CN100582080C - Epoxy ester wastewater reuse treatment method - Google Patents

Epoxy ester wastewater reuse treatment method Download PDF

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CN100582080C
CN100582080C CN200710157008A CN200710157008A CN100582080C CN 100582080 C CN100582080 C CN 100582080C CN 200710157008 A CN200710157008 A CN 200710157008A CN 200710157008 A CN200710157008 A CN 200710157008A CN 100582080 C CN100582080 C CN 100582080C
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waste water
reactor
filter
formic acid
epoxy ester
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CN101200423A (en
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赵伟荣
章金富
沈健
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ZHEJIANG JIAAO ENVIRONMENT PROTECTION TECHNOLOGY Co Ltd
Zhejiang University ZJU
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ZHEJIANG JIAAO ENVIRONMENT PROTECTION TECHNOLOGY Co Ltd
Zhejiang University ZJU
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Abstract

环氧酯废水回用处理方法，涉及从工业废水中回收资源生产化工产品的技术方法。本发明提出的工艺方案为：将环氧酯生产过程中的甲酸废水经隔油处理后，与碳酸钙反应得到甲酸钙溶液，经沉淀并进一步与碳酸钙多次中和后，通过向溶液投加混凝剂和沉淀剂，将重金属和固体杂质进一步去除，再经过滤、脱色、蒸发、干燥，最后得到甲酸钙粉末。本工艺可以适应饲料级和工业级等不同级别甲酸钙产品的生产，同时该工艺投资较少、收益高，并且副产的废气废水均可以回收再利用，既达到了减排废水的目的，又提高了经济效益。

Figure 200710157008

The epoxy ester wastewater reuse treatment method relates to a technical method for recycling resources from industrial wastewater to produce chemical products. The process scheme proposed by the present invention is: after the formic acid wastewater in the epoxy ester production process is subjected to oil separation treatment, it is reacted with calcium carbonate to obtain a calcium formate solution, and after being precipitated and further neutralized with calcium carbonate for many times, it is added to the solution by adding Add coagulants and precipitants to further remove heavy metals and solid impurities, and then filter, decolorize, evaporate, and dry to finally obtain calcium formate powder. This process can be adapted to the production of calcium formate products of different grades such as feed grade and industrial grade. At the same time, the process has less investment and high income, and the by-product waste gas and waste water can be recycled and reused, which not only achieves the purpose of reducing waste water, but also Improved economic efficiency.

Figure 200710157008

Description

Epoxy ester wastewater recycling treatment method
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
Formic acid 2～20％
Hydrogen peroxide 0.2～2.0％
Lipid 100～5000mg/L
COD Cr 10000～300000mg/L
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 Concentration
Formic acid
3～15％
Hydrogen peroxide 0.5～1.0％
Lipid 200～1000mg/L
COD Cr 10000～50000mg/L
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 Concentration
Formic acid
3～30％
Hydrogen peroxide 0.2～1.5％
Lipid 300～1000mg/L
COD Cr 10000～100000mg/L
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、环氧酯废水回用处理方法，所述废水为各种脂肪酸酯和植物油脂或回收的废油在甲酸的催化下与氧化剂反应产生的，含有甲酸、过氧化氢、油脂类、少量过氧甲酸及微量重金属等成分的混合水，其特征在于以下步骤：1. Epoxy ester wastewater reuse treatment method, the wastewater is produced by the reaction of various fatty acid esters and vegetable oils or recovered waste oil with oxidants under the catalysis of formic acid, containing formic acid, hydrogen peroxide, oils, a small amount of The mixed water of components such as peroxyformic acid and trace heavy metals is characterized in that the following steps: (1)废水进入隔油池进行油水分离，上层浮油收集后回用于生产，下层清液输送至调节池后进入反应器一：(1) Wastewater enters the grease trap for oil-water separation, the upper layer of floating oil is collected and reused for production, and the lower layer of clear liquid is transported to the regulating tank and then enters Reactor 1: (2)在反应器一中，甲酸废水与碳酸钙反应生成甲酸钙溶液，排出以二氧化碳为主的气体，排气由二氧化碳回收系统回收食品级二氧化碳；(2) In reactor one, formic acid waste water reacts with calcium carbonate to generate calcium formate solution, and discharges gas mainly based on carbon dioxide, and the exhaust gas is recovered food-grade carbon dioxide by the carbon dioxide recovery system; (3)甲酸钙溶液进入沉淀池，采用混凝沉淀的方法沉降溶液中的悬浮固体为污泥，上层清液进入反应器二，污泥汇集于污泥斗中定期排入污泥池，再进入污泥干化场或采用压滤机滤干，渗滤液通过废液回流系统回收再利用；(3) The calcium formate solution enters the sedimentation tank, and the suspended solids in the sedimentation solution are sludge by means of coagulation and sedimentation. Enter the sludge drying field or use a filter press to filter and dry, and the leachate is recycled and reused through the waste liquid return system; (4)甲酸钙溶液在反应器二中与碳酸钙进一步反应除去残留的甲酸，再经过滤后进入中间池；依据废水中甲酸的含量设置两个以上的反应器进行多步中和；(4) Calcium formate solution further reacts with calcium carbonate in reactor two to remove residual formic acid, then enters the intermediate pool after filtration; according to the content of formic acid in the waste water, more than two reactors are set to carry out multi-step neutralization; (5)汇集于中间池中的甲酸钙溶液在进入滤罐前先与混凝剂和沉淀剂充分混合，药剂与溶液中重金属和悬浮固体杂质作用形成絮凝沉淀，随水流带入滤罐滤除；(5) The calcium formate solution collected in the intermediate tank is fully mixed with coagulant and precipitant before entering the filter tank, and the agent reacts with heavy metals and suspended solid impurities in the solution to form flocculation precipitation, which is brought into the filter tank with water flow to filter out ; (6)经过滤后的甲酸钙溶液进入活性炭柱吸附脱色后蒸发浓缩，或直接进入蒸发系统蒸发浓缩成甲酸钙晶液混合物；(6) The filtered calcium formate solution enters the activated carbon column for adsorption and decolorization and then evaporates and concentrates, or directly enters the evaporation system for evaporation and concentrates into a calcium formate crystal liquid mixture; (7)甲酸钙晶液混合物经过滤分离后形成湿物料的甲酸钙晶体，滤出的母液收集后再利用；(7) the calcium formate crystal liquid mixture forms the calcium formate crystal of wet material after filtering and separating, and the mother liquor of filtering out is collected and reused; (8)甲酸钙晶体再进入干燥系统，控制终产品的含水率达到相应等级产品的质量标准。(8) The calcium formate crystal enters the drying system again, and the moisture content of the final product is controlled to reach the quality standard of the corresponding grade of product. 2、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(1)所述隔油池采用液位控制器自动出水；使用配制自动控制系统的曝气装置，工艺上采用间歇曝气。2. The epoxy ester waste water reuse treatment method as claimed in claim 1 is characterized in that the grease trap of step (1) adopts a liquid level controller to automatically discharge water; the aeration device of the automatic control system is used, and the technology adopts Intermittent aeration. 3、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(2)、(4)所述反应器一和反应器二采用流化床、填料罐、平流式反应器或循环反应器，内部不设搅拌器，利用废水的流速和浮力使碳酸钙填料处于流化状态，固液充分混合并反应。3. The epoxy ester waste water reuse treatment method as claimed in claim 1 is characterized in that step (2), (4) said reactor one and reactor two adopt fluidized bed, stuffed tank, flat flow reactor or The circulation reactor does not have a stirrer inside, and the flow rate and buoyancy of the waste water are used to make the calcium carbonate filler in a fluidized state, and the solid and liquid are fully mixed and reacted. 4、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(2)、(4)、(5)所述反应器和滤罐均设置反冲洗管路，当容器内截留的固体杂质过多时，通过清水反冲或气水反冲将填料中的杂质去除。4. The epoxy ester waste water reuse treatment method as claimed in claim 1 is characterized in that the reactor and filter tank described in steps (2), (4), and (5) are all provided with backwash pipelines, and when intercepted in the container When there are too many solid impurities in the filler, the impurities in the filler are removed by recoil with water or recoil with air and water. 5、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(3)所述污泥干化场的四周铺设穿孔出水管，底部做防渗处理后铺上砂石，或直接采用压滤机进行压滤，污泥中的甲酸钙溶液经过滤后回收再利用。5. The epoxy ester waste water reuse treatment method as claimed in claim 1, characterized in that perforated outlet pipes are laid around the sludge drying field in step (3), and the bottom is covered with gravel after anti-seepage treatment, or The filter press is directly used for pressure filtration, and the calcium formate solution in the sludge is filtered and recycled for reuse. 6、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(4)所述的多步中和法中反应器一的水流方向为由下至上，即先过滤后反应，反应器二的水流方向为由上至下，即先反应后过滤。6. The epoxy ester waste water reuse treatment method as claimed in claim 1 is characterized in that the flow direction of reactor one in the multi-step neutralization method described in step (4) is from bottom to top, that is, filter first and then react, The direction of water flow in the second reactor is from top to bottom, that is, to react first and then to filter. 7、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(6)所述活性炭脱色采用多级活性炭吸附柱脱色，内部装填颗粒活性炭、活性炭粉末、活性炭纤维或炭分子筛。7. The epoxy ester waste water reuse treatment method according to claim 1, characterized in that the activated carbon decolorization in step (6) adopts a multi-stage activated carbon adsorption column for decolorization, and the interior is filled with granular activated carbon, activated carbon powder, activated carbon fiber or carbon molecular sieve. 8、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(6)所述蒸发系统采用多效连续蒸发结晶器、机械压缩蒸发器、旋转蒸发器、薄膜蒸发器、离心式蒸发器和刮板式蒸发器其一，工艺采用连续进料出料的方式；蒸发出料的晶液混合物先经过滤槽过滤后再进行离心分离。8. The epoxy ester waste water reuse treatment method as claimed in claim 1 is characterized in that the evaporation system of step (6) adopts a multi-effect continuous evaporation crystallizer, a mechanical compression evaporator, a rotary evaporator, a thin film evaporator, a centrifugal One of type evaporator and scraper type evaporator, the process adopts the method of continuous feeding and discharging; the crystal liquid mixture that evaporates and discharges is first filtered through the filter tank and then centrifugally separated. 9、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(8)所述干燥系统采用隧道带式通风干燥器、气流干燥器、流化床干燥器、旋转闪蒸干燥器、滚筒一气流干燥器和滚筒一耙式干燥器其一：湿物料连续定量地加入干燥机中，干燥合格的物料从出料口排出经除尘器捕集后得到干燥成品，颗粒太大或湿度较高的物料被阻拦，在干燥机内继续得到进一步干燥直至被带出。9. The epoxy ester waste water reuse treatment method as claimed in claim 1 is characterized in that the drying system of step (8) adopts tunnel belt type ventilated dryer, airflow dryer, fluidized bed dryer, spin flash drying Dryer, drum-air dryer and drum-rake dryer: Wet materials are continuously and quantitatively added to the dryer, and the dried materials are discharged from the outlet and collected by the dust collector to obtain dried products. The particles are too large or Materials with higher humidity are blocked and continue to be further dried in the dryer until they are taken out. 10、如权利要求1所述环氧酯废水回用处理方法，其特征在于步骤(6)所述蒸发系统产生的蒸汽冷凝水温在60～80℃，其热量回用于供暖系统、沐浴加热、普通工业加热、小型发电机组、蓄热器，热水经冷却塔冷却后用于反应器和滤罐设备的反冲洗，反冲洗前反应器和滤罐中的残液以及污泥滤液放空至回收沟内，通过废液回流系统回收后再利用。10. The epoxy ester waste water reuse treatment method according to claim 1, characterized in that the steam condensed water temperature generated by the evaporation system in step (6) is 60-80°C, and its heat is reused for heating systems, bath heating, General industrial heating, small generator sets, heat accumulators, hot water is used for backwashing of reactors and filter tank equipment after being cooled by cooling towers, and the residual liquid in reactors and filter tanks before backwashing and sludge filtrate are emptied to recovery In the ditch, it is recycled through the waste liquid return system for reuse.
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