CN102942276B - Boiler feedwater treatment method and treatment system related to reuse of reclaimed water - Google Patents
Boiler feedwater treatment method and treatment system related to reuse of reclaimed water Download PDFInfo
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Abstract
The invention provides a boiler feedwater treatment method and a treatment system related to the reuse of reclaimed water. The treatment method comprises the following steps: (1) carrying out self-cleaning filtration on raw water with a conductivity of 500-1700muS/cm and then carrying out microfiltration, thus obtaining water with a fouling index being lower than 3, turbidity being equal to or lower than 0.05NTU and suspended solid concentration being smaller than 1mg/L; (2) carrying out pre-desalination through primary reverse osmosis and secondary reverse osmosis on the water obtained by microfiltration in step (1), thus obtaining water with the conductivity being smaller than 20muS/cm; and (3) by adopting a continuous electrodeionization method, carrying out deep desalination on the primarily desalinated water obtained by pre-desalination in step (2), thus obtaining desalinated water with conductivity being smaller than or equal to 0.2muS/cm. The treatment method is efficient and environment-friendly and has various advantages in the aspects of investment, operation and maintenance.
Description
Technical field
The present invention is a kind of Boiler water Feeding System method and treatment system that relates to middle water reuse.
Background technology
Along with the continuous expansion of throughput and the continuous input of new production line, the demand of water resources is also grown with each passing day.Under water resources situation day by day in short supply, formulate a strict ton steel and consumed new water index.For this reason, company has strengthened the dynamics of sewage disposal and middle water reuse.Under this background, the research and development of the 1500000 tons of project assorted engineering 2 × 300MW of stainless steel generating set Boiler water Feeding System systems, waterborne in just naturally former water being set in.
The water source of traditional boiler feedwater adopts and draws yellow water, and its composition is equivalent to domestic water---tap water substantially, and specific conductivity is about 500 μ S/cm.Preparation technology mainly utilizes coagulating sedimentation+mechanical filter+cation bed+anion bed+mixed bed technique, produces de-mineralized water.Coagulation, clarification, filtration remove suspended substance and colloid, and ion exchange technique is removed various salt ions in water, but it exists two subject matters: the one, and the efficiency of pretreatment system is not high, long flow path, floor space is large, and effect is unstable.The 2nd, ion exchange resin need, with the regeneration of high density soda acid, discharge acidic and alkaline waste water in a large number, particularly exceedes the middle water of 1000mg/L for saltiness, and its ion exchange regenerant is very frequent, and environmental pollution is serious, running cost is high.
In recent years, microfiltration membrane utilization is more and more extensive, because of its flow process short, maintenance is little, many-sided reasons such as shock resistance is strong, the water source of applicable water quality relative mistake, just progressively replace traditional boiler feedwater pretreatment method (mainly utilizing coagulating sedimentation+mechanical filter).Reverse osmosis technology (RO) the at home and abroad application of water treatment field is also day by day ripe, has progressively substituted the multiple bed process that adopts ion exchange resin.Micro-filtration and reverse osmosis technology (RO) coupling can farthest be brought into play to reverse osmosis technology in the technical superiority aspect sewage disposal.Continuous electrodeionization technology (CEDI) ratio of desalinization is high, stable water outlet, level of automation is high, concentrate operation, maintenance workload is few, use it for boiler feed water system deep desalting, will be greatly reduce and use in the past the many problems that run in mixed bed, eliminated simultaneously and used the pollution to environment of high density soda acid regenerative wastewater that ion exchange technique brings.
But so far, there is no a kind of technology, can, in conjunction with the advantage of above-mentioned three kinds of technology, realize higher effect, stable, save energy, and environmentally friendly process the water source that comprises the middle water that saltiness is high, thus by middle water treatment for can be used in boiler feedwater.
Summary of the invention
In order to realize the reuse of centering water, water source using middle water as boiler feedwater, thereby reduce the production cost of whole industrial chain and economize on resources, the present inventor has developed micro-filtration+two steps ro+continuous electrodeionization " full embrane method " Boiler water Feeding System method, by specific conductivity 1200～1700 μ S/cm, the water hardness is 5～10mmol/L approximately, the middle water treatment of silicon-dioxide 2000～8000 μ g/L is high-quality de-mineralized water, for 2 × 300MW subcritical boiler supplementary feed and other mesohigh waste heat boiler supplementary feed etc.
Under the object that strengthens sewage disposal and middle water reuse dynamics promotes, contriver has carried out the research and development of the 1500000 tons of project assorted engineering 2 × 300MW of stainless steel generating set Boiler water Feeding System systems, in aiming under the prerequisite of water as former water, by contrasting new and old different process, consider for many kinds, final Application and Development " full embrane method " water treatment method of micro-filtration+two steps ro+CEDI, be specific conductivity≤0.2 μ S/cm by middle water treatment, hardness ≈ 0 μ mol/L, the high-quality de-mineralized water of silicon-dioxide≤20 μ g/L, thereby for 2 × 300MW subcritical boiler supplementary feed, two electric medium pressure boiler supplementary feed and newly steel-making, new coking high pressure waste heat boiler supplementary feed etc.
Main thought of the present invention is: utilize various membrane separation techniques to build the Boiler water Feeding System flow process of micro-filtration+two steps ro+CEDI, replace the de-mineralized water water preparation process of traditional coagulating sedimentation+mechanical filter+cation bed+anion bed+mixed bed, and by the introducing Boiler water Feeding System system water source of middle water novelty.Wherein, micro-filtration is compared with traditional preconditioning technique, and it is better that it produces water water quality, can provide best protection for downstream reverse osmosis membrane, and making sewage or waste water enter reverse osmosis desalination becomes possibility; Reverse osmosis is the core of desalination in this technique, and it can remove more than 98% various ions; CEDI replaces traditional mixed bed, without consuming just high purity water continuously of soda acid, is the new technology of an environmental protection.
The present invention relates to a kind of water treatment method for boiler feed water system, comprise the following steps:
(1) centering water carries out micro-filtration processing;
(2) micro-filtration step () micro-filtration being obtained produces water and carries out pre-desalting treatment;
And the one-level de-mineralized water that (three) obtain the pre-desalting treatment of step (two) carries out deep desalting treatment by continuous electrodeionization method, obtain final high-quality de-mineralized water.
The invention still further relates to a kind of water treatment system for boiler feed water system, comprise following apparatus:
(1) the following system connecting successively: microfiltration systems; Pre-desalination system; Continuous electrodeionization system.
(2) before microfiltration systems, connect self-cleaning filter device, before self-cleaning filter device, preferably connect unboiled water heating unit.Preferably, chemicals addition control system is set before micro-filtration, comprises coagulating agent and oxidizing bactericide.Micro-filtration arranges backwash and chemically-cleaning device.
(3) pre-desalination system comprises first-stage reverse osmosis device and second level reverse osmosis apparatus, preferably, first-stage reverse osmosis device with before second level reverse osmosis apparatus, be connected respectively cartridge filter.Preferably, chemicals addition control system is all set before a two-stage reverse osmosis system, before first-stage reverse osmosis system, chemicals addition control system comprises hydrochloric acid, reductive agent and Scale inhibitors, and before two-stage reverse osmosis system, chemicals addition control system comprises sodium hydroxide.Pre-desalination system is preferably shared a set of chemically-cleaning device.
(4) continuous electrodeionization system arranges chemically-cleaning device.
The water source treatment process that the invention still further relates to a kind of boiler feedwater, comprises the following steps:
(1) raw water of specific conductivity 500～1700 μ S/cm is carried out to self-cleaning filtering, then carry out micro-filtration processing, obtain dirty stifled index < 3, turbidity≤0.05NTU, the water of suspended substance < 1mg/L; Preferably 5～10mmol/L of the water hardness of described middle water, silicon-dioxide is 2000～8000 μ g/L preferably;
(2) water step () micro-filtration being obtained processes by first-stage reverse osmosis and pre-desalting treatment is carried out in two-pass reverse osmosis processing, obtains the water of specific conductivity <20 μ s/cm; Water free chlorine residual that step (two) obtains preferably≤0.01mg/l, Fe, Mn preferably≤0.01mg/l, hardness is with CaCO
3count preferred <1mg/l, silicon-dioxide preferably≤0.5mg/l;
And the water that (three) obtain the pre-desalting treatment of step (two) carries out deep desalting treatment by continuous electrodeionization method, obtain the de-mineralized water of specific conductivity≤0.2 μ S/cm; The preferred ≈ 0 μ mol/L of water hardness that described (three) step obtains, silicon-dioxide preferably≤20 μ g/L.
Preferably, in use, for fear of cleaning unit, over-burden, and the industrial fresh water that the middle water of the mass ratio with 30%～50% is blent respective amount obtains raw water.
The water that described treatment process obtains is for the application of boiler feedwater.
" full embrane method " of the present invention technique is the scavenging process of " physics ", its efficient, environmental protection, and aspect investing, moving, safeguard, having many advantages: high to removal of impurity, product water water quality is high; Greatly reduce the use of chemical agent, reduce secondary pollution; System is easy to automatization control, and reliability is high, moves simple and easy; Floor space is little; With conventional water treatment system appropriate litigation fees." full embrane method " technique, in simple and direct, the efficient and environmental protection that realizes Boiler water Feeding System method, is also explored Yi Tiaoxin road for middle water reuse.
Brief description of the drawings
Fig. 1 is the process flow sheet of a kind of embodiment of the present invention.
Fig. 2 is the self-cleaning filter work principle of filter schematic diagram of a kind of embodiment of the present invention.
Fig. 3 is the principle of reverse osmosis schematic diagram of a kind of embodiment of the present invention.
Embodiment
Describe in detail with following example as follows, but, one skilled in the art will appreciate that protection scope of the present invention should not be confined to this.
According to the process flow sheet of Fig. 1, describe technique of the present invention in detail as follows:
1 water source design
The water source of original boiler feed water system adopts and draws yellow water, and its composition is equivalent to domestic water---tap water substantially, and specific conductivity is about 500 μ S/cm, hardness 5～6mmol/L, silicon-dioxide 3000～4000 μ g/L.
In order to save valuable water resources, realize the target of " zero new water ", water during the water source of full embrane method boiler feed water system of the present invention uses, preferably blends industrial fresh water, draws yellow water as alternate source; Two 1000m are set
3underground tank as the equalizing tank of system buffer and different quality.The present invention the index of treatable water be: specific conductivity 500 ~ 1700 μ S/cm, the water hardness is 5～10mmol/L preferably, silicon-dioxide is 2000～8000 μ g/L preferably.
Middle water is through Sewage Treatment Facilities water outlet after treatment, specific conductivity 1200 ~ 1700 μ S/cm, and the water hardness is 5～10mmol/L preferably, and silicon-dioxide is 2000～8000 μ g/L preferably, COD
mn17mg/L, saltiness and organic content all draw yellow water (COD
mn4.2mg/L) higher.
Industrial fresh water is through the water outlet after treatment of smelting wastewater treatment facility.Specific conductivity 700 ~ 1000 μ S/cm, the water hardness is 5～8mmol/L preferably, and silicon-dioxide is 2000～8000 μ g/L preferably.
Preferably, blend industrial fresh water with the middle water of weight 30%～50% and can realize efficient processing of the present invention.But method of the present invention is not limited only to above-mentioned middle water or blends the middle water of industrial fresh water, in fact can process all waste water of specific conductivity 500～1700 μ S/cm, the water hardness is 5～10mmol/L preferably, and silicon-dioxide is 2000～8000 μ g/L preferably.
2 technological designs
By to To Several Traditional Preconditioning Methods coagulation, clarification, filtration and micro-filtration pre-treatment, the Technological Economy comparison of tradition yin, yang ion-exchange demineralization technology and reverse osmosis technology and mixed bed and CEDI continuous electrodeionization technology, simultaneously for middle water water quality characteristics, the membrane water treatment system that adopts self-cleaning filter+micro-filtration+first-stage reverse osmosis+two-pass reverse osmosis+CEDI is high-quality de-mineralized water by middle water treatment.
Self-cleaning filter+micro-filtration is pretreatment system, in order to remove suspended substance and colloid and part bacterium and the germ in unboiled water.Than the coagulating sedimentation+mechanical filter in past, it is little that self-cleaning filter+micro-filtration has volume, compact construction, and failure rate is low, can effectively remove algae remains, microorganism in water, reduces the dosage of medicament, to advantages such as change of water quality adaptability are stronger.Through the dirty stifled preferred < 3 of index of the water of pretreatment system, turbidity preferably≤0.05NTU, the preferred < 1mg/L of suspended substance.
First-stage reverse osmosis+two-pass reverse osmosis is pre-desalination system, and in order to remove into the most ions in water, all bacteriums and germ, make its effluent quality meet the requirement of CEDI influent quality.Than the ion exchange form of the cation bed+anion bed in past, reverse osmosis, without acid-alkali regeneration, without regenerated sewage, has reduced the discharge of a large amount of acid-alkali regeneration waste liquids, has reduced the pollution to environment; Can not shut down because of regeneration, can move continuously, product water water conditioning; Desalination rate is high, reaches more than 98%; Level of automation is high, and workload is little, and personnel configure few convenient operation and management.Through electrical conductivity of water <20 μ s/cm after pre-desalination system, free chlorine residual (Cl
2) preferably≤0.01mg/l, Fe, Mn preferably≤0.01mg/l, hardness is with CaCO
3count preferred <1mg/l, silicon-dioxide (SiO
2) preferably≤0.5mg/l.
Continuous electrodeionization is deep desalting system, further, except the dissolved salts in anhydrating, makes its effluent quality reach high purity water water quality, specific conductivity≤0.2 μ S/cm, hardness ≈ 0, silicon-dioxide≤20 μ g/L.Than mixed bed, CEDI does not need to regenerate with chemical agent as deep desalting, has avoided the use of chemical agent operation, storage and waste water neutralized system, can be to environment; Ratio of desalinization is stabilized in >99.5%, produces water water quality 0.056-0.10 μ s/cm(10-18 million); Silicon decreasing ratio is 95-98%, and producing water silicone content can <10ppb; Floor space is minimum; Be convenient to realize automatization control; The assembling of employing cell modular, maintenance of equipment, replacing are conveniently; The operation rate of recovery high (being that consumable water consumption is few), can reach 95%, and the dense water of discharge is recyclable.
3 water balances
According to each water unit rate of water make-up, determine that membrane water treatment station exerts oneself, complete water balance according to the rate of recovery of design.With 600m
3/ h is example, and design system total yield 65% needs former water 920m
3/ h.
4 cell locations:
4.1 pre-treatment
Pre-treatment adopts the technique of raw water heater+self-cleaning filter+micro-filtration, configures online medicine system simultaneously.
Raw water heater: because Yuan Shui water source water temperature when the winter is lower, and the optimal working temp of reverse osmosis is 25 ± 3 DEG C.Hybrid heater is set for this reason, utilizes hot water to heat former water, improve reverse osmosis in the winter rate of recovery.
Self-cleaning filter: remove the large granular impurities such as suspended substance in former water, prevent that microfiltration membrane original paper from scratching, and ensures the normal operation of microfiltration systems.
Self-cleaning filter principle of work, shown in figure 2:
In upper figure, wash water valve cuts out.Equipment is in filtration condition.P1>P2，P3=P1。
In figure below, wash water valve is opened, and causes P3=normal atmosphere, P1>P2>P3.The very close filter screen of suction nozzle, makes most of current flow into P3 via P2, thereby reaches the object of reverse cleaning filter screen.Obviously strainer can not stop in the time of backwash.
The advantage of self-cleaning filter:
1) filtration medium is stainless steel filtering net, and work-ing life is more than 10 years.
2) in water, the filtration of suspended substance and anti-cleaning all complete automatically.
3) backwash process of strainer only needs just complete for 5 ~ 15 seconds.In backwash process, system current are uninterruptedly supplied.
4) volume is little, only has 1/10th of husky filter, valveless filtering pool, more medium filter.Compact construction, failure rate is low.
5), in industrial circulating water, the filtering accuracy of filter screen is selected conventionally between 50 microns to 120 microns.If filter screen precision is selected suitablely, can effectively remove algae remains, microorganism etc. in water.Correspondingly can reduce the dosage of medicament.
Medicine system:
1) sterilant medicine system
Micro-filtration water inlet water temperature approaches 25 DEG C, contains organism and mineral substance in former water, is beneficial to this understanding the growth of bacterium, adds sterilant in unboiled water for this reason, prevents that bacterium amount reproduction from affecting the safe operation of system.
2) flocculation agent medicine system
Consider in former water and contain more colloid and macrobead suspended substance, adopt the method that adds flocculation agent to be removed.Flocculation agent can be hydrolyzed into colloid and high valence ion after dropping in water, and these colloids and high valence ion utilize in its surface adsorption ability and water-borne glue surface electric charge and the moisture film that destroys colloid, and other impurity absorption, agglomerate in water are formed to macrobead precipitation.In self-cleaning filter, be removed.Can better ensure the normal operation of micro-filtration.
Micro-filtration: for large size materials such as the thalline in effective removal unboiled water, colloid, particulate matter, organic macromolecules, adopt external-compression type hollow fiber microfiltration membrane assembly.Micro-filtration is divided into external-compression type and inner pressed by operation scheme.Suppose that the contamination level that external-compression type filters and inner pressed filters is certain, the permeable membrane area filtering due to external-compression type is large, and the load of the pollutent in unit surface is little.And because resistance and the physical strength of film silk are high, system can be carried out high-frequency backwash and air bump rinse operation, often keep the clean of film surface, the operation that therefore system can maintain a long-term stability.
Micro-filtration principle: micro-filtration is to utilize microfiltration membrane for filtration medium, under the promotion of pressure difference, acts on by " screening " of film the process separating.The aperture of microfiltration membrane is generally at 0.1 μ m～1 μ m, and micro-filtration is generally used for separating or removing relatively large particle, for example suspended substance, microorganism, bacterium.
Micro-filtration advantage: it is little that micro-filtration has floor space, effluent quality is good, level of automation high.It is PVDF(polyvinylidene difluoride (PVDF) that microfiltration membrane adopts material) tubular fibre, its surface active layer densification, supporting layer is spongy network structure, therefore withstand voltage, antipollution, long service life and can ensure to produce water water quality for a long time.
In membrane filtration processes, it is a problem often running into that film pollutes.The so-called macromole solutes such as the particulate, colloidal particle, organism and the microorganism that refer in processed liquid and the film of polluting produces physics chemical action or mechanical effect and causes on film surface or fenestra internal adsorption, precipitation diminish fenestra or stop up, and causes the permeable amount of film or the phenomenon of separating power decline.
For film is cleaned timely, be provided with air water backwash, maintainability cleaning and chemical cleaning system.
Back flushing: taking pump as power, make water produce water end (W.E.) from micro-filtration and enter micro-filtration, get back to rinse bath from concentrated end.In order to prevent microfiltration membrane physical abuse, backwash pressure general control is at 0.1MPa, Clean after every time 30min.
Air purge: use high velocity air backwash, the gel coat that film surface can be formed is removed.
Matting: in the time that physical method cleaning can not make flux recovery, clean in conjunction with chemical agent.Utilize chemical substance to reach the object of cleaning as soda acid, tensio-active agent, oxygenant etc. and pollutent generation chemical reaction.
In order to prevent that influent quality from worsening microfiltration membrane and subsequent film treatment facility are caused to expendable infringement suddenly, configurable unboiled water water quality on-line monitoring instrument table (chemical oxygen demand, ammonia nitrogen, nitre nitrogen, oil, turbidity), to monitor continuously unboiled water change of water quality, adjust operation mode in time.
4.2 pre-desalinations
Reverse osmosis: the core of desalination in technique, it can remove more than 98% various ions.
Principle of reverse osmosis: with reference to Fig. 3, left hand view is the situation under state of nature, water diffusion enters the particle intensity of strong solution side with balanced solution through semi-permeable membranes, at trim point, the permeable pressure head between the corresponding both sides of difference of altitude between strong solution and dilute solution.As shown in right part of flg, in the time carrying out reverse osmosis, applying working pressure in water inlet (strong solution) side presses to overcome naturally osmotic, in the time that the working pressure of pressing higher than naturally osmotic puts on strong solution side, the flow direction of water molecules naturally osmotic will reverse, water is produced in the purification that water molecules part in water inlet (strong solution) becomes dilute solution side by film, thereby is defined as reverse osmosis.
The relative ion exchange method of reverse osmosis technology, has the following advantages:
1) without acid-alkali regeneration, without regenerated sewage, must sewage treatment facility, reduce the discharge of a large amount of acid-alkali regeneration waste liquids, reduce the pollution to environment;
2) can not shut down because of regeneration, can move continuously, product water water conditioning;
3) desalination rate is high, reaches more than 98%, produces high purity water with high yield water rate;
4) level of automation is high, and workload is little, and personnel configure few convenient operation and management;
5) floor space is little;
6) operation and maintenance cost is low;
7) by adopting multilevel system can remove into the most ions in water, all bacteriums and germ, make its effluent quality meet the requirement of CEDI influent quality.
System configuration:
Produce water water quality, the requirement of CEDI influent quality, system ratio of desalinization and expect the rate of recovery according to required water production rate, unboiled water water quality, microfiltration systems, considering membrane element cost, by film system design computed in software, can determine reverse osmosis system level section array mode.With 600m
3/ h DW system demineralized water system is example, adopts two-stage two-part:
First-stage reverse osmosis system: be set to six groups, every group of 21 pressurized vessels, one section 14, two sections 7;
Two-stage reverse osmosis system: be set to six groups, every group of 14 pressurized vessels, one section 10, two sections 4.
In order to ensure reverse osmosis system safe and stable operation, cartridge filter, chemicals addition control system and online water quality monitoring instrument are set.
5 μ m precision safety strainers are set, prevent that reverse osmosis membrane from being scratched by trace suspension particle remaining in water.
Reductive agent chemicals dosing plant is set, prevents that membrane element is by strong oxidizing property material damage.
Acid adding is set and adds Scale inhibitors device, the fouling of controlling diaphragm element.
The instrument such as online SDI, ORP, PH, specific conductivity, temperature are installed, to monitor variation of water.
In order to reduce the carbon dioxide content in CEDI water inlet, ensure the efficient operation of CEDI, the import of first-stage reverse osmosis water tank is installed three decarbonizers and is removed carbonic acid gas in water, sodium hydroxide medicine system is set to regulate PH before two-pass reverse osmosis, reduces secondary and produces water conductivity and carbon dioxide content.
Be in operation, first-stage reverse osmosis RO film is inevitably subject to some micro-inorganics dirts, pollution or the obstruction of colloid, microorganism, metal oxide etc.These electrodeposition substances, will be cumulative on film surface, thereby cause that RO film transit dose declines and ratio of desalinization reduces.Therefore,, in order to recover transit dose and the desalting performance of RO film, need to regularly carry out matting to RO.
4.3 deep desalting
CEDI: continuous electrodeionization deep desalting system, further, except the dissolved salts in anhydrating, makes its effluent quality reach high purity water water quality, specific conductivity≤0.2 μ S/cm, hardness ≈ 0, silicon-dioxide≤20 μ g/L.
CEDI continuous electrodeionization principle: CEDI technology is the product that ion-exchange and electrodialytic technique combine.The core of CEDI has been loaded anion and cation exchange resin in fact exactly in electrodialysis.In operational process without adding analytical pure salt and dense water circle device.
In CEDI operational process, can carry out three main process simultaneously
1), under DC electric field effect, in water, ionogen is by ion-exchange membrane generation selective migration;
2) anion-cation exchange resin is carrying out ion-exchange to ionogen in water, and formation " ionic channel ";
3) there is the H that polarization produces in ion exchange resin interfacial water
+and OH
-exchange resin is carried out to electrochemical regeneration.
CEDI is sequentially identical to the absorption order of ion with ion exchange resin to removing of ion.Meanwhile, the ion exchange resin in CEDI assembly, along freshet to can be divided into three aspects by its working order, the first layer is saturated resin layer, and the second layer is hybrid resin layer, and the 3rd layer is protection resin layer.Saturated resin layer mainly plays absorption and moves the electrolytical effect of large portion, and hybrid resin layer is being born removing as the ion of the more difficult removings such as weak electrolyte of task, and protection resin layer resin is in higher active state, and it plays a part final purified water.
The advantage of CEDI continuous electrodeionization desalting system:
1) do not need to regenerate with chemical agent, avoided the use of chemical agent operation, storage and waste water neutralized system, can be to environment;
2) running cost is conventionally low;
3) ratio of desalinization is stabilized in >99.5%;
4) produce water water quality 0.056-0.10 μ s/cm(10-18 million);
5) silicon decreasing ratio is 95-98%, and producing water silicone content can <10ppb;
6) be 60-90% to the decreasing ratio of TOC;
7) floor space is minimum;
8) be convenient to realize automatization control;
9) operator's number reduces, and reduces human operational error's possibility;
10) adopt cell modular assembling, maintenance of equipment, replacing are conveniently;
11) the operation rate of recovery high (being that consumable water consumption is few), can reach 95%, and the dense water of discharge is recyclable.
Contriver carries out secret test in its free factory, use middle water treatment method of the present invention to be applied to power plant's subcritical boiler supplementary feed, and contrast with the method for prior art, respectively each important parameter of the water that obtained is separately compared, confirm that method of the present invention obtains effect better.
The source of following examples instrument and equipment is as shown in table 1 below:
Table 1 Boiler water Feeding System system major equipment
The raw materials used source of following examples is as shown in table 2 below:
Embodiment:
The former water of different quality (the middle water of 30% weight and the industrial fresh water of 70% weight, concrete water-quality guideline sees the following form shown in 3) first enters two 1000m
3underground tank as the equalizing tank of system buffer and different quality.Then be delivered to film treatment plant via three (dual-purpose one standby) raw water pumps, successively through raw water heater, chemical-dosing mixer, self-cleaning filter laggard enter microfiltration systems.
The water quality parameter of table 3 embodiment raw water
Raw water heater: water temperature can be lower than 10 DEG C when the winter due to Yuan Shui water source, and the optimal working temp of reverse osmosis is 25 ± 3 DEG C.Be provided with raw water heater for this reason, in carrying out heat exchange, saving water resource to greatest extent, the concrete parameter of well heater is as shown in table 4 below.
Table 4: heater parameter
| Model: | SCDZJS |
| Quantity: | 3 |
| Flow: | 500m 3/h |
| Heating steam pressure: | 0.8MPa |
| Steam consumption | 30m3/h |
| Heating temperature: | 25±3℃ |
| Type of heating: | The direct mixed heat transfer of carbonated drink |
| Inlet and outlet water bore: | DN350 |
| Air inlet/outlet footpath: | DN300 |
| Control mode: | Automatic temperature-controlled |
| Material: | Core+the Stainless Steel Helices of carbon steel shell+brass |
| Pattern: | Hybrid |
Chemical-dosing mixer:
Sterilant medicine system: micro-filtration water inlet water temperature approaches 25 DEG C, contains organism and mineral substance in former water, is beneficial to this understanding the growth of bacterium, adds sterilant in unboiled water for this reason, prevents that bacterium amount reproduction from affecting the safe operation of system.
Flocculation agent medicine system: consider in former water and contain more colloid and macrobead suspended substance, adopt the method that adds flocculation agent to be removed.Flocculation agent can be hydrolyzed into cotton-shaped macrobead flocks and high valence ion after dropping in water, utilize its surface adsorption ability, in and water-borne glue surface electric charge and destroy the moisture film of colloid, other impurity absorption, agglomerate in water are formed to macrobead precipitation.In self-cleaning filter, be removed.Can better ensure the normal operation of micro-filtration.
Self-cleaning filter: for removing the large granular impurities such as suspended substance in former water, prevent that microfiltration membrane original paper from scratching, ensure the normal operation of microfiltration systems, 3 self-cleaning filters are set.Self-cleaning filter is selected AMIAD full-automatic filter CTF-M30, and design parameter is as shown in table 5 below.The filtration medium of self-cleaning filter is stainless steel filtering net, and aperture of filter screen is 100 microns, that is can filter 100 microns of above impurity such as suspended particle or microorganism.
Table 5: self-cleaning filter parameter
| Filter the water yield: | 400m 3/ h(cover) |
| The rate of recovery: | ≥99.5％ |
| Produce water water quality: | Suspended particle size≤100 μ m |
| Filtration cycle: | >=2 hours |
| Backwash always lasts: | ≤ 15 seconds |
Micro-filtration: utilize microfiltration membrane for filtration medium, under the promotion of pressure difference, separate by " screening " effect of film, the aperture of microfiltration membrane is generally at 0.51 μ m.Can remove the large size materials such as thalline in unboiled water, colloid, particulate matter, organic macromolecule.Adopt external-compression type hollow fiber microfiltration membrane assembly, material is PVDF(polyvinylidene difluoride (PVDF)), resistance to chlorine and physical strength are the highest.
Native system micro-filtration assembly is made up of housing, tube sheet, end cap, flow-guiding screen, pipe core and tubular fibre, has stoste import, filtered liquid outlet and concentrated solution outlet to be connected with system.Its feature: the one, fiber is directly bonded on epoxy resin tube sheet, without supporter, has high film packing density, and volume is little and simple in structure, can reduce the possibility of bacterial contamination, simplifies cleaning operation.The 2nd, leak detection is repaired convenient, and rejection is stable, long service life.The design parameter of micro-filtration assembly is as shown in table 6 below.
Table 6: micro-filtration component parameter
Micro-filtration produces water and delivers to two 800m via producing jellyfish pipe
3micro-filtration produce in water tank.Micro-filtration water tank exports female pipe and is connected with one-level lift pump, after promoting, sends into first-stage reverse osmosis system after chemicals addition control, cartridge filter, high-pressure pump via one-level lift pump.
First-stage reverse osmosis chemicals addition control system: reductive agent dosing (NaHSO is set
3) device, prevent that membrane element from being destroyed by strong oxidizing property material (as chlorine residue).Acid adding is set and adds Scale inhibitors (organophosphorus) device, the fouling of controlling diaphragm element.
One-level cartridge filter: 5 μ m precision safety strainers are set, prevent that reverse osmosis membrane from being scratched by trace suspension particle remaining in water, every array apparatus arranges a precision safety strainer, in-built 70 5 μ mPP filter cores.
First-stage reverse osmosis system: reverse-osmosis membrane element is selected the BW30-400/34i of DOW company membrane element.Be set to six groups, every group of 21 pressurized vessels, one section 14, two sections 7,7 membrane elements of every pressurized vessel filling.
First-stage reverse osmosis system is produced water after decarbonizing tower removing carbon dioxide, enters two 200m
3intermediate water tank.Then again through two-stage hoisting pump promote after, after chemicals addition control, cartridge filter, high-pressure pump, send into two-stage reverse osmosis system.
Decarbonizing tower: in order to reduce the carbon dioxide content in CEDI water inlet, ensure the efficient operation of CEDI, the import of first-stage reverse osmosis water tank is installed three decarbonizers and removed carbonic acid gas in water, reduces secondary water inlet sodium hydroxide concentration and carbon dioxide content.Water is broken up and is entered decarbonizing tower from decarbonizing tower top spray, air passes into from decarbonizing tower bottom by gas blower, because the gas concentration lwevel in water is high, according to Henry's law, carbonic acid gas stripping in water in air, thereby on acquiring a certain degree, remove the object of carbonic acid gas in water.
Two-pass reverse osmosis chemicals addition control system: in order to reduce the carbon dioxide content in CEDI water inlet, ensure the efficient operation of CEDI, two-pass reverse osmosis water inlet arranges sodium hydroxide medicine system, thus be that bicarbonate ion form is removed by residual carbon dioxide conversion.
Secondary cartridge filter: 5 μ m precision safety strainers are set, prevent that reverse osmosis membrane from being scratched by trace suspension particle remaining in water, every array apparatus arranges a precision safety strainer, in-built 60 5 μ mPP filter cores.
Two-stage reverse osmosis system: reverse-osmosis membrane element is selected the BW30-400/34i of DOW company membrane element.Be set to six groups, every group of 14 pressurized vessels, one section 10, two sections 4,7 membrane elements of every pressurized vessel filling.
Two-stage reverse osmosis system produces water and enters two 200m
3secondary water tank, then enter CEDI system via EDI lift pump, cartridge filter.
CEDI system: adopting CEDI continuous electrodeionization is deep desalting system, further, except the dissolved salts in anhydrating, makes its effluent quality reach high purity water water quality, specific conductivity≤0.2 μ S/cm, hardness ≈ 0, silicon-dioxide≤20 μ g/L.
CEDI technology is the product that ion-exchange and electrodialytic technique combine.The core of CEDI has been loaded anion and cation exchange resin in fact exactly in electrodialysis.Native system adopts the CEDI of American I/O NPIURE.This CEDI is that unique deep or light hydroecium all adds the CEDI of ion exchange resin in the world.In operational process, without adding analytical pure salt and dense water circle device, (CEDI of other brands, because dense hydroecium does not add resin, must improve to salt adding in dense water its specific conductivity, improves desalination effect.Occur fouling and pollution problem for fear of equipment long-time running, the purity salt using is necessary for analytical pure.Due to the higher meeting of CEDI running voltage brine electrolysis, add salt can produce chlorine and hydrogen,, if do not noted ventilating, easily cause danger).
In CEDI operational process, can carry out three main process simultaneously:
Under DC electric field effect, in water, ionogen is by ion-exchange membrane generation selective migration;
Anion-cation exchange resin is carrying out ion-exchange to ionogen in water, and formation " ionic channel ";
There is the H that polarization produces in ion exchange resin interfacial water
+and OH
-exchange resin is being carried out to electrochemical regeneration.
The water inlet of the IP-LX mould heap that the present embodiment adopts requires as shown in table 7 below.
The water inlet requirement of table 7:IP-LX membrane stack
| Water inlet source | RO product water |
| The suitable specific conductivity of water inlet (comprises CO 2) | <40μS/cm |
| Silicon-dioxide (SiO 2) | <1ppm |
| Iron, manganese, sulfide | <0.01ppm |
| Total chlorine is (with Cl 2Meter) | <0.02ppm |
| Total hardness is (with CaCO 3） | <1.0ppm |
| The organism (TOC) dissolving | <0.5ppm |
| Operation pH scope | 4-11 |
| Operating temperature | 5-45°C |
| Intake pressure | <7bar |
Via the product water after CEDI system advanced treatment, be high-quality de-mineralized water, deliver to two 2000m by producing jellyfish pipe
3sweet-water tank, in sweet-water tank, establish floating roof, prevent that carbonic acid gas from dissolving in and air plankton pollutes.
Reference examples
The pretreatment mode of tradition coagulating sedimentation+mechanical filter, its effluent quality is difficult to meet the strict demand of reverse osmosis to influent quality, cannot be used in conjunction with reverse osmosis at all.Self-cleaning filter+microfiltration membrane technology of the embodiment of the present invention is done pretreatment mode for the water inlet of reverse osmosis provides guarantee.Can be verified from the data of following table 8 and table 9, the micro-filtration of embodiment produces the dirty stifled index of water and reaches <3, and turbidity reaches 0.02NTU, free chlorine residual (Cl
2) <0.1mg/l, dirty stifled index (SDI) <4, COD chemistry oxygen consumption (KMnO
4method) (O
2) <3mg/l, meet the water inlet requirement of reverse osmosis membrane completely, and the suspended substance <1mg/L recording, be better than the <5mg/L of traditional water outlet, the water quality that the pretreatment mode of visible traditional coagulating sedimentation+mechanical filter obtains cannot meet the water inlet requirement of first-stage reverse osmosis device.
Table 8: first-stage reverse osmosis device influent quality requirement
Table 9: water water quality is produced in pre-treatment
The detection method of water-quality guideline is as shown in table 10 below.
Table 10: detection method, instrument, the model of water-quality guideline and the GB relating to.
Each stage technique index of embodiment is as shown in table 11 below.
Table 11: each system water-quality guideline and operating performance
Micro-filtration produces water water-quality guideline
| Project | Unit | Index |
| Dirty stifled index SDI | ? | <3 |
| Turbidity A | NTU | <0.2 |
| Ss suspended solid | mg/l | <1 |
| Water production rate | m 3/h | 138m 3/h |
| The rate of recovery | ? | ≥90％ |
First-stage reverse osmosis water inlet index request
| Project | Unit | Index |
| PH value | ? | 4-11 (pH=2～12 when matting) |
| Turbidity | NTU | ﹤ 0.2NTU is ﹤ 1.0NTU in short-term |
| Dirty stifled index (SDI) | ? | ﹤4 |
| Free chlorine residual | mg/l | It is 0.0 that ﹤ 0.1 controls |
| COD chemistry oxygen consumption KMnO 4Method) (O 2) | mg/l | ﹤3 |
| First-stage reverse osmosis ratio of desalinization | ? | ＞98% |
| The first-stage reverse osmosis rate of recovery | ? | ≥75% |
Two-pass reverse osmosis effluent index
| Project | Unit | Index |
| Specific conductivity | μS/cm | <20μS/cm |
| PH value | ? | 6～8 |
| Hardness is (with CaCO 3Meter) | mg/l | <1.0mg/l |
| Free chlorine | mg/l | <0.01mg/l |
| Iron | mg/l | <0.01mg/l |
| Manganese | mg/l | <0.01mg/l |
| Water production rate | m 3/h | ≥111m 3/ h(cover) |
| The rate of recovery | ? | ≥90% |
| Ratio of desalinization | ? | ≥90% |
The EDI index request of intaking
| Project | Unit | Index |
| Free chlorine residual (Cl 2) | mg/l | ≤0.05mg/l |
| Fe,Mn | mg/l | ≤0.01mg/l |
| Hardness is (with CaCO 3Meter) | mg/l | <1mg/l |
| Silicon-dioxide (SiO 2) | mg/l | ≤0.5mg/l |
| PH | ? | 5～9 |
| Feedwater conductivity | μs/cm | <40μs/cm |
EDI effluent quality index
| Project | Unit | Index |
| Silicon-dioxide (SiO 2) | μg/L | ≤20μg/L |
| Specific conductivity (25 ° of C) | μS/cm | ≤0.2μS/cm |
| Hardness is (with CaCO 3Meter) | mg/l | ≈0 |
| Water production rate | ? | Normal water production rate >=100m 3/ h(cover) |
| The rate of recovery | ? | ≥90% |
The technical process of this project is simple and direct, and level of automation is high, and maintenance personnel is few, simple to operate, stable.Because water in using is as water source, only 2.774 yuan/m of this project high purity water production cost
3, compare domestic similar technical finesse cost lower.
Effect assessment: can draw from above test-results, " full embrane method " the Boiler water Feeding System method being built by micro-filtration+two steps ro+CEDI, scientific and reasonable, stable equipment operation, effluent quality is high, overall operation effect is better than traditional technology, so to apply to middle water treatment be that high-quality de-mineralized water is more successful.
Application in practice
The 1500000 tons of project assorted engineering 2 × 300MW of stainless steel generating set Boiler water Feeding System systems started experimental study and put into operation from March, 2008, unit's monthly output water in 2009, and all go into operation in April, 2009.Adopt " full embrane method " water treatment method of micro-filtration+two steps ro+CEDI.
After operation, according to micro-filtration and reverse osmosis membrane running condition, the water yield in progressively increasing.From starting not enough kiloton every day, exceed 7000 tons to water usage quantity in 2010 4 months, produce the water water yield, water quality reaches design requirements.
CEDI effluent quality:
| Project | Water quality |
| Silicon-dioxide (SiO 2) | 2.0μg/L |
| Specific conductivity (25 ° of C) | 0.06μS/cm |
| Hardness is (with CaCO 3Meter) | ≈0mg/l |
Since going into operation, whole engineering process is reasonable, and equipment, facility operation are stablized, and product water water quality is high.Level of automation is high, and backwash, the matting of micro-filtration, reverse osmosis all realize automatic control, and worker's labour intensity is little, and maintenance of the equipment amount is few.After the project implementation, every day 0.72 ten thousand ton of reuse water, through full embrane method processing, 1.1 ten thousand tons of production high-quality de-mineralized waters, be that 2 × 300MW subcritical boiler, two electric boilers, new steel-making, new coking high pressure waste heat boiler and company's de-mineralized water pipe network provide high-quality de-mineralized water, ensure safety and economic operation and the requirement of company's high-end product to water quality of generating set, reduced the draining of boiler water yield and blowdown thermosteresis, saved fire coal.Simultaneously, reduce 0.72 ten thousand ton and drawn yellow water buying, also having reduced water in 0.72 ten thousand ton arranges outward, alleviate the problem of water resources anxiety, improve Taiyuan City's water system quality, for energy-saving and emission-reduction, improve environment and make positive contribution, produce huge economy and environment benefit, realized the target of enterprise and city harmonious development, Green Development.
Economic benefit
Cost composition:
1366818 tons of reuse waters in 2009,0.6 yuan/ton, middle water, draws 3.8 yuan/ton of yellow waters;
Cost-saving: (3.8-0.6) ten thousand yuan of * 1366818=437;
Two electric boiler blow-down rates drop to 5% by 10%, and steam is in 100 yuan/ton, and boiler average evaporation capacity is by 600t/h;
Cost-saving: ten thousand yuan of the * 24*365=2628 of 600t/h*5%*100 unit.
3,065 ten thousand yuan of wound effects in 2009.
2300974 tons of reuse waters in 2010,0.6 yuan/ton, middle water, 3.8 yuan/ton of Huanghe water;
Cost-saving: (3.8-0.6) ten thousand yuan of * 2300974=736
Two electric boiler blow-down rates are reduced to 5% by 10%, and steam is in 130 yuan/ton, and boiler average evaporation capacity is by 600t/h;
600t/h(steam) ten thousand yuan of × 5% × 130 yuan × 24 × 365=3416.
4,152 ten thousand yuan of wound effects in 2010.
Within 2009,2010, create effect: 7,217 ten thousand yuan of accumulative total wound effects.
After CCPP unit, newly steel-making and new coking high pressure waste heat unit adopt de-mineralized water as boiler feedwater, greatly improve Unit Steam Water quality, reduce the metallic corrosion of unit heat power equipment, reduce the fouling salification of unit, extend unit durability, improved security and the economy of unit operation.
Social benefit
1) development of Steel Plant constantly increases the demand of the water yield, but underground water and to draw yellow water amount limited cannot meet scale and rapidly expand the demand to water, and the restriction of shortage of water resources to scale development alleviated in this project implementation.
2) in, water reaches high purity water water quality standard after full embrane method is processed, for good water sources is provided, for the updating and upgrading of a product provides energy safeguard.
3) in full embrane method, the Boiler water Feeding System of water reuse is that water rich and influential family's thermal power generation corporations have opened up second water source, is electric power enterprise energy-saving and emission-reduction, and cleaner production provides successful case.
4) in, water is back to production, has reduced the quantity discharged of urban pollutant, alleviates the pressure of municipal sector, has improved Taiyuan City's water body environment, realizes energy-saving and emission-reduction, and cleaner production reaches the target of enterprise and city harmonious coexistence.
Claims (3)
1. a water treatment method for boiler feedwater, is characterized in that, comprises the following steps:
(1) raw water of specific conductivity 500～1700 μ S/cm is carried out to self-cleaning filtering, then carry out micro-filtration processing, obtain dirty stifled index < 3, turbidity≤0.05NTU, the water of suspended substance < 1mg/L; The water hardness 5～the 10mmol/L of described raw water, silicon-dioxide 2000～8000 μ g/L;
(2) water step () micro-filtration being obtained processes by first-stage reverse osmosis and pre-desalting treatment is carried out in two-pass reverse osmosis processing, obtains the water of specific conductivity <20 μ s/cm; Water free chlorine residual≤0.01mg/l that step (two) obtains, Fe≤0.01mg/l, Mn≤0.01mg/l, hardness is with CaCO
3meter <1mg/l, silicon-dioxide≤0.5mg/l;
And the water that (three) obtain the pre-desalting treatment of step (two) carries out deep desalting treatment by continuous electrodeionization method, obtain the de-mineralized water of specific conductivity≤0.2 μ S/cm; The water hardness ≈ 0 μ mol/L that described (three) step obtains, silicon-dioxide≤20 μ g/L;
The micro-filtration processing of step () comprises continuous dosing adjusting, backwash, air bump rinse operation and matting step, wherein, described continuous dosing regulates and referred to before raw water carries out self-cleaning filtering, and poly-flocculation agent aluminium and sterilant NaClO are joined in raw water;
Wherein, step () raw water used is that the middle water of 30% weight is blent the industrial fresh water of 70% weight, and the water hardness of described middle water is 10.2mmol/L, and silicon-dioxide is 6.784mg/L; The specific conductivity of described industrial fresh water is 720 μ S/cm, water hardness 5.2mmol/L, silicon-dioxide 3.862mg/L;
Micro-filtration is processed and is used citric acid C
6h
8o
7h
2o carries out micro-filtration pickling, uses NaOH to carry out micro-filtration alkali cleaning;
First-stage reverse osmosis is processed and is used organophosphorus as Scale inhibitors, uses HCl as acid for adjust pH, uses NaHSO
3as reductive agent, using bromine analog derivative as non oxidizing bactericide; Two-pass reverse osmosis is processed and is used NaOH as adjust pH alkali; And, taking disodium ethylene diamine tetraacetate as reverse osmosis matting EDTA, taking Sodium dodecylbenzene sulfonate as reverse osmosis matting dodecane, taking NaOH as reverse osmosis matting alkali, with citric acid C
6h
8o
7h
2o is the acid of reverse osmosis matting.
2. water treatment method as claimed in claim 1, is characterized in that, comprises unboiled water heating steps before described self-cleaning filtering step.
3. water treatment method as claimed in claim 1 or 2, is characterized in that, the pre-desalting treatment step of described step (two) comprises that continuous dosing regulates and matting step.
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