CN101092258A - Method for processing high temperature condensed water by integration technique of membrane - Google Patents
Method for processing high temperature condensed water by integration technique of membrane Download PDFInfo
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Abstract
This invention relates to a method for treating high-temperature condensate by membrane integration process. The method comprises: filtering 50-95 deg.C high-temperature condensate by using a microfiltration or ultrafiltration membrane with 0.01-1 mu.m pore sizes under 0.01-1.5 MPa, intercepting the majority of oils, colloids and suspending impurities in water, and performing the following adsorption or ion exchange treatment. The method solves the problems of unstable treatment effect and frequent change of adsorption material faced by the conventional method, and provides a stable and effective route for treatment of high-temperature condensate.
Description
Technical field
The present invention relates to a kind of method of purifying treatment condensed water in high temperature, particularly a kind of integration technique of membrane was handled the method for boiler hot steam condensed water in high temperature, belonged to water treatment and energy recovery technical field.
Background technology
Industry such as chemical industry, thermoelectricity extensively adopts superheated vapour to use as heat power and thermal source, and superheated vapour is condensed into condensed water in high temperature through power consumption and heat exchange, and water temperature is generally at 50 ℃～95 ℃, has quite high hot monodrome.It is calculated that 1 ton 90 ℃ condensed water in high temperature has 4.94 yuan hot monodrome, the remarkable in economical benefits that reclaims.
If it is not comtaminated, steam condenses is bordering on purified distilled water, can the back boiler recycling, but the steam condenses of most of enterprises is because reasons such as corrosive pipeline, material from leakage, mismanagements, exist pollutents such as small amount of solid impurity, oil, colloid, solubility small organic molecule and mineral ion, so can not directly advance the boiler recycling, causing now, the condensed water in high temperature great majority of most of enterprises discharge on the spot, not only wasted great amount of water resources and heat energy, also caused thermal pollution to a certain degree to environment.
In general, condensing water temperature is generally at 50 ℃～95 ℃, and traditional boiler water treatment equipment only can be handled the condensed water below 50 ℃, therefore before advancing traditional boiler water treatment equipment, need the condensed water processing that cools, need the large-scale heat-exchange equipment of configuration, not only increased facility investment, wasted heat energy, but also may make water quality further contaminated.Given this plant the result, the patent No. is that 200410030636.7 patent of invention adopts lost efficacy as yet regenerated resin anion(R.A) bed not of water treatment workshop section to remove micro oil and organism in the steam condensate, but this method is embodied as the intermittent operation process, the resin regeneration process is more loaded down with trivial details, and the oil in the condensed water stops up the resin duct easily, and resin is caused the harm of irrecoverable property; The patent No. is that 02236450.1 utility model discloses a kind of condensed water in high temperature deironing apparatus, employing can be removed iron ion in the condensed water in high temperature with iron ion quick response filler, but this device is primarily aimed at the removal of the iron ion in the condensed water in high temperature and designs, and very poor to the removal effect of oil, colloid, solubility small organic molecule and mineral ion, also exist oil simultaneously and coat the drawback that filler can not effectively carry out the iron ion removal; Fushun petrochemical industry branch office of Sweet natural gas company limited of PetroChina Company Limited. introduction of foreign technology, adopt the activated charcoal filter pre-treatment to add powdered resin precoat filter advanced treatment condensed water in high temperature, can effectively remove iron, silicon, wet goods impurity in the condensed water, but because the oil in the condensed water stops up the duct easily, cause the filtering capacity of gac and resin absorption to significantly reduce, so will frequently change, it is loaded down with trivial details to exist the operation operation, the expense problem of higher.
One contains oil steam condenses, solid impurity, colloid, pollutents such as solubility small organic molecule and mineral ion, and temperature is than higher, the reuse of condensed water is very high to reliability requirement to boiler, handling technology of water supply brings bigger difficulty, the scope that has exceeded the conventional boiler water technology, the many employings of existing condensed water in high temperature treatment technology are directly advanced adsorption bed the method that pollutent carries out adsorption treatment are handled condensed water in high temperature, yet the hole of sorbing material is generally very little in the adsorption treatment, big elaioleucite and other pollutents can block the aperture very soon, if fail with this part pollutant removal, then pollutent such as elaioleucite can adsorb the duct with the outside very soon and blocks, make the inner duct of sorbing material ineffective, adsorptive power descends, and it is saturated to cause sorbing material to produce " hunger " property.
At present China also has the condensed water of quite a lot of relevant enterprise not reclaim to make boiler feed water, and its major cause is to lack stabilizing effective water treatment method.
Summary of the invention
The objective of the invention is water quality characteristics at condensed water in high temperature, a kind of processing high temperature condensed water by integration technique of membrane method is provided, solve conventional treatment method treatment effect instability, need the frequent problem of changing sorbing material, realize treat effluent reuse up to standard, handling with reuse for the condensed water in high temperature of relevant enterprise provides stable, a valid approach.
The method that condensed water in high temperature film of the present invention is handled is to be that 50 ℃～95 ℃ condensed water in high temperature is under 0.01～1.5MPa pressure with temperature, via hole diameter is micro-filtration or the ultrafiltration membrance filter of 0.01～1 μ m, most of oil, colloid and suspended contamination in the trap water, except that pollutents such as remaining solubilised state oil, colloid, small organic molecule in anhydrating, said sorbent material is selected from one or more in gac, expanded graphite, modified fibre, hard coal, quartz sand, the polymeric adsorbent to the film permeate water through adsorbents adsorb.
For the condensed water in high temperature that contains type impurity ion, then after adsorption step or before wherein mineral ion impurity is removed in feed liquid spent ion exchange resin absorption.
Condensed water in high temperature after above processing reaches the oiler feed index, and direct reuse is made the boiler supplementary feed.
Said micro-filtration or ultrafiltration membrance filter can adopt dead-end filtration or cross flow filter mode.
The dead-end filtration mode is: the feed liquid of condensed water in high temperature is pumped to the feeding side of film, sees through the side that sees through that liquid enters film, and the thing that do not see through that is trapped is stranded on the face of feeding side.Lower (＜10mg/L) condensed water in high temperature, the oil in its water is many to be existed with solubilised state, is easy to see through fenestra, film is polluted lighter, is applicable to the dead-end filtration mode for oleaginousness.
Therefore the pollution layer on dead-end filtration palpus periodic purge film surface mostly is periodical operation.The film cleaning way adopts the pressurized air recoil or adds the mode of chemical agent high flow rate flushing face, and the recoil time is 3-20s.For ease of cleaning, preferentially adopt film hollow-fibre membrane or tubular membrane.
The operational process of cross flow filter is: the feed liquid of condensed water in high temperature is admitted to the feeding side of film under pumping action, be parallel to face continuous flow, crossflow velocity is 0.5-5m/s, wherein the part clear liquid sees through the side that sees through that fenestra enters film, not seeing through liquid discharges and the returns flow container from the outlet of film feeding side at last, feed liquid is constantly circulation between material liquid tank and film filter, constantly leach simultaneously clear liquid, the contained pollutent of feed liquid thickens gradually, after membrane flux is reduced to a certain degree, clean the crossflow velocity 3-8m/s during cleaning with spissated sewage discharge and to film.
Adopt the cross flow filter mode to make feed liquid be parallel to face and flow, produce shearing force when flowing through face the particle that does not see through that is trapped on the face is taken away, thereby make the pollution of face remain on lower level, entire operation is continuous working cycle.Higher (＞20mg/L) condensed water in high temperature exists with dispersed and emulsification attitude because of the oil in the water is many, more easily pollutes face, adopts wrong filter side comparatively favourable for oleaginousness.
Adopt the film of cross flow filter to can be hollow-fibre membrane, tubular membrane or rolled film.
For the steam condenses of oleaginousness, can select the operating method of dead-end filtration or cross flow filter for use in conjunction with practical situation at 10mg/L～20mg/L.
After condensed water in high temperature passed through micro-filtration or ultra-filtration membrane pre-treatment, oleaginousness can be reduced to below the 5mg/L in the water, has solid suspension content＜5mg/L substantially with solubilised state oil.
Micro-filtration of the present invention or ultra-filtration membrane are to use under 50 ℃～95 ℃ high temperature, and membrane flux is 3-5 times under the normal temperature, so facility investment and working cost reduce greatly, hydromining per ton is no more than 1.5 yuan with the working cost of cross flow filter.Compare with cross flow filter, dead-end filtration is because of adopting acyclic filter type, energy consumption can drop to cross flow filter 1/10 in addition lower, its water running expense per ton is no more than 0.15 yuan.Present method adopts micro-filtration or ultra-filtration membrane pre-treatment, removed oil particles bigger in the condensed water and other easily stop up the pollutent in sorbing material ducts, make the water conditioning of follow-up adsorption system water inlet, can not produce the situation that the sorbing material duct is stopped up by oil, therefore the replacement cycle of sorbing material prolongs greatly, ratio prolonged more than 9 times without the pretreated replacement cycle of film, and then reduced labour intensity, helped equipment operation steady in a long-term.
Adsorption treatment adopts the fixed bed mode, filtration velocity is 4～20m/h, because the foreign matter content of micro-filtration or ultrafiltration membrance filter water outlet seldom, can prolong greatly the work-ing life of sorbing material, can reach more than one month general working time, conversion materials more when the oil-contg in the adsorption treatment water outlet surpasses 5mg/L.If the ion content in the condensed water exceeds standard, then follow-uply to add ion-exchange treatment process in addition in order to remove ion; If the ion content in the condensed water is original just lower, can satisfy the oiler feed water-quality guideline, then can save follow-up ion-exchange treatment process in conjunction with practical situation.
Ion exchange treatment adopts the fixed bed mode, can handle condensed water by cation exchange resin bed and anion exchange resin bed respectively, or directly adopt ion-exchange to mix bed and handle, because the ion content in the steam condenses is very low, just can make water outlet up to standard so generally adopt ion-exchange to mix bed, condensed water is 4～20m/h by the speed of ion exchange resin bed.The introducing of impurity has not only been avoided in the airtight operation of total system, and the iron ion that also helps control ion exchange resin pollutes, and goes out water power and leads and generally can be stabilized in below the 10 μ S/cm, when going out water power and lead greater than 20 μ S/cm, resin is regenerated.
The present invention has following beneficial effect:
(1) owing to move under hot conditions, the filtration flux of micro-filtration or ultra-filtration membrane is bigger, miniaturization that can implement device and reduce process cost.
(2) the airtight operation of total system has avoided water to introduce new pollution with extraneous the contact, and stable effluent quality is reliable.
(3) because FEOL adopts micro-filtration or ultrafiltration membrance filter membrane filtration, pollutents such as most of solid impurity, oil and colloid have been removed, make that the water quality that enters subsequent technique is simple relatively, help the long-term stability operation of subsequent technique, prolonged the work-ing life of sorbing material and ion-exchange material more than 9 times, and then reduction labour intensity, help equipment operation steady in a long-term.
(4) the various impurity of various impurity such as the suspended substance in the condensed water in high temperature, oil, colloid, solvability small organic molecule and mineral ion are all had good effect of removing, the condensed water in high temperature that is widely used in industries such as chemical industry, thermoelectricity is handled, and effluent quality is good.
Description of drawings
Accompanying drawing 1 is the process flow sheet of integrated absorption of film and ion exchange process condensed water in high temperature;
Accompanying drawing 2 is the process flow sheet of integrated ion-exchange of film and absorbing process condensed water in high temperature;
Accompanying drawing 3 is the process flow sheet of the integrated absorbing process condensed water in high temperature of film;
Wherein A is the condensed water in high temperature water inlet, and B is the condensed water in high temperature water outlet after handling, and 1 is container for storing liquid, and 2 is transferpump, and 3 is the membrane filtration processing unit, and 4 is the adsorption treatment unit, and 5 is the ion exchange treatment unit.
Embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment 1 (flow process such as Fig. 1)
50L65 ℃ steam condenses A is fed condensate polishing system, and the water quality of steam condenses is as shown in table 1.
It is the modified poly (ether-sulfone) hollow fiber microfiltration membrane of 0.8 μ m that membrane filter unit 3 adopts the aperture, and membrane area is 8m
2Adopt dead-end filtration mode as shown in Figure 1, membrane filter unit 3 is the modified poly (ether-sulfone) hollow fiber microfiltration membrane, it is placed in the condensed water in high temperature basin 1, provide power by the suction pump 2 that is connected the membrane permeation side, working pressure is 0.02MPa, with this understanding, the stabilized flux through microfiltration membrane is 0.5m
3/ h, the membrane filtration effluent quality is as shown in table 1.
Aspirate out the film permeate water of membrane filter unit 3 and send into adsorption treatment unit 4 by pump 2, the fixed adsorption bed that the adsorption treatment unit adopts 20 order active fruit shell carbons to fill, flow velocity is 10m/h, absorption effluent water quality is as shown in table 1.
Ion-exchange unit 5 is advanced in the adsorption treatment water outlet, successively through D001 type cation exchange resin bed and D201 type anion exchange resin bed, effluent quality is as shown in table 2, every index reaches boiler water-filling water-quality guideline (GB1576-2001) fully, and boiler water-filling is made in treated water outlet B reuse.
Table 1 film processing system Inlet and outlet water is with each step effluent quality data
| The water quality project | Influent quality | Membrane filtration water quality | Adsorption treatment water quality | Ion exchange treatment water quality |
| Oil, mg/L | 15 | 4.5 | 0.5 | 0.1 |
| Specific conductivity, μ S/cm | 78 | 76 | 53 | 8 |
| Chemical oxygen demand, mg/L | 53 | 18 | 12 | 5 |
| Suspended substance, mg/L | 18 | 5 | 0.5 | 0.3 |
| Iron, μ g/L | 850 | 453 | 131 | 23 |
| Silicon-dioxide, μ g/L | 4 | 3 | 0.5 | 0.3 |
| Dissolved oxygen, μ g/L | 5 | 5 | 3 | 3 |
| Temperature, ℃ | 65 | 65 | 65 | 65 |
Embodiment 2 (flow process such as Fig. 2)
50L, 80 ℃ steam condenses A are fed condensate polishing system, and the water quality of steam condenses is as shown in table 1.
It is the 19 passage tubular type ceramic microfiltration membranes of 200nm that membrane filter unit 3 adopts the aperture, and membrane area is 0.5m
2Adopt dead-end filtration mode as shown in Figure 2, membrane filter unit 3 is the hyperchannel tube type filter membrance of zirconia material, be connected with condensed water in high temperature basin 1, provide power by the impeller pump 2 that is connected between condensed water in high temperature basin and the film import, working pressure 1.2MPa, the average flux of microfiltration membrane is 1.7m3/h with this understanding, when membrane flux drops to 0.5m
3During/h, the logical pressurized air of ceramic membrane per-meate side is carried out back flushing 10s, continue water inlet and pressure filtration then, the membrane filtration effluent quality is as shown in table 2.
The film permeate water of membrane filter unit 3 enters ion-exchange unit 5, and through the hybrid resin bed of D001 type positively charged ion and the filling of D201 type anionite-exchange resin, effluent quality is as shown in table 2.
Water after ion exchange treatment enters adsorption treatment unit 4, the hybrid resin bed that the adsorption treatment unit adopts quartz sand and macroporous adsorbent resin to fill, flow velocity is 8m/h, effluent quality is as shown in table 2, every index reaches boiler water-filling water-quality guideline (GB1576-2001) fully, and boiler water-filling is made in treated water outlet B reuse.
Table 2 film processing system Inlet and outlet water and each step effluent quality data
| The water quality project | Influent quality | Membrane filtration water quality | Ion exchange treatment water quality | Adsorption treatment water quality |
| Oil, mg/L | 9 | 3.2 | 0.6 | 0.2 |
| Specific conductivity, μ S/cm | 53 | 51 | 5 | 6 |
| Chemical oxygen demand, mg/L | 37 | 19 | 5 | 2 |
| Suspended substance, mg/L | 15 | 2 | 2.8 | 2.5 |
| Iron, μ g/L | 950 | 637 | 142 | 37 |
| Dissolved oxygen, μ g/L | 4 | 4 | 4 | 3 |
| Temperature, ℃ | 80 | 80 | 80 | 80 |
Embodiment 3 (flow process such as Fig. 3)
50L, 95 ℃ steam condenses A are fed condensate polishing system, and the water quality of steam condenses is as shown in table 3.
It is the 19 passage tubular type ceramic super-filtering films of 20nm that membrane filter unit 3 adopts the aperture, and membrane area is 3m
2Adopt cross flow filter mode as shown in Figure 3; membrane filter unit 3 is the hyperchannel tubular type ultra-filtration membrane of alumina material; be connected with condensed water in high temperature basin 1; provide power by the impeller pump 2 that is connected between condensed water in high temperature basin and the film import; working pressure 0.35MPa; condensed water in high temperature in the container for storing liquid 1 is sent into ultra-filtration membrane one side of membrane filtration processing unit 3 by pump 2; see through the opposite side (promptly seeing through side) that liquid penetrates film; not seeing through liquid continues to flow along face; return container for storing liquid 1 at last, form circulation, along with constantly carrying out of membrane filtration processes; the Pollutant levels of water are cumulative in the container for storing liquid 1, clean to seeing through to shut down when flow quantity obviously reduces.The membrane filtration effluent quality is as shown in table 2.
The membrane filtration permeate water outlet enters adsorption treatment unit 4, sorbing material adopts modified fibre and macroporous adsorbent resin, flow velocity is 5m/h, effluent quality is as shown in table 2, every index reaches boiler water-filling water-quality guideline (GB1576-2001) fully, and boiler water-filling is made in treated water outlet B reuse.
Table 3 film processing system Inlet and outlet water and each step effluent quality data
| The water quality project | Influent quality | Membrane filtration water quality | Adsorption treatment water quality |
| Oil, mg/L | 35 | 2.8 | 0.2 |
| Specific conductivity, μ S/cm | 10 | 9 | 9 |
| Chemical oxygen demand, mg/L | 113 | 12 | 3 |
| Suspended substance, mg/L | 24 | 2 | 2.9 |
| Iron, μ g/L | 950 | 156 | 13 |
| Silicon-dioxide, μ g/L | 5 | 3.8 | 0.6 |
| Dissolved oxygen, μ g/L | 4 | 4 | 3 |
| Temperature, ℃ | 95 | 95 | 95 |
Claims (9)
1. processing high temperature condensed water by integration technique of membrane method, it is characterized in that the condensed water in high temperature feed liquid under 0.01～1.5MPa pressure, with the aperture is micro-filtration or the ultrafiltration membrance filter of 0.01～1 μ m, most of oil, colloid and suspended contamination in the trap water, the membrane filtration fluid is handled with adsorbents adsorb, further, must purify waste water except that remaining solubilised state oil, colloid, small molecules organic pollutant in anhydrating.
2. processing high temperature condensed water by integration technique of membrane method according to claim 1, it is characterized in that after said adsorption step or before feed liquid is removed ionic impurity by ion exchange resin bed absorption.
3. processing high temperature condensed water by integration technique of membrane method according to claim 1 is characterized in that said sorbent material is selected from one or more in gac, expanded graphite, modified fibre, hard coal, quartz sand, the polymeric adsorbent.
4. processing high temperature condensed water by integration technique of membrane method according to claim 1 and 2 is characterized in that said micro-filtration or ultrafiltration membrance filter adopt the dead-end filtration mode.
5. processing high temperature condensed water by integration technique of membrane method according to claim 4 is characterized in that micro-filtration or ultra-filtration membrane adopt hollow-fibre membrane or tubular membrane.
6. processing high temperature condensed water by integration technique of membrane method according to claim 1 and 2 is characterized in that said micro-filtration or ultrafiltration membrance filter adopt the cross flow filter mode, and the crossflow velocity of feed liquid is 0.5-5m/s.
7. processing high temperature condensed water by integration technique of membrane method according to claim 6 is characterized in that micro-filtration or ultra-filtration membrane adopt hollow-fibre membrane, tubular membrane or rolled film.
8. processing high temperature condensed water by integration technique of membrane method according to claim 2 is characterized in that said ion exchange resin bed is a zwitterion hybrid resin bed.
9. processing high temperature condensed water by integration technique of membrane method according to claim 2, the said ion exchange resin bed of its feature comprises resin cation (R.C.) bed and resin anion(R.A) bed.
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| CN101857323A (en) * | 2010-06-18 | 2010-10-13 | 华电水处理技术工程有限公司 | Method and device for power station condensed water fine treatment |
| CN102295356A (en) * | 2010-06-28 | 2011-12-28 | 中国石油化工股份有限公司 | Method for treating steam condensed water by virtue of organic separation membrane |
| CN103657413A (en) * | 2012-09-14 | 2014-03-26 | 浙江中凯瑞普环境工程股份有限公司 | Purifying method of high-temperature condensed water |
| CN105923804A (en) * | 2016-05-23 | 2016-09-07 | 浙江中凯瑞普环境工程股份有限公司 | High-temperature-condensed-water oil removing technology |
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| CN110803735A (en) * | 2019-12-09 | 2020-02-18 | 陕西省石油化工研究设计院 | Steam condensate water treatment device and treatment method thereof |
| CN111204897A (en) * | 2020-01-16 | 2020-05-29 | 易通清源环保科技(北京)有限公司 | Condensed water treatment device and condensed water treatment process |
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| CN101857323A (en) * | 2010-06-18 | 2010-10-13 | 华电水处理技术工程有限公司 | Method and device for power station condensed water fine treatment |
| CN102295356A (en) * | 2010-06-28 | 2011-12-28 | 中国石油化工股份有限公司 | Method for treating steam condensed water by virtue of organic separation membrane |
| CN102295356B (en) * | 2010-06-28 | 2013-05-01 | 中国石油化工股份有限公司 | Method for treating steam condensed water by virtue of organic separation membrane |
| CN103657413A (en) * | 2012-09-14 | 2014-03-26 | 浙江中凯瑞普环境工程股份有限公司 | Purifying method of high-temperature condensed water |
| CN103657413B (en) * | 2012-09-14 | 2016-07-06 | 浙江中凯瑞普环境工程股份有限公司 | A kind of purification method of condensed water in high temperature |
| CN105923804A (en) * | 2016-05-23 | 2016-09-07 | 浙江中凯瑞普环境工程股份有限公司 | High-temperature-condensed-water oil removing technology |
| CN107540107A (en) * | 2016-06-29 | 2018-01-05 | 中国石油化工股份有限公司 | The depth of oil refining stripping purified water removes oil purification processes |
| CN110373706A (en) * | 2019-08-22 | 2019-10-25 | 电子科技大学 | A kind of on-line maintenance method of acid bright copper plating electroplate liquid |
| CN110373706B (en) * | 2019-08-22 | 2021-05-14 | 电子科技大学 | Online maintenance method of acidic bright copper plating electroplating solution |
| CN110803735A (en) * | 2019-12-09 | 2020-02-18 | 陕西省石油化工研究设计院 | Steam condensate water treatment device and treatment method thereof |
| CN111204897A (en) * | 2020-01-16 | 2020-05-29 | 易通清源环保科技(北京)有限公司 | Condensed water treatment device and condensed water treatment process |
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