CN104787925A - Device and method for treating high-fluorine-content water produced by oil well and coal-bed gas well - Google Patents
Device and method for treating high-fluorine-content water produced by oil well and coal-bed gas well Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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- C02F2101/14—Fluorine or fluorine-containing compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2303/00—Specific treatment goals
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- C02F2303/185—The treatment agent being halogen or a halogenated compound
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a device and method for treating high-fluorine-content water produced by an oil well and a coal-bed gas well. The device is characterized in that the high-fluorine-content water enters a primary fluoride removal device through a water pump A by an automatic pH control liquid adding machine and then simultaneously and equivalently flows into a secondary fluoride removal device A and a secondary fluoride removal device B, namely the two secondary fluoride removal devices are connected in parallel to run; when the content of fluorine in effluent does not reach the standards, the primary fluoride removal device, the secondary fluoride removal device A and the secondary fluoride removal device B are connected in series to run; when the content of the fluorine in the effluent still does not reach the standards, an alumina activation and regeneration unit and the primary fluoride removal device form a circulation loop to regenerate a fluoride removal filler, and meanwhile, the two secondary fluoride removal devices are regenerated; the high-fluorine-content water is discharged after reaching the standards. According to the device and the method disclosed by the invention, two adsorbents, namely activated aluminum oxide and a carbon ceramic composite material are combined during the use, advantages are enhanced, and disadvantages are avoided, so that the fluorine removal effect is effectively improved; the device is simple in structure, automatic in running and convenient to maintain and manage and reduces the running cost.
Description
Technical field
The invention relates to water treatment, particularly relate to a kind of oil well, the treatment unit of coal bed gas well output water of high fluorine content and treatment process thereof.
Background technology
Fluorine is one of requisite trace element of human life, and human body is respectively organized all fluorine-containing, maximum with the fluorine content of tooth, bone and hair.Appropriate fluorine can make bone tooth solid, reduces morbidity of dental caries, also has benifit to neural excitatory transmission, phosphorus metabolism, parathyroid function, cellular enzymes system and reproductive process.But the harm that the too much absorption of fluorine produces animals and plants and human body is considerably beyond the not enough impact on HUMAN HEALTH of fluorine.Oil repellent is too high, can affect the Ca,P metabolism of human body, and the substance metabolism of human body and physiological function are got muddled, thus causes some fluorosis symptoms such as skeletal fluorosis, spot tooth, and fluorosis also can cause anaemia, leukopenia etc.Current various countries are according to the temperature of locality and the fluorine quantity of everyone every daily ingestion, formulate the national fluorine-containing standard of tap water (within the scope of 0.5-2.0mg/L), Drinking Water in China fluorine content standard is 0.5-1.0mg/L (GB 5749-2006), agricultural irrigation water quality standard (GB 5084-2005) is general area≤2mg/L, high fluorice region≤3mg/L.
China's water of high fluorine content has a very wide distribution, and relates to and about has 27 provinces, municipalities and autonomous regions.Report that China has in people's tap water of more than 700,000,000 that fluorine is more than 1.0mg/L according to National survey, HUMAN HEALTH in water of high fluorine content serious threat, especially oil well, coal bed gas well production water, and its fluorine content is generally greater than 5mg/L, must carry out except fluorine process before discharge.The defluorination method used at present is broadly divided into two large classes: fractionation and physical partition method.Fractionation is divided into again coagulant sedimentation, calcium salt precipitation method, lime phosphate process, chemical process and the electrochemical methods such as electrodialysis, electrocoagulation such as alkali-lime method, thermooxidizing magnesium processes.Physical separation method is divided into adsorption filtration method (bone black method, zeolite process, activated carbon method and activated alumina method) and ion exchange method (ion exchange column method, reverse osmosis method) two kinds.Due to easy and simple to handle, equipment is simple, working cost is low, current application is activated alumina method the most widely.But there is the defects such as fluorine removing rate is low, defluorinating agent consumption is large, processing cost is high, effluent quality is unstable to some extent in existing defluorination method, as the calcium salt precipitation method added amount of chemical such as lime, calcium sulfate, calcium chloride are large, be only suitable for the pre-treatment of high fluorine waste water; Electroosmose process to raw water quality require strict, facility investment is large, processing cost is high and eliminate other Hubeiwans; There is electrode passivation phenomenon in electrocoagulation, causes defluorination effect and economic performance to be deteriorated; Containing a large amount of dissolved aluminums in the water outlet of aluminium salt precipitation method, there is detrimentally affect to neural system; Molysite deposition method is comparatively strong to metal protection, and when flocculation operation condition is not good, often using water-band has light yellow; The bone black method recovery time is long, and bone black is soluble in acid, need control former water pH to reduce the loss of filtrate when practical application; Zeolite process loading capacity is low, dosage large, the process water yield is little; Activated carbon method requires higher to pH, generally has stronger adsorptive power when pH < 3, there is no adsorptive power during pH > 3; The maximum deficiency of ion exchange column method is the mineral substance removed in water, introduces amine substance; Reverse osmosis method processing cost is high, membrane module easily pollutes, work-ing life is shorter.Therefore, efficient, cheap defluorinating agent is developed and suitable technology of Fluoride Removal needs the problem of solution present stage badly.
Through finding the literature search of prior art, existing water of high fluorine content treatment process, if CN200720097398.0 is a kind of ecosystem aluminium hydroxide and ultra-filtration membrane coupling fluorine removal device, adopt inorganic aluminate by generating the fluorine in ecosystem aluminium hydroxide Adsorption water, then Ultra filtration membrane alumen ustum is adopted, guarantee that in water outlet, fluorochemical reaches drinking water standard, this automation degree of equipment is high, is applicable to the water of high fluorine content process engineering of middle and small scale; CN200710058368.3 discloses the defluorination method of a kind of reverse osmosis method and absorption method Integrated predict model, reverse osmosis method and the former water of absorption method process is utilized respectively in the method, again the defluoroing water that two kinds of methods produce is carried out mixing preparation according to the ratio of 1:1, to make the Oil repellent in final outflow water up to standard; CN201410095887.7 provides a kind of novel all-in-one Removal of Fluorine From Underground Water device, comprise connect successively inlet unit, except fluorine reaction member, intermediate water tank and filtering unit, except fluorine reaction member is complete mixed form reactor, fill the mixture of inorganic aluminate and powdery hydroxyapatite, be provided with intermission aeration device bottom it, this apparatus structure is compact, floor space is little, easy to use, flexible operation, defluorination effect are good; CN201210373484.5 discloses a kind of tap water adsorption-defluorination device and method of plural serial stage, adopts modification with Fe activated alumina particle, to avoid the risk of aluminum ion stripping.Prior art mainly utilizes the combination of two kinds and above different defluorination method or defluorinating agent, to make up respective deficiency to a certain extent, thus improves defluorination effect and economic performance, but too increases the complicacy of plant running and maintenance simultaneously.
Summary of the invention
Object of the present invention, the shortcoming for prior art and deficiency, there is provided that a kind of fluorine removing rate is high, running cost is low, to load variations strong adaptability and the simple fluorine removal device of running maintenance and method, be specially a kind of oil well, the treatment unit of coal bed gas well output water of high fluorine content and treatment process thereof.
The present invention is achieved by following technical solution.
A treatment unit for oil well, coal bed gas well output water of high fluorine content, comprises water pump, pH and automatically controls liquid filler and fluorine removal device, it is characterized in that, pH is automatically controlled liquid filler 1 and is connected with the water-in of one-level fluorine removal device 2 lower end by water pump A6, valve B12; The water outlet of one-level fluorine removal device 2 upper end is connected with the water-in of secondary fluorine removal device A3, secondary fluorine removal device B4 upper end respectively by valve C13, valve D14, valve E15; The water outlet of secondary fluorine removal device B4 lower end is provided with the water outlet controlling detecting unit B9 and valve G17, secondary fluorine removal device A3 lower end and is provided with control detecting unit A8 and F16; Be provided with by-pass line at the control detecting unit A8 of secondary fluorine removal device A3 water outlet and between the coupling end of valve F16 and the water-in of secondary fluorine removal device B4 upper end, this by-pass line be provided with water pump B7 and valve H18; One-level fluorine removal device 2 and aluminum oxide activating regeneration unit 5 are connected to form circulation loop by pipeline, be provided with control unit 10 and valve I19 between the water side pipeline of aluminum oxide activating regeneration unit 5 and one-level fluorine removal device 2, between the feed-water end pipeline of aluminum oxide activating regeneration unit 5 and one-level fluorine removal device 2, be provided with valve J20; Automatically the feed-water end controlling liquid filler 1 at pH is provided with valve A11;
Described one-level fluorine removal device 2, secondary fluorine removal device A3 are identical with the constitutional features of secondary fluorine removal device B4, comprise housing, water-in, water outlet, bottom porous dividing plate, top porous barrier and defluoroing filling layer; The defluoroing filling layer of one-level fluorine removal device 2 is the activated alumina adsorbents of particle diameter 1 ~ 3mm, and the defluoroing filling layer of secondary fluorine removal device A3 and secondary fluorine removal device B4 is the charcoal ceramic composite material sorbent material of particle diameter 0.5 ~ 2.5mm;
The housing of described one-level fluorine removal device 2, secondary fluorine removal device A3 and secondary fluorine removal device B4 is cylindrical colourless transparent resin glass, and it is highly 80 ~ 100cm; Each connecting pipeline in this treatment unit is the pvc pipe of diameter 200mm; Described bottom porous dividing plate is identical with the constitutional features of top porous barrier, and be the circular acrylic resin plastic plate of thickness 5cm, diameter is identical with the diameter of the housing of one-level fluorine removal device 2, and orifice diameter is 2cm.
The loading capacity of the activated alumina adsorbents in described one-level fluorine removal device 2 is 0.8 ~ 2.0mg/g, and loading is highly 40 ~ 60cm; The loading capacity of the charcoal ceramic composite material sorbent material in described secondary fluorine removal device A3 and secondary fluorine removal device B4 is 1.4 ~ 2.4mg/g, and loading is highly 40 ~ 60cm.
Described one-level fluorine removal device 2 is bottom water inlet, top water outlet, flow velocity is 6 ~ 12 times of defluoroing filling layer volumes per hour, and secondary fluorine removal device A3 and secondary fluorine removal device B4 is top water inlet, bottom water outlet, and flow velocity is 5 ~ 10 times of defluoroing filling layer volumes per hour.
Described aluminum oxide activating regeneration unit 5 comprises reservoir and activating and regenerating liquid, and described activating and regenerating liquid is the alum liquor of 3%.
The defluorination method of the treatment unit of this oil well, coal bed gas well output water of high fluorine content, step is as follows:
(1) first water of high fluorine content enters pH and automatically controls liquid filler 1, regulates pH to 4.5 ~ 6;
(2) automatically control the water outlet after liquid filler 1 adjustment through pH, enter one-level fluorine removal device 2 by water pump A6 from bottom; When processing the water yield and being more, under the prerequisite ensureing effluent quality, valve H18, valve I19 and valve J20 close, all the other valves are all opened, secondary fluorine removal device A3 and secondary fluorine removal device B4 parallel running, the water outlet simultaneous equal gravity flow of one-level fluorine removal device 2 enters secondary fluorine removal device A3 and secondary fluorine removal device B4, the water fluoride content that goes out of secondary fluorine removal device A3, secondary fluorine removal device B4 is detected by control detecting unit A8, control detecting unit B9 respectively, if up to standard, then the final water outlet via secondary fluorine removal device A3 and secondary fluorine removal device B4 is discharged; When secondary fluorine removal device A3 and secondary fluorine removal device B4 parallel running, when in its water outlet, Oil repellent is not up to standard, valve-off E15, valve F16, valve I19 and valve J20, all the other valves are all opened, and make one-level fluorine removal device 2, secondary fluorine removal device A3 and secondary fluorine removal device B4 series operation;
(3) when one-level fluorine removal device 2, secondary fluorine removal device A3 and the B4 series operation of secondary fluorine removal device time water outlet in Oil repellent not up to standard time, valve-off A11, after water inlet in one-level fluorine removal device 2 is discharged completely, Open valve I19 and valve J20, valve-off B12 and valve C13, aluminum oxide activating regeneration unit 5 and one-level fluorine removal device 2 is made to form circulation loop, activating and regenerating liquid i.e. 3% alum liquor circulates to regenerate activated alumina adsorbents, and controlling the recovery time by control unit 10 is 1h; After water inlet in secondary fluorine removal device A3 being discharged completely, change the defluoroing filling layer of secondary fluorine removal device A3, regenerate the defluoroing filling layer be replaced, renovation process is that charcoal ceramic composite material sorbent material is incubated 1h at 500 DEG C, for subsequent use again; After water inlet in secondary fluorine removal device B4 being discharged completely, operation steps is with secondary fluorine removal device A3 again; During the adsorbent reactivation of above-mentioned defluoroing filling layer, water of high fluorine content is stored in other water storage device temporarily, to be regenerated complete after row relax again;
(4) repeating step 1 ~ 3 after the adsorbent reactivation of defluoroing filling layer, until water of high fluorine content rear discharge up to standard.
Abandon after described activated alumina adsorbents cyclic regeneration 4 ~ 5 times, abandon after charcoal ceramic composite material sorbent circulation regeneration 7 ~ 8 times.
Compared with prior art, tool has the following advantages in the present invention:
1. this device can series operation again can parallel running, porous barrier can make stable into water, evenly simultaneously, improves the adaptability of system to water quality and hydraulic load change.
2. activated alumina and charcoal ceramic composite material two kinds of sorbent materials are combined, maximize favourable factors and minimize unfavourable ones, effectively improve the defluorination effect of system.
3. sorbent material selected by this device has good regenerative power, has effectively saved running cost.
4. in this device, the structure of each fluorine removal device is simple and feature is identical, full-automaticly runs, and is convenient to safeguard and management.
Accompanying drawing explanation
Fig. 1 is the structural representation for the treatment of unit of oil well of the present invention, coal bed gas well output water of high fluorine content;
Fig. 2 is the structural representation of one-level fluorine removal device of the present invention;
Fig. 3 is the structural representation of bottom porous dividing plate in fluorine removal device of the present invention, top porous barrier.
Reference numeral of the present invention is as follows:
1---pH controls liquid filler 2 automatically---one-level fluorine removal device
3---secondary fluorine removal device A 4---secondary fluorine removal device B
5---aluminum oxide activating regeneration unit 6---water pump A
7---water pump B 8---controls detecting unit A
9---controlling detecting unit B 10---control unit
11---valve A 12---valve B
13---valve C 14---valve D
15---valve E 16---valve F
17---valve G 18---valve H
19---valve I 20---valve J
Embodiment
Below in conjunction with drawings and the specific embodiments, the present invention will be further described, but protection scope of the present invention is not limited to following specific embodiment.
Specific embodiment for handling object, implements the present invention with certain city of northern China oil well, coal bed gas well output water of high fluorine content.
The treatment unit of this oil well, coal bed gas well output water of high fluorine content, pH is automatically controlled liquid filler 1 and is connected with the water-in of one-level fluorine removal device 2 lower end by water pump A6, valve B12; The water outlet of one-level fluorine removal device 2 upper end is connected with the water-in of secondary fluorine removal device A3, secondary fluorine removal device B4 upper end respectively by valve C13, valve D14, valve E15; The water outlet of secondary fluorine removal device B4 lower end is provided with the water outlet controlling detecting unit B9 and valve G17, secondary fluorine removal device A3 lower end and is provided with control detecting unit A8 and F16; Be provided with by-pass line at the control detecting unit A8 of secondary fluorine removal device A3 water outlet and between the coupling end of valve F16 and the water-in of secondary fluorine removal device B4 upper end, this by-pass line be provided with water pump B7 and valve H18; One-level fluorine removal device 2 and aluminum oxide activating regeneration unit 5 are connected to form circulation loop by pipeline, be provided with control unit 10 and valve I19 between the water side pipeline of aluminum oxide activating regeneration unit 5 and one-level fluorine removal device 2, between the feed-water end pipeline of aluminum oxide activating regeneration unit 5 and one-level fluorine removal device 2, be provided with valve J20; Automatically the feed-water end controlling liquid filler 1 at pH is provided with valve A11;
Described one-level fluorine removal device 2, secondary fluorine removal device A3 are identical with the constitutional features of secondary fluorine removal device B4, comprise housing, water-in, water outlet, bottom porous dividing plate, top porous barrier and defluoroing filling layer; The defluoroing filling layer of one-level fluorine removal device 2 is the activated alumina adsorbents of particle diameter 1 ~ 3mm, and loading capacity is 0.8 ~ 2.0mg/g, and loading is highly 50cm; The defluoroing filling layer of secondary fluorine removal device A3 and secondary fluorine removal device B4 is the charcoal ceramic composite material sorbent material of particle diameter 0.5 ~ 2.5mm, and the loading capacity of sorbent material is 1.4 ~ 2.4mg/g, and loading is highly 50cm; Defluoroing filling layer is by bottom porous membrane support, and the bottom of top porous barrier is apart from defluoroing filling layer 10cm, and the top of bottom porous dividing plate and the bottom of top porous barrier are all equipped with 2 ~ 3 layers of cotton, falls into dividing plate blocking aperture to prevent sorbent material;
Connecting pipeline between described each device is the pvc pipe of diameter 200mm;
The housing of described one-level fluorine removal device 2, secondary fluorine removal device A3 and secondary fluorine removal device B4 is cylindrical colourless transparent resin glass, so that observe internal operation situation, it is highly 90cm, diameter 100cm (determine according to the process water yield, and the process water yield of the present embodiment is 50-100m by this diameter
3/ d); Described bottom porous dividing plate is identical with the constitutional features of top porous barrier, and be the circular acrylic resin plastic plate of thickness 5cm, diameter is identical with the diameter of the housing of one-level fluorine removal device 2, is 100cm, and orifice diameter is 2cm,
Described aluminum oxide activating regeneration unit 5 comprises reservoir and activating and regenerating liquid, and described activating and regenerating liquid is the alum liquor of 3%.
Described one-level fluorine removal device 2 is bottom water inlet, top water outlet, flow velocity is 6-12 per hour times of defluoroing filling layer volume, and secondary fluorine removal device A3 and secondary fluorine removal device B4 is top water inlet, bottom water outlet, and flow velocity is 5-10 per hour times of defluoroing filling layer volume.
It is CPH-2 double pump two-pack type that described pH controls liquid filler 1 model automatically; Described control detecting unit A8, control detecting unit B9 are the special water quality detection controller of the general sieve name of PROMINENT, and wherein Funing tablet survey sensor is FLE010 SE type; Described control unit 10 for model be the programmable time controller of XHST-10.
The defluorination method of the treatment unit of oil well of the present invention, coal bed gas well output water of high fluorine content, step is as follows:
(1) first water of high fluorine content enters pH and automatically controls liquid filler 1, regulates pH to 4.5 ~ 6;
(2) automatically control the water outlet after liquid filler 1 adjustment through pH, enter one-level fluorine removal device 2 by water pump A6 from bottom water-in, when processing the water yield and being more, under the prerequisite ensureing effluent quality, valve H18, valve I19 and valve J20 closes, all the other valves are all opened, secondary fluorine removal device A3 and secondary fluorine removal device B4 parallel running, water inlet in one-level fluorine removal device 2 is successively through bottom porous dividing plate, defluoroing filling layer and top porous barrier, secondary fluorine removal device A3 and secondary fluorine removal device B4 is entered finally by being flow automatically by water outlet simultaneous equal, at secondary fluorine removal device A3, in B4, water inlet is successively through top porous barrier, defluoroing filling layer and bottom porous dividing plate, go out water fluoride content respectively by control detecting unit A8, control detecting unit B9 to detect, if up to standard, then finally to discharge via bottom water outlet, when secondary fluorine removal device A3 and secondary fluorine removal device B4 parallel running, when in its water outlet, Oil repellent is not up to standard, valve-off E15, valve F16, valve I19 and valve J20, all the other valves are all opened, make one-level fluorine removal device 2, secondary fluorine removal device A3 and secondary fluorine removal device B4 series operation, namely the water outlet gravity flow of one-level fluorine removal device 2 enters secondary fluorine removal device A3, and the water outlet of secondary fluorine removal device A3 is promoted by water pump B7 and enters secondary fluorine removal device B4, up to standard to ensure final outflow water Oil repellent.
(3) when one-level fluorine removal device 2, secondary fluorine removal device A3 and the B4 series operation of secondary fluorine removal device time water outlet in Oil repellent not up to standard time, valve-off A11, after water inlet in one-level fluorine removal device 2 is discharged completely, Open valve I19 and valve J20, valve-off B12 and valve C13, aluminum oxide activating regeneration unit 5 and one-level fluorine removal device 2 is made to form circulation loop, activating and regenerating liquid i.e. 3% alum liquor circulates to regenerate activated alumina adsorbents, and controlling the recovery time by control unit 10 is 1h; After water inlet in secondary fluorine removal device A3 being discharged completely, change the defluoroing filling layer of secondary fluorine removal device A3, regenerate the defluoroing filling layer be replaced, renovation process is that charcoal ceramic composite material sorbent material is incubated 1h at 500 DEG C, for subsequent use again; After water inlet in secondary fluorine removal device B4 being discharged completely, operation steps is with secondary fluorine removal device A3 again; During the adsorbent reactivation of above-mentioned defluoroing filling layer, water of high fluorine content is stored in other water storage device temporarily, to be regenerated complete after row relax again;
Abandon after activated alumina adsorbents cyclic regeneration 4-5 time, abandon after charcoal ceramic composite material sorbent circulation regeneration 7-8 time;
(4) repeating step (1) ~ (3) after the adsorbent reactivation of defluoroing filling layer, until water of high fluorine content rear discharge up to standard.
The process water yield of this embodiment is 50-100m
3/ d, water inlet Oil repellent is 6.1-6.8mg/L.By actual motion, in the water outlet after device process, Oil repellent is lower than 1mg/L, reaches " drinking water sanitary standard " (GB 5749-2006).Illustrate utilize this device process oil well, coal bed gas well output water of high fluorine content is feasible.
Claims (7)
1. the treatment unit of an oil well, coal bed gas well output water of high fluorine content, comprise water pump, pH and automatically control liquid filler and fluorine removal device, it is characterized in that, pH is automatically controlled liquid filler (1) and is connected with the water-in of one-level fluorine removal device (2) lower end by water pump A (6), valve B (12); The water outlet of one-level fluorine removal device (2) upper end is connected with the water-in of secondary fluorine removal device A (3), secondary fluorine removal device B (4) upper end respectively by valve C (13), valve D (14), valve E (15); The water outlet of secondary fluorine removal device B (4) lower end is provided with and controls detecting unit B (9) and valve G (17), and the water outlet of secondary fluorine removal device A (3) lower end is provided with and controls detecting unit A (8) and F (16); Be provided with by-pass line at the control detecting unit A (8) of secondary fluorine removal device A (3) water outlet and between the coupling end of valve F (16) and the water-in of secondary fluorine removal device B (4) upper end, this by-pass line be provided with water pump B (7) and valve H (18); One-level fluorine removal device (2) and aluminum oxide activating regeneration unit (5) are connected to form circulation loop by pipeline, be provided with control unit (10) and valve I (19) between the water side pipeline of aluminum oxide activating regeneration unit (5) and one-level fluorine removal device (2), between the feed-water end pipeline of aluminum oxide activating regeneration unit (5) and one-level fluorine removal device (2), be provided with valve J (20); Automatically the feed-water end controlling liquid filler (1) at pH is provided with valve A (11);
Described one-level fluorine removal device (2), secondary fluorine removal device A (3) are identical with the constitutional features of secondary fluorine removal device B (4), comprise housing, water-in, water outlet, bottom porous dividing plate, top porous barrier and defluoroing filling layer; The defluoroing filling layer of one-level fluorine removal device (2) is the activated alumina adsorbents of particle diameter 1 ~ 3mm, and the defluoroing filling layer of secondary fluorine removal device A (3) and secondary fluorine removal device B (4) is the charcoal ceramic composite material sorbent material of particle diameter 0.5 ~ 2.5mm.
2. the treatment unit of a kind of oil well according to claim 1, coal bed gas well output water of high fluorine content, it is characterized in that, the housing of described one-level fluorine removal device (2), secondary fluorine removal device A (3) and secondary fluorine removal device B (4) is cylindrical colourless transparent resin glass, and it is highly 80 ~ 100cm; Each connecting pipeline in this treatment unit is the pvc pipe of diameter 200mm; Described bottom porous dividing plate is identical with the constitutional features of top porous barrier, and be the circular acrylic resin plastic plate of thickness 5cm, diameter is identical with the diameter of the housing of one-level fluorine removal device (2), and orifice diameter is 2cm.
3. the treatment unit of a kind of oil well according to claim 1, coal bed gas well output water of high fluorine content, it is characterized in that, the loading capacity of the activated alumina adsorbents in described one-level fluorine removal device (2) is 0.8 ~ 2.0mg/g, and loading is highly 40 ~ 60cm; Described secondary fluorine removal device A (3) is 1.4 ~ 2.4mg/g with the loading capacity of the charcoal ceramic composite material sorbent material in secondary fluorine removal device B (4), and loading is highly 40 ~ 60cm.
4. the treatment unit of a kind of oil well according to claim 1, coal bed gas well output water of high fluorine content, it is characterized in that, described one-level fluorine removal device (2) is bottom water inlet, top water outlet, flow velocity is 6 ~ 12 times of defluoroing filling layer volumes per hour, secondary fluorine removal device A (3) and secondary fluorine removal device B (4) is top water inlet, bottom water outlet, and flow velocity is 5 ~ 10 times of defluoroing filling layer volumes per hour.
5. the treatment unit of a kind of oil well according to claim 1, coal bed gas well output water of high fluorine content, it is characterized in that, described aluminum oxide activating regeneration unit (5) comprises reservoir and activating and regenerating liquid, and described activating and regenerating liquid is the alum liquor of 3%.
6. the defluorination method of a kind of oil well of claim 1, the treatment unit of coal bed gas well output water of high fluorine content, step is as follows:
(1) first water of high fluorine content enters pH and automatically controls liquid filler (1), regulates pH to 4.5 ~ 6;
(2) automatically control the water outlet after liquid filler (1) adjustment through pH, enter one-level fluorine removal device (2) by water pump A (6) from bottom, when processing the water yield and being more, under the prerequisite ensureing effluent quality, valve H (18), valve I (19) and valve J (20) closes, all the other valves are all opened, secondary fluorine removal device A (3) and secondary fluorine removal device B (4) parallel running, the water outlet simultaneous equal gravity flow of one-level fluorine removal device (2) enters secondary fluorine removal device A (3) and secondary fluorine removal device B (4), secondary fluorine removal device A (3), secondary fluorine removal device B (4) goes out water fluoride content respectively by control detecting unit A (8), control detecting unit B (9) to detect, if up to standard, then the final water outlet via secondary fluorine removal device A (3) and secondary fluorine removal device B (4) is discharged, when secondary fluorine removal device A (3) and secondary fluorine removal device B (4) parallel running, when in its water outlet, Oil repellent is not up to standard, valve-off E (15), valve F (16), valve I (19) and valve J (20), all the other valves are all opened, and make one-level fluorine removal device (2), secondary fluorine removal device A (3) and secondary fluorine removal device B (4) series operation,
(3) when one-level fluorine removal device (2), when in water outlet when secondary fluorine removal device A (3) and secondary fluorine removal device B (4) series operation, Oil repellent is not up to standard, valve-off A (11), after water inlet in one-level fluorine removal device (2) is discharged completely, Open valve I (19) and valve J (20), valve-off B (12) and valve C (13), aluminum oxide activating regeneration unit (5) and one-level fluorine removal device (2) is made to form circulation loop, activating and regenerating liquid i.e. 3% alum liquor circulates to regenerate activated alumina adsorbents, controlling the recovery time by control unit (10) is 1h, after again the water inlet in secondary fluorine removal device A (3) being discharged completely, change the defluoroing filling layer of secondary fluorine removal device A (3), regenerate the defluoroing filling layer be replaced, renovation process is that charcoal ceramic composite material sorbent material is incubated 1h at 500 DEG C, for subsequent use, after water inlet in secondary fluorine removal device B (4) being discharged completely, operation steps is with secondary fluorine removal device A (3) again, during the adsorbent reactivation of above-mentioned defluoroing filling layer, water of high fluorine content is stored in other water storage device temporarily, to be regenerated complete after row relax again,
(4) repeating step (1) ~ (3) after the adsorbent reactivation of defluoroing filling layer, until water of high fluorine content rear discharge up to standard.
7. the defluorination method of the treatment unit of a kind of oil well according to claim 6, coal bed gas well output water of high fluorine content, is characterized in that, abandons after described activated alumina adsorbents cyclic regeneration 4 ~ 5 times, abandons after charcoal ceramic composite material sorbent circulation regeneration 7 ~ 8 times.
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