CN102295356B - Method for treating steam condensed water by virtue of organic separation membrane - Google Patents
Method for treating steam condensed water by virtue of organic separation membrane Download PDFInfo
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Abstract
The invention relates to a method for treating steam condensed water by virtue of an organic separation membrane. The method is characterized in that by using a process that high-temperature condensed water in a condensed water collecting system is fed into a high-temperature-resistant ultrafiltration membrane filtration system under the action of a pump and then produced water is fed into a high-temperature reverse osmosis membrane system through a high-pressure pump, trace oil and iron, which are generated due to material leakage and pipeline corrosion, in the steam condensed water are effectively removed, simultaneously, the steam condensed water with higher oil and iron contents caused by impact of a system is also removed, dissolved oil and micromolecule organic matters in the steam condensed water are removed, and the treated steam condensed water can be directly fed into an oxygen removal system of the middle-low pressure boiler. According to the invention, the problem that the condensed water can not be recovered caused by impact of petrochemical steam condensed water is effectively solved by using the method provided by the invention so as to achieve the characteristics of the steam condensed water, such as stable water quality, high recovery rate and stable operation; and a stable and effective way is provided for reuse of high-temperature condensed water in a petrochemical enterprise through the high-temperature recovery of the steam condensed water.
Description
Technical field
The present invention relates to a kind of method that adopts high temperature resistant organic separation membrane technical finesse hot wastewater and reuse, particularly adopt the method for high temperature resistant organic separation membrane processing and reuse for the Petrochemical Enterprises condensed water in high temperature, belong to wastewater treatment and low grade heat energy recovery technology field.
Background technology
Chemical industry is the hot rich and influential family of using of industrial sector.In chemical industry, the recovery of steam condensate is exactly the difficult problem of chemical enterprise since the dawn of human civilization.In the oil refining production process, steam provides heat energy and power as a kind of main energy for the production of each device.Steam is after using, and major part changes into condensed water.In the condensed water removal process, because HCO in the water
3 -When running into high temperature, easily resolve into CO
2, CO
2Gas condenses in recovery tube with water vapor, causes condensed water pH value to descend and is acid, corroding metal, causes iron level to raise.And the pH of condensed water reduces with the rising of total alkalinity in the former water, reclaims in the process of carrying in condensed water and causes corrosion of piping.In addition in the oil refining production process, because corrosion failure appears in pipeline, cause containing in the condensed water oil content, or the organic materials in producing, hardness, the impurity such as ash, cause the condensed water water quality deterioration, if direct reuse causes the generation of boiler breakdowns etc. easily, can not be directly as oiler feed for this condensed water of being polluted, thereby the precision processing technology of steam condenses becomes focus and the difficult point of present research.
The precision processing technology that reclaims the condensed water in high temperature of oil-containing, iron for chemical process mainly comprises cooling treatment technology and the direct treatment technology of high temperature.Cooling treatment technology commonly used refers to that mainly the condensed water in high temperature that will reclaim carries out carrying out precision processing after the heat exchange again in the commercial run, mainly comprise ion exchange technique and normal temperature membrane filtration technique, but conventional ion exchange system can not be removed the oil or the hydro carbons organic molecule that contain in the condensed water, and it also can cause ion exchange resin to lose efficacy; The normal temperature membrane filtration technique can reach preferably removal effect to harmful ion and the deliquescent oils small-molecule substance in the condensed water after the cooling, makes condensed water water quality reach the oiler feed requirement.Although above-mentioned two kinds of method simple and reliable process, reclaimed the condensed water of excellent quality, but it has wasted a large amount of Low Temperature Thermals and the expense of the process for cooling that causes because of the vapor condenses water condensation, thereby, make a large amount of economic benefit of enterprises' loss, and lost the important meaning of condensation water recycling.
A large amount of patents are described for retrieving arrangement, the recovery system of condensed water in high temperature, but describe then relatively less for the patent of the precision processing technology of the contaminated condensed water after reclaiming.CN1718547A is used for the condensed water in high temperature that the petrochemical iy produced technological process produces, and pollutes the new technology that prevents that instead material from polluting by administering material.CN2545192A has described a kind of high-temp. condensed water deironing device, it mainly by housing, with water outlet plate, middle plate, the lower plate of inner walls welding, be fixed on filter element on the lower plate, be loaded on filler in the shell, the posticum that is installed on erosion control frame, water inlet and the case top of bottom in the housing consists of.Filter element is to be fixed on mechanical impurity filter element on the lower plate hole with the vitrified pipe of micropore and with self fastening piece, and filler has the irregular spheroid with iron ion rapid reaction performance.This high-temp. condensed water deironing device can directly be removed iron ion without the heat exchange cooling with the condensed water below 98 ℃, the condensed water of iron ion content 1000 μ g/L can be down to below the 20 μ g/L.This patent can only be removed a large amount of iron in the steam condenses, but because the limiting it and can not thoroughly remove the small organic molecule in the steam condenses or oily substance of invention itself.
CN101264956A relates to a kind of method of purifying high-temperature condensed water, adopt polymeric complexing agent, then adopt the method for ceramic membrane filter to hold back polymeric complexing agent, remove the solvability ionic impurity in the water, although the method can not introduced secondary pollution, it is only applicable to remove the solvability ion in the condensed water in high temperature.
CN101088922A relates to a kind of method of membrane sepn purified steam condensed water in high temperature, condensed water in high temperature is successively passed through micro-filtration or ultra-filtration membrane pre-treatment and nanofiltration membrane advanced treatment, remove the impurity such as suspended substance, oil, colloid, solvability small organic molecule and mineral ion in the water.Although ultra-filtration membrane described in the patent and nanofiltration membrane can be removed the suspended substance in the waste water, oil, colloid preferably, because the aperture of nanofiltration membrane, stainless steel nanofiltration membrane (＞1nm) can not remove fully the small organic molecule in the condensed water and dissolving oil more greatly.CN101092258A relates to the method for the processing high temperature condensed water by integration technique of membrane of a kind of micro-filtration or ultra-filtration membrane-absorption or ion-exchange, is used for purifying treatment and crosses boiler hot steam condensed water in high temperature.The described technical characterictic main manifestations of this patent is for adopting tubular fibre, tubular type, rolling ultrafiltration membrane to carry out dead-end filtration, although embodiment has described modified PES hollow fiber microfiltration membrane and ceramic micro filter and ultra-filtration membrane and removed suspended substance, oil, colloid in the steam condenses, adopt technology described in this patent can not effectively remove oil in the condensed water.
Although above-mentioned patent has been carried out the description of the suspended substance the steam condenses, oil, colloid and small organic molecule removal method from different angles, adopt technology described in the above-mentioned patent Fe in the steam condenses and oily substance effectively can not be removed simultaneously.
Summary of the invention
For the deficiencies in the prior art, water quality characteristics in conjunction with the Petrochemical Enterprises steam condenses, the invention provides the COMBINED PROCESS of a kind of " high temperature ultrafiltration-high temperature reverse osmosis ", adopt the technology of the present invention simultaneously the suspended substance in the high-temperature steam condensed water, colloid, wet goods small organic molecule effectively to be removed, solve and adopt prior art the iron in the steam condenses, wet goods small organic molecule effectively can not be removed simultaneously and produced the unsettled problem of water water quality.
High-temperature steam condensed water after employing the technology of the present invention is processed can directly feed water as middle low-pressure boiler and carry out reuse.Adopt this Technology to have to produce that water water quality is good, treatment effect stable, shock-resistance is strong, the low grade heat energy utilising efficiency is high, investment 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 of method for the treatment of steam condensed water by virtue of organic separation membrane, comprise the steps: the first step, the condensed water in high temperature of condensate water collecting system is sent into high temperature resistant ultrafiltration membrance filter system under the effect of pump, remove in the condensed water system oil in water emulsion (particle size range 0.1-0.2 μ m) or because impacting oil slick (＞100 μ m) and dispersed oil (particle size range 10-100 μ m) and the metallic colloid (particle size range 0.001-0.1 μ m) that produces; Second step, the product water of the first step is sent into the high temperature reverse osmosis membrane system through high-pressure pump, further remove the dissolving oil or small organic molecule or a small amount of ionic state inorganic pollutant that contain in the condensed water that causes because of material from leakage or because of impact, the product water of above-mentioned second step is reuse water.The product water of above-mentioned second step satisfies middle low-pressure boiler moisturizing requirement, and the deaerating type of cycles that can directly send into middle low-pressure boiler enters boiler, thereby realizes the recovery of Low Temperature Thermal and water.
Condensed water in high temperature of the present invention refers to the steam indirect heating material in the refinery process, such as the steam condenses that produces by processes such as coil pipe heating in crude oil and steam direct heating material such as catalytic reforming, the principal feature of this process steam condenses is: temperature 75-95 ℃, oil-contg 1-40mg/L, total iron content 0.5-2.0mg/L, SiO
2Content 50-150 μ g/L.
High temperature resistant ultrafiltration membrance filter of the present invention system can adopt 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 and curtain type film assembly.
The material of above-mentioned high temperature resistant hyperfiltration membrane assembly comprises and contains phthalazine biphenyl structure poly (aryl ether sulfone ketone) PPESK, poly (arylene ether nitrile) ketone PPENK, copolyether sulfone PPBES and polytetrafluoroethylene PTFE.
The aperture of the high temperature resistant ultra-filtration membrane of above-mentioned kind is 0.001-0.1 μ m, preferred 0.005-0.05 μ m.
The operation scheme of high temperature resistant ultra-filtration membrane of the present invention comprises cross flow filter technique and dead-end filtration technique, and wherein dead-end filtration technique can realize that go-and-retum is every water inlet.When the online detection of oil numerical value surpasses 30mg/L, the operation scheme of high temperature resistant ultrafiltration system adopts cross flow filter.When oil-contg was lower than 20mg/L, the operation scheme of high temperature resistant ultrafiltration system adopted the dead-end filtration mode, and adopted time variable control to realize alternately water inlet of two ends.When oil-contg during between 20mg/L-30mg/L, the operation scheme of high temperature resistant ultrafiltration system adopts the alternate run mode of dead end-cross-flow-dead end-cross-flow, and dead end working time is 30-60min, and the cross-flow cycle of operation is 60-120min.
The crossflow velocity of cross flow filter is 1m/s-6m/s in the above-mentioned high temperature resistant ultra-filtration membrane operation scheme; Can realize disperseing to wash, strengthening washing and soaking the periodical operation of washing in the operational process, wherein disperse to wash and can realize alternately water inlet of two ends, the water inlet cycle was respectively 15-30 minute; Backwashing time is 5-30 second; Operating flux in the ultrafiltration operational process is 50-1000L/m
2H, optimum is 100-300L/m
2H; The reinforcement of ultra-filtration membrane is washed and immersion is washed in the process mainly take the soda acid dosing as main.Wherein, acid mainly comprises: HC1, oxalic acid, citric acid, nitric acid, sulfuric acid and with composite clean-out system of EDTA etc.; Alkali mainly comprises: NaClO, NaOH etc. and the composite clean-out system that forms with EDTA thereof etc.
The membrane module of high temperature resistant reverse osmosis membrane filtration of the present invention system mainly adopts aromatic polyamides and the aromatic polyamides take polyethersulfone as counterdie take PPESK as counterdie, and high temperature resistant reverse osmosis membrane assembly type mainly comprises Duratherm-HWS-HR, Duratherm-STD, Duratherm-PRO, Duratherm-EXCEL, Duratherm-ELITE.
Above-mentioned high temperature resistant reverse osmosis system can improve by the mode of dense water cycle the system recoveries rate, has simultaneously dense water end (W.E.) counterflush function, can realize dense water end (W.E.) not timing flushing operation.The high temperature reverse osmosis system adopts n-2 assembly to produce water, 2 alternate run modes that assembly washes in operational process.
The operating parameter of above-mentioned high temperature resistant reverse osmosis system comprises: the reverse osmosis operating flux is 40-100L/m
2H, optimum is 50-80L/m
2H; RO system recoveries rate 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, under hot conditions, directly processes and little pollution steam condenses of reuse Petrochemical Enterprises, not only directly utilize the heat energy of high-temperature steam condensed water itself, and can reduce facility investment and the cooling-water consumption that treating processes is carried out in cooling, simultaneously the membrane sepn process has higher solution flux under hot conditions, miniaturization that can implement device and reduce process cost.
2, treatment process of the present invention produce water tank without other and system airtight, avoided water to contact with the external world and introduced new pollution, effluent quality is more reliable and more stable.
3, adopt high temperature resistant organic separation membrane that the removal of the oil in the condensed water in high temperature of Petrochemical Enterprises, colloid, suspended substance, small organic molecule and mineral ion is had the clearance height, produces water water quality is good, system run all right can be widely used in chemical industry the processing of non-normal temperature condensed water and reuse.
4, whole membrane treatment process operates under the hot conditions, and employing high temperature resistance diaphragm parting material, guaranteed the continuous and steady operation of whole system, and owing to the strong adaptability of film separating system to change of water quality, so do not need to be equipped with a large amount of online water quality monitoring instruments.
5, adopt most of assembly operating to produce the operation scheme that water, minute quantity assembly clean, can reduce effectively that pollutent is conducive to prolongation and the increase of film system cleaning interval in the accumulation of face in the membrane process.
6, high-temperature operation can be avoided the ultrafiltration in the normal-temperature operation process, flux decline and the shortening of cleaning interval that the pollution that causes because of microbial growth in the reverse osmosis membrane filtration process causes.
Description of drawings
Figure 1 shows that the processing of steam condenses high temperature embrane method and recovering process flow.Wherein:
A, condensed water withdrawing can come water; B, reverse osmosis produced water; C, ultrafiltration concentrate recirculation; D, reverse osmosis concentrated water reflux; E, reverse osmosis concentrated water discharging; F, ultrafiltration concentrated water discharge;
1, ultrafiltration service pump; 2, ultrafiltration membrane system; 3, reverse osmosis feedwater pump; 4, reverse osmosis membrane system
Embodiment
Below in conjunction with description of drawings of the present invention detailed process of the present invention.
The condensed water in high temperature that produces in the refinery process is sent into ultrafiltration membrane system 2 through ultrafiltration service pump 1, and the dense return pipe of the dense water part ultrafiltration road C that contains high oil, colloid concentration after ultrafiltration membrance filter separates returns the entrance of ultrafiltration service pump 1 or partly enters dense row pipeline F; Product water after the purification enters reverse osmosis system 4 and further removes small organic molecule or dissolving oil after high-pressure pump 3 is boosted, produce water and send into boiler systems; Reverse osmosis concentrated water section D is back to the entrance of ultrafiltration system, and the dense water E of part suitably processes rear discharging.
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not subjected to the restriction of these embodiment.
The technique of steam condenses precision processing as shown in Figure 1, come water to send into ultrafiltration membrane system by the ultrafiltration service pump vapor condenses water recovery tank, wherein the water quality of vapor condenses water recovery tank mainly comprises: wastewater temperature is 75 ℃, and oil-contg is 1.0mg/L, total iron content is 2.0mg/L, SiO
2Content is 150 μ g/L.Above-mentioned waste water is through being pumped into high temperature resistant ultrafiltration membrane system, and it is the rolled membrane module of membrane material that ultra-filtration membrane is selected PPESK, and the ultra-filtration membrane pore size is 0.005 μ m, and single ultra-filtration membrane useful area is 1.0m
2, the filtration flux size of ultra-filtration membrane is 50L/m
2H.The product water water quality of this ultrafiltration system is: 74 ℃ of temperature, and pH is 6.38, and hardness is 2.18mg/L, and oil-contg is 0.2mg/L, and total iron content is 447 μ g/L, SiO
2Content is 90 μ g/L, and TOC is 3.5mg/L.
Pollution of Ultrafiltration Membrane control mode in the present embodiment adopts the alternately mode of water inlet of two ends, and alternately flooding time is spaced apart 60 minutes, carries out acid adding and disperses to wash operation, and the acid adding scavenging period is 10 seconds, and the pH that controls respectively scavenging solution is 2 and 10; Carry out separately proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out acid soak after 8 times and strengthen cleaning operation; The acid soak time is 20 minutes, adopts the method for airflow stirring acid or washing lotion to strengthen iron colloid or the oily dissolving on ultra-filtration membrane surface in the immersion process, carries out afterwards 5 seconds flushing operations.
Ultrafiltration is produced the impact of water water quality for reducing the ultrafiltration intermediate water tank, patent of the present invention does not arrange intermediate water tank in implementation process, for the stability that guarantees operational process and the needs that clean, all the other were at the operation cleaning operation when membrane module of process using 2/3 of the present invention moved, and the technological process that employing operation and cleaning are carried out is simultaneously controlled the pollution and product water process of ultra-filtration membrane.
Ultrafiltration is produced water and is promoted to reverse osmosis system 4 through high-pressure pump 3, and the high temperature reverse osmosis system adopts DurathermEXCEL 2540 membrane modules, and the useful area of single membrane module is 2.3m
2, adopting the cross-flow operation scheme, the recovery per pass of control RO system is 15%, and it is 90% that the mode of employing part concentrate recirculation is adjusted the reverse osmosis system rate of recovery, and the reverse osmosis membrane flux is 40L/m
2H.Reverse osmosis produced water pH under this condition is 9.5, and hardness is 0.64mg/L, and oil-contg is 0.08mg/L, and total iron content is less than 40 μ g/L, SiO
2Content is less than 40 μ g/L, and TOC is 0.3mg/L; Product water water quality standard meets the regulation of middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2008).
CI in the reverse osmosis operational process and dissolving oil are to pollution reduction and the method for removing of film: the reverse osmosis membrane assembly for operational process adopts operation and cleans the mode of carrying out simultaneously, reverse osmosis membrane assembly is after moving 120 days continuously, Controlling System automatically switches to automatic cleaning running status, reverse osmosis membrane assembly under this state adopts the operation of (n-2) group, alternation procedure is carried out in 2 groups of cleanings, RO film system cleans and adopts respectively row acid, alkali soaks to be washed, above-mentioned membrane module carries out low pressure operation 10min under the atmosphere of scavenging solution, soak 15min, then soak after the circulation primary and adopt behind the 15min large flow cleaning to produce with UF after 10 minutes to enter normal operating condition after water is replaced scavenging solution.Finish follow-up reforwarding row when reverse osmosis membrane assembly all alternately cleans, thereby realize the overall circulation of operational process.
The technique of steam condenses precision processing as shown in Figure 1, come water to send into ultrafiltration membrane system by the ultrafiltration service pump vapor condenses water recovery tank, wherein the water quality of vapor condenses water recovery tank mainly comprises: wastewater temperature is 95 ℃, and oil-contg is 40mg/L, total iron content is 0.5mg/L, SiO
2Content is 50 μ g/L.The waste water of above-mentioned water quality is through being pumped into ultrafiltration membrane system, and ultra-filtration membrane is selected the PTFE hollow fiber film assembly, and the pore size of hollow fiber ultrafiltration membrane is 0.1 μ m, and single membrane module useful area is 1.0m
2, the filtration flux size of ultra-filtration membrane is 1000L/m
2H, the crossflow velocity of cross flow filter are 6m/s.The product water water quality of this ultrafiltration system is: 93 ℃ of temperature, and pH is 6.38, and hardness is 2.28mg/L, and oil-contg is 7.88mg/L, and total iron content is 380 μ g/L, SiO
2Content is 25 μ g/L, and TOC is 3.8mg/L.
Pollution of Ultrafiltration Membrane control mode in the present embodiment adopts the alternately mode of water inlet of cross-flow, two ends, and alternately flooding time is spaced apart 120 minutes, carries out acid adding and disperses to wash operation, and the soda acid scavenging period is 5 seconds, and control feedwater pH is 2 and 10 respectively; Carry out separately proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out acid soak after 6 times and strengthen cleaning operation; The acid soak time is 15 minutes, adopts the method for airflow stirring acid or washing lotion to strengthen iron colloid or the oily dissolving on ultra-filtration membrane surface in the immersion process, carries out afterwards 5 seconds flushing operations.
Ultrafiltration is produced the impact of water water quality for reducing the ultrafiltration intermediate water tank, patent of the present invention does not arrange intermediate water tank in implementation process, for the stability that guarantees operational process and the needs that clean, all the other were moving cleaning operation when the membrane module of process using 2/3 of the present invention moved, and the technological process that adopts operation and cleaning to replace, carry out is simultaneously controlled ultrafiltration membrane washing and the stable water process of producing.
Ultrafiltration is produced water and is promoted to reverse osmosis system 4 through high-pressure pump 3, and the high temperature reverse osmosis system adopts DurathermELITE 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 9%, and it is 70% that the mode of employing part concentrate recirculation is adjusted the reverse osmosis system rate of recovery, and the reverse osmosis membrane flux is 80L/m
2H.Reverse osmosis produced water pH under this condition is 7.5, and hardness is 0.78mg/L, and oil-contg is 0.12mg/L, and total iron content is less than 40 μ g/L, SiO
2Content is less than 40 μ g/L, and TOC is 0.5mg/L; Product water water quality standard meets the regulation of middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2008).
CI in the reverse osmosis operational process and dissolving oil are to pollution reduction and the method for removing of film: the reverse osmosis membrane assembly for operational process adopts operation and cleans the mode of carrying out simultaneously, reverse osmosis membrane assembly is after moving 30d continuously, Controlling System automatically switches to automatic cleaning running status, reverse osmosis membrane assembly under this state adopts the operation of (n-2) group, alternation procedure is carried out in 2 groups of cleanings, RO film system cleans and adopts respectively row acid, alkali soaks to be washed, above-mentioned membrane module carries out low pressure operation 30min under the atmosphere of scavenging solution, soak 15min, then soak after the circulation primary and adopt behind the 15min large flow cleaning to produce with UF after 60 minutes to enter normal operating condition after water is replaced scavenging solution.Finish follow-up reforwarding row when reverse osmosis membrane assembly all alternately cleans, thereby realize the overall circulation of operational process.
The technique of steam condenses precision processing as shown in Figure 1, come water to send into ultrafiltration membrane system by the ultrafiltration service pump 80 ℃ of vapor condenses water recovery tanks, wherein the water quality of vapor condenses water recovery tank mainly comprises: wastewater temperature is 80 ℃, and oil-contg is 10mg/L, total iron content is 1.0mg/L, SiO
2Content is 100 μ g/L.The waste water of above-mentioned water quality is through being pumped into ultrafiltration membrane system, and ultra-filtration membrane is selected the PPENK hollow fiber film assembly, and the pore size of hollow fiber ultrafiltration membrane is 0.001 μ m, and the effective film area is 1.0m
2, the filtration flux size of ultra-filtration membrane is 300L/m
2H, ultrafiltration system adopts the operation scheme of dead-end filtration.The product water water quality of this ultrafiltration system is 80 ℃ of temperature, and pH is 7.53, and hardness is 2.23mg/L, and oil-contg is 1.53mg/L, and total iron content is 313 μ g/L, SiO
2Content is 80 μ g/L, and TOC is 3.2mg/L.
Pollution of Ultrafiltration Membrane control mode in the present embodiment adopts the alternately mode of water inlet of two ends, and alternately flooding time is spaced apart 30 minutes, carries out acid adding and disperses to wash operation, and the soda acid scavenging period is 8 seconds, and control feedwater pH is 2 and 10 respectively; Carry out separately proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out acid soak after 4 times and strengthen cleaning operation; The acid soak time is 10 minutes, adopts the method for airflow stirring acid or washing lotion to strengthen iron colloid or the oily dissolving on ultra-filtration membrane surface in the immersion process, carries out afterwards 2 seconds flushing operations.
Ultrafiltration is produced the impact of water water quality for reducing the ultrafiltration intermediate water tank, patent of the present invention does not arrange intermediate water tank in implementation process, for the stability that guarantees operational process and the needs that clean, all the other were moving cleaning operation when the membrane module of process using 2/3 of the present invention moved, and the technological process that adopts operation and cleaning to replace, carry out is simultaneously controlled ultrafiltration membrane washing and the stable water process of producing.
Ultrafiltration is produced water and is promoted to reverse osmosis system 4 through high-pressure pump 3, and the high temperature reverse osmosis system adopts Duratherm HWS-HR 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 it is 85% 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.Reverse osmosis produced water pH under this condition is 9.0, and hardness is 0.71mg/L, and oil-contg is 0.07mg/L, and total iron content is less than 40 μ g/L, SiO
2Content is less than 40 μ g/L, and TOC is 0.27mg/L; Product water water quality standard meets the regulation of middle low-pressure boiler supplementary feed water quality standard (GB/T 1576-2008).
CI in the reverse osmosis operational process and dissolving oil are to pollution reduction and the method for removing of film: the reverse osmosis membrane assembly for operational process adopts operation and cleans the mode of carrying out simultaneously, reverse osmosis membrane assembly is after moving 90d continuously, Controlling System automatically switches to automatic cleaning running status, reverse osmosis membrane assembly under this state adopts the operation of (n-2) group, alternation procedure is carried out in 2 groups of cleanings, RO film system cleans and adopts respectively row acid, alkali soaks to be washed, above-mentioned membrane module carries out low pressure operation 20min under the atmosphere of scavenging solution, soak 10min, then soak after the circulation primary and adopt behind the 10min large flow cleaning to produce with UF after 20 minutes to enter normal operating condition after water is replaced scavenging solution.Finish follow-up reforwarding row when reverse osmosis membrane assembly all alternately cleans, thereby realize the overall circulation of operational process.
The technique of steam condenses precision processing as shown in Figure 1, come water to send into ultrafiltration membrane system by the ultrafiltration service pump vapor condenses water recovery tank, wherein the water quality of vapor condenses water recovery tank mainly comprises: wastewater temperature is 90 ℃, and oil-contg is 25mg/L, total iron content is 1.5mg/L, SiO
2Content is 80 μ g/L.The waste water of above-mentioned water quality is through being pumped into ultrafiltration membrane system, and ultra-filtration membrane is selected PPBEN curtain formula hyperfiltration membrane assembly, and the pore size of ultra-filtration membrane is 0.05 μ m, and the effective film area is 1.0m
2, the filtration flux size of ultra-filtration membrane is 100L/m
2The operation scheme that h, ultrafiltration system adopt dead end and cross flow filter to hocket, wherein the dead end cycle of operation is that 30 minutes, the cross-flow cycle of operation are 60min, the crossflow velocity of cross flow filter is 3m/s; Ultrafiltration system rate of recovery size is controlled to be 90%.The product water water quality of this ultrafiltration system is: 89 ℃ of temperature, and pH is 5.54, and hardness is 2.08mg/L, and oil-contg is 0.71mg/L, and total iron content is 655 μ g/L, SiO
2Content is 50 μ g/L, and TOC is 4.3mg/L.
Pollution of Ultrafiltration Membrane control mode in the present embodiment adopts the alternately mode of water inlet of two ends, wherein the alternately flooding time interval in dead end operation and the cross-flow operational process was respectively 15 minutes and 30 minutes, carry out acid adding and disperse to wash operation, the soda acid scavenging period is 15 seconds, and control feedwater pH is 2 and 10 respectively; Carry out separately proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out acid soak after 2 times and strengthen cleaning operation; The acid soak time is 10 minutes, adopts the method for airflow stirring acid or washing lotion to strengthen iron colloid or the oily dissolving on ultra-filtration membrane surface in the immersion process, carries out afterwards 3 seconds flushing operations.
Ultrafiltration is produced the impact of water water quality for reducing the ultrafiltration intermediate water tank, patent of the present invention does not arrange intermediate water tank in implementation process, for the stability that guarantees operational process and the needs that clean, all the other were moving cleaning operation when the membrane module of process using 2/3 of the present invention moved, and the technological process that adopts operation and cleaning to replace, carry out is simultaneously controlled ultrafiltration membrane washing and the stable water process of producing.
Ultrafiltration is produced water and is promoted to reverse osmosis system 4 through high-pressure pump 3, and the high temperature reverse osmosis system adopts 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 11%, 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 100L/m
2H.Reverse osmosis produced water pH under this condition is 6.71, and hardness is 0.50mg/L, and oil-contg is 0.06mg/L, and total iron content is less than 40 μ g/L, SiO
2Content is less than 40 μ g/L, and TOC is 0.66mg/L; Product water water quality standard meets the regulation of middle low-pressure boiler supplementary feed water quality standard (GB/T1576-2008).
CI in the reverse osmosis operational process and dissolving oil are to pollution reduction and the method for removing of film: the reverse osmosis membrane assembly for operational process adopts operation and cleans the mode of carrying out simultaneously, reverse osmosis membrane assembly is after moving 45d continuously, Controlling System automatically switches to automatic cleaning running status, reverse osmosis membrane assembly under this state adopts the operation of (n-2) group, alternation procedure is carried out in 2 groups of cleanings, RO film system cleans and adopts respectively row acid, alkali soaks to be washed, above-mentioned membrane module carries out low pressure operation 25min under the atmosphere of scavenging solution, soak 10min, then soak after the circulation primary and adopt behind the 10min large flow cleaning to produce with UF after 40 minutes to enter normal operating condition after water is replaced scavenging solution.Finish follow-up reforwarding row when reverse osmosis membrane assembly all alternately cleans, thereby realize the overall circulation of operational process.
Claims (6)
1. the method for a treating steam condensed water by virtue of organic separation membrane comprises the steps:
(1) condensed water in high temperature of condensate water collecting system is sent into high temperature resistant ultrafiltration membrance filter system under the effect of pump, removed the oil in water emulsion of particle size range 0.1～0.2 μ m in the condensed water system or because impacting oil slick and particle size range 10～100 μ m dispersed oils and particle size range 0.001～0.1 μ m metallic colloid that produces＞100 μ m;
(2) the product water of the first step is sent into the high temperature reverse osmosis membrane system through high-pressure pump, further remove the dissolving oil or small organic molecule or a small amount of ionic state inorganic pollutant that contain in the condensed water that causes because of material from leakage or because of impact, the product water of above-mentioned second step is reuse water;
Wherein, described condensed water in high temperature refers to the steam condenses that the steam indirect heating material process in the refinery process produces, and the principal feature of described steam condenses is: 75～95 ℃ of temperature, oil-contg 1～40mg/L, total iron content 0.5～2.0mg/L, SiO2 content 50～150 μ g/L; The material of described high temperature resistant hyperfiltration membrane assembly comprises and contains phthalazine biphenyl structure poly (aryl ether sulfone ketone) PPESK, poly (arylene ether nitrile) ketone PPENK, copolyether sulfone PPBES and polytetrafluoroethylene PTFE; The membrane module material of described high temperature reverse osmosis membrane system mainly adopts aromatic polyamides and the aromatic polyamides take polyethersulfone as counterdie take PPESK as counterdie.
2. method according to claim 1, the form of wherein said high temperature resistant hyperfiltration membrane assembly adopts hollow fiber film assembly or curtain type film assembly.
3. method according to claim 1, the aperture of wherein said high temperature resistant ultra-filtration membrane is 0.001～0.1 μ m.
4. method according to claim 3, the aperture of wherein said high temperature resistant ultra-filtration membrane is 0.005～0.05 μ m.
5. method according to claim 1, wherein said high temperature reverse osmosis membrane assembly type mainly comprises Duratherm-HWS-HR, Duratherm-STD, Duratherm-PRO, Duratherm-EXCEL, Duratherm-ELITE.
6. method according to claim 1, high temperature resistant reverse osmosis system adopt n-2 assembly to produce water, 2 alternate run modes that assembly washes in operational process.
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