CN100582080C - Epoxy ester wastewater recycling treatment method - Google Patents
Epoxy ester wastewater recycling treatment method Download PDFInfo
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Abstract
The present invention discloses a method for recycling and processing epoxy-ester sewage, relating to a technical method that resources are reclaimed from industrial wastewater to produce chemical products. The technical proposal of the invention is: formic acid sewage generated during the process of epoxy-ester production is treated by oil separating, and then formic acid solution is achieved by reaction with calcium carbonate; and the formic acid solution is further neutralized with calcium carbonate for a plurality of times after sedimentation; coagulant and precipitator are added into the solution to further remove heavy metal and solid impurities, and then is filtered, decolored, evaporated and dried to achieve formic acid powder. The process is applicable to the production of fodder-grade, industrial-grade and other grades of formic acids; besides, the process is characterized in less investment and high yield; and in addition, byproducts such as waste gas and waste water can be reclaimed for reuse. As a result, the reduction of waste water is realized and economic efficiency is improved.
Description
Technical field
The invention belongs to chemical industry and environmental technology field, relate to the technological method that from trade effluent, reclaims resource production chemical product, be specially and from epoxy ester waste water, reclaim the Processes and apparatus that formic acid is produced calcium formiate.
Background technology
The epoxy ester softening agent comprises epoxy methyl esters, epoxy soybean wet goods, can produce the waste water that contains formic acid in the production process of this series products, its COD concentration height, and intractability is bigger, is one of difficult problem in the chemical wastewater treatment.
The production method of epoxy soybean oil mainly adopts solventless method at present, be under catalyst action, to generate epoxidizing agent with the hydrogen peroxide reaction with formic acid, in a certain temperature range, epoxidizing agent is added drop-wise in the soybean oil then, reaction finishes after alkali cleaning, washing, underpressure distillation obtain product at last.Play the formic acid of instrumentality in the production process in whole epoxy reaction system, its concentration drops to 3～15% backs with discharge of wastewater by 85%.Its waste water ph 2～4 contains lipid 500mg/L, and formic acid is about 3～15%, and hydrogen peroxide is about 0.9%, also has a small amount of peroxyformic acid, the on average about 20000mg/L of COD concentration.
The production method and the epoxy soybean oil of epoxy methyl esters are similar, i.e. fatty acid methyl ester and hydrogen peroxide initial ring oxidizing reaction under the catalysis of formic acid, and reaction product finally obtains finished product through standing demix, alkali cleaning, washing and underpressure distillation.Its concentration of formic acid as catalyzer in the production process drops to 5～25% backs with discharge of wastewater by 85%, and its waste water ph 1～4 contains lipid 600mg/L, formic acid about 5～25%, hydrogen peroxide is about 0.6%, also has a small amount of peroxyformic acid, the on average about 25000mg/L of COD concentration.
It is acid that the epoxy ester factory effluent is, and principal pollutant matter is formic acid, and it is big and processing cost is very high directly to handle the difficulty of discharging up to standard.Therefore, must reclaim the formic acid in the epoxy ester factory effluent, realize recycling, increase economic benefit when reducing cost for wastewater treatment.
From epoxy soybean oil waste water, reclaim formic acid and produce the method (CN 1793103) of calcium formiate, set forth and a kind ofly utilized that formic acid reacts in lime carbonate and the epoxy soybean oil waste water, thereby reach processing waste water and produce the method for calcium formiate product.Its process program is: earlier the epoxy soybean oil waste water oil removal is handled, lime carbonate will also under agitation be added then in the waste water injecting reactor, utilize the calcium hydroxide emulsion regulator solution to pH6～8, add precipitation agent again and remove beavy metal impurity, remove solid impurity with the precipitator method and filter core, at last filtrate evaporative crystallization, centrifugation and air stream drying are obtained the formic acid product.
The present invention is directed to the water quality characteristic of all kinds of epoxy esters (epoxy methyl esters, epoxy soybean wet goods) factory effluent, proposed to reclaim a whole set of technology that the formic acid in the waste water is produced the calcium formiate product, and this technology can reclaim the waste water and gas that produces in the production process simultaneously, accomplish to make full use of resource, reduce the discharging of pollutent, even realize zero release.
Summary of the invention
The purpose of this invention is to provide a kind of operational path that reclaims the formic acid in the epoxy ester factory effluent and adopt lime carbonate neutralisation production calcium formiate product, reclaim the waste water and gas in the production process simultaneously.The theory that is intended to reclaim resource and preparing product applies in the practice, thereby realizes industrialization and mass-producing.By recovery of resources, thereby reduce cost for wastewater treatment and the quantity discharged that reduces pollutent, in the protection environment, increase economic efficiency.
The present invention proposes the processing method that epoxy ester wastewater recycling is handled.The source of described waste water is: the factory effluent that the waste oil of various fatty acid esters and Vegetable oil lipoprotein or recovery produces with oxidant reaction under the catalysis of formic acid.Therefore, this type of waste water is that the waste oil of various fatty acid esters and Vegetable oil lipoprotein or recovery produces with oxidant reaction under the catalysis of formic acid, contains the mixing water of compositions such as formic acid, hydrogen peroxide, lipid, a small amount of peroxyformic acid and micro heavy.And, can produce the product of different grades, to adapt to the demand of various industries such as food, chemical industry, building materials, process hides, oil by the indivedual operations in the adjusting process.
Technical process of the present invention may further comprise the steps:
(1) waste water is introduced into oil trap and carries out oily water separation, is back to production behind the floating oil collecting of upper strata, and subnatant enters reactor one after being delivered to equalizing tank.
(2) in reactor one, formic acid wastewater and calcium carbonate reaction generate calcium formate solution.Reactor one regular back flushing, raffinate utilizes after reclaiming by the waste liquid return-flow system again in jar.Reactor one exhaust is reclaimed food-grade carbon-dioxide by carbon dioxide recovery system, in accordance.
(3) calcium formate solution enters settling tank (as inclined tube-type, flat flow, width of cloth streaming, vertical-flow etc.) subsequently, adopts the suspended solids in the method sedimentation solution of coagulating sedimentation, and supernatant liquid enters reactor two subsequently.Mud comes together in and regularly enters sludge sump in the sludge bucket, enters sludge drying bed again or adopts the press filtration machine filter to do, and percolate is by the recycling of waste liquid return-flow system.
(4) calcium formate solution is removed residual formic acid, pond in the middle of entering after filtering again with the further reaction of lime carbonate in reactor two.Reactor two regular back flushinges, raffinate recycling in jar.If formic acid content is higher in the waste water, still have residually in a large number after the neutralization of two steps, then can reactor two after, establish some reactors again and carry out the multistep neutralization, with raising formic acid utilization ratio.
(5) through in the multistep and after, in the middle of the calcium formate solution crude product comes together in the pond, solution before entering filter tank earlier with coagulating agent and precipitation agent thorough mixing, heavy metal and suspended solid impurities effect formation flocculation sediment is brought the filter tank filtering into current in medicament and the solution.
(6) calcium formiate product solution after filtering has certain colourity.Carry out adsorption bleaching according to the requirement of the quality product activated carbon column of handling that can enter that need decolour, the solution of dispense with decoloration can directly enter vapo(u)rization system and evaporate.
(7) the calcium formiate final mean annual increment solution is removed part moisture by evaporation concentration system, forms brilliant liquid mixture, and (as filter pocket, whizzer etc.), separation back form wet stock more after filtration.After collecting, the mother liquor that leaches utilizes again.
(8) the dried calcium formiate crystal of preliminary filter enters dehumidification system again, and the water ratio of control product makes calcium formiate product and packing warehouse-in at last.
Can produce a certain amount of waste water and gas in the whole process of production, wherein waste oil recycling, CO 2 waste gas is made product after collection and purification, the heat of steam condensate is back to heating system, take a shower heating, general industry heating, small power generation unit, thermophore etc., hot water is back to the equipment back flushing after the cooling tower cooling, the raffinate in reactor and the filter tank and the percolate of sludge drying bed utilize after can reclaiming by the waste liquid return-flow system again, and the mud after filter is done can be used as paves the way or brickmaking etc.Accompanying drawing 4 is seen in technical process of the present invention.
The described reactor of above step (1,2,3,4), inner filling filtering material, as fibrous bundle, fibrous nodules, ultra-filtration membrane, micro-filtrate, sandstone and filter core etc., and on filtering layer filling calcium carbonate reaction layer, gas trap, back flushing loop and dumping device are set simultaneously, and the outfit automatic charging device, as belt conveyor, chapelet, worm conveyor, embedded scraper transporter etc.Can produce great amount of carbon dioxide gas in the reactor, the gas trap venting port can be connected with air water separator, will send into carbon dioxide recovery system, in accordance after the gas filtration, so that produce the comprehensive utilization of tail gas; Formic acid raffinate during back flushing in the jar can enter the utilization of recovery trench internal recycle.
The described sludge drying bed of above step (3) is laid the perforation rising pipe all around, and gravel packing is laid in the bottom, and ground need be done antiseepage and be handled, and perhaps directly adopts the pressure filter press filtration.Mud filtrate is utilized after reclaiming by the waste liquid return-flow system again, and mud is transported outward after filtering dried or press filtration naturally.
The described filter tank of above step (5), inner filling filtering material, as fibrous bundle, fibrous nodules, ultra-filtration membrane, micro-filtrate, sandstone and filter core etc., and configuration back flushing loop and gas blow-off valve.
The described active carbon adsorption column of above step (6) adopts plural serial stage, but inside loaded particles gac, active carbon powder, activated carbon fiber, carbon molecular sieve etc., and supporting electrically heated or steam regenerating unit (taking-up regeneration).
The described evaporation concentration system of above step (7) can adopt multiple-effect continuous evaporative crystallization device, mechanically compress vaporizer, rotatory evaporator, thin-film evaporator, centrifugal evaporator and scraper-type vaporizer etc.The steam condensate leaving water temperature(LWT) can reach 60～80 ℃ can be back to heating system, shower heating, general industry heating, small power generation unit, thermophore etc., and hot water can be used for the back flushing of other equipment after the cooling tower cooling.
The described filter pocket of above step (7), bucket-shaped container and bottom are built on stilts, and with bottom hole, interior shop 20～200 order filter clothes carry out preliminary liquid-solid separation on the wall.
The described dehumidification system of above step (8) can adopt tunnel belt circulation dryer, pneumatic dryer, fluidized bed dryer, spin flash dryer, cylinder-pneumatic dryer and cylinder-rake type dryer etc.Wet stock adds in the drying machine continuously and quantitatively, by tornado dust collector and sack cleaner the product powder is collected behind the product drying.
Technical essential of the present invention is as follows:
One, control automatically
1, fluid level controller: the automatic water outlet of fluid level controller is adopted in the oil trap draining, prevents waste water outflow in the pond when guaranteeing enough hydraulic detention times and causes waste.
2, automatic intermittent aeration: oil trap aerating apparatus preparation automatic control system, intermittent aeration guarantees that oil removal efficient also reduces energy consumption.
3, automatic medicament feeding system: settling tank and line mixer all adopt quantitative dosing coagulant of volume pump and precipitation agent, make added amount of chemical and wastewater treatment capacity be complementary, and guarantee treatment effect and save dosing.
Two, equipment characteristic
1, filters: fill and the placement filter material in reactor and the filter tank, as fibrous bundle, fibrous nodules, ultra-filtration membrane, micro-filtrate, sandstone and filter core etc., by grating and the ratio that the various types of filtration material rationally is set, to reach best filter effect, and spigot discharge is set, make things convenient for filler to change and maintenance of the equipment.
2, solid-liquid reaction: reactor can adopt fluidized-bed, filling tank, flat flow reactor or recirculation reactor, agitator is not established in inside, utilize the flow velocity and the buoyancy of waste water to make pearl filler be in fluidized state, solid-liquid thorough mixing and reaction, thus cut down the consumption of energy.
3, back flushing: reactor and filter tank all are provided with counter-flushing pipeline, when the solid impurity of holding back in the container is too much, can guarantee the quality of product by clear water recoil or air water back washing with the Impurity removal in the filler.
4, charging system: the pearl filler consumption rate needs more rapidly to replenish at any time in the reactor one, by disposing mechanical charging system, as belt conveyor, chapelet, worm conveyor, embedded scraper transporter etc., realizes self-feeding, reduces labour intensity.
5, sludge drying: adopt the pressure filter press filtration or enter sludge drying bed and filter naturally and do, lay the rising pipe of boring a hole around sludge drying bed, sandstone is spread, the recycling after filtering of the product solution in the mud after doing the antiseepage processing in the bottom.
Three, craft feature
1, multistep neutralization: be introduced into reactor one after formic acid wastewater is handled through oil removal and carry out neutralization reaction, also contain a small amount of formic acid in the calcium formate solution of formation, enter reactor two again by post precipitation and further neutralize, remove residual formic acid.Water (flow) direction is served as reasons down supreme (promptly filtering afterreaction earlier) in the reactor one, and water (flow) direction (is promptly reacted after-filtration earlier) for from top to bottom in the reactor two.If formic acid content is higher in the waste water, still have residual in a large number after the neutralization of two steps, then can after reactor two, establish some reactors again and carry out the multistep neutralization, can guarantee that like this formic acid wastewater and lime carbonate fully react, thereby the turbidity that can effectively control product solution again improves product purity.
2, activated carbon decolorizing: active carbon adsorption column is set before the solution evaporation crystallization.If the higher or quality product of solution colourity need reach feed grade when requiring, can adopt multistage charcoal absorption decolouring; If when the lower or quality product of solution colourity only need reach the technical grade requirement, can directly enter the vapo(u)rization system crystallization.So setting can increase the production handiness so that production technique can adapt to the requirement of different grades product, cuts down the consumption of energy.
3, vapo(u)rization system: can adopt multiple-effect continuous evaporative crystallization device, mechanically compress vaporizer, rotatory evaporator, thin-film evaporator, centrifugal evaporator and scraper-type vaporizer etc., take the mode of continuously feeding discharging.The brilliant liquid mixture of evaporation discharging carries out centrifugation after filtering through filter pocket earlier again, cuts down the consumption of energy when enhancing productivity.
4, dehumidification system: can adopt tunnel belt circulation dryer, pneumatic dryer, fluidized bed dryer, spin flash dryer, cylinder-pneumatic dryer and cylinder-rake type dryer etc.Wet stock adds in the drying machine continuously and quantitatively, and dry qualified material is discharged after fly-ash separator captures from discharge port and obtained dry finished product; The too big or higher material of humidity of particle is stopped, and continues to obtain further dry until being taken out of in drying machine.Adopt above technology drying products not only can enhance productivity, and can reduce the product water ratio significantly to reach the quality product requirement.
Four, recycling
1, waste oil: the production that can be back to epoxy ester after the waste oil in the oil trap is collected.
2, waste gas: formic acid wastewater and calcium carbonate reaction rapidly and discharge a large amount of carbonic acid gas can utilize air water separator with the most of liquid filtering in the carbon dioxide gas stream in the reactor, send into the gas delivery purification system again and make carbon dioxide product.
3, waste water: the vapor condensation water temp that vaporizer produces is higher, generally at 60～80 ℃, its heat can be back to heating system, take a shower heating, general industry heating, small power generation unit, thermophore etc., and hot water can be used for the back flushing of equipment after the cooling tower cooling.Raffinate before the equipment back flushing in reactor and the filter tank and the percolate emptying in the sludge drying bed are to recovery trench, by utilizing after the recovery of waste liquid return-flow system again.
4, mud: mud through press filtration or after filter is done naturally can outside operate and pave the way or brickmaking is used.
Description of drawings
Fig. 1 is the reactor synoptic diagram.The 1-main body, 2-advances (going out) water pipe, and 3-advances (going out) water valve, and 4-back flushing water intaking valve, 5-go out (advancing) water pipe, and 6-goes out (advancing) water valve, 7-back flushing water discharge valve, 8-blow-down pipe, 9-blow-off valve, 10-recovery valve, 11-manhole, 12-spigot discharge.
Fig. 2 is the air water separator synoptic diagram.1-stainless steel cylinder, 2-Stainless Steel Cloth filler, 3-swash plate, 4-draining cinclides, 5-stainless steel baffle plate, 6-scupper hose, 7-inlet mouth, 8-venting port, the 9-chamber that catchments.
Fig. 3 is a mud filter tank synoptic diagram.1-pond body, the 2-rising pipe of boring a hole, 3-sandstone filtering layer.
Fig. 4 is a process flow sheet of the present invention.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Generally see Table 1 from the formic acid wastewater water quality in the epoxy soybean oil production.
Table 1 formic acid wastewater water quality
| The material title | Concentration |
| |
2～20％ |
| Hydrogen peroxide | 0.2～2.0％ |
| Lipid | 100～5000mg/L |
| COD Cr | 10000～300000mg/ |
| pH | |
| 2～4 | |
| Color | Colourless～lead |
Implementation step one: oil removal
Formic acid wastewater from epoxy soybean oil production is introduced into oil trap, to the surface, flows into recovery oil drum after coming together in the oil removal groove through the come-up of the grease 99% or more in the waste water behind water distribution and the aeration.Lower floor's formic acid water is delivered to equalizing tank through automatic bailer.
Implementation step two: neutralization reaction
After formic acid water comes together in equalizing tank, squeeze in the reactor one, generate calcium formate solution, utilize rotary conveyor to replenish pearl filler at any time simultaneously with the pearl filler reaction by lift pump.Reactor one top vent links to each other with gas recovery system, CO 2 waste gas is reclaimed to purify form product.Regularly reactor one is carried out back flushing according to actual condition.
Implementation step three: precipitation
Contain a large amount of solid impurities in the calcium formate solution crude product,, utilize volume pump quantitatively to add the PAC coagulating agent at the inhalant region of settling tank.The control hydraulic detention time is at 1～10h, suspended solids and coagulating agent fully act on back formation flocculation sediment and accumulate in the sludge bucket of bottom, drain into sludge sump by shore pipe, cause too much can carrying out back flushing to settling tank under the not smooth situation of spoil disposal in sludge accumulation.
Implementation step four: remove residual formic acid
Calcium formate solution comes out to enter successively reactor two and reactor three from settling tank, further with calcium carbonate reaction, residual formic acid removed, and the about respectively 0.3～3h of controlling reaction time and 0.1～1h, water outlet pH value is greatly about 4～8.Consume situation according to lime carbonate in the jar, suitably replenish pearl filler, and regularly carry out back flushing.
Implementation step five: removing heavy metals impurity
Before calcium formate solution in the middle pond is squeezed into filter tank by lift pump, need earlier through the dosing mixing system.Calcium formate solution in line mixer with ferric-polysilicate coagulating agent and TMT precipitation agent thorough mixing, the about respectively 20～200ppm of added amount of chemical and 10～100ppm.The reaction of heavy metal and precipitation agent generates insolubles, and various solid impurities are brought filter tank further with the coagulating agent effect and precipitate into current.
Implementation step six: filter
Calcium formate solution enters filter tank, adopts micro-filtrate to filter, and air is discharged by top venting valve in the filter tank, guarantees certain hydraulic pressure, accelerates filtration velocity and guarantees filter effect.2 filter tanks are set, are used alternatingly, regularly back flushing.
Implementation step seven: decolouring
The active carbon adsorption column that filtration back clear soln enters two-stage series connection decolours, and active carbon adsorption column one is equipped with a usefulness, adopts the regeneration of electrically heated or steam.
Implementation step eight: evaporation
Adopt 2～5 to imitate continuous evaporator, continuous feeding and discharging, discharging is brilliant liquid mixture, concentration about 10～60%.Mixture is delivered to the filter pocket filter by water pump and is done (or whizzer drying), and the solid water ratio about 5～25% behind preliminarily dried.Mother liquor is back to mother liquor tank, squeezes into water reservoir again and utilizes.Evaporative process needs the discharged steam water of condensation, and about 50～80 ℃ of leaving water temperature(LWT), heat can be back to heating system, take a shower heating, general industry heating, small power generation unit, thermophore etc., and hot water can be used for the back flushing of equipment after the cooling tower cooling.
Implementation step nine: drying
The calcium formiate crystal enters pneumatic dryer at last, wet stock is added in the moisture eliminator by the screw feeder continuous and quantitative, the exsiccant product is taken out of in company with warm air self-desiccation device top outlet pipe, by tornado dust collector and sack cleaner, the product powder is collected in the woven bag.Product sealing back warehouse-in, and carry out moistureproof the processing.
The calcium formiate quality product of producing through above step sees table 2 for details.
Table 2 calcium formiate quality product
| Index name | Desired value |
| Outward appearance | White powder |
| Calcium formiate content | ≥98.0％ |
| Total calcium | ≥30.2％ |
| PH value (50g/L) | 7.0～7.5 |
| Heavy metal (in Pb) | ≤0.002％ |
| Arsenic (As) | ≤0.0005％ |
| Weight loss on drying | ≤1.0％ |
| Water-insoluble | ≤0.2％ |
Complete process embodiment one: 45000t/a epoxy soybean oil formic acid wastewater is handled and reuse project, and Fig. 4 is seen in the present embodiment technical process.
1, wastewater source
Formic acid wastewater is from the production process of epoxy soybean oil, the about 45000t/a of generation.Its waste water quality sees Table 3.
Table 3 epoxy soybean oil formic acid wastewater water quality
| The material title | |
| Formic acid | |
| 3～15％ | |
| Hydrogen peroxide | 0.5～1.0％ |
| Lipid | 200～1000mg/L |
| COD Cr | 10000～50000mg/ |
| pH | |
| 2～4 | |
| Color | Colourless～little yellow |
2, technical process
Certain 45000t/a epoxy soybean oil formic acid wastewater processing and reuse project are as shown in Figure 4.
(1) oil removal
Formic acid wastewater is introduced into oil trap, stop about 0.2～4h by water distribution uniformity and intermittent aeration after in the waste water come-up of the grease more than 99% to the surface, oil flows into after the weir plate obstruct is gathered in the oil removal groove and reclaims oil drum, and lower floor's formic acid water is delivered to equalizing tank through automatic bailer.
(2) neutralization reaction
The formic acid wastewater of handling through preliminary oil removal comes together in the equalizing tank, and thin oil droplet continues come-up to surperficial behind stop 2～20h, and lower floor's formic acid is squeezed in the reactor one by lift pump, generates calcium formate solution, the about 0.5～6h of controlling reaction time with calcium carbonate reaction.Reactor one top vent links to each other with gas recovery system, CO 2 waste gas is reclaimed to purify form product.According to actual condition regularly to reactor-clean.
(3) precipitation
Formic acid wastewater enters the inclined tube-type settling tank after preliminary neutralization, utilize volume pump quantitatively to add the PAC coagulating agent before the water inlet, the about 10～200ppm of dosage.The clearance of suspended solids is more than 90%, and mud drains in the sludge sump, sends into sludge drying bed after stable or the filter of press filtration machine room is done, and filtrate is back to through recovery trench and regulates attached pond.
(4) remove residual formic acid
Calcium formate solution comes out to enter reactor two from settling tank, further with calcium carbonate reaction, residual formic acid removed, and the about 0.2～5h of controlling reaction time, water outlet pH about 5～7.Consume situation according to lime carbonate in the jar, suitably replenish pearl filler, and regularly carry out back flushing, raffinate emptying is to recovery trench in jar.After the neutralization of two steps, pond in the middle of calcium formate solution comes together in, the carbon dioxide behind stop 5～20h in the solution volatilizees substantially.
(5) removing heavy metals impurity
Calcium formate solution is squeezed in the filter tank way by middle pond, connects a line mixer, utilizes volume pump quantitatively to add Na in mixing tank
2S precipitation agent and PAC coagulating agent, the about respectively 5～100ppm of dosage and 20～400ppm make that heavy metal and the suspended solids formation flocculation sediment in the waste water brought filter tank into.Na
2S can discharge H under acidic conditions
2S gas needs to be adjusted to neutrality or the use of alkalescence back with NaOH.
(6) filter
Calcium formate solution enters filter tank, will be disposed to water reservoir after the throw out filtering.Two pressure filters are used alternatingly and regularly carry out back flushing.
(7) decolouring
Solution after the filtration loads activated carbon granule, active carbon powder and activated carbon fiber respectively by processings of decolouring of three sections series connection active carbon adsorption columns, and the about 2～10m/h of filtering velocity adopts steam heating to regenerate.
(8) evaporation
Adopt triple effect continuous evaporative crystallization device, adopt stainless steel with material contact part material.Whole system continuously feeding in 24 hours, discharging continuously.Discharging is brilliant liquid mixture, and after separating to filter pocket (or whizzer), mother liquor returns water reservoir.The vapor condensation water yield 2～20t/h that produces, 40～80 ℃ of temperature, heat can be back to heating system, take a shower heating, general industry heating, small power generation unit, thermophore etc., and hot water can be used for the back flushing of equipment after the cooling tower cooling.
(9) drying
The calcium formiate crystal enters spin flash dryer at last, and wet stock is sent in the moisture eliminator continuously and quantitatively by screw feeder, and at high temperature product is by rapid evaporate to dryness, and by tornado dust collector and sack cleaner the product powder is collected in the woven bag.Put and carry out moistureproof the processing after the product sealing in storage.
3, quality product
The epoxy soybean oil formic acid wastewater obtains the calcium formiate product after above operation is handled every index specifically sees Table 4, and the industry standard of feed grade calcium formiate product specifically sees Table 5.By table 4 and table 5 as can be known, the calcium formiate product of this engineering preparation can reach the top grade product standard in the feed grade.
The calcium formiate quality product that table 445000t/a epoxy soybean oil formic acid wastewater is handled and reuse project prepares
| Project | Index |
| Outward appearance | White powder |
| Calcium formiate content | 99.2％ |
| Total calcium | 30.6％ |
| PH value (50g/L) | 7.2～7.4 |
| Heavy metal (in Pb) | ≤0.002％ |
| Arsenic (As) | ≤0.0005％ |
| Weight loss on drying | 0.48％ |
| Water-insoluble | 0.05％ |
Table 5 feed grade calcium formiate product industry standard (Q/TOIO 05-2002)
4, economic benefit
Through measuring and calculating, the about 100 yuan/t of project operation expense waste water, the about 250 yuan/t of product income waste water, 150 yuan/t of net income waste water.About 7,000,000 yuan of project direct economic benefit is saved nearly 4,500,000 yuan of cost of sewage disposal simultaneously, can be enterprise and brings nearly 1,150 ten thousand yuan/year of total economic benefit.
Complete process embodiment two: 6000t/a epoxy methyl esters formic acid wastewater is handled and reuse project.
1, wastewater source
Formic acid wastewater is from the production process of epoxy methyl esters, the about 6000t/a of generation.Its waste water quality sees Table 6.
Table 6 epoxy methyl esters formic acid wastewater water quality
| The material title | |
| Formic acid | |
| 3～30％ | |
| Hydrogen peroxide | 0.2～1.5％ |
| Lipid | 300～1000mg/L |
| COD Cr | 10000～100000mg/ |
| pH | |
| 2～4 | |
| Color | Colourless～yellow-green colour |
2, technical process
(1) oil removal
Formic acid wastewater is introduced into oil trap, stops about 1～8h.Employing water distributor water distribution uniformity and electric control gear intermittent aeration, the grease come-up in the waste water more than 98% are to the surface, and oil flows into after the weir plate obstruct is gathered in the oil removal groove and reclaims oil drum, and lower floor's formic acid water is delivered to equalizing tank through automatic bailer.
(2) neutralization reaction
The formic acid wastewater that the preliminary oil removal of warp is handled comes together in the equalizing tank, and thin oil droplet continuation come-up is to the surface after the time to stop 3～24h, and lower floor's formic acid is squeezed in the reactor one by lift pump, generates calcium formate solution, the about 0.8～8h of controlling reaction time with calcium carbonate reaction.Reactor one top vent links to each other with gas recovery system, CO 2 waste gas is reclaimed to purify form product.Regularly reactor one is cleaned according to actual condition.
(3) precipitation
Formic acid wastewater enters the inclined tube-type settling tank after preliminary neutralization, utilize volume pump quantitatively to add the PFS flocculation agent before the water inlet, the about 10～200ppm of dosage.The clearance of suspended solids is more than 95%, and mud drains in the sludge sump, sends into sludge drying bed after stable or the filter of press filtration machine room is done, and filtrate is back to through recovery trench and regulates attached pond.
(4) remove residual formic acid
Formic acid content is higher in this engineering formic acid wastewater, after coming out from settling tank, calcium formate solution enters reactor two, reactor three and reactor four successively, further with calcium carbonate reaction, residual formic acid is removed, the about respectively 0.5～5h of controlling reaction time, 0.1～3h and 0.1～1h, water outlet pH about 5～7.Consume situation according to lime carbonate in the jar, suitably replenish pearl filler, and regularly carry out back flushing, raffinate emptying is to recovery trench in jar.After the neutralization of four steps, pond in the middle of calcium formate solution comes together in, the carbon dioxide behind stop 5～20h in the solution volatilizees substantially.
(5) removing heavy metals impurity
Calcium formate solution is squeezed in the filter tank way by middle pond, connect a line mixer, utilize volume pump in mixing tank, quantitatively to add HL-X precipitation agent and PAM coagulating agent, the about respectively 10～150ppm of dosage and 10～300ppm make that heavy metal and the suspended solids formation flocculation sediment in the waste water brought filter tank into.
(6) filter
Calcium formate solution enters filter tank, will be disposed to water reservoir after the throw out filtering.Two pressure filters are used alternatingly and regularly carry out back flushing.This engineering manufacture level calcium formiate product and solution colourity are lower, therefore need not to handle by decolouring.
(7) evaporation
Adopt mechanically compress evaporative crystallization device, adopt stainless steel with material contact part material.Whole system continuously feeding in 24 hours, discharging continuously.Discharging is brilliant liquid mixture, and after separating to filter pocket (or whizzer), mother liquor returns water reservoir.The vapor condensation water yield 0.5～3t/h that produces, 50～80 ℃ of temperature, heat can be back to heating system, take a shower heating, general industry heating, small power generation unit, thermophore etc., and hot water can be used for the back flushing of equipment after the cooling tower cooling.
(8) drying
The calcium formiate crystal enters fluidized bed dryer at last, and wet stock is sent in the moisture eliminator continuously and quantitatively by rotary conveyor, and at high temperature product is by rapid evaporate to dryness, and by tornado dust collector and sack cleaner the product powder is collected in the woven bag.Put and carry out moistureproof the processing after the product sealing in storage.
3, quality product
The every index of calcium formiate product that epoxy methyl esters formic acid wastewater obtains after above operation is handled specifically sees Table 7, and technical grade calcium formiate product industry standard specifically sees Table 8.By table 7 and table 8 as can be known, the calcium formiate product of this project preparation can reach the technical grade standard.
The calcium formiate quality product that table 76000t/a formic acid wastewater is handled and reuse project prepares
| Project | Index |
| Outward appearance | Micro-yellow powder |
| Calcium formiate content | 99.5％ |
| Total calcium | 30.7％ |
| PH value (50g/L) | 7.1～7.3 |
| Heavy metal (in Pb) | ≤0.002％ |
| Arsenic (As) | ≤0.0005％ |
| Weight loss on drying | 0.35％ |
| Water-insoluble | 0.08％ |
Table 8 technical grade calcium formiate product industry standard (Q/TOIO 05-2002)
| Calcium formiate | Technical grade |
| Project | Index |
| Content [Ca (HCOO) 2]％ | 90％ |
4, economic benefit
Through measuring and calculating, the about 120 yuan/t of project operation expense waste water, the about 280 yuan/t of product income waste water, 160 yuan/t of net income waste water.About 1,000,000 yuan of project direct economic benefit is saved nearly 600,000 yuan of cost of sewage disposal simultaneously, can be enterprise and brings nearly 1,600,000 yuan/year of total economic benefit.
Claims (10)
1, epoxy ester wastewater recycling treatment method, described waste water is that the waste oil of various fatty acid esters and Vegetable oil lipoprotein or recovery produces with oxidant reaction under the catalysis of formic acid, contain the mixing water of compositions such as formic acid, hydrogen peroxide, lipid, a small amount of peroxyformic acid and micro heavy, it is characterized in that following steps:
(1) waste water enters oil trap and carries out oily water separation, is back to production behind the floating oil collecting of upper strata, and subnatant is delivered to and enters reactor one behind the equalizing tank:
(2) in reactor one, formic acid wastewater and calcium carbonate reaction generate calcium formate solution, discharge the gas based on carbonic acid gas, and exhaust is reclaimed food-grade carbon-dioxide by carbon dioxide recovery system, in accordance;
(3) calcium formate solution enters settling tank, suspended solids in the method sedimentation solution of employing coagulating sedimentation is a mud, supernatant liquid enters reactor two, mud comes together in and regularly enters sludge sump in the sludge bucket, enter sludge drying bed again or adopt the press filtration machine filter to do, percolate is by the recycling of waste liquid return-flow system;
(4) calcium formate solution is removed residual formic acid, pond in the middle of entering after filtering again with the further reaction of lime carbonate in reactor two; According to the content of formic acid in the waste water plural reactor is set and carries out the multistep neutralization;
(5) come together in the middle of calcium formate solution in the pond before entering filter tank earlier with coagulating agent and precipitation agent thorough mixing, heavy metal and suspended solid impurities effect formation flocculation sediment is brought the filter tank filtering into current in medicament and the solution;
(6) calcium formate solution after filtering enters evaporation concentration behind the activated carbon column adsorption bleaching, or directly enters the brilliant liquid mixture of vapo(u)rization system evaporation concentration formic acid calcium;
(7) the brilliant liquid mixture of calcium formiate separates the calcium formiate crystal that the back forms wet stock after filtration, utilizes after the mother liquor that leaches is collected again;
(8) the calcium formiate crystal enters dehumidification system again, and the water ratio of control finished product reaches the quality standard of respective level product.
2, epoxy ester wastewater recycling treatment method according to claim 1 is characterized in that the described oil trap of step (1) adopts the automatic water outlet of fluid level controller; Use the aerating apparatus of preparation automatic control system, adopt intermittent aeration on the technology.
3, epoxy ester wastewater recycling treatment method according to claim 1, it is characterized in that step (2), (4) described reactor one and reactor two adopt fluidized-bed, filling tank, flat flow reactor or recirculation reactor, agitator is not established in inside, utilize the flow velocity and the buoyancy of waste water to make pearl filler be in fluidized state, solid-liquid thorough mixing and reaction.
4, epoxy ester wastewater recycling treatment method according to claim 1, it is characterized in that step (2), (4), (5) described reactor and filter tank all are provided with counter-flushing pipeline, when the solid impurity of holding back in the container is too much, by clear water recoil or air water back washing with the Impurity removal in the filler.
5, epoxy ester wastewater recycling treatment method according to claim 1, the perforation of the laying all around rising pipe that it is characterized in that the described sludge drying bed of step (3), the bottom is done and is spread sandstone after antiseepage is handled, or directly adopt pressure filter to carry out press filtration, the recycling after filtering of the calcium formate solution in the mud.
6, epoxy ester wastewater recycling treatment method according to claim 1, the water (flow) direction that it is characterized in that reactor one in the described multistep neutralisation of step (4) is served as reasons down supreme, promptly filter afterreaction earlier, the water (flow) direction of reactor two is promptly reacted after-filtration earlier for from top to bottom.
7, epoxy ester wastewater recycling treatment method according to claim 1 is characterized in that the described activated carbon decolorizing of step (6) adopts multistage active carbon adsorption column decolouring, inner loaded particles gac, active carbon powder, activated carbon fiber or carbon molecular sieve.
8, epoxy ester wastewater recycling treatment method according to claim 1, it is characterized in that the described vapo(u)rization system of step (6) adopts multiple-effect continuous evaporative crystallization device, mechanically compress vaporizer, rotatory evaporator, thin-film evaporator, centrifugal evaporator and scraper-type vaporizer one, the mode of process using continuously feeding discharging; The brilliant liquid mixture of evaporation discharging carries out centrifugation after filtering through filter pocket earlier again.
9, epoxy ester wastewater recycling treatment method according to claim 1, it is characterized in that the described dehumidification system of step (8) adopts tunnel belt circulation dryer, pneumatic dryer, fluidized bed dryer, spin flash dryer, cylinder one pneumatic dryer and cylinder one rake type dryer one: wet stock adds in the drying machine continuously and quantitatively, dry qualified material is discharged after fly-ash separator captures from discharge port and is obtained dry finished product, the too big or higher material of humidity of particle is stopped, and continues to obtain further dry until being taken out of in drying machine.
10, epoxy ester wastewater recycling treatment method according to claim 1, the vapor condensation water temperature that it is characterized in that the described vapo(u)rization system generation of step (6) is at 60～80 ℃, its heat is back to heating system, take a shower heating, general industry heating, small power generation unit, thermophore, hot water is used for the back flushing of reactor and filter tank equipment after the cooling tower cooling, raffinate before the back flushing in reactor and the filter tank and the emptying of mud filtrate are to recovery trench, by utilizing after the recovery of waste liquid return-flow system again.
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| CA2796789C (en) * | 2010-05-24 | 2019-10-15 | Xyleco, Inc. | Processing biomass |
| CN102517132A (en) * | 2011-12-09 | 2012-06-27 | 中国科学院新疆理化技术研究所 | Method for synthesizing lubricating oil additive from low-molecular weight polyisobutene |
| CN103360231A (en) * | 2012-03-28 | 2013-10-23 | 江苏卡特新能源有限公司 | Method for extracting formic acid from sewage from production of epoxy biological plasticizer |
| CN103663843B (en) * | 2012-09-06 | 2015-05-13 | 中国石油化工股份有限公司 | Treatment method of p-aminodiphenylamine production device wastewater |
| CN103772184B (en) * | 2012-10-25 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method utilized containing formic acid wastewater |
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| CN107922192A (en) * | 2015-05-29 | 2018-04-17 | ambuja中间体私人有限公司 | New-type environmentally friendly " zero solid discharge " processing for dye and dye intermediate industry |
| CN105417825A (en) * | 2015-12-28 | 2016-03-23 | 河北科瑞达仪器科技股份有限公司 | Waste liquid flash evaporation treatment method |
| CN107973472A (en) * | 2017-12-12 | 2018-05-01 | 江西艾迪尔新能源有限公司 | A kind of environment-friendly treatment method of epoxy soybean oil waste water |
| CN109133418A (en) * | 2018-09-13 | 2019-01-04 | 宛兴友 | A kind of printing and dyeing wastewater processing equipment that cooling efficiency is high |
| CN109534528B (en) * | 2018-11-20 | 2021-11-12 | 新昌县泰如科技有限公司 | Method for treating ciprofibrate process wastewater |
| CN112408705B (en) * | 2020-11-12 | 2022-04-29 | 江西挺进环保科技股份有限公司 | Domestic sewage treatment system with tidal flow percolation system and treatment process |
-
2007
- 2007-11-13 CN CN200710157008A patent/CN100582080C/en active Active
Non-Patent Citations (4)
| Title |
|---|
| 环氧脂肪酸酯类增塑剂生产废水综合利用的探讨. 张建伟.中国油脂，第19卷第2期. 1994 |
| 环氧脂肪酸酯类增塑剂生产废水综合利用的探讨. 张建伟.中国油脂，第19卷第2期. 1994 * |
| 采用化学和生物接触氧化法处理环氧大豆油的废水. 陈度德.广州化工，第28卷第2期. 2000 |
| 采用化学和生物接触氧化法处理环氧大豆油的废水. 陈度德.广州化工，第28卷第2期. 2000 * |
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