 100 ℃ of thermostatic drying chambers and dried 8h, finally prepared the Ni-Co catalyst for the modification of film separating layer.
(2) preparation of coating liquid
Will
-Al
2o
3(average grain diameter 30
) micro mist, bentonite and camwood knag grind 30 minutes at ball mill, and put into a certain amount of dispersant and water (by 1:3.5) obtains stable suspension, and suitably regulate after its viscosity, make the preparation liquid that film is used.
Table 4: film separating layer component proportion list
(3) film
Adopt infusion process film forming, will clean in advance, be dried porous Al after treatment
2o
3the outer surface of ceramic supporting body seals with Polypropylence Sheet, then immerses in coating liquid and from coating liquid, takes out after 36 h; Then the supporter after film is dry, put into baking oven in 120 ℃ of dry 4h; Finally be placed in temp .-elevating electric furnace, according to the sintering schedule of 5 ℃/min, be warmed up to 1600 ℃, and constant temperature 3 hours, come out of the stove after naturally cooling, obtain the membrane module of modification separating layer and modification supporter.
three, the cleaning agent of concrete film:
Membrane module
cleaning agent to prepare scheme as follows:
By following component, mixed by mass percentage: 15% methylol benzylcellulose, 33% hydroxy ethylidene-diphosphate, 4% EDTA, 19% polyacrylic acid, 8% neopelex, 4% natrium citricum, 8% sodium polyphosphate and 7% sodium carbonate.Said components is according to the condition of water quality of film ozone catalytic reactor for treatment, with pure water by volume 1:2 proportioning go out cleaning fluid.
Treatment effect: before and after transformation, sewage disposal plant effluent water quality is as shown in table 6.
(mg/L) of sewage disposal plant effluent water-quality ratio before and after table 6 transformation
As seen from the above table, adopt the present invention to carry out after upgrading, effluent index meets designing requirement completely, obtains good treatment effect.
Four, the regenerative process of the inactivation catalytic membrane assembly described in the embodiment of the present invention is as follows:
(1) first inactivation membrane module is put into inactivation membrane module organic residue removal device, passed into air, adjust the temperature at 700 ℃ roasting and remove and remain in organic pollution in membrane module;
(2), after then membrane module is cooling, put into inactivation membrane module regeneration recovery device, the mixed liquor of the nitric acid with 66% and 37% hydrochloric acid heat of solution 20min at 120 ℃, removal is attached to the metal oxide in film Catalytic Layer;
(3), after the modification Mn-Si-Ti catalyst suspension atomization that is 25% by mass concentration again, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by clear water spray irrigation, remove and be adsorbed on the modification Mn-Si-Ti catalyst on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is 25% modification Ni-Co catalyst suspension 10min;
(5) by the sample obtaining after 80 ℃ of dry 12h, obtain regeneration catalytic membrane assembly.
Above-mentioned formula can be used as for this type of water quality optimization technique formula.Effect after catalytic regeneration is as shown in the table.
(mg/L) of sewage disposal plant effluent water-quality ratio before and after the regeneration of inactivation membrane module
As seen from the above table, the performance of inactivation membrane module has obtained good recovery.
embodiment 3
background general introduction
Certain Production in Chemical Plant methyl diphenylene diisocyanate (MDI), it is one of primary raw material of producing polyurethane products, but its factory effluent salt content is high, biodegradability is poor, change of water quality is large and toxic, main organic components is aniline, chlorobenzene, formaldehyde and methyl alcohol etc., and conventional method is difficult to process.Therefore adopt film ozone catalytic technology of the present invention that organic matter in MDI high slat-containing wastewater is removed and reclaimed, and brackish water is carried out to reuse, become the raw materials for production of caustic soda processed enterprise, realize cleaner production between enterprise and the efficient utilization of resource.
treatment effect
After enterprise implement cleaner production, its waste water to be processed as the raw material of periphery alkaline enterprise, its treatment effect and water quality are as shown in table 7.
(mg/L) of sewage disposal plant effluent water-quality ratio before and after table 7 transformation
Adopt after film ozone catalytic technology, MDI waste water can meet the water quality requirement of cooling water completely, and can carry out cleaner production, this salt solution can be used as chlor-alkali factory electrolysis with ion-exchange film raw material, the resources such as sodium chloride in MDI effluent brine, water are regenerated, the consumption that has reduced crude salt and water, has reduced production cost, has reached the object of water-saving and emission-reducing.
two, the preparation of membrane module
(1) preparation of supporter modified catalyst
The element of modified catalyst is mainly: Si, Mn and Ti.Preparation process is as follows:
1. with SiO 2 molecular sieve (average grain diameter 3
) with deionized water by being uniformly mixed, form suspension;
2. slowly add the Mn (Ac) of 0.5 mole
2solution 100mL, and lasting stirring makes Mn
2+with H
+exchange (swap time: 72 hours), obtained mixed liquor is repeatedly filtered, washed 5 times, by the Mn on absorption molecular sieve surface
2+remove;
3. the sample that obtains of filter is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and finally dried sample is calcined at 600 ℃ 3 hours in Muffle furnace, obtains Mn-Si catalyst intermediate;
4. by Mn-Si catalyst intermediate and TiO
2powder after 3:1 mixes in mass ratio, adds deionized water mix and blend, then sample is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and has prepared supporter modification Mn-Si-Ti catalyst.
(2) selection of aggregate and additive and proportioning
Aggregate is:
-Al
2o
3(average grain diameter 30
), bentonite; Pore former is: camwood knag; Additive is: modification Mn-Si-Ti catalyst, copper nitrate; Dispersant is: lecithin; Above-mentioned each component is mixed with certain proportion, and each component quality proportioning is in Table 3.
Table 3: film support component proportion list
(3) mix
After the composition of above-mentioned film support is mixed, 1:2 adds a certain amount of water and at ball mill, grinds the regular hour (45min) and obtain stable suspension by volume, adds a small amount of flower bulb alkali to regulate the pH value of suspension to increase the stability of suspension in 10.5 left and right in ball milling.The stable suspension that ball milling is obtained with
-Al
2o
3powder and fully ground scattered carbon dust and mix by a certain percentage.Control liquid slowly and add speed, inhomogeneous to prevent from mixing, avoid supporter to produce defect.And utilize mixer fully to stir, obtain uniform pug.
(4) mud refining
Adopt vacuum mud refining mode, the pug mixing stirring mud refining 2 hours in vacuum pugmill." mud refining-ageing " process of repetition is more than three times.Moisture in pug and additive are mixed more even with powder, remove the bubble in pug simultaneously, obtain the plasticity meeting the demands.
(5) ageing
By through the pug of mud refining in uniform temperature (26 ℃) and humidity (relative humidity: 20%) place 36 hours in environmental condition, improve its performance.
(6) moulding
Adopt extrusion moulding.Extrusion pressure is: 1.2 atmospheric pressure; Rate of extrusion is: 30mm/min; The plastic mud material having refined is added in screw extruder, under the effect of pressure, extrude the tubular support of 19 passages.
(7) body drying
By the base substrate of extrusion molding, at certain ambient humidity, (relative humidity: (26 ℃) are dried the moisture removing in base substrate 15%) and under baking temperature guarantees that base substrate is indeformable in the middle of dry run, does not ftracture.
(8) sintering
Dried supporter green compact are put into program control temp .-elevating electric furnace, according to the sintering schedule of 4 ℃/min, be warmed up to 1500 ℃, then constant temperature 3 hours, comes out of the stove after naturally cooling.Then after polishing and detection, obtain qualified supporter.
2, the preparation of film separating layer
(1) preparation of film separating layer modified catalyst
The essential element of modified catalyst is: NiO and Co
3o
4.Preparation process is as follows:
1. with
-Al
2o
3(average grain diameter 30
) micro mist, NiO and Co
3o
4al:Ni:Co=1:2:5 configuration in molar ratio, and by volume 1:4 with deionized water by being uniformly mixed, formation suspension;
2. put into baking oven in 100 ~ 120 ℃ of dry 4h, then immersed the Na of 3w t%
2cO
3solution, after 110 ℃ of dry 4h, washs with distilled water after taking-up;
3. the sample obtaining is put at 100 ℃ of thermostatic drying chambers and dried 8h, finally prepared the Ni-Co catalyst for the modification of film separating layer.
(2) preparation of coating liquid
Will
-Al
2o
3(average grain diameter 30
) micro mist, bentonite and camwood knag grind 30 minutes at ball mill, and put into a certain amount of dispersant and water (by 1:3.5) obtains stable suspension, and suitably regulate after its viscosity, make the preparation liquid that film is used.
Table 4: film separating layer component proportion list
(3) film
Adopt infusion process film forming, will clean in advance, be dried porous Al after treatment
2o
3the outer surface of ceramic supporting body seals with Polypropylence Sheet, then immerses in coating liquid and from coating liquid, takes out after 36 h; Then the supporter after film is dry, put into baking oven in 100 ~ 120 ℃ of dry 4h; Finally be placed in temp .-elevating electric furnace, according to the sintering schedule of 5 ℃/min, be warmed up to 1600 ℃, and constant temperature 3 hours, come out of the stove after naturally cooling, obtain the membrane module of modification separating layer and modification supporter.
three, the cleaning agent of concrete film:
Membrane module
cleaning agent:
By following component, mixed by mass percentage: 12% methylol benzylcellulose, 30% hydroxy ethylidene-diphosphate, 5% EDTA, 20% polyacrylic acid, 5% neopelex, 5% natrium citricum, 7% sodium polyphosphate and 16% sodium carbonate.Said components is according to the condition of water quality of film ozone catalytic reactor for treatment, with pure water by volume 1:3.5 proportioning go out cleaning fluid.
treatment effect
After enterprise implement cleaner production, its waste water to be processed as the raw material of periphery alkaline enterprise, its treatment effect and water quality are as shown in table 7.
(mg/L) of sewage disposal plant effluent water-quality ratio before and after table 7 transformation
Adopt after film ozone catalytic technology, MDI waste water can meet the water quality requirement of cooling water completely, and can carry out cleaner production, this salt solution can be used as chlor-alkali factory electrolysis with ion-exchange film raw material, the resources such as sodium chloride in MDI effluent brine, water are regenerated, the consumption that has reduced crude salt and water, has reduced production cost, has reached the object of water-saving and emission-reducing.
four, the regenerative process of the inactivation catalytic membrane assembly described in the embodiment of the present invention is as follows:
(1) first inactivation membrane module is put into inactivation membrane module organic residue removal device, passed into air, adjust the temperature at 750 ℃ roasting and remove and remain in organic pollution in membrane module;
(2), after then membrane module is cooling, put into inactivation membrane module regeneration recovery device, the nitric acid with 35% and the mixed liquor of hydrochloric acid heat of solution 15min at 100 ℃, removal is attached to the metal oxide in film Catalytic Layer;
(3), after the modification Mn-Si-Ti catalyst suspension atomization that is 20% by mass concentration again, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by clear water spray irrigation, remove and be adsorbed on the modification Mn-Si-Ti catalyst on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is 20% modification Ni-Co catalyst suspension 8min;
(5) by the sample obtaining after 150 ℃ of dry 4h, obtain regeneration catalytic membrane assembly.
Above-mentioned formula can be used as for this type of water quality optimization technique formula.Effect after catalytic regeneration is as shown in the table.
(mg/L) of sewage disposal plant effluent water-quality ratio before and after the regeneration of inactivation membrane module
As seen from the above table, the performance of inactivation membrane module has obtained good recovery.
Claims (6)
1. for a renovation process for film ozone catalytic reactor inactivation Catalytic Layer, it is characterized in that being undertaken by following step:
(1) first pass into air roasting at 600～850 ℃ remove remain in membrane module in organic pollution;
(2) by concentration, be then hydrochloric acid mixed solution heat of solution 5～20min at 75～160 ℃ that 66% nitric acid and concentration are 37%, remove the metal oxide being attached in film Catalytic Layer; The wherein mol ratio 1:3 of nitric acid and hydrochloric acid;
(3) by mass concentration, be 5%～30%(w/w again) the atomization of modification Mn-Si-Ti catalyst suspension after, negative pressure suction, enters in film support it, its internal surface of hole of load;
(4) finally by spray irrigation, remove the modification Mn-Si-Ti catalyst that is adsorbed on film separating layer surface, and after the outer surface of membrane module is immersed in to mass concentration and is modification Ni-Co catalyst suspension 5～10min of 15%～25%;
(5) by 80～150 ℃ after dry 4～12 hours again, the sample obtaining, obtain the catalytic membrane assembly of regeneration.
Described in claim 1 for the renovation process of film ozone catalytic reactor inactivation catalytic membrane assembly, wherein concentration of nitric acid is 66%, concentration of hydrochloric acid is 37%, the mol ratio 1:3 of nitric acid and hydrochloric acid.
Described in claim 1 for the renovation process of film ozone catalytic reactor inactivation catalytic membrane assembly, the preparation method of wherein said modification Mn-Si-Ti catalyst is as follows:
1. with SiO 2 molecular sieve, average grain diameter 3
by being uniformly mixed, form suspension with deionized water;
2. slowly add the Mn (Ac) of 0.5 mole
2solution 100mL, and lasting stirring makes Mn
2+with H
+exchange swap time: 36～100 hours, obtained mixed liquor is repeatedly filtered, washed 5 times, the Mn2+ on absorption molecular sieve surface is removed;
3. the sample that obtains of filter is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and finally dried sample is calcined at 600 ℃ 3 hours in Muffle furnace, obtains Mn-Si catalyst intermediate;
4. by Mn-Si catalyst intermediate and TiO
2powder 3:1 by ratio of weight and the number of copies～5:1 adds deionized water mix and blend after mixing, and then sample is put at 60 ℃ of thermostatic drying chambers and is dried and spend the night, and obtains modification Mn-Si-Ti catalyst.
Described in claim 1 for the renovation process of film ozone catalytic reactor inactivation catalytic membrane assembly, the preparation method of wherein said modification Ni-Co catalyst is as follows:
1. with
-Al
2o
3average grain diameter 30
micro mist, NiO and Co
3o
4al:Ni:Co=1:2:3 in molar ratio～1:2:5 configuration, and by volume 1:2～1:5 with deionized water by being uniformly mixed, formation suspension;
2. put into baking oven in 100 ~ 120 ℃ of dry 4h, then immersed the Na of 3wt%
2cO
3solution, after 100-120 ℃ of dry 4h, washs with distilled water after taking-up;
3. the sample obtaining is put at 100 ℃ of thermostatic drying chambers and dried 8h, obtain modification Ni-Co catalyst.
Described in claim 1 for the device of film ozone catalytic reactor inactivation catalytic membrane assembly, it is characterized in that comprising inactivation membrane module organic residue removal device, inactivation membrane module regeneration recovery device; Wherein
Inactivation membrane module organic residue removal device: mainly formed by air compressor, temp controlling heater and roasting case, temp controlling heater with being connected of roasting case is: temp controlling heater regulates and controls the heating electrode of its inside by the temperature sensor in roasting case, so that temperature wherein reaches setting value; Air compressor is connected with air inlet in roasting case by wireway, air is entered in roasting case, for oxidation provides oxygen source, by inactivation membrane module is put into airtight device, control temperature and time roasting in roasting case, the organic pollution that makes to remain in membrane module is oxidized to carbon dioxide;
Inactivation membrane module regeneration recovery device: mainly comprise that main reactor (1), catalysis system (2), purging system (3), robot control system(RCS) (4), temperature control heating system (5) and water tank (6) form, wherein catalysis system (2) is connected with main reactor by measuring pump and corrosion-resistant pvc pipe with purging system (3); Robot control system(RCS) is controlled measuring pump in the motor in rotary separator in main reactor, spray and atomising device and negative pressure suction pump and catalysis system by PLC etc.; Temperature control heating system regulates and controls the heating electrode of its inside by the temperature sensor in main body reactor;
Rotary separator (1a), spray and atomising device (1b), negative pressure suction (1c), waste liquid storage tank (1d) are installed in described main body reactor (1);
Described catalysis system (2) comprises supporter catalyst (2a), the allotment of film top layer catalyst and storage system (2b), clarifier (2c); Wherein supporter catalyst (2a) is connected with main reactor with atomising device (1b) by spray; The catalyst allotment of film top layer is connected with main body reactor by measuring pump and pipeline with clarifier (2c) with storage system (2b);
Supporter catalyst suspension is forming water smoke (1b) by pressure type rotary atomizer in main body reactor (1), by forming negative pressure suction (1c) at film core inner, catalyst water smoke is entered and is attached to the top layer of supporter internal voids by film surface; The suspension of film top layer catalyst adopts submergence mode after entering main reactor (1), make catalysis medicament be adsorbed on membrane module top layer, and after immersion processes finishes, by clarifier (2c), medicament is reclaimed, and be stored in the catalyst regulating tank of film top layer (2b);
Purging system (3): comprise (3a) cleaning agent storage bin, (3b): clean waste liquid and reclaim and store basin; Clear water spray and catalysis atomization are actual is to share a system, in the time of catalysis, and opening pressure formula rotary atomizer; When clear water sprays, close atomizer, open shower nozzle; To the allotment of cleaning fluid, be wherein to after hydrochloric acid and nitric acid component proportion, by stirring, realize evenly and mixing; The mol ratio of described hydrochloric acid and nitric acid component is 3:1;
Robot control system(RCS) (4): robot control system(RCS) mainly realizes assembly cleaning in main reactor, the absorption of catalysis liquid and centrifugal process control;
Temperature control heating system (5): be mainly inorganic acid cleaning fluid in inactivation membrane module to be carried out to heating for dissolving be attached to the metal oxide in film Catalytic Layer, and realization is dried the membrane module of adsorption catalyst;
Water tank (6): be mainly that clear water in water tank is passed through to spray and atomising device (1b), realize spray and flushing to membrane module in main body reactor.
6. the device for film ozone catalytic reactor inactivation catalytic membrane assembly claimed in claim 1, is characterized in that the rotary separator material in described inactivation membrane module regeneration recovery device is polytetrafluoroethylene (PTFE).
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Cited By (6)
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| CN109201023A (en) * | 2018-10-17 | 2019-01-15 | 陈育宁 | Sewage filtering material regenerating unit |
| CN109201024A (en) * | 2018-10-17 | 2019-01-15 | 陈育宁 | A kind of sewage filtering material regenerating unit and application method |
| CN110152637A (en) * | 2018-02-25 | 2019-08-23 | 彭万喜 | The digester regeneration method of microenvironment pollution control |
| CN110436607A (en) * | 2019-09-02 | 2019-11-12 | 北京林业大学 | A kind of assembling of controllable interfacial catalysis performance catalytic separation film and its application method in water process |
| CN110734122A (en) * | 2019-11-05 | 2020-01-31 | 苏州科环环保科技有限公司 | ozone catalytic layer in-situ cleaning treatment system and method |
| CN113318608A (en) * | 2021-05-17 | 2021-08-31 | 浙江理工大学 | Dynamically catalyzed water treatment ceramic membrane and application thereof |
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| CN110152637A (en) * | 2018-02-25 | 2019-08-23 | 彭万喜 | The digester regeneration method of microenvironment pollution control |
| CN109201023A (en) * | 2018-10-17 | 2019-01-15 | 陈育宁 | Sewage filtering material regenerating unit |
| CN109201024A (en) * | 2018-10-17 | 2019-01-15 | 陈育宁 | A kind of sewage filtering material regenerating unit and application method |
| CN110436607A (en) * | 2019-09-02 | 2019-11-12 | 北京林业大学 | A kind of assembling of controllable interfacial catalysis performance catalytic separation film and its application method in water process |
| CN110436607B (en) * | 2019-09-02 | 2022-09-16 | 北京林业大学 | Assembly of catalytic separation membrane capable of regulating and controlling interface catalytic performance and application method of catalytic separation membrane in water treatment |
| CN110734122A (en) * | 2019-11-05 | 2020-01-31 | 苏州科环环保科技有限公司 | ozone catalytic layer in-situ cleaning treatment system and method |
| CN113318608A (en) * | 2021-05-17 | 2021-08-31 | 浙江理工大学 | Dynamically catalyzed water treatment ceramic membrane and application thereof |
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| CN103752354B (en) | 2015-09-09 |
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