CN103787539B

CN103787539B - A kind of method of membrane separation nitro-chlorobenzene hot wastewater

Info

Publication number: CN103787539B
Application number: CN201210434216.XA
Authority: CN
Inventors: 李正琪; 杨永强; 张新妙; 彭海珠; 侯秀华
Original assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Current assignee: Sinopec Beijing Research Institute of Chemical Industry; China Petroleum and Chemical Corp
Priority date: 2012-11-02
Filing date: 2012-11-02
Publication date: 2015-10-07
Anticipated expiration: 2032-11-02
Also published as: CN103787539A

Abstract

The present invention relates to a kind of method of membrane separation nitro-chlorobenzene hot wastewater, more specifically relate to and a kind ofly utilize high temperature ultrafiltration, high temperature reverse osmosis and vacuum membrane distillation technical finesse and the method for reuse nitro-chlorobenzene waste water, the outer draining of nitro-chlorobenzene waste water after oxidation-gravity settling that the method comprises the steps: (1) is through high temperature ultra-filtration membrane direct filtration; (2) by the product water positive delivery of ultrafiltration membrance filter in step (1) to first-stage reverse osmosis membrane filtration; (3) the product water of first-stage reverse osmosis in step (2) is entered two-pass reverse osmosis membrane filtration through positive delivery; (4) by the dense water heating of first-stage reverse osmosis in step (2); (5) the product water in step (4) is sent into membrane distillation unit and carry out membrane distillation, the product water of two-pass reverse osmosis and membrane distillation unit is technique reuse water.Adopt described method effectively can solve the deficiency of nitro-chlorobenzene Sewage advanced treatment and reuse method in prior art, reduce wastewater discharge, improve Waste Heat Reuse efficiency.

Description

A kind of method of membrane separation nitro-chlorobenzene hot wastewater

Technical field

The present invention relates to a kind of nitro-chlorobenzene hot wastewater advanced treatment and reuse method, to give up the method for hot wastewater in particular to a kind of membrane separation technique process and reuse nitro-chlorobenzene of utilizing, more particularly, relate to and a kind ofly utilize high temperature ultrafiltration, high temperature reverse osmosis and vacuum membrane distillation technical finesse and the method for reuse nitro-chlorobenzene waste water.

Background technology

Nitro-chlorobenzene is the intermediate of preparation medicine, azoic dyestuff and thioxine dyes, is also manufacture agricultural chemicals, the raw material of rubber.The production of nitro-chlorobenzene take chlorobenzene as raw material, and adopt nitration mixture to be that nitrating agent carries out nitrated, the nitrated crude product obtained needs through alkali cleaning and washing, then carries out separating-purifying with rectifying tower, obtains p-Nitrophenyl chloride and o-Nitrochlorobenzene.Adopt above-mentioned production technique, produce nitro-chlorobenzene product per ton and will produce 1.2-1.8t waste water, this waste water is mainly containing the pollutent such as nitro-chlorobenzene, nitrophenols, above-mentioned substance is all harmful, there is mutagenesis, teratogenesis and carinogenicity, be strictly controlled in wastewater discharge standard, in GB8978-1996, the highest permission discharge quality concentration of nitro-chlorobenzene and aldehydes matter is 5mg/L (three grades of emission standards), and current nitro-chlorobenzene manufacturing enterprise can reach the less of this emission standard.

It is high that nitro-chlorobenzene production technique waste water has colourity, salinity is high, the features such as difficult for biological degradation, this production technique waste water reclaims a large amount of organism through stripping, tower reactor leaving water temperature(LWT) is between 80 ~ 95 DEG C, after the processing method of employing Chinese patent ZL102040302 carries out the main organism such as the most of nitro-chlorobenzene in oxidation removal waste water, leaving water temperature(LWT) is 75 ~ 85 DEG C, small organic molecule and inorganic salt are removed further for above-mentioned high-temperature technology waste water, not only nitro-chlorobenzene processing wastewater can be obtained advanced treatment and reclamation, but also recyclable a large amount of low temperature latent heat realizes the object of saving water and energy.

Chinese patent CN102372356A discloses a kind of by 1，2，3-trichlorobenzene synthesis 4, the treatment process of washing water in 6-dinitrobenzene-1，2，3-trichlorobenzene process, 60 ~ 90 DEG C are warming up in highly acid wash water by reactor, then add oxygenant ferrous sulfate and hydrogen peroxide continuously, maintain this temperature of reaction 10 ~ 50min, sampling and measuring COD, the oxidizing reaction of the nitro-chlorobenzene described in this invention is gentle, thorough to organic oxidation in washing, technique is simple, and labour intensity is low.

Chinese patent CN102417265A discloses and a kind of effectively removes organic method in chloronitrobenzene producing wastewater, and this inventive method mainly comprises the following steps: 1. waste water enter after heating up with the water outlet of stripping tower tower reactor and stripper overhead steam indirect heat exchange successively stripping tower carry out indirect heat exchange cool afterwards direct reuse in production technique; 2. utilizing chloronitrobenzene producing wastewater to carry out the stripping tower tower reactor water outlet pH regulator of indirect heat exchange cooling to acid; 3. couple pH carries out catalytic oxidation treatment in acid waste water, and oxygenant is hydrogen peroxide, and catalyzer is copper sulfate.This invention effectively can reduce the colourity of waste water, TOC and nitro-chlorobenzene content.

Chinese patent ZL102040302 discloses a kind for the treatment of process of chloronitrobenzene producing wastewater, this invention mainly comprises the treatment process of a kind of chloronitrobenzene producing wastewater of following steps, relate to the treatment process of organic chemical waste water, comprise following steps: 1. waste water enters stripping tower after heating up with the water outlet of stripping tower tower reactor and stripper overhead steam indirect heat exchange successively and carries out stripping process, the stripper overhead steam being rich in nitro-chlorobenzene after indirect heat exchange cooling direct reuse in production technique; 2. utilizing chloronitrobenzene producing wastewater to carry out the pH regulator of the stripping tower tower reactor water outlet of indirect heat exchange cooling to acid; 3. couple pH carries out catalytic oxidation treatment in acid waste water, and oxygenant is hydrogen peroxide, and catalyzer is ferrous sulfate; 4. by the pH regulator of catalytic oxidation treatment water outlet to close to neutral, and carry out precipitating, decomposition reaction; 5. pulp water separation is carried out in reaction water outlet, isolated slag for comprehensive utilizes, and water then can qualified discharge.

Chinese patent CN102417263A mono-kind administers the method for chloronitrobenzene producing wastewater, comprise the following steps successively: the first step, chloronitrobenzene producing wastewater enters stripping tower after heating up with slag-water separator water outlet, the water outlet of stripping tower tower reactor and stripper overhead steam indirect heat exchange successively and carries out stripping process; Second step, pH regulator to 2.0 ~ 4.5 utilizing chloronitrobenzene producing wastewater to carry out the stripping tower tower reactor water outlet of indirect heat exchange cooling; 3rd step, carries out catalytic oxidation treatment to having regulated the stripping tower tower reactor water outlet of pH; 4th step, by the pH regulator to 6.5 of catalytic oxidation treatment water outlet ~ 9, to carry out the decomposition reaction of residual H2O2 in soluble iron, the precipitin reaction of copper and water; 5th step, four-step reaction effluent is carried out pulp water separation, the pulp water separating measure that can take comprises gravity settling, centrifugal settling and filtration, isolated slag can adopt ordinary method to carry out disposing or carry out to fully utilize or recycle, and isolated water is at qualified discharge after lowering the temperature with chloronitrobenzene producing wastewater indirect heat exchange.

Chinese patent CN102417264A mono-kind processes the method for chloronitrobenzene producing wastewater, comprise following steps: 1. waste water enters stripping tower after heating up with the water outlet of precipitate and separate device, the water outlet of stripping tower tower reactor and stripper overhead steam indirect heat exchange successively and carries out stripping process, the stripper overhead steam being rich in nitro-chlorobenzene after indirect heat exchange cooling direct reuse in production technique; 2. the pH regulator utilizing chloronitrobenzene producing wastewater to carry out the stripping tower tower reactor water outlet of indirect heat exchange cooling to acid and carry out catalytic oxidation treatment; 3. by the pH regulator of catalytic oxidation treatment water outlet to close to neutral, to carry out the decomposition reaction of residual H2O2 in the precipitin reaction of soluble iron and water; 4. reaction effluent is carried out gravity settling separation, isolated iron precipitate all recycles, and isolated water is at qualified discharge after lowering the temperature with chloronitrobenzene producing wastewater indirect heat exchange.Method of the present invention, effectively can reduce the colourity of waste water, COD and nitro-chlorobenzene content, realize discharged wastewater met the national standard.

Above-mentioned patent all adopts the method for oxidation to carry out the organic oxide treatment of middle and high concentration of nitro-chlorobenzene waste water from different perspectives, water outlet COD, colourity all can reach the standard of qualified discharge, but above-mentioned patent does not define the waste water advanced reuse after up to standard.

Chinese patent CN 101993165A discloses the technical process that a kind of nitro-chlorobenzene height salt organic waste water adopts " acid adjustment+membrane distillation+reverse osmosis+crystallisation by cooling ", although this patent p-Nitrophenyl chloride high-salt wastewater adopts membrane technique direct reuse method to limit, but for first adopting oxidation effectively not cleared up by the high-enriched organics in nitro-chlorobenzene waste water, the nitro-chlorobenzene containing higher concentration in the crystallisate adopting this patented technology to obtain and the organic solid pollutant of nitropheneol.

What existing Patents related in sum is that nitro-chlorobenzene waste water adopts oxidation and then realizes the method for qualified discharge, does not relate to and adopts membrane technique to carry out advanced treatment and reclamation for above-mentioned qualified discharge waste water.Although Chinese patent CN 101993165A relate to the advanced treatment and reclamation method that a kind of nitro-chlorobenzene height salt organic waste water adopts " acid adjustment+membrane distillation+reverse osmosis+crystallisation by cooling " technique, but the nitro-chlorobenzene that this patent relates to is not oxidised waste water, containing a large amount of high-enriched organics in nitro-chlorobenzene waste water, effectively do not cleared up and decrement.

Summary of the invention

The technical problem to be solved in the present invention:

For above-mentioned the deficiencies in the prior art, the present invention is intended to adopt the full scale plant of oxidation strengthening technique to arrange hot wastewater outward for nitro-chlorobenzene waste water and adopts membrane technique to carry out advanced treatment and reuse, with recycle-water resource to greatest extent, reduce wastewater discharge, improve Waste Heat Reuse efficiency.The water quality of nitro-chlorobenzene after oxidation related in above-mentioned patent and the present invention has diverse water quality characteristics, and thus, the present invention is when based on the art inventions carried out when water quality characteristics.

Application method technical scheme of the present invention is:

The outer draining water quality principal character of nitro-chlorobenzene waste water after oxidation-gravity settling is: temperature 55 ~ 65 DEG C, pH7.0 ~ 9.5, COD _cr80 ~ 120mg/L, colourity 150 ~ 200 times, total iron content 30 ~ 55mg/L, conductance between 15000 ~ 30000 μ s/cm, Cl ^-content is 100 ~ 200mg/L.

A method for membrane separation nitro-chlorobenzene hot wastewater, described method comprises following step:

(1) the outer draining of nitro-chlorobenzene waste water after oxidation-gravity settling is through high temperature ultra-filtration membrane direct filtration, main purpose removes the ferric hydroxide colloid in oxidation water outlet, described ultra-filtration membrane aperture is 0.01 ~ 0.2 μm, preferably 0.01 ~ 0.1 μm, more preferably 0.01 ~ 0.03 μm;

(2) by the product water positive delivery of ultrafiltration membrance filter in step (1) to first-stage reverse osmosis membrane filtration, remove the dissolved organic matter in water and part mineral ion further;

(3) the product water of first-stage reverse osmosis in step (2) is entered two-pass reverse osmosis membrane filtration through positive delivery, remove remaining mineral ion and small organic molecule, the product water of two-stage reverse osmosis system is technique reuse water;

(4) by the dense water heating of first-stage reverse osmosis in step (2), and send into membrane distillation unit and carry out membrane distillation, the product water of two-pass reverse osmosis and membrane distillation unit is technique reuse water.

The technical characteristics of high temperature ultra-filtration membrane unit of the present invention is:

1, the high temperature ultrafiltration membrance filter system in the first step of the present invention comprises immersion membrane filtration system, and adopt one or more in hollow fiber film assembly, tubular membrane component or curtain type film assembly, optimum is polysulfone hollow fiber ultrafiltration membrane system or curtain type film assembly.

2, the organic film material of membrane module described in step (1) adopts one or more in polysulfones, polyolefins, tetrafluoroethylene, polyvinylidene difluoride (PVDF) class; Wherein polysulfones comprises: bisphenol-a polysulfone, polyethersulfone, phenolic polyether sulphone, phenolphthalein type polyetherketone, the poly (aryl ether sulfone ketone) containing phthalazine biphenyl structure, the poly (arylene ether nitrile) ketone containing phthalazine biphenyl structure.One or more in preferred polyvinylidene difluoride (PVDF), tetrafluoroethylene, poly (aryl ether sulfone ketone) or polypropylene; 0.01 ~ 0.2 μm, organic ultra-filtration membrane aperture, preferably 0.01 ~ 0.1 μm, more preferably 0.01 ~ 0.03 μm;

3, the mineral membrane of membrane module described in step (1) adopts Al ₂o ₃ceramic membrane, TiO ₂ceramic membrane, ZrO ₂one or more in ceramic membrane or stainless steel metal film, optimum is TiO ₂ceramic membrane; Membrane pore size size is 0.01 ~ 0.03 μm, and optimum is 0.015 ~ 0.025 μm;

4, the operation scheme of hyperfiltration membrane assembly comprises cross flow filter or dead-end filtration technique, and wherein dead-end filtration technique can realize go-and-retum every water inlet, and optimum is cross-flow technique;

5, can realize disperseing to wash, strengthen washing and soak the periodical operation washed in the automatic operational process of hyperfiltration membrane assembly, wherein dispersion is washed and can be realized two ends alternately water inlet, be respectively 15 ~ 30 minutes filtration cycle, optimum is 20 ~ 25 minutes, backwashing time is 60 ~ 120 seconds, and the operating flux in ultrafiltration operational process is 90 ~ 200L/m ²h, optimum is 126 ~ 150L/m ²h;

6, the reinforcement of ultrafiltration membrance filter system membranes described in step (1) wash and the pickling of soaking in washed journey can be selected in following acid one or more, described acid comprises HCl, oxalic acid, citric acid, nitric acid, sulfuric acid and cleans with the acid of the composite clean-out system of EDTA; Organism cleaning can select one or more in following organism, described organism comprises methyl alcohol, ethanol or ethylene glycol only son hydrochlorate, ultra-filtration membrane cleaning way described in this invention can select one or more of following manner, described cleaning way comprise wash online, off-line washes or steam-water mixing is washed, optimum to wash for steam-water mixing.

The principal character of reverse osmosis membrane unit of the present invention is:

The membrane module of reverse osmosis filtration system mainly adopts high temperature resistant aromatic polyamides reverse osmosis organic membrane, and commercialization membrane module type comprises Duratherm-HWSHR, Duratherm-STD, Duratherm-PRO, Duratherm-EXCEL, Duratherm-ELITE.Reverse osmosis process of the present invention has dense water end (W.E.) counterflush function, can realize dense water end (W.E.) not timing flushing operation; First-stage reverse osmosis operating flux in this processing wastewater treating processes is 10 ~ 20L/m ²h, optimum is 10 ~ 15L/m ²h; The system recoveries rate of reverse osmosis membrane apparatus controls 50 ~ 62%, and optimum is 55%; Hydromechanics flushing cycle is 16 ~ 24h, and optimum is 18 ~ 24h; The matting cycle is 60 ~ 120 days, and optimum is 80 ~ 90 days; The pH of reverse osmosis operational process controls to be 6.0 ~ 7.5, and optimum is 6.5 ~ 7.0.

The principal character of membrane distillation unit of the present invention is:

By dense for first-stage reverse osmosis water through being pumped into high-temperature membrane distillation unit, adopt the mode of heating that reverse osmosis concentrated water temp is increased to 65 ~ 80 DEG C, vacuumize in the per-meate side of membrane distillation hydrophobic membrane assembly, under vacuum action, gas in waste water, water vapor etc. form product water through fenestra in per-meate side condensation, a small amount of dense water centrally disposes, and so just achieves the isolation and identification of Pollutants in Wastewater.

Vacuum membrane distillation unit adopts polyvinylidene difluoride (PVDF) or polytetrafluoroethylhollow hollow fiber hydrophobic membrane assembly, and membrane pore size scope is 0.1 ~ 0.5 μm, and optimum is 0.15 ~ 0.2 μm; The mode of the tube side or shell side (namely pressure or external pressure) that adopt dense water to enter tubular fibre respectively carries out membrane distillation process.Crucial operational condition is: wastewater pH 7 ~ 9, and preferred pH is 7.5 ~ 8.5; Wastewater temperature 65 DEG C ~ 80 DEG C, is preferably 68 ~ 75 DEG C; Crossflow velocity 0.6 ~ 1.0m/s, is preferably 0.7 ~ 0.9m/s; Cold side vacuum tightness-0.01 ~-0.1MPa, is preferably-0.085 ~-0.095MPa; The controlling diaphragm distillation unit rate of recovery is 75 ~ 90%, and the flux of membrane distillation under this condition is 8 ~ 30L/m ²h, ratio of desalinization is higher than 99%.

The invention has the beneficial effects as follows:

1, membranous system runs under the high temperature conditions, ultrafiltration and reverse osmosis membrane operating pressure is lower, Membrane Filtration Flux is higher, can realize the miniaturization of hot wastewater process and retrieving arrangement and lower process cost, and the advanced treatment of high temperature reverse osmosis can realize effective clearance of mineral ion and dissolved organic matter;

2, whole high temperature film treatment technological process is run under the high temperature conditions, and adopt high temperature resistance diaphragm separation assembly, ensure that the continuous and steady operation of whole membranous system, and because film separating system is to the strong adaptability of change of water quality, so do not need to be equipped with a large amount of online water quality monitoring instrument;

3, the high temperature reverse osmosis in technique of the present invention has good removal effect to the mineral ion in processing wastewater and the small organic molecule such as nitro-chlorobenzene, nitrophenols, effluent quality is good, and (main water quality comprises: product water temp 55 ~ 65 DEG C, pH6.84, specific conductivity (25 DEG C) are less than 150 μm of cm can be widely used in the mesolow such as chemical industry, thermoelectricity Industrial Boiler moisturizing water quality requirement ^-1, COD _mn≤ 3mg/L, Fe≤0.03mg/L, Cu≤0.005mg/L, SiO ₂≤ 0.0005mg/L etc.);

4, the membrane distillation in technique of the present invention has higher removal effect to the high-enriched organics in reverse osmosis concentrated water and mineral ion, and the product water power of this cell process leads≤40 μ S/cm, and produce water TOC≤25mg/L, Water Sproading rate is higher than 80%.

5, high-temperature operation pollution that the ultrafiltration in normal-temperature operation process, reverse osmosis units can be avoided to cause because of microbial growth and the flux that causes declines and the shortening etc. of cleaning interval.Whole membranous system runs under the high temperature conditions and effectively can control the pollution to ultra-filtration membrane and reverse osmosis membrane of microorganism under normal temperature condition, effectively can reduce adding of sterilant and reductive agent, reduce manipulation strength and running cost.

6, the COMBINED PROCESS of membrane distillation and ultrafiltration, reverse osmosis is adopted, the discharge of reverse osmosis concentrated water can be reduced to a greater extent, efficiently solve a discharge difficult problem for high organism, the dense water of supersalinity, the height that effectively can realize nitro-chlorobenzene height salt organic waste water is recycled, reclaim water resources to greatest extent, substantially achieved " zero release " of nitro-chlorobenzene height salt organic waste water.

Accompanying drawing explanation

Fig. 1 is the process flow diagram of the embodiment of the present invention.

Fig. 2 is present invention process equipment flowsheet schematic diagram.

In Fig. 2: 1, nitro-chlorobenzene oxidation hot wastewater; 2, ultrafiltration service pump; 3 ~ 6, high temperature hyperfiltration membrane assembly; 7, water is produced in ultrafiltration; 8, hyperfiltration reverse-rinsing water; 9, the dense water of ultrafiltration (backwash water); 10, first-stage reverse osmosis high-pressure pump; 11 ~ 13, high temperature reverse osmosis membrane assembly; 14, pipe circle pump; 15, first-stage reverse osmosis produces water; 16, first-stage reverse osmosis rinse water; 17, the dense row of first-stage reverse osmosis; 18, two-pass reverse osmosis high-pressure pump; 19 ~ 20, two-pass reverse osmosis high temperature components; 21, two-pass reverse osmosis produces water transferpump; 22, the dense water of two-pass reverse osmosis; 23, the dense water tank of two-pass reverse osmosis; 24, ultrafiltration and first-stage reverse osmosis scavenging pump; 25, well heater; 26, membrane component; 27, the dense water of membrane distillation; 28, condenser; 29, membrane distillation produces water tank; 30, vacuum pump

Wherein, v1 ~ v7 is water intaking valve; V8 ~ v14 is dense water valve; V15 ~ v18 is for producing water valve; V19 ~ v25 is cleaning water intaking valve; V26 ~ v32 is cleaning outlet valve; V33 is concentrated water discharge valve

Embodiment

Embodiment 1

The water outlet of nitro-chlorobenzene waste water after oxidation-gravity settling treatment process under the high temperature conditions as shown in Figure 1, outer for technique after 55 DEG C of oxidation-sedimentations draining is sent into the ultrafiltration membrane system of cross flow filter through ultrafiltration service pump, wherein, the main water quality parameter entering ultrafiltration system comprises: feed temperature 55 DEG C, and pH is 7.0, COD is 80mg/L, colourity 150 times, total iron content is 30mg/L, and conductance is 15000 μ s/cm, Cl ^-content is 100mg/L.The PVDF hollow fiber ultrafiltration membrane of 0.01 μm is selected in ultrafiltration under hot conditions, and effective film area is 45m ², the Membrane Filtration Flux under feed pressure is 0.3bar condition is 180L/m ²h, the adjustment ultrafiltration system rate of recovery is 50%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 7.4, and colourity is 5 times, and iron level is 0.5mg/L.

The mode that ultrafiltration system adopts cross flow filter, two ends alternately intake, alternately flooding time is spaced apart a filtration cycle, the filtration cycle of ultrafiltration system is 15min, namely the working procedure opening and closing respective valves of ultra-filtration membrane immediately by PLC after carrying out the product water of 15min enters backwash procedure, and the backwash time of this process is 60 seconds; After reaching 2 filtration cycles filtration cycle, program starts dosing chemical dispersion and washes and soak washed journey, regulating online administration timing of drug and chemical feeding quantity to control matting pH is 3, and soak time is 5min, proceeds normal operation after carrying out the flushing operation of 5 seconds afterwards; The flow that the backwash process after washing with chemical immersion is washed in above-mentioned washing, chemical dispersion is 8.5t/h.

Ultrafiltration is produced water and is promoted to one-level high temperature reverse osmosis membrane system through high-pressure pump 10, and first-stage reverse osmosis system high temperature film adopts Duratherm-HWS-HR8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass of control reverse osmosis filtration system is 9%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 60%, and reverse osmosis membrane flux is 20L/m ²h, the feed pressure of reverse osmosis system is 1.2MPa, and reverse osmosis produced water conductance is 1250 μ s/cm, COD is 16mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 6.0, hydromechanics flushing cycle is 16h, the matting cycle is 120 days, reverse osmosis filtration system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis filtration system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 54 DEG C, conductance 78 μ s/cm, COD is 1.9mg/L, pH is 6.8, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 70 DEG C and regulates feedwater pH to be 7.0 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the tetrafluoroethylene plate and frame membrane module 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.15 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.8m/s, the water vapor produced through tetrafluoroethylene plate and frame membrane module and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control side vacuum tightness be-0.085MPa, the membrane distillation unit rate of recovery 82% time the average flux of tetrafluoroethylene plate and frame membrane module remain on 12 ~ 25L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 2

The water outlet of nitro-chlorobenzene waste water after oxidation-gravity settling treatment process under the high temperature conditions as shown in Figure 1, outer for technique after 60 DEG C of oxidation-sedimentations draining is sent into the ultrafiltration membrane system of cross flow filter through ultrafiltration service pump, wherein, the main water quality parameter entering ultrafiltration system comprises: feed temperature 60 DEG C, and pH is 7.5, COD is 90mg/L, colourity 160 times, total iron content is 35mg/L, and conductance is 25000 μ s/cm, Cl ^-content is 120mg/L.The PTFE hollow fiber ultrafiltration membrane of 0.01 μm is selected in ultrafiltration under hot conditions, and effective film area is 50m ², the Membrane Filtration Flux under feed pressure is 0.25bar condition is 126L/m ²h, the adjustment ultrafiltration system rate of recovery is 55%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 7.2, and colourity is 10 times, and iron level is 0.4mg/L.

The mode that ultrafiltration system adopts cross flow filter, two ends alternately intake, alternately flooding time is spaced apart a filtration cycle, the filtration cycle of ultrafiltration system is 20min, namely the working procedure opening and closing respective valves of ultra-filtration membrane immediately by PLC after carrying out the product water of 20min enters backwash procedure, and the backwash time of this process is 80 seconds; After reaching 4 filtration cycles filtration cycle, program starts dosing chemical dispersion and washes and soak washed journey, regulating online administration timing of drug and chemical feeding quantity to control matting pH is 1.5, and soak time is 8min, proceeds normal operation after carrying out the flushing operation of 5 seconds afterwards; The flow that the backwash process after washing with chemical immersion is washed in above-mentioned washing, chemical dispersion is 6.3t/h.

Ultrafiltration is produced water and is promoted to one-level high temperature reverse osmosis membrane system through high-pressure pump 10, and first-stage reverse osmosis system high temperature film adopts Duratherm-PRO 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass controlling reverse osmosis filtration system is 11%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 55%, and reverse osmosis membrane flux is 13L/m ²h, the feed pressure of reverse osmosis system is 1.4MPa, and reverse osmosis produced water conductance is 2036 μ s/cm, COD is 18mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 7.0, hydromechanics flushing cycle is 24h, the matting cycle is 60 days, reverse osmosis filtration system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis filtration system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 95%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 58 DEG C, conductance 126 μ s/cm, COD is 2.2mg/L, pH is 6.9, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 70 DEG C and regulates feedwater pH to be 8.5 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the tetrafluoroethylene plate and frame membrane module 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.2 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.9m/s, the water vapor produced through tetrafluoroethylene plate and frame membrane module and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control side vacuum tightness be-0.095MPa, the membrane distillation unit rate of recovery 82% time the average flux of tetrafluoroethylene plate and frame membrane module remain on 14 ~ 30L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 3

The water outlet of nitro-chlorobenzene waste water after oxidation-gravity settling treatment process under the high temperature conditions as shown in Figure 1, outer for technique after 65 DEG C of oxidation-sedimentations draining is sent into the ultrafiltration membrane system of cross flow filter through ultrafiltration service pump, wherein, the main water quality parameter entering ultrafiltration system comprises: feed temperature 65 DEG C, and pH is 8.0, COD is 100mg/L, colourity 180 times, total iron content is 55mg/L, and conductance is 30000 μ s/cm, Cl ^-content is 200mg/L.The PES tubular fibre curtain hyperfiltration membrane assembly of 0.05 μm is selected in ultrafiltration under hot conditions, and effective film area is 48m ², the Membrane Filtration Flux under negative pressure is-0.5bar condition is 91L/m ²h, the adjustment ultrafiltration system rate of recovery is 60%, and the dense water of ultrafiltration is delivered to the gravity settling basin of oxidation strengthening technique through recycle pump; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 7.8, and colourity is 15 times, and iron level is 0.3mg/L.

The mode that curtain ultrafiltration system adopts cross flow filter, two ends alternately intake, alternately flooding time is spaced apart a filtration cycle, the filtration cycle of ultrafiltration system is 25min, namely the working procedure opening and closing respective valves of ultra-filtration membrane immediately by PLC after carrying out the product water of 25min enters backwash procedure, and the backwash time of this process is 100 seconds; After reaching 6 filtration cycles filtration cycle, program starts dosing chemical dispersion and washes and soak washed journey, regulating online administration timing of drug and chemical feeding quantity to control matting pH is 2, and soak time is 10min, proceeds normal operation after carrying out the flushing operation of 5 seconds afterwards; The flow that the backwash process after washing with chemical immersion is washed in above-mentioned washing, chemical dispersion is 4.5t/h.

Ultrafiltration is produced water and is promoted to one-level high temperature reverse osmosis membrane system through high-pressure pump 10, and first-stage reverse osmosis system high temperature film adopts Duratherm-EXCEL 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass controlling reverse osmosis filtration system is 13%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 50%, and reverse osmosis membrane flux is 10L/m ²h, the feed pressure of reverse osmosis system is 1.8MPa, and reverse osmosis produced water conductance is 2540 μ s/cm, COD is 20mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 7.5, hydromechanics flushing cycle is 24h, the matting cycle is 80 days, reverse osmosis filtration system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis filtration system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 64 DEG C, conductance 145 μ s/cm, COD is 2.4mg/L, pH is 7.1, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 72 DEG C and regulates feedwater pH to be 9.0 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the Pvdf Microporous Hollow Fiber Membrane assembly 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.2 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 1.0m/s, the water vapor produced through Pvdf Microporous Hollow Fiber Membrane assembly and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control cold side vacuum tightness be-0.095MPa, the membrane distillation unit rate of recovery 85% time the average flux of Pvdf Microporous Hollow Fiber Membrane assembly remain on 10 ~ 17L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 4

The water outlet of nitro-chlorobenzene waste water after oxidation-gravity settling treatment process under the high temperature conditions as shown in Figure 1, outer for technique after 55 DEG C of oxidation-sedimentations draining is sent into the ultrafiltration membrane system of cross flow filter through ultrafiltration service pump, wherein, the main water quality parameter entering ultrafiltration system comprises: feed temperature 55 DEG C, and pH is 8.5, COD is 110mg/L, colourity 170 times, total iron content is 50mg/L, and conductance is 20000 μ s/cm, Cl ^-content is 110mg/L.The PPESK hollow fiber ultrafiltration membrane of 0.03 μm is selected in ultrafiltration under hot conditions, and effective film area is 40m ², the Membrane Filtration Flux under feed pressure is 0.4bar condition is 200L/m ²h, the adjustment ultrafiltration system rate of recovery is 65%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 8.2, and colourity is 7 times, and iron level is 0.1mg/L.

The mode that ultrafiltration system adopts cross flow filter, two ends alternately intake, alternately flooding time is spaced apart a filtration cycle, the filtration cycle of ultrafiltration system is 20min, namely the working procedure opening and closing respective valves of ultra-filtration membrane immediately by PLC after carrying out the product water of 20min enters backwash procedure, and the backwash time of this process is 90 seconds; After reaching 2 filtration cycles filtration cycle, program starts dosing chemical dispersion and washes and soak washed journey, regulating online administration timing of drug and chemical feeding quantity to control matting pH is 3, and soak time is 5min, proceeds normal operation after carrying out the flushing operation of 5 seconds afterwards; The flow that the backwash process after washing with chemical immersion is washed in above-mentioned washing, chemical dispersion is 8.0t/h.

Ultrafiltration is produced water and is promoted to one-level high temperature reverse osmosis membrane system through high-pressure pump 10, and first-stage reverse osmosis system high temperature film adopts Duratherm-STD 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass of control RO system is 9%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 62%, and reverse osmosis membrane flux is 15L/m ²h, the feed pressure of reverse osmosis system is 1.3MPa, and reverse osmosis produced water conductance is 1735 μ s/cm, COD is 22mg/L.The inlet flow-patterm of level reverse osmosis is adjusted to 6.5, hydromechanics flushing cycle is 18h, the matting cycle is 90 days, reverse osmosis filtration system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis filtration system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 53 DEG C, conductance 106 μ s/cm, COD is 2.6mg/L, pH is 7.4, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 72 DEG C and regulates feedwater pH to be 7.5 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the Pvdf Microporous Hollow Fiber Membrane assembly 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.2 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.7m/s, the water vapor produced through Pvdf Microporous Hollow Fiber Membrane assembly and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control cold side vacuum tightness be-0.095MPa, the membrane distillation unit rate of recovery 90% time the average flux of Pvdf Microporous Hollow Fiber Membrane assembly remain on 8 ~ 17L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 5

The water outlet of nitro-chlorobenzene waste water after oxidation-gravity settling treatment process under the high temperature conditions as shown in Figure 1, outer for technique after 60 DEG C of oxidation-sedimentations draining is sent into the ultrafiltration membrane system of cross flow filter through ultrafiltration service pump, wherein, the main water quality parameter entering ultrafiltration system comprises: feed temperature 60 DEG C, and pH is 9.0, COD is 120mg/L, colourity 200 times, total iron content is 55mg/L, and conductance is 27000 μ s/cm, Cl ^-content is 150mg/L.The PP hollow fiber ultrafiltration membrane of 0.1 μm is selected in ultrafiltration under hot conditions, and effective film area is 20m ², the Membrane Filtration Flux under feed pressure is 0.2bar condition is 165L/m ²h, the adjustment ultrafiltration system rate of recovery is 50%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 8.5, and colourity is 10 times, and iron level is 0.05mg/L.

The mode that ultrafiltration system adopts cross flow filter, two ends alternately intake, alternately flooding time is spaced apart a filtration cycle, the filtration cycle of ultrafiltration system is 25min, namely the working procedure opening and closing respective valves of ultra-filtration membrane immediately by PLC after carrying out the product water of 25min enters backwash procedure, and the backwash time of this process is 100 seconds; After reaching 4 filtration cycles filtration cycle, program starts dosing chemical dispersion and washes and soak washed journey, regulating online administration timing of drug and chemical feeding quantity to control matting pH is 2, and soak time is 8min, proceeds normal operation after carrying out the flushing operation of 5 seconds afterwards; The flow that the backwash process after washing with chemical immersion is washed in above-mentioned washing, chemical dispersion is 3.5t/h.

Ultrafiltration is produced water and is promoted to one-level high temperature reverse osmosis membrane system through high-pressure pump 10, and first-stage reverse osmosis system high temperature film adopts Duratherm-PRO 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass controlling reverse osmosis filtration system is 11%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 53%, and reverse osmosis membrane flux is 10L/m ²h, the feed pressure of reverse osmosis system is 1.5MPa, and reverse osmosis produced water conductance is 2314 μ s/cm, COD is 24mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 7.5, hydromechanics flushing cycle is 24h, the matting cycle is 100 days, reverse osmosis filtration system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis filtration system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 59 DEG C, conductance 142 μ s/cm, COD is 2.8mg/L, pH is 7.6, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 80 DEG C and regulates feedwater pH to be 7.0 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the tetrafluoroethylene plate and frame membrane module 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.1 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.6m/s, the water vapor produced through tetrafluoroethylene plate and frame membrane module and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control cold side vacuum tightness be-0.095MPa, the membrane distillation unit rate of recovery 75% time the average flux of tetrafluoroethylene plate and frame membrane module remain on 25 ~ 30L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 6

The water outlet of nitro-chlorobenzene waste water after oxidation-gravity settling treatment process under the high temperature conditions as shown in Figure 1, outer for technique after 65 DEG C of oxidation-sedimentations draining is sent into the ultrafiltration membrane system of cross flow filter through ultrafiltration service pump, wherein, the main water quality parameter entering ultrafiltration system comprises: feed temperature 65 DEG C, and pH is 9.5, COD is 80mg/L, colourity 120 times, total iron content is 25mg/L, and conductance is 29000 μ s/cm, Cl ^-content is 170mg/L.The 19 passage inorganic ceramic TiO of 0.01 μm are selected in ultrafiltration under hot conditions ₂tubular ultra-filtration membrane, effective film area is 10m ², the Membrane Filtration Flux under feed pressure is 0.15bar condition is 150L/m ²h, the adjustment ultrafiltration system rate of recovery is 60%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 8.9, and colourity is 10 times, and iron level is 0.03mg/L.

The mode that ultrafiltration system adopts cross flow filter, two ends alternately intake, alternately flooding time is spaced apart a filtration cycle, the filtration cycle of ultrafiltration system is 30min, namely the working procedure opening and closing respective valves of ultra-filtration membrane immediately by PLC after carrying out the product water of 30min enters backwash procedure, and the backwash time of this process is 120 seconds; After reaching 6 filtration cycles filtration cycle, program starts dosing chemical dispersion and washes and soak washed journey, regulating online administration timing of drug and chemical feeding quantity to control matting pH is 3, and soak time is 10min, proceeds normal operation after carrying out the flushing operation of 5 seconds afterwards; The flow that the backwash process after washing with chemical immersion is washed in above-mentioned washing, chemical dispersion is 2.5t/h.

Ultrafiltration is produced water and is promoted to one-level high temperature reverse osmosis membrane system through high-pressure pump 10, and first-stage reverse osmosis system high temperature film adopts Duratherm-ELITE 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass controlling reverse osmosis filtration system is 13%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 50%, and reverse osmosis membrane flux is 12L/m ²h, the feed pressure of reverse osmosis system is 1.6MPa, and reverse osmosis produced water conductance is 2430 μ s/cm, COD is 16mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 6.0, hydromechanics flushing cycle is 16h, the matting cycle is 120 days, reverse osmosis filtration system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis filtration system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 63 DEG C, conductance 150 μ s/cm, COD is 1.8mg/L, pH is 7.8, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 68 DEG C and regulates feedwater pH to be 8.5 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the Pvdf Microporous Hollow Fiber Membrane assembly 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.22 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.8m/s, the water vapor produced through Pvdf Microporous Hollow Fiber Membrane assembly and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control side vacuum tightness be-0.085MPa, the membrane distillation unit rate of recovery 85% time the average flux of Pvdf Microporous Hollow Fiber Membrane assembly remain on 10 ~ 13L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 7

The treatment process of the product water of nitro-chlorobenzene waste water after oxidation-gravity settling as shown in Figure 1, wherein, the water quality principal character of producing water comprises: temperature 65 DEG C, pH is 9.5, COD is 80mg/L, colourity 120 times, and total iron content is 25mg/L, conductance is 29000 μ s/cm, and C 1 content is 170mg/L.Technique after 65 DEG C of oxidation-sedimentations is produced water sends into cross flow filter ultrafiltration membrane system through ultrafiltration service pump, the Stainless steel 316 L ultra-filtration membrane of 0.015 μm is selected in the ultrafiltration under hot conditions, and effective film area is 10m ², the Membrane Filtration Flux under feed pressure is 0.15bar condition is 180L/m ²h, the adjustment ultrafiltration system rate of recovery is 60%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 8.9, and colourity is 10 times, and iron level is 0.03mg/L.

Ultrafiltration is produced water and is promoted to first-stage reverse osmosis membranous system through high-pressure pump 10, and first-stage reverse osmosis system membranes adopts Duratherm-ELITE 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass controlling reverse osmosis membrane system is 13%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 50%, and reverse osmosis membrane flux is 12L/m ²h, the feed pressure of reverse osmosis system is 1.6MPa, and reverse osmosis produced water conductance is 2430 μ s/cm, COD is 16mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 7.0, hydromechanics flushing cycle is 18h, the matting cycle is 60 days, reverse osmosis membrane system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis membrane system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 63 DEG C, conductance 150 μ s/cm, COD is 1.8mg/L, pH is 7.8, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 70 DEG C and regulates feedwater pH to be 9.0 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the tetrafluoroethylene plate and frame membrane module 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.15 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.8m/s, the water vapor produced through tetrafluoroethylene plate and frame membrane module and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control side vacuum tightness be-0.085MPa, the membrane distillation unit rate of recovery 82% time the average flux of tetrafluoroethylene plate and frame membrane module remain on 12 ~ 25L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 8

As shown in Figure 1, wherein, the water quality principal character of producing water comprises the treatment process of the product water of nitro-chlorobenzene waste water after oxidation-gravity settling: temperature 65 DEG C, pH is 9.5, COD is 80mg/L, colourity 120 times, total iron content is 25mg/L, and conductance is 29000 μ s/cm, Cl ^-content is 170mg/L.Technique after 65 DEG C of oxidation-sedimentations is produced water sends into cross flow filter ultrafiltration membrane system through ultrafiltration service pump, the 19 passage TiO of 0.025 μm are selected in the ultrafiltration under hot conditions ₂ceramic pipe type ultra-filtration membrane, effective film area is 10m ², the Membrane Filtration Flux under feed pressure is 0.15bar condition is 190L/m ²h, the adjustment ultrafiltration system rate of recovery is 60%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 8.9, and colourity is 10 times, and iron level is 0.03mg/L.

Ultrafiltration is produced water and is promoted to first-stage reverse osmosis membranous system through high-pressure pump 10, and first-stage reverse osmosis system membranes adopts Duratherm-ELITE 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass controlling reverse osmosis membrane system is 13%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 50%, and reverse osmosis membrane flux is 12L/m ²h, the feed pressure of reverse osmosis system is 1.6MPa, and reverse osmosis produced water conductance is 2430 μ s/cm, COD is 16mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 7.5, hydromechanics flushing cycle is 24h, the matting cycle is 80 days, reverse osmosis membrane system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis membrane system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 63 DEG C, conductance 150 μ s/cm, COD is 1.8mg/L, pH is 7.8, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 72 DEG C and regulates feedwater pH to be 7.5 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the Pvdf Microporous Hollow Fiber Membrane assembly 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.2 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.9m/s, the water vapor produced through Pvdf Microporous Hollow Fiber Membrane assembly and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control cold side vacuum tightness be-0.01MPa, the membrane distillation unit rate of recovery 85% time the average flux of Pvdf Microporous Hollow Fiber Membrane assembly remain on 2 ~ 10L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Embodiment 9

As shown in Figure 1, wherein, the water quality principal character of producing water comprises the treatment process of the product water of nitro-chlorobenzene waste water after oxidation-gravity settling: temperature 65 DEG C, pH is 9.5, COD is 80mg/L, colourity 120 times, total iron content is 25mg/L, and conductance is 29000 μ s/cm, Cl ^-content is 170mg/L.Technique after 65 DEG C of oxidation-sedimentations is produced water sends into cross flow filter ultrafiltration membrane system through ultrafiltration service pump, the 19 passage ZrO of 0.03 μm are selected in the ultrafiltration under hot conditions ₂ceramic pipe type ultra-filtration membrane, effective film area is 10m ², the Membrane Filtration Flux under feed pressure is 0.15bar condition is 200L/m ²h, the adjustment ultrafiltration system rate of recovery is 60%, and the dense water cycle of ultrafiltration is to the gravity settling basin of oxidation strengthening technique; Ultrafiltration membrane system product water water quality under this hot conditions is pH is 8.9, and colourity is 10 times, and iron level is 0.03mg/L.

Ultrafiltration is produced water and is promoted to first-stage reverse osmosis membranous system through high-pressure pump 10, and first-stage reverse osmosis system membranes adopts Duratherm-ELITE 8040 industrial membrane assembly, and the effective film area of assembly is 32.5m ², adopt cross-flow operation scheme, the recovery per pass controlling reverse osmosis membrane system is 13%, and the rate of recovery adopting the mode of part concentrate recirculation to adjust reverse osmosis system is 50%, and reverse osmosis membrane flux is 12L/m ²h, the feed pressure of reverse osmosis system is 1.6MPa, and reverse osmosis produced water conductance is 2430 μ s/cm, COD is 16mg/L.The inlet flow-patterm of first-stage reverse osmosis is adjusted to 6.5, hydromechanics flushing cycle is 24h, the matting cycle is 90 days, reverse osmosis membrane system carries out the acidleach foam washing under pH condition afterwards, reverse osmosis membrane system carries out low pressure operation 2h, soaks the operation of 4h under the atmosphere of scavenging solution, continuous circulation runs after 3 all after date ultrafiltration product water carry out scavenging solution displacement and enters normal operating condition, and the main purpose of this process removes the part iron colloid pollution of face in reverse osmosis operational process.First-stage reverse osmosis produces water and enters conventional reverse osmosis membrane filtration unit through secondary high-pressure pump 18, this process adopts the high temperature reverse osmosis membrane assembly identical with first-stage reverse osmosis system, the system recoveries rate controlling this process is 90%, to realize further advanced desalination and the part small organic molecule that first-stage reverse osmosis produces water, produce water multiparity water transferpump and send into middle low-pressure boiler unit, the product water water quality parameter of two-pass reverse osmosis process comprises: producing water temp is 63 DEG C, conductance 150 μ s/cm, COD is 1.8mg/L, pH is 7.8, Cu content is less than 0.05mg/L, total silicone content is less than 0.5 μ g/L, produce water water quality and meet middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).

Dense for first-stage reverse osmosis water is adjusted to 65 DEG C and regulates feedwater pH to be 8.0 by the dense water of first-stage reverse osmosis 17 direct heater via 25 after concentrated water discharge valve regulation, enter the tetrafluoroethylene plate and frame membrane module 26 of membrane distillation unit, the aperture of this membrane module hydrophobic membrane is 0.5 μm, the crossflow velocity of the mode controlling diaphragm distillation unit refluxed by dense water section is 0.6m/s, the water vapor produced through tetrafluoroethylene plate and frame membrane module and a small amount of volatile organism enter membrane distillation and produce water tank under the suction function of vacuum pump 30 after condenser 28 is converted into liquid water, produced after water is disposed to the mixing of two-pass reverse osmosis product water tank by Liquid level membrane distillation and be delivered to middle low-pressure boiler water charging system through producing water pump 24.Water production control cold side vacuum tightness be-0.01MPa, the membrane distillation unit rate of recovery 75% time the average flux of tetrafluoroethylene plate and frame membrane module remain on 30 ~ 35L/m ²h, the membrane distillation under this condition produces water power and leads≤40 μ S/cm, and produce water TOC≤25mg/L, ratio of desalinization is higher than 99.5%.

Claims

1. a method for membrane separation nitro-chlorobenzene hot wastewater, is characterized in that, comprises following step:

(1) the outer draining of nitro-chlorobenzene waste water after oxidation-gravity settling is through high temperature ultrafiltration membrance filter;

(2) by the product water positive delivery of ultrafiltration membrance filter in step (1) to first-stage reverse osmosis membrane filtration;

(3) by the product water of first-stage reverse osmosis in step (2) through positive delivery to two-pass reverse osmosis membrane filtration;

(4) by the dense water heating of first-stage reverse osmosis in step (2), and send into membrane distillation unit and carry out membrane distillation, the product water of two-pass reverse osmosis and membrane distillation unit is technique reuse water;

The outer draining water quality of nitro-chlorobenzene waste water after oxidation-gravity settling is characterized as: temperature 55 ~ 65 DEG C, pH is 7.0 ~ 9.5, COD _crbe 80 ~ 120mg/L, colourity 150 ~ 200 times, total iron content is 30 ~ 55mg/L, conductance between 15000 ~ 30000 μ s/cm, Cl ^-content is 100 ~ 200mg/L.

2. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 1, is characterized in that, it is 65 DEG C ~ 80 DEG C that the dense water of described first-stage reverse osmosis is heated to temperature.

3. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 1, is characterized in that, described high temperature ultra-filtration membrane adopt in hollow fiber film assembly, tubular membrane component or curtain type film assembly one or more.

4. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 3, it is characterized in that, the organic film material of described membrane module adopt in polyvinylidene difluoride (PVDF), polyethersulfone, tetrafluoroethylene, poly (aryl ether sulfone ketone), polypropylene one or more, 0.01 ~ 0.2 μm, organic membrane aperture; The mineral membrane of described membrane module adopts ceramic membrane or metallic membrane, and mineral membrane aperture is 0.01 ~ 0.03 μm; The operation scheme of described membrane module adopts cross flow filter or dead-end filtration, and filtration cycle is 15 ~ 30 minutes, and backwashing time is 60 ~ 120 seconds, and operating flux is 90 ~ 200L/m ²h.

5. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 4, is characterized in that, described 0.01 ~ 0.1 μm, organic ultra-filtration membrane aperture, described mineral membrane ceramic membrane is TiO ₂ceramic membrane, the operation scheme of described membrane module adopts cross flow filter, and membrane module filtration cycle is 20 ~ 25 minutes, and operating flux is 126 ~ 150L/m ²h.

6. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 1, is characterized in that, the cleaning way of described ultra-filtration membrane comprise wash online, off-line wash or steam-water mixing wash in one or more; Cleaning process comprises acid cleaning and organism cleaning.

7. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 1, is characterized in that, the membrane module of described osmosis filtration is high temperature resistant aromatic polyamides reverse osmosis organic membrane, and reverse osmosis operating flux is 10 ~ 20L/m ²h, the rate of recovery is 50 ~ 62%, and hydromechanics flushing cycle is 16 ~ 24h, and the matting cycle is 60 ~ 120 days, and pH is 6.0 ~ 7.5.

8. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 7, is characterized in that, the reverse osmosis operating flux of described osmosis filtration is 10 ~ 15L/m ²h, the rate of recovery is 55%, and hydromechanics flushing cycle is 18 ~ 24h, and the matting cycle is 80 ~ 90 days, and pH is 6.5 ~ 7.0.

9. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 1, is characterized in that, described membrane distillation unit adopts the vacuum hydrophobic membrane assembly of polyvinylidene difluoride (PVDF) or polytetrafluoroethylhollow hollow fiber; Membrane pore size is 0.1 ~ 0.5 μm; Membrane distillation operational condition is: wastewater pH 7 ~ 9, wastewater temperature 65 DEG C ~ 80 DEG C, crossflow velocity 0.6 ~ 1.0m/s, cold side vacuum tightness-0.01 ~-0.1MPa, and the membrane distillation unit rate of recovery is 75 ~ 90%, and flux of membrane distillation is 8 ~ 30L/m ²h.

10. the method for a kind of membrane separation nitro-chlorobenzene hot wastewater as claimed in claim 9, it is characterized in that, described membrane pore size is 0.15 ~ 0.2 μm; Membrane distillation operational condition is: wastewater pH is 7.5 ~ 8.5, and wastewater temperature is 68 ~ 75 DEG C, and crossflow velocity is 0.7 ~ 0.9m/s, and cold side vacuum tightness is-0.085 ~-0.095MPa.