CN101962235B - Method for high temperature wastewater treatment and reuse in MTO process - Google Patents
Method for high temperature wastewater treatment and reuse in MTO process Download PDFInfo
- Publication number
- CN101962235B CN101962235B CN 200910157314 CN200910157314A CN101962235B CN 101962235 B CN101962235 B CN 101962235B CN 200910157314 CN200910157314 CN 200910157314 CN 200910157314 A CN200910157314 A CN 200910157314A CN 101962235 B CN101962235 B CN 101962235B
- Authority
- CN
- China
- Prior art keywords
- high temperature
- membrane
- water
- temperature
- wastewater treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a method for treating and reusing high-temperature stripping purified wastewater produced in the process of transferring oxygenated compounds into olefins by using a high-temperature separation membrane. The combination process can effectively remove the impurities such as metal ions and organic micro-molecules and the like in stripping purified water, and the treated purified water in a tower kettle can meet the quality requirements of makeup water for middle and low-pressure boilers or the quality requirements of the makeup water in the MTO process. The invention effectively overcomes the defects exiting in the method for treating and reusing the stripping purified water without condensation in the MTO process, and lowers or reduces the consumption of circulating cooling water in the process of cooling firstly and then treating, thereby saving a large amount of boiler water and recycling the thermal energy of produced high temperature wastewater, and providing a stable and efficient way for high temperature wastewater treatment and reuse of relevant enterprises.
Description
[technical field]
The present invention relates to field of waste water treatment, particularly a kind of method of utilizing membrane separation technique to process MTO process high-temperature waste water.
[background technology]
The low-carbon alkene such as ethene, propylene is important Organic Chemicals, has a very important role in modern oil and chemical industry.The source of ethene and propylene mainly is the hydrocarbon vapours cracking traditionally, and raw material mainly is petroleum naphtha.And the research and development of preparing low carbon olefinic hydrocarbon with methanol (MTO) process then are brand-new operational paths producing Chemicals from non-oil resource.Along with the day by day maturation of coal or natural gas via synthetic gas methanol technology, MTO becomes a production line that receives much concern.
The chemical equation of ethene processed and propylene and thermal effect should be take methyl alcohol as raw material:
2CH
3OH→C
2H
4+2H
2O (ΔH＝11.72KJ/mol，427℃)
3CH
3OH→C
3H
6+3H
2O (ΔH＝30.98KJ/mol，427℃)
It is generally acknowledged that this technique is that methyl alcohol at first dewaters and is dme (DME), continues dehydration and generates the low-carbon alkene that comprises ethene and propylene; Only methanol dehydration becomes the DME process, and DME per ton needs water consumption steam (0.8MPa) about 1.4 tons, about 100 tons of recirculated cooling water (≤3 ℃), thereby this technique belongs to high water consumption technique.Simultaneously, because MTO technique itself is the heat release of a height, high dehydration reaction, usually account for more than 50% of gross weight of outflow material stream with regard to whole technique by-product water, and has higher temperature and pressure, the temperature of this processing wastewater after material-heat-exchanging and energy recovery is about 60～8 ℃, the waste water that this part has low-grade heat enters follow-up waste water treatment process, so will cause the waste of most of low-grade heat and the consumption of recirculated cooling water.Along with the fast development of MTO technology, produce to the increase of water demand and technological process heat energy rationally, take full advantage of and country in the increasing of water-saving and emission-reducing, energy-saving and cost-reducing policy dynamics, also will limit to a certain extent and hinder the MTO project implementation.
For the MTO operational path, the wastewater treatment scheme that Lurgi company adopts is: water can be used as the technique generating steam, and excessive water then can be for agriculture production after special processing.This processing wastewater should can be used as the middle low-pressure boiler feedwater behind which kind of pre-treatment or treatment process or boiler systems is sent in moisturizing but specifically do not set forth in the concrete processing scheme.
The mixture that the MTO technique of UOP/Hydro is left reactor enters separator after by a custom-designed charging/effluent exchanger.In separator, most water and unreacted methyl alcohol are removed.For the processing of by-product water, Uop Inc.'s patent (US5914433) proposes to utilize scheme: the one, the water byproduct that the MTO operation produces is directly delivered to the synthetic gas production process, and need not remove hydrocarbon and oxygenatedchemicals; The 2nd, with the excessive water of MTO operation part, produce the 2-isopropyl ether by the propylene etherificate, these measures have all been saved significantly investment and have been reduced process cost.
Mention in the US Patent No. 6444869 and will contain methane and the light olefin cut partly is back to conversion reaction zone, methane replaces water as thinner, thereby has reduced the disadvantageous effect of water to catalyst stability and life-span.Wherein, demethanizing tower adopts 1 revolution adsorption technology with pressure that methane and water are removed from reactant, has saved investment.But the use of these methods all needs to build according to full scale plant the actual needs of geographical position and peripheral facilities, suits measures to local conditions, realizes the comprehensive utilization of technique by-product water.
Chinese patent application CN101139117A and CN101139118A disclose a kind of waste water treatment process that contains methyl alcohol and dme, its concrete grammar is: the waste water that will contain methyl alcohol and dme, after the pressurization and the heat exchange of purifying waste water at the bottom of the stripping Tata, then enter stripping tower, the gaseous mixture such as methyl alcohol that the stripping tower cat head produces enter return tank after heat exchange, a part is returned the stripping tower cat head as backflow; It is outer or as the raw material of MTO device that another part is delivered to device; Stripping tower tower reactor after heat exchange is purified waste water, with deliver to outside the device after the wastewater heat exchange that contains methyl alcohol and dme, purify waste water middle methyl alcohol and dme total content behind stripping are not more than 100ppm, can satisfy sewage-farm influent quality requirement, adopting biochemical treatment is that the qualified discharge that main flow carries out processing wastewater is processed, but the high-temperature technology waste water of the stripping tower reactor not being discharged in the patent is directly processed to reclaim the reduction of discharging reuse of low-grade heat and waste water and specifically reported.
Above-mentioned foreign patent mainly is to consider that from technique itself technique self needs the reuse situation of water spot, but because MTO technique itself is the process that an alkene and water constantly produce, when the water circuit of technique own reach stable after, still have large water gaging and discharge, above-mentioned patent is not all processed the report of reuse for remaining processing wastewater; And Chinese patent application mainly adopts steam stripped method when large amount of organic is recycled in the processing wastewater, so that processing wastewater purifies the water quality requirement reach sewage effluent treatment plant, as for the direct processing of the tower reactor high-temperature technology waste water behind stripping, indirectly process and detailed reuse method patent application in have no report.
In addition, although patent application CN101088922A and CN101092258A disclose respectively a kind of method of membrane sepn purifying high-temperature condensed water and the method for processing high temperature condensed water by integration technique of membrane, adopt inorganic ceramic micro-filtration or ultra-filtration membrane and nanofiltration membrane to remove the method for the impurity such as suspended substance, oil, colloid, solvability small organic molecule and part mineral ion the steam condenses from different angles respectively, but the two is not all being studied and is reporting aspect the relevant MTO process high-temperature waste water of processing.Thereby, also do not find the advanced treatment of relevant MTO process high-temperature waste water and the document announcement of reuse at present.
[summary of the invention]
For the deficiencies in the prior art, the invention provides a kind of direct advanced treatment of MTO process high-temperature waste water and the technology method of reuse.Using Technology of the present invention that MTO technique stripping is purified waste water carries out can satisfying middle low-pressure boiler supplementary feed water quality requirement after the advanced treatment; This Technology has that the high and low grade utilization efficiency of heat energy of processing efficiency is high, running cost is low, easy handling and be easy to realize the advantage of industrial applications.
The present invention adopts following technical scheme: a kind for the treatment of process of MTO process high-temperature waste water comprises following three steps: the first step, and process stripping and purify waste water, may further comprise the steps: transfer alkali, aeration, filtration; Second step, the product water of the first step enters high temperature microfiltration membrane system or high temperature ultrafiltration membrane system, and the aperture of described high temperature microfiltration membrane or high temperature ultra-filtration membrane is 0.01-0.2 μ m, preferred 0.01～0.1 μ m, more preferably 0.01～0.03 μ m removes part oil, colloid and suspended substance in the water; In the 3rd step, the product water of second step enters the high temperature reverse osmosis system, further removes dissolved organic matter and mineral ion in the water, and the product water of high temperature reverse osmosis system is the technique reuse water.The product water in above-mentioned the 3rd step also can satisfy the compensating water system that the middle low-pressure boiler moisturizing requires to send into middle low-pressure boiler, is used for reclaiming low-grade heat and processing wastewater.
Processing wastewater water quality characteristic of the present invention is: the stripping temperature of purifying waste water is 60～9 ℃; PH is 4～9; COD
CrBe 400～1000mg/L, main organism kinds comprises the organic mixtures such as methyl alcohol, dme, acetic acid, propionic acid, and wherein methanol content is 50～100mg/L, and acetic acid content is 100～500mg/L; The mineral ion kind mainly comprises Fe
2+, Al
3+, Na
+, SiO
3 2-Deng, it is 30～400 μ s/cm etc. that electricity is led.
In the above-mentioned the first step: the purify waste water alkali lye that arranges through transfer line of stripping tower adds entrance, flocculation agent dosing mouth and line mixer and carries out dosing and mix, and adopts NaOH to regulate the pH of above-mentioned processing wastewater to 8-10; The mode that adopts known aeration method and conventional sedimentation to filter is carried out aeration and precipitation, and the delivery turbidity after the sedimentation is less than 1NTU.Accent alkali aeration filtration device of the present invention mainly comprises two functions: one for transferring alkali aeration mixing, two to be precipitate and separate.The concrete technology parameter comprises following main contents: the aeration residence time is 5～40 minutes, and optimum is 10～20 minutes; Then enter the settling region and carry out sedimentation, the hydromechanics residence time is 30～90 minutes herein, and optimum is 50～70 minutes.
The principal character of high temperature micro-filtration of the present invention or high temperature ultrafiltration membrane system is:
1, the high temperature micro-filtration in the second step of the present invention or high temperature ultrafiltration membrance filter system (comprising immersion membrane filtration system) adopt one or more in following: hollow fiber film assembly, tubular membrane component, rolled membrane module, curtain type film assembly and plate and frame module, and optimum is polysulfone hollow fiber ultrafiltration membrane system, tubular membrane component and curtain type film assembly;
2, the organic film material of membrane module described in (1) adopts one or more in following: polysulfones, polyimide, polyetherimide, polyvinylidene difluoride (PVDF) class, or the blend film of the matrix material of aforementioned four kinds of materials; Described polysulfones comprises: bisphenol-a polysulfone, polyethersulfone, phenolic polyether sulphone, phenolphthalein type polyetherketone, contain phthalazine biphenyl structure poly (aryl ether sulfone ketone), contain the poly (arylene ether nitrile) ketone of phthalazine biphenyl structure.Preferred poly (aryl ether sulfone ketone), polyethersulfone, polyvinylidene difluoride (PVDF); Organic ultra-filtration membrane aperture is less than 0.2 μ m, and optimum is 0.01～0.1 μ m;
3, the inorganic material film of membrane module described in (1) mainly comprises inorganic ceramic film class (Al
2O
3, TiO
2, ZrO
2And inorganic organic hybrid films etc.), metallic membrane (stainless steel membrane etc.), optimum is Al
2O
3, TiO
2Ceramic membrane; The membrane pore size size is 10～30nm, and optimum is 15～25nm;
4, the operation scheme of hyperfiltration membrane assembly comprises cross flow filter technique and 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, strengthening washing and soaking the periodical operation of washing in the automatic operational process of hyperfiltration membrane assembly, wherein disperse to wash and can realize alternately water inlet of two ends, the water inlet cycle was respectively 30～120 minutes, and optimum is 45～90 minutes; Backwashing time is 5～30 seconds; Operating flux in the ultrafiltration operational process is 50～1000L/m
2H, optimum are 100～300L/m
2H;
6, the reinforcement of ultra-filtration membrane is washed and immersion washes in the process mainly that (acid mainly comprises: HCl, oxalic acid, citric acid, nitric acid, sulfuric acid and with the composite clean-out system of EDTA etc. as main take the soda acid cleaning; Alkali mainly comprises: NaClO, NaOH etc. and the composite clean-out system that forms with EDTA thereof etc.; Organism class clean-out system such as methyl alcohol, ethanol and vinyl glycol monomethyl butyrates etc.), this invents the operations such as described ultra-filtration membrane cleaning way has comprised online and off-line cleaning operation, gas are cleaned, steam-water mixing is washed, and optimum is washed technological process for steam-water mixing.
The principal character of high temperature reverse osmosis membrane system of the present invention is: the membrane module of reverse osmosis filtration system mainly adopts high temperature resistant reverse osmosis organic membrane such as the aromatic polyamides take PPESK as counterdie and the aromatic polyamides take polyethersulfone as counterdie, and commercial membrane module type mainly comprises Duratherm-HWS-HR, Duratherm-STD, Duratherm-PRO, Duratherm-EXCEL, Duratherm-ELITE etc.;
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;
Reverse osmosis operating flux in this high-temperature technology wastewater treatment process is 40～100L/m
2H, optimum are 50～80L/m
2H; The system recoveries rate of RO device is controlled at 70～90%, and optimum is 75%; Cleaning interval is 30～120 days, and optimum is 45～90 days; The pH of reverse osmosis operational process is controlled to be 7.0～9.5, and optimum is 7.5～9.0.
The present invention has following beneficial effect:
1, moves under hot conditions owing to the high temperature membrane system, the operating pressure of ultrafiltration and reverse osmosis membrane is lower, Membrane Filtration Flux is higher, can realize that hot wastewater is processed and the miniaturization of retrieving arrangement and reduction process cost, and the advanced treatment of high temperature reverse osmosis can have higher clearance to mineral ion and dissolved organic matter, therefore can reach higher system recoveries rate and better effluent quality;
2, whole high temperature film treatment technological process is moved under hot conditions, and employing high temperature resistance diaphragm separation assembly, guaranteed the continuous and steady operation of whole film system, and since film separating system 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 (WQM) instruments;
3, the high temperature reverse osmosis in the technique of the present invention has good removal effect to the dissolving oil in the MTO processing wastewater, mineral ion and small organic molecule etc., effluent quality is good, and (main water quality comprises: producing water temp is: 65～85 ℃, COD can be widely used in the mesolow Industrial Boiler moisturizing water quality requirements such as chemical industry, thermoelectricity
Mn≤ 2mg/L, Fe≤0.03mg/L, Cu≤0.005mg/L, oil≤0.3mg/L, SiO
2≤ 0.02mg/L etc.);
4, the high-temperature operation flux that can avoid the ultrafiltration in the normal-temperature operation process, pollution that reverse osmosis system causes because of microbial growth to cause descends and the shortening of cleaning interval etc.
[description of drawings]
Fig. 1 is the embodiment of the invention 1,2,3 process flow diagram.
Fig. 2 is the process flow diagram of the embodiment of the invention 4.
Among the figure:
A, stripping are purified waste water; B, pressurized air; C, sludge from sedimentation tank mouth; D, reverse osmosis produced water; E, ultrafiltration concentrate recirculation; F, reverse osmosis concentrated water reflux; G, reverse osmosis concentrated water discharging; H, ultrafiltration concentrated water discharge;
1, settling tank; 2, ultrafiltration service pump; 3, hyperfiltration membrane assembly; 4, reverse osmosis feedwater pump; 5, reverse osmosis membrane assembly.
[embodiment]
Below in conjunction with accompanying drawing, by the form of specific embodiment, the present invention is further detailed.
Embodiment 1
Stripping tower reactor hot wastewater treatment process enters precipitate and separate pond 1 with 70 ℃ of MTO technique stripping towers A that purifies waste water as shown in Figure 1, and wherein main water quality parameter comprises: wastewater temperature is 70 ℃, pH is 5.5, and turbidity is 86.9NTU, and oil-contg is 8.9mg/L, total iron content is 45.2mg/L, SiO
2Content is 8.9 μ g/L.
At first, stripping is purified waste water and enter precipitate and separate pond 1 after pH regulator to 8.0 is mixed by line mixer, adopt microporous aeration device B to carry out the aeration operation in bottom, precipitate and separate pond, aerate flux is 50L/min, the hydromechanics residence time through transferring the alkali aeration is 20min, colloidalmaterial after the precipitation is discharged through mud discharging mouth C, transfer the mixed waste water of alkali aeration after heavy the separation, to enter settling section, the pretreated main water quality parameter of purifying waste water is: pH is 8.0, turbidity is 0.64NTU, oil-contg is 1.2mg/L, and total iron content is less than 0.04mg/L, SiO
2Content is 3.7 μ g/L.
Pretreated waste water is sent into ultrafiltration system 3 through impeller pump 2, and the high temperature resistant PPESK hollow fiber ultrafiltration membrane of 0.01 μ m is selected in the ultra-filtration membrane aperture, and the effective film area is 1m
2, Membrane Filtration Flux is 300L/m
2H, ultrafiltration membrane system feed pressure are 0.3bar, and adjusting the ultrafiltration system rate of recovery is 98%, and the dense water cycle of ultrafiltration is to settling tank 1, and it is that pH is 8.1 that water water quality is produced in ultrafiltration, and turbidity is 0.57NTU, and oil-contg is 0.85mg/L, and total iron content is less than 0.04mg/L, SiO
2Content is 3.6 μ g/L.Ultrafiltration system adopts the alternately mode of water inlet of cross flow filter, two ends, and alternately flooding time is spaced apart 30 minutes, carries out adding after the first acid adding dispersion of alkali and washes operation, and soda acid dosing scavenging period is 10 seconds, carries out afterwards proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out soda acid after 10 times and soak and strengthen cleaning operation; The soda acid soak time is 10 minutes, carries out afterwards 5 seconds flushing operation.This ultrafiltration system continuously operation carried out the steam-water mixing cleaning operation one time after 15 days, and scavenging period is 10 minutes.
Ultrafiltration is produced water and is promoted to reverse osmosis system 5 through high-pressure pump 4, and the high temperature membrane of reverse osmosis system adopts Duratherm-STD, Duratherm-PRO 2540 membrane modules, and the effective film area of assembly is 2.3m
2, adopting the cross-flow operation scheme, the recovery per pass of control RO system is 13%, and the rate of recovery that the mode of employing part concentrate recirculation is adjusted reverse osmosis system is 80%, and the reverse osmosis membrane flux is 50L/m
2H, the feed pressure of reverse osmosis system are 0.4MPa, and reverse osmosis produced water water quality pH is 7.4, and oil-contg is 0.41mg/L, SiO
2Content is 0.41 μ g/L, and hardness is 0.66mg/L, produces the regulation that water water quality meets middle low-pressure boiler supplementary feed water quality standard (GB/T1576-2007).The cycle of operation of RO system is 60 days, RO film system carries out respectively acid afterwards, alkali soaks and washes, the RO system carries out low pressure operation 2h, soaks 4h under the atmosphere of scavenging solution operation, 3 all after dates of continuous circulation operation are produced water with ultrafiltration and are carried out entering normal operating condition after the scavenging solution displacement.
The hot wastewater treatment process as shown in Figure 1,80 ℃ of MTO technique stripping towers A that purifies waste water is entered precipitate and separate pond 1, wherein stripping tower is purified waste water water quality as described in example 1 above, adopts identical pretreatment technology among the embodiment 1, and pretreated technique is produced water water quality as described in example 1 above.
Pretreated stripping is purified waste water and is sent into ultrafiltration system 3 through impeller pump 2, and high temperature resistant organic ultra-filtration membrane Duratherm HWS UF 2540 of 0.1 μ m is selected in the ultra-filtration membrane aperture, and the effective film area is 2.3m
2, the ultrafiltration membrance filter flux is 200L/m
2H, ultrafiltration membrane system feed pressure are 0.2bar, and adjusting the ultrafiltration system rate of recovery is 95%, and the dense water cycle of ultrafiltration is to settling tank 1, and it is that pH is 8.6 that water water quality is produced in ultrafiltration, and turbidity is 0.47NTU, and oil-contg is 1.2mg/L, and total iron content is less than 0.04mg/L, SiO
2Content is 3.6 μ g/L.Ultrafiltration system adopts the alternately mode of water inlet of cross flow filter, two ends, and alternately flooding time is spaced apart 45 minutes, carries out adding after the first acid adding dispersion of alkali and washes operation, and soda acid dosing scavenging period is 8 seconds, carries out afterwards proceeding normal operation behind 3 seconds the flushing operation; This process reruns and carries out soda acid after 8 times and soak and strengthen cleaning operation; The soda acid soak time is 8 minutes, carries out afterwards 5 seconds flushing operation.This ultrafiltration system continuously operation carried out the steam-water mixing cleaning operation one time after 25 days, and scavenging period is 8 minutes.
Ultrafiltration is produced water and is promoted to reverse osmosis system 5 through high-pressure pump 4, and the high temperature membrane of reverse osmosis system adopts Duratherm-EXCEL 2540 membrane modules, and the effective film area of assembly is 2.3m
2, adopting the cross-flow operation scheme, the recovery per pass of control RO system is 10%, and the rate of recovery that the mode of employing part concentrate recirculation is adjusted reverse osmosis system is 75%, and the reverse osmosis membrane flux is 65L/m
2H, the feed pressure of reverse osmosis system are 0.6MPa, and reverse osmosis produced water water quality is that pH is 7.76, and oil-contg is 0.47mg/L, SiO
2Content is 0.51 μ g/L, and hardness is 0.58mg/L, produces the regulation that the water water quality standard meets middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).The cycle of operation of RO system is 90 days, RO film system carries out alkali respectively afterwards, acid soak is washed, the RO system carries out low pressure operation 2h, soaks the cyclical operation of 4h under the atmosphere of scavenging solution, 3 all after dates of circular flow produce water with ultrafiltration to carry out entering normal operating condition after the displacement of scavenging solution.
The hot wastewater treatment process as shown in Figure 1,80 ℃ of MTO technique stripping towers A that purifies waste water is entered precipitate and separate system 1, wherein stripping tower tower reactor water quality adopts identical pretreatment technology among the embodiment 1 as described in example 1 above, and pretreated technique is produced water water quality as described in example 1 above.
Pretreated waste water is sent into ultrafiltration system 3 through impeller pump 2, and the 19 passage tubular type ceramic super-filtering films of 0.02 μ m are selected in the ultra-filtration membrane aperture, and the effective film area is 1m
2, Membrane Filtration Flux is 100L/m
2H, ultrafiltration membrane system feed pressure are 0.15MPa, and the rate of recovery of ultrafiltration system is 90%, the dense water cycle of ultrafiltration is to settling tank 1, and it is that ultrafiltration product water water quality is that pH is 8.63 that water water quality is produced in ultrafiltration, and turbidity is 0.52NTU, oil-contg is 1.2mg/L, and total iron content is less than 0.04mg/L, SiO
2Content is 3.02 μ g/L.Ultrafiltration system adopts the alternately mode of water inlet of cross flow filter, two ends, and alternately flooding time is spaced apart 90 minutes, carries out adding after the first acid adding dispersion of alkali and washes operation, and soda acid dosing scavenging period is 10 seconds, carries out afterwards proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out soda acid after 20 times and soak and strengthen cleaning operation; The soda acid soak time is 10 minutes, carries out afterwards 5 seconds flushing operation.This ultrafiltration system continuously operation carried out the steam-water mixing cleaning operation one time after 60 days, and scavenging period is 20 minutes.
Ultrafiltration is produced water and is promoted to reverse osmosis system 5 through high-pressure pump 4, and the high temperature membrane of reverse osmosis system adopts Duratherm-EXCEL 2540 membrane modules, and the effective film area of assembly is 2.3m
2, adopting the cross-flow operation scheme, the recovery per pass of control RO system is 10%, and the rate of recovery that the mode of employing part concentrate recirculation is adjusted reverse osmosis system is 70%, and the reverse osmosis membrane flux is 80L/m
2H, the feed pressure of reverse osmosis system are 0.8MPa, and reverse osmosis produced water water quality is that pH is 7.49, and oil-contg is 0.43mg/L, SiO
2Content is 0.35 μ g/L, and hardness is 0.64mg/L, produces the regulation that the water water quality standard meets middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).The cycle of operation of RO system is 120d, RO film system carries out respectively acid afterwards, alkali soaks and washes, the RO system carries out low pressure operation 2h, soaks the cyclical operation of 4h under the atmosphere of scavenging solution, move continuously 4 all after dates and produce water with ultrafiltration and carry out entering normal operating condition after the displacement of scavenging solution.
The hot wastewater treatment process as shown in Figure 2, the MTO technique stripping tower water quality of purifying waste water is: the temperature of purifying waste water is 90 ℃, and pH is 7.2, and turbidity is 316NTU, and hardness is 33.2mg/L, and oil-contg is 468.8mg/L, and total iron content is 0.9mg/L, SiO
2Content is 0.2 μ g/L, and feedwater TOC is 26.01mg/L.
The stripping tower tower reactor A that purifies waste water sends into ultrafiltration system 3 through impeller pump 2, and ultra-filtration membrane is selected the 19 passage tubular type ceramic super-filtering films of 0.02 μ m, and the effective film area is 1m
2, Membrane Filtration Flux is 200L/m
2H, ultrafiltration membrane system feed pressure are 0.4MPa, and the rate of recovery of ultrafiltration system is 98%, and the dense water cycle of ultrafiltration is to the suction culvert of ultrafiltration service pump 2, and the dense water of part is through discharge outlet and discharging after the reverse osmosis waste discharge mixes.Water water quality is produced in the ultrafiltration of this process: 90 ℃ of temperature, and pH is 7.8, and turbidity is 0.8NTU, and hardness is 31.2mg/L, and oil-contg is 2.4mg/L, total iron content is 40 μ g/L, SiO
2Content is 0.1 μ g/L, and TOC is 15.4mg/L; Ultrafiltration system adopts the alternately mode of water inlet of cross flow filter, two ends, and alternately flooding time is spaced apart 60 minutes, adds first behind the alkali dispersion of acid adding and washes operation, and soda acid dosing scavenging period is 10 seconds, carries out afterwards proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out soda acid after 15 times and soak and strengthen cleaning operation; The soda acid soak time is 15 minutes, carries out afterwards 10 seconds flushing operation.This ultrafiltration system continuously operation carried out the steam-water mixing cleaning operation one time after 90 days, and scavenging period is 15 minutes.
Ultrafiltration is produced water and is promoted to reverse osmosis system 5 through high-pressure pump 4, and the high temperature membrane of reverse osmosis system adopts Duratherm-ELITE 2540 membrane modules, and the effective film area of assembly is 2.3m
2, adopting the cross-flow operation scheme, the recovery per pass of control RO system is 12%, and it is 75% that the mode of employing part concentrate recirculation is adjusted the reverse osmosis system rate of recovery, and the reverse osmosis membrane flux is 50L/m
2H, the feed pressure of reverse osmosis system are 0.4MPa.Reverse osmosis produced water pH under this condition is 7.5, and hardness is 0.58mg/L, and oil-contg is 0.5mg/L, and total iron content is 20 μ g/L, SiO
2Content is 0.05 μ g/L, and TOC is 3.2mg/L; Product water water quality standard meets the regulation of middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2007).The cycle of operation of RO system is 120 days, RO film system carries out respectively acid afterwards, alkali soaks and washes, the RO system carries out low pressure operation 2h, soaks the cyclical operation of 4h under the atmosphere of scavenging solution, move continuously 4 all after dates and produce water with ultrafiltration and carry out entering normal operating condition after the displacement of scavenging solution.
Claims (13)
1. the treatment process of a MTO process high-temperature waste water is characterized in that: the first step, and process stripping and purify waste water, may further comprise the steps: transfer alkali, aeration, filtration; Second step, the product water of the first step enters high temperature microfiltration membrane system or high temperature ultrafiltration membrane system, and the aperture of described high temperature microfiltration membrane or high temperature ultra-filtration membrane is 0.01-0.2 μ m, removes part oil, colloid and suspended substance in the water; In the 3rd step, the product water of second step enters the high temperature reverse osmosis system, further removes dissolved organic matter and mineral ion in the water, and the product water of high temperature reverse osmosis system is process water.
2. MTO process high-temperature method of wastewater treatment according to claim 1, it is characterized in that the described stripping water quality characteristic of purifying waste water is: temperature is 60 ℃, 70 ℃, 80 ℃ or 90 ℃; PH is 4～9; COD
CrBe 400～1000mg/L, main organism comprises methyl alcohol, dme, acetic acid, propionic acid, and wherein methanol content is 50～100mg/L, and acetic acid content is 100～500mg/L; Mineral ion mainly comprises Fe
2+, Al
3+, Na
+, SiO
3 2-, it is 30～400 μ s/cm that electricity is led.
3. MTO process high-temperature method of wastewater treatment according to claim 1, it is characterized in that in the first step: the purify waste water alkali lye that arranges through transfer line of stripping tower adds entrance, flocculation agent dosing mouth and line mixer and carries out dosing and mix, and adopts NaOH to regulate the pH of above-mentioned processing wastewater to 8-10; Carry out aeration and precipitation, the delivery turbidity after the sedimentation is less than 1NTU.
4. MTO process high-temperature method of wastewater treatment according to claim 1, the mould material that it is characterized in that high temperature microfiltration membrane system in the described second step or high temperature ultrafiltration membrane system adopts one or more in following: polysulfones, polyimide, polyetherimide, polyvinylidene difluoride (PVDF) class, or the blend film of the matrix material of aforementioned four kinds of materials;
Described polysulfones comprises: bisphenol-a polysulfone, polyethersulfone, phenolic polyether sulphone, phenolphthalein type polyetherketone, contain phthalazine biphenyl structure poly (aryl ether sulfone ketone), contain the poly (arylene ether nitrile) ketone of phthalazine biphenyl structure.
5. MTO process high-temperature method of wastewater treatment according to claim 4 is characterized in that described high temperature microfiltration membrane or high temperature ultra-filtration membrane are the high temperature resistant separatory membrane of poly (aryl ether sulfone ketone) or the high temperature resistant ultra-filtration membrane of Duratherm series.
6. according to claim 4 or 5 described MTO process high-temperature method of wastewater treatment, it is characterized in that: the pore diameter range of described high temperature microfiltration membrane or high temperature ultra-filtration membrane is 0.01～0.1 μ m.
7. MTO process high-temperature method of wastewater treatment according to claim 1, the mould material that it is characterized in that high temperature microfiltration membrane system in the described second step or high temperature ultrafiltration membrane system adopt one or both in following: ceramic membrane and metallic membrane;
Described ceramic membrane comprises: use Al
2O
3, TiO
2, ZrO
2Ceramic membrane for main material; Metallic membrane comprises stainless steel membrane.
8. MTO process high-temperature method of wastewater treatment according to claim 7, it is characterized in that: the pore diameter range of described high temperature microfiltration membrane or high temperature ultra-filtration membrane is 0.01～0.03 μ m.
9. MTO process high-temperature method of wastewater treatment according to claim 1 is characterized in that: one or more during the high temperature microfiltration membrane system of second step or the employing of the membrane module form in the high temperature ultrafiltration membrane system are following: hollow fiber film assembly, tubular membrane component, curtain type film assembly, rolled membrane module or plate and frame module.
10. MTO process high-temperature method of wastewater treatment according to claim 1, it is characterized in that: the high temperature microfiltration membrane system of second step or the operation scheme of high temperature ultrafiltration membrane system are cross flow filter mode or dead-end filtration mode.
11. MTO process high-temperature method of wastewater treatment according to claim 1 is characterized in that: the membrane module of the high temperature reverse osmosis system in the 3rd step adopts aromatic polyamides and the reverse osmosis of Duratherm series high temperature take PPESK as counterdie.
12. MTO process high-temperature method of wastewater treatment according to claim 1 is characterized in that: the high temperature reverse osmosis system in the 3rd step adopts the operation format of dense water end (W.E.) counterflush when moving.
13. a MTO process high-temperature reuse of wastewater method, it is characterized in that: according to the described treatment process of one of the claims 1-12, the product water after the processing directly enters the compensating water system of middle low-pressure boiler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910157314 CN101962235B (en) | 2009-07-24 | 2009-07-24 | Method for high temperature wastewater treatment and reuse in MTO process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200910157314 CN101962235B (en) | 2009-07-24 | 2009-07-24 | Method for high temperature wastewater treatment and reuse in MTO process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101962235A CN101962235A (en) | 2011-02-02 |
| CN101962235B true CN101962235B (en) | 2013-05-01 |
Family
ID=43515327
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200910157314 Active CN101962235B (en) | 2009-07-24 | 2009-07-24 | Method for high temperature wastewater treatment and reuse in MTO process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101962235B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021113916A1 (en) * | 2019-12-09 | 2021-06-17 | Akvotek Pty Ltd | Methods and apparatus for removing contaminants from an aqueous material |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2653451A1 (en) * | 2012-04-20 | 2013-10-23 | CS Carbon Solutions | Method and apparatus for the treatment of process water from an organic material conversion process |
| CN103771562B (en) * | 2012-10-19 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of nitro-chlorobenzene hot wastewater advanced treatment and reuse method |
| CN103951098B (en) * | 2014-04-25 | 2015-12-30 | 江苏久吾高科技股份有限公司 | In MTO technology, quenched water and washing water take off method and the device of solid oil removing |
| CN103922546A (en) * | 2014-04-29 | 2014-07-16 | 江苏科沛达环境工程科技有限公司 | Heavy metal wastewater treatment equipment and method |
| CN105271585A (en) * | 2014-06-11 | 2016-01-27 | 中国石油化工股份有限公司 | Method for processing wastewater generated in a process for preparing butadiene through oxidative dehydrogenation of industrial butylene |
| US10781122B2 (en) * | 2015-12-15 | 2020-09-22 | Kemco Systems Co. Llc | Membrane filtration apparatus and process for reuse of industrial wastewater |
| CN107540107B (en) * | 2016-06-29 | 2021-08-10 | 中国石油化工股份有限公司 | Deep oil-removing purification method for steam stripping purified water of oil refining |
| CN108373180A (en) * | 2018-04-19 | 2018-08-07 | 浙江兴兴新能源科技有限公司 | A kind of methanol-to-olefins sour water stripper and its sewage water treatment method |
| CN114920404A (en) * | 2022-04-08 | 2022-08-19 | 成都瀚川环境科技有限公司 | Evaporation wastewater pretreatment process |
| CN114920414A (en) * | 2022-07-19 | 2022-08-19 | 天津渤化化工发展有限公司 | Purification water treatment system of methanol-to-olefin process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088922A (en) * | 2007-07-05 | 2007-12-19 | 南京九思高科技有限公司 | Membrane separating process for purifying high temperature condensated water |
| CN101376550A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Method for processing process waste water of dimethyl ether preparation by dehydrating methyl alcohol |
| CN101462811A (en) * | 2007-12-21 | 2009-06-24 | 栗田工业株式会社 | Biological treatment method and apparatus for organic containing water |
-
2009
- 2009-07-24 CN CN 200910157314 patent/CN101962235B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101088922A (en) * | 2007-07-05 | 2007-12-19 | 南京九思高科技有限公司 | Membrane separating process for purifying high temperature condensated water |
| CN101376550A (en) * | 2007-08-31 | 2009-03-04 | 中国石油化工股份有限公司 | Method for processing process waste water of dimethyl ether preparation by dehydrating methyl alcohol |
| CN101462811A (en) * | 2007-12-21 | 2009-06-24 | 栗田工业株式会社 | Biological treatment method and apparatus for organic containing water |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021113916A1 (en) * | 2019-12-09 | 2021-06-17 | Akvotek Pty Ltd | Methods and apparatus for removing contaminants from an aqueous material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101962235A (en) | 2011-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101962235B (en) | Method for high temperature wastewater treatment and reuse in MTO process | |
| CN103803752B (en) | Treatment method of wastewater with high salinity and high organic matters | |
| CN101962246B (en) | Method for treating and recycling MTO process wastewater | |
| CN104176857B (en) | The treatment process of Mn-bearing waste water in wet method electrolysis manganese production process | |
| CN102659283B (en) | Process for treating and recovering dye industrial wastewater | |
| CN103771641B (en) | A kind of nitro-chlorobenzene Sewage advanced treatment and reuse method | |
| CN105417775A (en) | Reverse osmosis membrane treating and recycling method for printing and dyeing wastewater | |
| CN201424407Y (en) | Reverse osmosis and nanofiltration system used in treating high-density organic wastewater | |
| CN102050548A (en) | Treatment and reuse method of waste water in methanol-to-olefin process | |
| CN102701326A (en) | Seawater desalinizing technology deeply treated by reverse osmosis membrane after mixing wastewater with seawater | |
| CN108409050B (en) | Zero-emission treatment process for high-salinity wastewater | |
| CN117049755B (en) | Reclaimed water recycling treatment process for coal gas wastewater | |
| CN101229936A (en) | A method and equipment for recycling oil refinery and chemical wastewater | |
| JP2013119523A (en) | Method for producing cyclohexanone oxime, and method and system of effluent treatment | |
| CN103787539B (en) | A kind of method of membrane separation nitro-chlorobenzene hot wastewater | |
| CN109231606B (en) | Advanced treatment and recycling device and method for cotton pulp waste water | |
| CN216863920U (en) | Urea production waste liquid treatment device | |
| CN103771562B (en) | A kind of nitro-chlorobenzene hot wastewater advanced treatment and reuse method | |
| CN112979038B (en) | Zero-discharge treatment process for printing and dyeing wastewater | |
| CN113880293A (en) | Alkali reduction wastewater treatment method and treatment system | |
| CN100375726C (en) | Mambrane method of recovery and utilization of refining oil and chemical polluted water and its equipment | |
| CN219044900U (en) | High temperature coal tar hydrogenation effluent treatment plant | |
| CN116495944B (en) | Method and device for treating industrial wastewater in membrane production | |
| CN114772826B (en) | Reclaimed water recycling method | |
| CN215946831U (en) | STRO equipment for concentrated brine decrement treatment of coking wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |