CN103214115A - Water treatment method of strong acid cation exchange resin incomplete regeneration - Google Patents
Water treatment method of strong acid cation exchange resin incomplete regeneration Download PDFInfo
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- CN103214115A CN103214115A CN2013100850764A CN201310085076A CN103214115A CN 103214115 A CN103214115 A CN 103214115A CN 2013100850764 A CN2013100850764 A CN 2013100850764A CN 201310085076 A CN201310085076 A CN 201310085076A CN 103214115 A CN103214115 A CN 103214115A
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- 239000002253 acid Substances 0.000 title claims abstract description 153
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 230000008929 regeneration Effects 0.000 title claims abstract description 40
- 238000011069 regeneration method Methods 0.000 title claims abstract description 40
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003729 cation exchange resin Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002351 wastewater Substances 0.000 claims abstract description 41
- 239000012528 membrane Substances 0.000 claims abstract description 24
- 238000005374 membrane filtration Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 150000001768 cations Chemical class 0.000 claims description 116
- 239000007788 liquid Substances 0.000 claims description 58
- 239000011347 resin Substances 0.000 claims description 36
- 229920005989 resin Polymers 0.000 claims description 36
- 238000000746 purification Methods 0.000 claims description 28
- 230000002378 acidificating effect Effects 0.000 claims description 26
- 238000001223 reverse osmosis Methods 0.000 claims description 20
- 150000002500 ions Chemical class 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 125000002091 cationic group Chemical group 0.000 claims description 15
- 238000001728 nano-filtration Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 11
- 239000012530 fluid Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 5
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 239000012492 regenerant Substances 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 abstract description 12
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 2
- 230000003134 recirculating effect Effects 0.000 abstract 1
- 239000011575 calcium Substances 0.000 description 13
- 229910001415 sodium ion Inorganic materials 0.000 description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 230000001172 regenerating effect Effects 0.000 description 8
- 239000003456 ion exchange resin Substances 0.000 description 7
- 229920003303 ion-exchange polymer Polymers 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 238000005342 ion exchange Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- Treatment Of Water By Ion Exchange (AREA)
Abstract
The invention provides a water treatment method of strong acid cation exchange resin incomplete regeneration. The method comprises the following steps: (1) removing hardness of waste water by a combination of a strong acid cation exchange device and a weak acid cation exchange device: A, introducing wastewater with suspended solids removed into the strong acid cation exchange device, so as to remove part hardness in the waste water; and introducing the outlet water into the weak acid cation exchange device, in order to remove remaining or all hardness in the waste water; B, conducting incomplete regeneration on the strong acid cation exchange device by using a regeneration agent 1.4-1.8 times chemical equivalent weight, so as to reduce the load of the strong acid cation exchange device and improve the load of the weak acid cation exchange device; and C, recirculating the outlet water from the weak acid cation exchange device into the outlet water of the strong acid cation exchange device to re-send the water into the weak acid cation exchange device, thereby ensuring that the alkalinity in the weak acid cation exchange device is always greater than the hardness, and removing all hardness in wastewater; and (2) decarburizing the waste water with hardness removed and conducting membrane filtration through a membrane concentration device.
Description
Technical field
The present invention relates to the poor regenerated water treatment method of a kind of strong-acid cation-exchange resin.
Background technology
Usually, in actual applications, when total hardness is not more than 350mg/L(CaCO
3Meter) time, can directly adopt the mode of cationic exchange to remove hardness (also having removed other polyvalent cations in the water simultaneously) in the water.Zeo-karb is divided into strong acid type and weak-type.Strong acid sodium type exchange resin is removed the principle following (is example with the Na type) of hardness in the water:
2R-Na+Ca
2+→2R-Ca+2Na
+
Weak acid Hydrogen exchange resin is removed the principle following (is example with the Hydrogen) of hardness in the water:
2R-COO-H+Ca
2+→2R-COO-Ca+2H
+
The basic characteristics of strong-acid cation-exchange resin: 1, can remove all hardness (comprising permanent hardness and temporary hardness) substantially; 2, operating capacity is 800～1000mmoL/L; 3, during holomorphosis, need to consume about 2.5 times of stoichiometric regenerated liquids; 4, water outlet absolute precision is lower, the two-stage series connection operation, and it goes out the water hardness and can only guarantee at 1mg/L.
The basic characteristics of weakly acidic cationic exchanger resin: 1, can only remove temporary hardness; 2, operating capacity reaches 1800～2200mmoL/L; 3, during holomorphosis, only need about 1.15 times of stoichiometric regenerated liquids; 4, the absolute precision height of water outlet has only in water inlet under the situation of temporary hardness, and it goes out water hardness and can guarantee below 0.2mg/L.
According to above characteristics, generally for going out the water hardness less demanding (promptly going out the water hardness allows when 1mg/L is above), often adopt the mode of Weak-acid cation switch+strong-acid cation switch, can give full play to the advantage of strong acid and Weak-acid cation switch.But when removing hardness in the water or polyvalent cation comparatively fully (go out the water hardness and require to be not more than 0.2mg/L), then need to adopt the technology of strong-acid cation switch+Weak-acid cation switch.
At strong-acid cation switch+when the Weak-acid cation switch is used for removing water hardness, for guaranteeing to enter hardness in the Weak-acid cation switch always less than basicity, and the hardness that enters the Weak-acid cation switch is entirely temporary hardness, when the strong-acid cation switch is regenerated, be holomorphosis, promptly used 2.5 times regeneration liquid measure to regenerate.Can there be following weakness in the mode of so this routine: the main load that 1, goes hardness is to be born by the less relatively strong-acid cation switch of exchange capacity, can not bring into play the big advantage of Weak-acid cation switch exchange capacity; 2, the strong-acid cation switch of bearing main load will use 2.5 times regenerated liquid to regenerate, and not only consumes a large amount of regenerators, and can produce a large amount of waste liquids.Can not bring into play simultaneously load few advantage of Weak-acid cation switch regenerating agent consumption when identical.
In the prior art, Chinese patent 97197289.3 discloses and has a kind ofly reduced water hardness and remove the water treatment method of the basicity of non-hydroxide simultaneously with weakly acidic cationic exchanger resin through membrane sepn, and this method comprises the composition that makes ionization lower, for example SiO
2, reach and make it from change more than 10.5 or 10.5 by regulating the pH value.With film their separation is improved significantly.Boron, SiO
2With TOC reduce to commercial weight 1/10 or more.There is most the rate of recovery of the raw water of saline taste can reach 90% or higher, realizes purifying the substantial reduction of frequency simultaneously.The employed equipment of water treatment method comprises reverse osmosis membrane, mixed bed ion exchange device, micro-filter, apparatus for ultraviolet disinfection, decarbonization device and ionization device.Disclosed in this patent with the single unit that comprises the Weak-acid cation exchange system and removed hardness and basically all basicity relevant simultaneously with hardness.
Chinese patent application 200910214305.1 has been announced a kind of wastewater recovery processing technique, this technology is: former water is by strainer removal suspended matter, solid particulate wherein, the water outlet of strainer enters ion-exchanger, thereby remove the hardness in the water by calcium, magnesium ion that ion-exchange is removed in the former water, the water outlet of ion-exchanger enters decarbonizing tower, under the stripping effect of revolution blower fan, the basicity of former water is removed; The former water that decarbonizing tower comes out enters accurate filter under the effect of lift pump, the water outlet of accurate filter is under the effect of high-pressure pump, be promoted to nanofiltration/reverse osmosis system, nanofiltration/reverse osmosis system is mainly in parallel and/or be composed in series by nanofiltration membrane and reverse osmosis membrane, the trapped fluid discharging of nanofiltration/reverse osmosis system, the product water of nanofiltration/reverse osmosis system enters and produces the pond, becomes final water outlet.Thereby remove the hardness in the water though this technology has disclosed calcium, the magnesium ion removed in the former water with ion-exchange, do not disclose the type and the configuration of ion-exchange.For example select strong acidic ion resin, or acidulous cation resin, or the combination of the two; If the situation of the combination of the two, the two makes up in which way, and in order to realize this array mode need satisfy what condition or the like.In fact, in this application ins and outs disclose and insufficient, and if select the type of ion exchange resin arbitrarily, cause the result of water treatment not up to standard probably, regenerator expends unfavorable consequences such as huge.
Therefore, how to provide a kind of poor regenerated water treatment method of strong-acid cation-exchange resin that reduces the regenerating agent consumption of strong-acid cation-exchange resin to become the problem that industry need solve.
Summary of the invention
At the shortcoming of prior art, the purpose of this invention is to provide the poor regenerated water treatment method of a kind of strong-acid cation-exchange resin, it can significantly reduce the regenerating agent consumption of strong-acid cation-exchange resin.
To achieve these goals, the invention provides the poor regenerated water treatment method of a kind of strong-acid cation-exchange resin, it comprises the steps:
(1) by the combination of strong-acid cation switch and Weak-acid cation switch, removes the hardness in the waste water; Wherein,
Waste water behind A, the removal suspended substance is introduced into the strong-acid cation switch, the part hardness in this removal waste water; The water outlet of strong-acid cation switch enters the Weak-acid cation switch, removes rest parts or whole hardness in the waste water at this;
B, employing 1.4-1.8 are doubly stoichiometric, the required regenerant consumption of the theoretical regeneration of strong-acid cation switch, the strong-acid cation switch is carried out poor regeneration, thereby reduce the load of strong-acid cation switch, improve the load of Weak-acid cation switch; In the technology of prior art, the actual holomorphosis of strong-acid cation switch needs 2.5 times of normal regenerators of theoretical chemistry at least, the present invention is then by using the doubly stoichiometric regenerator of 1.4-1.8, make the strong-acid cation switch realize incomplete regen-eration, be poor regeneration, to reduce the actual required regenerated liquid of whole technology intermediate ion exchange resin regeneration;
C, make the effluent recycling of Weak-acid cation switch to the water outlet of strong-acid cation switch, to reenter the Weak-acid cation switch, and then the basicity in the assurance Weak-acid cation switch is always greater than hardness, to remove all hardness in the waste water;
(2) waste water after the removal hardness carries out carbonization treatment and carries out membrane filtration by film condensing device and handle.
Among the present invention, so-called " hardness " is meant the summation of divalence and polyvalent metal ion content in the water, and these ions comprise Ca
2+, Mg
2+, Fe
2+, Mn
2+, Fe
3+, Al
3+Deng.So-called " permanent hardness " claims non-carbonate hardness again, mainly refer to calcium, the muriate of magnesium, the content of vitriol in the water, salts such as a spot of calcium, Mg nitrate, silicate are still arranged in addition, heat under normal pressure (constancy of volume) situation, these salts can not separated out precipitation.Correspondingly, " temporary hardness " is carbonate hardness.So-called " basicity " is meant with the bicarbonate radical to be the non-hydroxide basicity of representative.
Among the present invention,, remove the hardness in the waste water by the combination of strong-acid cation switch and Weak-acid cation switch.Wherein, the advantage of strong-acid cation-exchange resin is to remove all hardness (comprising permanent hardness and temporary hardness).But its weakness is also more, and for example its operating capacity is relatively low, is 800～1000mmoL/L; During its holomorphosis, need the regenerated liquid of consumption more, about 2.5 times of chemical equivalents; Its water outlet absolute precision is lower, the two-stage series connection operation, and it goes out the water hardness and can only guarantee at 1mg/L.Compare with strong-acid cation-exchange resin, though weakly acidic cationic exchanger resin can only be removed temporary hardness, its operating capacity is bigger, can reach 1800～2200mmoL/L; The required regenerated liquid of its holomorphosis is less, only about 1.15 times of stoichiometric regenerated liquids; And the absolute precision height of its water outlet, having only in water inlet under the situation of temporary hardness, it goes out water hardness and can guarantee below 0.2mg/L.
In order to bring into play the advantage of weakly acidic cationic exchanger resin, reduce the chemical equivalent of the required regenerated liquid of whole technology intermediate ion exchange resin regeneration, need to improve the working load of weakly acidic cationic exchanger resin; Because weakly acidic cationic exchanger resin can only be removed temporary hardness, the hardness that needs assurance to enter the Weak-acid cation switch all is temporary hardness simultaneously.
Among the present invention,, improve the working load of Weak-acid cation switch by reducing the working load of strong-acid cation switch; And, promptly come regenerating resin with the regenerator that is less than actual amount by strong-acid cation-exchange resin being carried out the working load that poor regeneration reduces the strong-acid cation switch.For example, usually, be not more than the water inlet of 350mg/L, adopt the strong-acid cation-exchange resins after 2.5 times of stoichiometric regeneration dosage are regenerated, hardness can be reduced to 10mg/L for total hardness.If adopt chemical equivalent 1.4-1.8 regenerant consumption doubly, then it goes out water hardness and will correspondingly can be elevated to the concentration that 100-50mg/L(promptly enters the Weak-acid cation switch), the load of strong-acid cation switch can reduce like this, and the load of Weak-acid cation switch can increase.
Like this, by strong-acid cation-exchange resin is carried out the working load that poor regeneration reduces the strong-acid cation switch, and then improved the working load of Weak-acid cation switch, thereby reduced the needed regenerant consumption of whole regeneration.
Be exemplified below:
The hardness of supposing water inlet is 350mg/L (in CaCO3, following concentration is all in this), and basicity is 80mg/L, and then the result after strong-acid cation switch employing conventional operation mode and the poor regeneration operation scheme is compared as follows:
Running condition one: strong acid ion exchange resin adopts 2.5 times of chemical equivalent regenerator regeneration
Running condition two: strong acid ion exchange resin adopts 1.4 times of chemical equivalent regenerator regeneration
As seen from the above table, adopt poor regeneration, can reduce by total regenerating agent consumption of 50%.In fact, go out water hardness and be not more than 0.2mg/L owing to will control the Weak-acid cation switch, under the condition of running condition one, the Weak-acid cation switch only arrives 1/3 o'clock of its operating capacity, just need regenerate; And under the condition of running condition two, can after its complete failure, regenerate.So will reducing, actual regenerating agent consumption surpasses 50%.
At this moment, the water hardness that goes out of strong-acid cation switch is 100mg/L.And basicity is 80mg/L, and the permanent hardness of 20mg/L is arranged, and directly enters the Weak-acid cation switch and does not adjust, and then the water hardness that goes out of Weak-acid cation switch is the requirement that 20mg/L(can not be less than 0.2mg/L), and basicity is constant.The water outlet of 40% Weak-acid cation switch is to the water outlet of strong-acid cation switch if reflux this moment, then the basicity total amount is 112mg/L(80+40% * 80=112), then big than hardness total amount 100mg/L, after this adjusts, because basicity is greater than hardness, hardness can all be removed, and the Weak-acid cation switch goes out water hardness just can remove (requirement that can be less than 0.2mg/L) substantially fully.
In addition, among the present invention, the effluent recycling by making the Weak-acid cation switch to reenter the Weak-acid cation switch, guarantees that basicity in the Weak-acid cation switch is always greater than hardness to the water outlet of strong-acid cation switch.Because hardness has been removed in the water outlet of Weak-acid cation switch, but does not remove basicity.If its part effluent recycling to water inlet, then can be increased the basicity that enters the Weak-acid cation switch fully.As long as quantity of reflux is suitable, even the strong-acid cation switch goes out water hardness greater than basicity, also can it be adjusted to basicity greater than hardness by the water outlet of backflow Weak-acid cation switch fully, enter the Weak-acid cation switch again, thereby satisfy the condition of Weak-acid cation switch operation.
Among the present invention, the waste water after the removal hardness carries out carbonization treatment and carries out membrane filtration by membrane filter appts and handle, thus the water after obtaining purifying.The carbonization treatment here can be, and for example adds acid so that bicarbonate radical is converted into CO in waste water
2, make waste water pass through decarbonizing tower (air blast decarbonizer or vacuum decarburization device) then and remove CO
2
The present invention only adopts the 1.4-1.8 times of normal regenerated liquid of theoretical chemistry that strong-acid cation-exchange resin is regenerated, and has reduced the working load of strong-acid cation switch simultaneously, has improved the working load of Weak-acid cation switch.Though wanting after the water outlet hardness ratio regular regeneration of regeneration back strong-acid cation switch is high a lot, owing to improved the working load of Weak-acid cation switch, can satisfy the needs of removing hardness fully, thereby has significantly reduced the amount of expending of regenerated liquid.
Another embodiment according to the present invention in the step (2), is carried out one or more levels membrane filtration by one or more levels film condensing device (for example nanofiltration membrane device or reverse osmosis membrane apparatus) and is handled.By the separation of film condensing device, with water and ion wherein (NH for example
4 +Ion or Na
+Ion) separates.
Another embodiment according to the present invention, membrane filtration in the step (2) is handled and is comprised first step membrane filtration processing (for example nanofiltration membrane treatment), and waste water is separated into the first step purification liquid that contains the part univalent ion, the first step trapped fluid that contains polyvalent ion and part univalent ion.
Another embodiment according to the present invention, membrane filtration in the step (2) is handled and is comprised that further second stage membrane filtration handles (for example reverse osmosis membrane processing), and the first step purification liquid that will contain the part univalent ion is separated into second stage purification liquid after the impure few purification, is rich in the second stage trapped fluid of univalent ion.
Another embodiment according to the present invention, first step film condensing device are the nanofiltration membrane device, and second stage film condensing device is a reverse osmosis membrane apparatus.
It is pointed out that in film condensing device, owing to there is spissated process, generally have four kinds of pollutions and dirty stifled: organic fouling, living fouling, the fouling of difficulty soluble salt and the pollution of silicon isocolloid.For preventing that producing these in film condensing device pollutes, and generally can be provided with the pretreatment technology of removing suspended substance and colloid, removal polyvalent cation, removing basicity in the prior art before film condensing device.When membrane treatment appts moved, the highly basic that adds sodium hydroxide for example was with the film condensing device water inlet
pThe H value is increased to more than 10.5, can effectively prevent the dirt stifled (being efficient reverse osmosis process) of organism, biology and silicon.But problem is that this installs when Ammonia-Containing Wastewater Treatment, also has following weakness: 1, owing to contain a certain amount of ammonia nitrogen in the waste water, regulate feed water by reverse osmosis when adding alkali, need to consume a large amount of alkali (ammonia nitrogen of 1mg/L consumes 2.35mg/L sodium hydroxide in theory); 2, surpass under 10.5 the condition in the pH value, this moment, ammonia nitrogen was present in the water with the form of amino molecule, and all amino molecules can see through for example reverse osmosis membrane fully, without any crown_interception, produced water and directly enter into; This ammonia-nitrogen content that causes producing water is consistent with water inlet, and the quality of influence product water can not direct reuse.And among the present invention, do not need to add highly basic in this link.
Another embodiment according to the present invention is moved several hrs (for example about four hours) afterwards continuously at film condensing device especially first step film condensing device, it is washed greater than 10.5 water with the pH value, to remove COD, SiO
2, organism, the biological pollution that forms and dirty stifled.Because in the practice of sewage disposal, organism, biological pollution to film condensing device need the certain hour accumulation, moving about 4 hours continuously, the whole contaminated degree of film condensing device is less than 2%, wash 5 minute greater than 10.5 water with the pH value this moment, can be with the pollution clean-up of organism, biology, to recover the performance of film condensing device fully.So, when film condensing device moves, can not add alkali and improve the pH value, only need after operation 4 hours, the pH value of intaking be elevated to more than 10.5, film condensing device was washed 5 minutes, just can control organism and biological pollution very ideally.Like this, both can remove the ammonia nitrogen in the waste water, can remove organism, biology, COD and SiO in the waste water again
2Deng.
Another embodiment according to the present invention, it further comprises strong-acid cation-exchange resin is carried out the regenerated step; This step comprises:
Extracting part second stage trapped fluid, add sodium-chlor, is 5-7% with its concentration adjustment, to obtain regenerated liquid;
Regenerated liquid is back to the strong-acid cation switch, strong-acid cation-exchange resin is regenerated, thus the usage quantity of minimizing strong-acid cation-exchange resin regenerator.
Another embodiment according to the present invention, wherein, when handling the waste water of oil-containing or high organic content, strong-acid cation-exchange resin is carried out the regenerated step comprise:
After A, extraction part second stage purification liquid are heated to 50-80 ℃, are delivered to the strong-acid cation switch strong-acid cation-exchange resin is cleaned, soaks for some time;
B, regenerated liquid is heated to 50-80 ℃ after, with regenerated liquid strong-acid cation-exchange resin is regenerated, adopt displacement of second stage purification liquid and rinsing;
C, add sodium hydroxide in rinsing liquid, keeping its concentration is 1-4%, and then soaks for some time;
D, with second stage purification liquid to strong-acid cation-exchange resin is replaced and rinsing.
Another embodiment according to the present invention, it further comprises weakly acidic cationic exchanger resin is carried out the regenerated step; This step comprises:
Part second stage purification liquid is extracted in the first step regeneration, to wherein adding acid, and it is delivered to the Weak-acid cation switch replaces, and generates h type resin;
Part second stage purification liquid is extracted in the second step regeneration, to wherein adding alkali, and it is delivered to the Weak-acid cation switch with h type resin is replaced, generation sodium type resin.
Another embodiment according to the present invention, wherein, when handling the waste water of oil-containing or high organic content, strong-acid cation-exchange resin is carried out the regenerated step comprise:
After A, extraction part second stage purification liquid are heated to 50-80 ℃, are delivered to the Weak-acid cation switch weakly acidic cationic exchanger resin is cleaned, soaks for some time;
Part second stage purification liquid is extracted in the regeneration of B, the first step, to wherein adding acid, and it is delivered to the Weak-acid cation switch regenerates, and generates h type resin, replaces with clear water then;
Part second stage purification liquid is extracted in C, the second step regeneration, to wherein adding alkali, and it is delivered to the Weak-acid cation switch replaces, and generates sodium type resin;
D, weakly acidic cationic exchanger resin is replaced and rinsing with second stage purification liquid or clear water.
Compared with prior art, the present invention possesses following beneficial effect:
The present invention only adopts the 1.4-1.8 times of normal regenerated liquid of theoretical chemistry that strong-acid cation-exchange resin is regenerated, and has reduced the working load of strong-acid cation switch simultaneously, has improved the working load of Weak-acid cation switch.Though wanting after the water outlet hardness ratio regular regeneration of regeneration back strong-acid cation switch is high a lot, owing to improved the working load of Weak-acid cation switch, can satisfy the needs of removing hardness fully, thereby has significantly reduced the amount of expending of regenerated liquid.
Description of drawings
Fig. 1 is a system architecture synoptic diagram of realizing the water treatment method of embodiment 1.
Embodiment
Embodiment 1
The system of the water treatment method of realization present embodiment as shown in Figure 1.Be stored in the raw water box 1 through the former water of removing suspended substance and turbidity, under the lifting of raw water pump 1, enter Na-ion exchanger 3, polyvalent cations such as the calcium in the waste water, magnesium carry out ion-exchange at this and sodium ion exchange resin wherein, sodium ion in the resin enters in the waste water, and polyvalent cations such as the calcium in the waste water, magnesium then enter in the resin and removed.The Na-ion exchanger water outlet enters in the weakly acidic cation exchanger 4, sodium ion in the waste water in polyvalent cation such as remaining calcium, magnesium and the weakly acidic cationic exchanger resin exchanges, after exchange, polyvalent cation such as all calcium, magnesium is all removed in weakly acidic cation exchanger in the waste water, and the positively charged ion in the waste water mainly is univalent cations such as potassium, sodium, ammonia.At this moment, reflux pump to regulate the basicity of weakly acidic cation exchanger, makes the basicity that enters weakly acidic cation exchanger always greater than hardness the extremely water inlet of effluent recycling of a part.The water outlet of weakly acidic cation exchanger adds its pH value to 3.8～4.5 of acid back adjusting through adding sour device 18, and wherein basicity is converted into carbonic acid gas.Being adjusted to weakly acidic cation exchanger water outlet after the acidity enters and carries out decarburization in the decarbonizing tower 5 to remove basicity.
Waste water through removing all polyvalent cations and basicity enters nanofiltration membrane device 7 under the castering action of topping-up pump 6, it produces water and enters in the reverse osmosis membrane apparatus 8, because nanofiltration membrane device 7 can be removed polyvalent ion and organism, only contain univalent positively charged ion such as sodium ion so enter the first step purification liquid (nanofiltration product water) of reverse osmosis membrane apparatus 8, and univalent negatively charged ion such as chlorion.After reverse osmosis concentration, the second stage trapped fluid that reverse osmosis membrane apparatus 8 is held back contains the sodium-chlor of high level, is stored in the second stage trapped fluid water tank 15.Second stage trapped fluid adds sodium chloride solution by sodium-chlor chemicals dosing plant 12 after lift pump 16 promotes, the concentration of regulating sodium-chlor can be used as the regenerated liquid of Na-ion exchanger 3 to 5-7%, and Na-ion exchanger 3 is regenerated.Can reduce the consumption of salt (sodium-chlor) like this.
The product water of reverse osmosis membrane apparatus 8 (second stage purification liquid) is stored in the product water tank 9, when weakly acidic cation exchanger 4 needs regeneration, by regeneration water pump 14 second stage liquid of purifying is promoted, and after sour throwing device 10 adds acid, carries out the first step regeneration; After regeneration is finished, the second stage liquid of purifying is promoted in the weakly acidic cation exchanger 4 and replaces by regenerative pump; And then raw water pump continues the second stage liquid of purifying is promoted in the weakly acidic cation exchanger, starts alkali throwing device 11 simultaneously, carries out the regeneration of second step, makes the resin of Hydrogen be converted to the resin of sodium type.After regeneration is finished, replace and rinsing.
Ion-exchanger is when handling the waste water of oil-containing or high organic content, and after the long period, resin can be had pollution by oil or organism.Be to recover the higher operating capacity of resin, adopt heating unit that the second stage liquid of purifying is heated, be warming up to 50～80 ℃, by regenerative pump 14 hot water is delivered to Na-ion exchanger then or weakly acidic cation exchanger cleans, soaks resin.(1) for sodium ion exchange resin, after cleaning, soaking for some time, restart reproducer, to regenerate, regenerated liquid need be heated to 50～80 ℃ equally.Add sodium hydroxide by alkali throwing device 13 in hot water, keeping its concentration is 1～4%.And then soak for some time, replace and rinsing with second stage purification liquid again.(2), then after cleaning, soaking for some time, start reproducer for weakly acidic cation exchanger 4.After the first step acid regeneration is finished, replace, start the second step alkali reproducer then, but this moment, alkali liquid temperature was 50～80 ℃ with clear water.Replace and rinsing with clear water at last.
Embodiment 2
The difference of present embodiment and embodiment 1 is: only be provided with reverse osmosis membrane apparatus, and the nanofiltration membrane device is not set; Promptly the waste water through removing all polyvalent cations and basicity does not carry out the nanofiltration processing, directly carries out reverse osmosis concentration and handles.
Though the present invention discloses in conjunction with the preferred embodiments, these embodiment are not in order to limit scope of the invention process.Any those of ordinary skill in the art in not breaking away from invention scope of the present invention, when can doing suitable improvement, promptly everyly anyly according to the present invention did is equal to replacement, all in protection scope of the present invention.
Claims (10)
1. poor regenerated water treatment method of strong-acid cation-exchange resin, it comprises the steps:
(1) by the combination of strong-acid cation switch and Weak-acid cation switch, removes the hardness in the waste water; Wherein,
Waste water behind A, the removal suspended substance is introduced into the strong-acid cation switch, the part hardness in this removal waste water; The water outlet of strong-acid cation switch enters the Weak-acid cation switch, removes rest parts or whole hardness in the waste water at this;
B, the required doubly stoichiometric regenerant consumption of 1.4-1.8 of the theoretical regeneration of employing strong-acid cation switch, the strong-acid cation switch is carried out poor regeneration, thereby reduce the load of strong-acid cation switch, improve the load of Weak-acid cation switch;
C, make the Weak-acid cation switch effluent recycling to the water outlet of strong-acid cation switch, reentering the Weak-acid cation switch, so guarantee in the Weak-acid cation switch basicity always greater than hardness to remove all hardness in the waste water;
(2) waste water after the removal hardness carries out carbonization treatment and carries out membrane filtration by film condensing device and handle.
2. water treatment method as claimed in claim 1 wherein, in the described step (2), carries out one or more levels membrane filtration by one or more levels film condensing device and handles.
3. water treatment method as claimed in claim 2, wherein, membrane filtration in the described step (2) is handled and is comprised the processing of first step membrane filtration, and waste water is separated into the first step purification liquid that contains the part univalent ion, the first step trapped fluid that contains polyvalent ion and part univalent ion.
4. water treatment method as claimed in claim 3, wherein, membrane filtration in the described step (2) is handled and is comprised that further second stage membrane filtration handles, and the first step purification liquid that will contain the part univalent ion is separated into impure few second stage purification liquid, is rich in the second stage trapped fluid of univalent ion.
5. water treatment method as claimed in claim 4, wherein, described first step film condensing device is the nanofiltration membrane device, described second stage film condensing device is a reverse osmosis membrane apparatus.
6. water treatment method as claimed in claim 1 wherein, after described film condensing device moves several hrs continuously, washes it greater than 10.5 water with the pH value, to remove COD, SiO
2, organism, the biological pollution that forms and dirty stifled.
7. water treatment method as claimed in claim 4, it further comprises strong-acid cation-exchange resin is carried out the regenerated step; This step comprises:
Extract part second stage trapped fluid, add sodium-chlor, with its concentration adjustment be 5-7%, to obtain regenerated liquid;
Regenerated liquid is back to the strong-acid cation switch, strong-acid cation-exchange resin is regenerated, thus the usage quantity of minimizing strong-acid cation-exchange resin regenerator.
8. water treatment method as claimed in claim 7, wherein, when handling the waste water of oil-containing or high organic content, carry out the regenerated step to strong-acid cation-exchange resin and comprise:
After A, extraction part second stage purification liquid are heated to 50-80 ℃, are delivered to the strong-acid cation switch strong-acid cation-exchange resin is cleaned, soaks for some time;
B, regenerated liquid is heated to 50-80 ℃ after, with regenerated liquid strong-acid cation-exchange resin is regenerated, adopt purification liquid in the second stage to replace and rinsing;
C, add sodium hydroxide in rinsing liquid, keeping its concentration is 1-4%, and then soaks for some time;
D, with second stage purification liquid to strong-acid cation-exchange resin is replaced and rinsing.
9. water treatment method as claimed in claim 4, it further comprises weakly acidic cationic exchanger resin is carried out the regenerated step; This step comprises:
Part second stage purification liquid is extracted in the first step regeneration, to wherein adding acid, and it is delivered to the Weak-acid cation switch replaces, and generates h type resin;
Part second stage purification liquid is extracted in the second step regeneration, to wherein adding alkali, and it is delivered to the Weak-acid cation switch with h type resin is replaced, generation sodium type resin.
10. water treatment method as claimed in claim 9, wherein, when handling the waste water of oil-containing or high organic content, carry out the regenerated step to weakly acidic cationic exchanger resin and comprise:
After A, extraction part second stage purification liquid are heated to 50-80 ℃, are delivered to the Weak-acid cation switch weakly acidic cationic exchanger resin is cleaned, soaks for some time;
Part second stage purification liquid is extracted in the regeneration of B, the first step, to wherein adding acid, and it is delivered to the Weak-acid cation switch replaces, and generates h type resin, replaces with clear water then;
Part second stage purification liquid is extracted in C, the second step regeneration, to wherein adding alkali, and it is delivered to the Weak-acid cation switch replaces, and generates sodium type resin;
D, weakly acidic cationic exchanger resin is replaced and rinsing with second stage purification liquid or clear water.
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