A kind of method of sewage disinfection treatment in hydrogen peroxide industry
Technical field
The present invention relates to the method for sewage disinfection treatment in a kind of hydrogen peroxide industry.
Background technology
In hydrogen dioxide solution production by anthraquinone process, be filled with a large amount of palladium catalyst in hydrogenation tower, there is hydrogenation in working fluid and hydrogen in tower, makes the effective anthraquinone in working fluid change hydrogen anthraquinone into, hydrogen anthraquinone enter after oxidation operation with oxygen reaction Hydrogen Peroxide.Along with duration of service increases, hydrogenation tower hydrogenation efficiency drops to a certain degree, just must regenerate certain tower joint, working fluid in tower is mainly first discharged by renovation process, re-use steaming out, working fluid in hydrogenation tower is purged clean, then catalyst is unloaded out and carry out sub-sieve, be subsequently installed onto in tower and use Hydrogen activation.A large amount of activated alumina balls is filled with in hydrogenation carclazyte bed and aftertreatment carclazyte bed, hydrogenation carclazyte bed role mainly becomes effective anthraquinone the epoxy anthraquinone degradation products reduction in hydride, aftertreatment carclazyte bed role is the anthraquinone degradation products of regeneration hydrogenation generation and adsorbs solution of potassium carbonate, the moisture content carried secretly in working fluid, and decompose remaining hydrogen peroxide, therefore, activated alumina ball in hydrogenation carclazyte bed and aftertreatment carclazyte bed needs periodic replacement, to ensure stably manufactured.The working fluid of the inside is first discharged, then is purged with steam after stopping using by hydrogenation carclazyte bed or aftertreatment carclazyte bed, and the working fluid adsorbed by alumina balls purges clean, alumina balls could be drawn off after lowering the temperature.The process of above-mentioned steaming out can produce a large amount of sewage, accounts for more than 60% of whole hydrogen peroxide trade effluent.This kind of COD of sewage is often up to tens thousand of, intractability is very big, major cause is: with in steaming out hydrogenation tower, hydrogenation carclazyte bed or aftertreatment carclazyte bed process, steam condensate fully mixes with residual working fluid, working fluid with very tiny oil droplet form dispersion suspension in sewage, be difficult to allow working fluid separate out by the way left standstill, so the COD of this kind of sewage is often up to tens thousand of, use conventional way process be not only difficult to the COD of sewage to be down to qualified, and running cost is very high, cause the waste of working fluid simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is, the method of sewage disinfection treatment in a kind of hydrogen peroxide industry is provided, first by alum purification of water by the working fluid that suspends in sewage with the isolated in form of flocs unit out, reduce the oils in sewage, reduce the COD of sewage, re-use alkaline matter to destroy the flucculation structure of flocs unit, working fluid is separated, improve working fluid yield, reduce production cost.
The technical scheme solved the problems of the technologies described above is: a kind of method of sewage disinfection treatment in hydrogen peroxide industry, comprises the following steps:
Step one: the waste water of discharging when hydrogenation tower, hydrogenation carclazyte bed or aftertreatment carclazyte bed steam blowing is introduced layering pond and carries out stratification, bottom one deck is sewage;
Step 2: bottom one deck sewage is sent into sewage stirring tank;
Step 3: the agitator opening sewage stirring tank, and add concentration 80 ~ 90% phosphoric acid to sewage stirring tank, every cubic metre of sewage need use phosphatase 11 ~ 1.5kg, then continues to add mineral acid the pH of sewage is adjusted to 5 ~ 6;
Step 4: add alum to sewage stirring tank, every cubic metre of sewage need use alum 1.5 ~ 2.5kg, stirs 15 ~ 25 minutes;
Step 5: respectively add anionic flocculant and cationic flocculant to sewage stirring tank, every cubic metre of sewage need use anionic flocculant and cationic flocculant to be 0.001 ~ 0.002kg, continues stirring 3 ~ 8 minutes;
Step 6: when seeing that flocs unit appears in sewage, all enters settling bowl by the sewage in still, carries out stratification;
Step 7: sewage left standstill after 1 ~ 2 hour, flocs unit and water stratification, upper strata is flocculation waste residue, and lower floor is the water that COD drops to below 3000mg/L;
Step 8: the waste residue that flocculated on upper strata is concentrated and received in configuration still by blowback, is furnished with whipping appts in configuration still;
Step 9: the whipping appts opening configuration still stirs, makes the original agglomerate shape waste residue that flocculates try one's best pulp;
Step 10: add appropriate alkaline matter in configuration still, every cubic metre of flocculation waste residue need use alkaline matter 80 ~ 120kg, and ceaselessly stirs, and allows alkaline matter dissolve as early as possible; Described alkaline matter be one in salt of wormwood, soda ash, caustic soda and potassium hydroxide, two kinds, three kinds or four kinds;
Step 11: all dissolve from flocculation waste residue and become liquid and see that working fluid is counted separating out gradually, close the whipping appts of configuration still after 15 ~ 40 minutes, stratification, after stratification, upper strata is working fluid, and lower floor is aqueous phase;
Step 12: the working fluid in recycling step 11, the lower floor's aqueous phase in step 11 and the water in step 7 can process according to a conventional method further.
Also be provided with heating unit in described configuration still, in step 8, add after flocculation waste residue terminates and open heating unit, make heating material to 50 ~ 60 DEG C in configuration still, and maintain this temperature, when step 11 closes the whipping appts of configuration still, stop heating.
In step 3, the mineral acid for adjust ph is nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid.
The whipping appts be furnished with in described configuration still is air stirrer or mechanical stirring device.
Described anionic flocculant is anionic polyacrylamide, and described cationic flocculant is cationic polyacrylamide.
After step one stratification, layering pond topmost one deck is working fluid, and the working fluid that step one and step 11 stratification obtain reclaims and cleans into configuration still, qualified rear feeding production system.
Described layering pond is made up of the N number of pond be communicated with by overflow manner successively, the value of N is 3 ~ 10, by the flow direction of waste water, the pond that waste water finally flows to is Shi great pond, N number of pond, the 1st pond above, the 2nd pond are to Shi little pond, N-1 pond, and large pond volume is 10 ~ 20 times of little pond volume.
Described overflow manner refers to that the wall bottom between adjacent 2 ponds has overflow hole, corresponding overflow hole is provided with divider wall, divider wall height is lower than pond height 1/5, after sewage flows through overflow hole, be isolated wall to block, only have the water level in current 1 pond overflow could enter rear 1 pond higher than divider wall.
The present invention first by alum purification of water by the working fluid that suspends in sewage with the isolated in form of flocs unit out, reduce the oils in sewage, reduce the COD of sewage, re-use the flucculation structure that alkaline matter (preferred salt of wormwood) destroys flocs unit, working fluid is separated, compared with prior art, the present invention has following beneficial effect:
1, after pre-treatment, the oily substance in sewage reduces by more than 70%, COD and greatly reduces, and sewage disposal expense reduces.
2, by a large amount of practical production experience, this kind of sewage of every 100m3 can produce throw out and be about 2.5m3, the ratio that throw out transforms rear working fluid and water is after treatment about about 1:2.5, therefore every 100m3 sewage working fluid yield increase about 0.8m3 after pretreatment, add working fluid yield, reduce and consume, reduce production cost.
Below, the technical characteristic of the method for sewage disinfection treatment in a kind of hydrogen peroxide industry of the present invention is further described in conjunction with the embodiments.
Accompanying drawing explanation
Fig. 1: the apparatus structure schematic diagram that in a kind of hydrogen peroxide industry of the present invention, the method for sewage disinfection treatment uses.
Fig. 2-Fig. 3: the layering pool structure schematic diagram that the embodiment of the present invention one uses.
Fig. 2: vertical view; The Q-Q sectional view of Fig. 3: Fig. 2.
In figure: 1-layering pond, 101-divider wall, 102-overflow hole, 2-surge pump I, 3-configures still, and 31-configures still agitator, 32-visor, 4-configures still pump, 5-sump pump I, 6-sewage Buffer Pool, 7-sump pump II, 8-sewage stirring tank, 81-stirring tank agitator, 9-settling bowl, 10-surge pump II, 11-reaction tank, 12-surge pump III.
In figure: P1 represents the sewage from hydrogenation tower, hydrogenation carclazyte bed or aftertreatment carclazyte bed, P2 represents working fluid, P3 represents sewage, and P4 represents air, and P5 represents steam, P6 represents recirculated water backwater, P7 represents water on recirculated water, and P8 represents phlegma, and P9 represents that working fluid sends into system, P10 represents and sends to subsequent processing process, and P11 represents flocculation waste residue.
Embodiment
Embodiment one:
A method for sewage disinfection treatment in hydrogen peroxide industry, the device (as shown in Figure 1) that the method uses comprises the equipment such as layering pond 1, surge pump I 5, configuration still 3, configuration still pump 4, sump pump I 5, sewage stirring tank 8, settling bowl 9, surge pump II 10, reaction tank 11, surge pump III 12, the length in layering pond, wide, height is respectively 10m, 8m, 2.5m, inside is divided into 4 little ponds and a large pond, by the flow direction of waste water, be respectively successively by little pond A that overflow manner is communicated with, little pond B, little pond C, little pond D(length × wide × high=2 × 2 × 2.5, unit is m) He 1 large pond E(length × wide × high=8 × 8 × 2.5, unit is m), as shown in accompanying drawing 2-Fig. 3, described overflow manner refers to that the wall bottom between adjacent 2 ponds has overflow hole 102, corresponding overflow hole is provided with divider wall 101, divider wall height is lower than pond height 1/5, after sewage flows through overflow hole, be isolated wall to block, only have the water level in current 1 pond overflow could enter rear 1 pond higher than divider wall.The overflow hole height in each pond is 0.4m, and wide is 0.4m, and the overflow divider wall in each pond is long is 0.4m, and wide is 0.4m, and height is 2m; Configuration still cubic capacity is 6m3, is accompanied with the chuck of whipping appts and heating or cooling; Sewage stirring tank cubic capacity is 8m3, is accompanied with whipping appts; The length of reaction tank is respectively 6m, 5m, 2m.
The method realizes the pre-treatment of sewage in hydrogen peroxide industry by following steps.(1) waste water of discharging when hydrogenation tower, hydrogenation carclazyte bed or aftertreatment carclazyte bed steam blowing is introduced in the A pond in layering pond, sewage successively flows into B, C, D pond by overflow manner, final inflow E pond, because working fluid density ratio water is little, therefore working fluid rests in ABCD tetra-little ponds substantially, the sewage in E pond is substantially without working fluid; (2) with surge pump I, the working fluid in ABCD pond is reclaimed into configuration still, add-on is about 4m3, open the stirring of configuration still, add 1m3 deionized water simultaneously and carry out cleaning about 15 minutes, stirring of stopping, after working fluid and water stratification, open configuration still and lead the forward and backward valve of pouring visor, water is entered sewage lagoon, and this cleaning step carries out three times altogether, after working fluid cleaning is qualified, by configuration still pump, working fluid is sent into production system; (3) by sump pump I, the sewage in layering pond is sent into sewage stirring tank, add-on is 6m3; (4) open the agitator of sewage stirring tank, and add 9kg phosphoric acid (phosphoric acid concentration about 85%) to sewage stirring tank, then continue to add about 50kg dust technology (concentration of nitric acid is 42%), the pH of sewage is adjusted to 5 ~ 6; (5) alum 2kg need be used by every cubic metre of sewage, add the alum of 12kg to sewage stirring tank, stir 20 minutes; (6) respectively add the anions and canons flocculation agent of 0.006kg to sewage stirring tank, continue stirring 5 minutes; (7) when see in sewage there is flocs unit (alumen ustum) time, open sewage stirring tank outlet valve, the sewage in still all entered settling bowl; (8) sewage left standstill after about 1 hour, flocs unit and water stratification, and upper strata is flocculation waste residue, and lower floor is water, and now the COD of water drops to below 3000mg/L, and additive method can be used to process further; (9) by surge pump II, waste residue centralized recovery is flocculated to reaction tank (being furnished with steam heater and air stirrer in reaction tank) in upper strata; (10) when the flocculation waste residue yield in reaction tank reaches 15m3, the air intlet valve opening reaction tank stirs, the original agglomerate shape waste residue that flocculates is tried one's best pulp, open reaction tank steam inlet valve and condensate outlet valve simultaneously, give the heating of flocculation waste residue, the temperature of heating is 60 DEG C; After (11) 20 minutes, in reaction tank, slowly add the salt of wormwood of 1.5 tons, and ceaselessly stir and heat, make temperature maintain 60 DEG C, allow salt of wormwood dissolve as early as possible; Suitably heat to waste residue while adding salt of wormwood, not only can accelerate the dissolving of salt of wormwood, reduce the treatment time, and be conducive to follow-up work liquid and aqueous phase layering.(12) waste residue that flocculates all dissolves and becomes liquid and see that working fluid is separated out gradually, close pneumatic blending after 40 minutes and stop heating, allow material stratification in reaction tank, after stratification, upper strata is working fluid, the volume of working fluid is 4.5 m3, and lower floor is water, and the volume of water is 10.5 m3; (13) enter to configure still by the working fluid in surge pump III recycling step 12 to clean, cleaning process is identical with step (2), and the water of lower floor is delivered to next sewage disposal operation and done further process together with the water in step (8).
In embodiment one, the salt of wormwood used is technical grade salt of wormwood, should not use the waste product of salt of wormwood, in order to avoid introduce other impurity, pollutes working fluid; One as embodiment one converts, and can adjust the consumption of salt of wormwood according to different situations, salt of wormwood consumption is more, and effect is better, but salt of wormwood will be avoided too much can not to dissolve completely, causes waste; Generally salt of wormwood 80 ~ 120kg need be used to calculate by every cubic metre of flocculation waste residue.In addition, the basic materials such as soda ash, caustic soda, potassium hydroxide can also be used to be used alone or as a mixture, to replace salt of wormwood, but use the effect of salt of wormwood best.
Embodiment two:
A method for sewage disinfection treatment in hydrogen peroxide industry, the device that the method uses is identical with embodiment one, and the method realizes the pre-treatment of sewage in hydrogen peroxide industry by following steps.(1) waste water of discharging when hydrogenation tower, hydrogenation carclazyte bed or aftertreatment carclazyte bed steam blowing is introduced in the A pond in layering pond, sewage successively flows into B, C, D pond by overflow manner, final inflow E pond, because working fluid density ratio water is little, therefore working fluid rests in ABCD tetra-little ponds substantially, the sewage in E pond is substantially without working fluid; (2) with surge pump I, the working fluid in ABCD pond is reclaimed into configuration still, add-on is about 4m3, open the stirring of configuration still, add 1m3 deionized water simultaneously and carry out cleaning about 15 minutes, stirring of stopping, after working fluid and water stratification, open configuration still and lead the forward and backward valve of pouring visor, water is entered sewage lagoon, and this cleaning step carries out three times altogether, after working fluid cleaning is qualified, by configuration still pump, working fluid is sent into production system; (3) by sump pump I, the sewage in layering pond is sent into sewage stirring tank, add-on is 6m3; (4) open the agitator of sewage stirring tank, and add 9kg phosphoric acid (phosphoric acid concentration about 85%) to sewage stirring tank, then continue to add about 70kg hydrochloric acid (concentration of hydrochloric acid is 33%), the pH of sewage is adjusted to 5 ~ 6; (5) alum 2kg need be used by every cubic metre of sewage, add the alum of 12kg to sewage stirring tank, stir 20 minutes; (6) respectively add the anions and canons flocculation agent of 0.006kg to sewage stirring tank, continue stirring 5 minutes; (7) when see in sewage there is flocs unit (alumen ustum) time, open sewage stirring tank outlet valve, the sewage in still all entered settling bowl; (8) sewage left standstill after about 1 hour, flocs unit and water stratification, and upper strata is flocculation waste residue, and lower floor is water, and now the COD of water drops to below 3000mg/L, and additive method can be used to process further; (9) by surge pump II, waste residue centralized recovery is flocculated to reaction tank (being furnished with steam heater and air stirrer in reaction tank) in upper strata; (10) when the flocculation waste residue yield in reaction tank reaches 15m3, the air intlet valve opening reaction tank stirs, the original agglomerate shape waste residue that flocculates is tried one's best pulp, open reaction tank steam inlet valve and condensate outlet valve simultaneously, give the heating of flocculation waste residue, the temperature of heating is 60 DEG C; After (11) 20 minutes, in reaction tank, add the caustic soda of 1.2 tons of salt of wormwood and 0.7 ton successively, and ceaselessly stir and heat, make temperature maintain 60 DEG C, allow salt of wormwood and caustic soda dissolve as early as possible; Suitably heat to waste residue while adding salt of wormwood and caustic soda, not only can accelerate the dissolving of salt of wormwood and caustic soda, reduce the treatment time, and be conducive to follow-up work liquid and aqueous phase layering.(12) waste residue that flocculates all dissolves and becomes liquid and see that working fluid is separated out gradually, closes pneumatic blending and stop heating after 40 minutes, allows material stratification in reaction tank, after stratification, the volume of working fluid is 4 m3, and lower floor is water, and the volume of water is 11 m3; (13) enter to configure still by the working fluid in surge pump III recycling step 12 to clean, cleaning process is identical with step (2), and the water of lower floor is delivered to next sewage disposal operation and done further process together with the water in step (8).
In various embodiments of the present invention, described anionic flocculant is anionic polyacrylamide, and described cationic flocculant is cationic polyacrylamide.As one conversion, other positive and negative ionic flocculants satisfactory can also be used.
One as each embodiment converts, and the alkaline matter added in step (11) can be the one in salt of wormwood, soda ash, caustic soda and potassium hydroxide, or the mixture of two kinds, three kinds or four kinds in salt of wormwood, soda ash, caustic soda and potassium hydroxide.
One as each embodiment converts, and also can not arrange heating unit in described reaction tank, by stirring, salt of wormwood is dissolved, but effect is not best.Other equipment with mechanical stirring and heating unit can also be selected to come surrogate response pond.
One as each embodiment converts, and other acid such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid can be used to regulate the pH value of sewage; But suitable phosphoric acid add-on can significantly improve flocculating effect; Generally adopt phosphoric acid or the composition of phosphoric acid and other acid is to regulate the pH value of sewage.
As another conversion of each embodiment, described layering pond also without separating into several little pond, but can be made up of a large pond.