CN101602560A - The concentrated recovery method and the device of low-concentration industrial waste acid water - Google Patents
The concentrated recovery method and the device of low-concentration industrial waste acid water Download PDFInfo
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- CN101602560A CN101602560A CNA2009100696534A CN200910069653A CN101602560A CN 101602560 A CN101602560 A CN 101602560A CN A2009100696534 A CNA2009100696534 A CN A2009100696534A CN 200910069653 A CN200910069653 A CN 200910069653A CN 101602560 A CN101602560 A CN 101602560A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002253 acid Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000002440 industrial waste Substances 0.000 title claims abstract description 22
- 238000011084 recovery Methods 0.000 title claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 111
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 80
- 238000004821 distillation Methods 0.000 claims abstract description 66
- 230000003204 osmotic effect Effects 0.000 claims abstract description 66
- 238000001728 nano-filtration Methods 0.000 claims abstract description 49
- 238000001704 evaporation Methods 0.000 claims abstract description 22
- 230000008020 evaporation Effects 0.000 claims abstract description 22
- 239000002699 waste material Substances 0.000 claims abstract description 21
- 230000018044 dehydration Effects 0.000 claims abstract description 16
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000005273 aeration Methods 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 239000002351 wastewater Substances 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 6
- 230000008595 infiltration Effects 0.000 claims abstract description 5
- 238000001764 infiltration Methods 0.000 claims abstract description 5
- 238000002203 pretreatment Methods 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 229920002521 macromolecule Polymers 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims description 32
- -1 iron ion Chemical class 0.000 claims description 15
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 14
- 230000008676 import Effects 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000001110 calcium chloride Substances 0.000 claims description 5
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 241001388119 Anisotremus surinamensis Species 0.000 claims description 2
- 239000011552 falling film Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 2
- 239000012267 brine Substances 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 description 19
- 238000013461 design Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001038 titanium pigment Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The concentrated recovery method of low-concentration industrial waste acid water comprises the steps: the pre-treatment of (1) waste acid water: with aeration method dissolved difficulty in the waste water is removed material earlier and separate out, use macromolecular substance in the high-efficiency fiber filter filtering water then; (2) osmotic distillation: the waste acid water after step (1) is handled enters the osmotic distillation membrane module, is to contain the aqueous solution that removes agent at the opposite side of osmotic distillation membrane module, removes agent and selects the lower salt brine solution of infiltration activity ratio, and concentration is generally at 25%-43%; Between 20～30 ℃, carry out the osmotic distillation dehydration, (3) remove the agent evaporation concentration: diluted remove agent with what step (2) obtained, carry out evaporation concentration, recycling (4) gelled acid water purification handles: the sour water after will concentrating filters through the nanofiltration membrane component of anti-strong acid, and impurity such as the iron ion in the sour water are removed.
Description
Technical field
The invention belongs to trade effluent recovery and utilization technology field, particularly a kind of concentrated recovery method and device of low-concentration industrial waste acid water.
Background technology
China's annual discharging spent acid enormous amount, it is more to relate to industry.As the dilute hydrochloric acid that forms in the chlor-alkali industry production, dilute sulphuric acid that produces in the pickling iron and steel process and dilute hydrochloric acid, the dilute hydrochloric acid that produces in the production of chlorinated polyethylene, the dilute sulphuric acid that produces in the sulfuric acid method titanium pigment production process etc., the spent acid quantity discharged of these industries is very huge, be example with Production By Sulfuric Acid Process titanium dioxide only, one ton of titanium dioxide of every production will produce the spent acid of 8-10 ton about 20%.Because the concentration of discharging spent acid is relatively low, can not be directly used in the production, need to concentrate the back and utilize, but the general energy consumption of concentration method of diluted acid is bigger at present.Most of corporate boss will adopt the method that adds lime to discharge therein with after the acid, and lime consumption is big, and produces a large amount of mud, causes secondary pollution.
Summary of the invention
The purpose of this invention is to provide a kind of concentrated recovery method and equipment of low-concentration industrial waste acid water, installation and maintenance is convenient in the EM equipment module design, and the gelled acid quality of output is good.
The concentrated recovery method of low-concentration industrial waste acid water comprises the steps:
(1) pre-treatment of waste acid water: with aeration method dissolved difficulty in the waste water is removed material earlier and separate out, use macromolecular substance in the high-efficiency fiber filter filtering water then;
(2) osmotic distillation: the waste acid water after step (1) is handled enters the osmotic distillation membrane module, in a side of osmotic distillation membrane module is waste acid water after step (1) is handled, opposite side at the osmotic distillation membrane module is to contain the aqueous solution that removes agent, remove agent and select the lower inorganic salt solution of infiltration activity ratio, as magnesium chloride, sal epsom, calcium chloride, any or several mixing of dipotassium hydrogen phosphate, its concentration is at 25%-43%; Carry out the osmotic distillation dehydration between 20～30 ℃, the abraum salt acid concentration is increased to 17-21% from 2%-6% after the osmotic distillation dehydration concentrates, or the sulfur waste acid concentration is increased to 40%-52% from 5%-10%.
(3) remove the agent evaporation concentration: diluted remove agent with what step (2) obtained, carry out evaporation concentration, be concentrated into saturated the salts contg that removes agent or supersaturation, be back to use the osmotic distillation step, recycle;
(4) the gelled acid water purification is handled: the sour water after will concentrating filters with the nanofiltration membrane component of anti-strong acid, removes the impurity such as iron ion in the sour water, reaches technical grade standard GB 320-2006, or GB/T534-2002.(the former is the standard of hydrochloric acid, and the latter is the vitriolic standard)
According to aforesaid method, the present invention also provides a kind of concentrated recovery system of low-concentration industrial waste acid water, it is characterized in that, comprise as lower device: the spent acid collecting tank is communicated with the aeration tank by pipeline; The water-in of feed pump A inserts in the aeration tank, and the water outlet of feed pump A is by the water-in of pipe connection to efficient fabric filter; The water outlet of high-efficiency fiber filter inserts the sour pond of storage by pipeline; The water-in of feed pump B inserts the sour pond of storage, and the water outlet of feed pump B is by the liquor inlet of pipe connection to the osmotic distillation membrane module, in parallel or series connection between the osmotic distillation membrane module, and the material liquid outlet of osmotic distillation membrane module inserts the sour pond of storage by pipeline; To removing the developing agent storage pond, what the water outlet that removes agent pump A inserted the osmotic distillation membrane module removes the agent import to the water-in that removes agent pump A by pipe connection, and the agent outlet that removes of osmotic distillation membrane module inserts by pipeline and removes the developing agent storage pond; The water-in that removes agent pump B inserts and to remove the developing agent storage pond, removes the import of the water outlet of agent pump B by the pipe connection evaporation concentration device, the outlet of evaporation concentration device by pipe connection to removing the developing agent storage pond; The water-in of high-pressure pump inserts the sour pond of storage, and the water outlet of high-pressure pump is by the nanofiltration membrane component of the anti-strong acid of pipe connection.
(traditional method is the steam heating evaporation to the invention solves the high problem of traditional heating evaporation concentration sour water energy consumption, steam consumption is many, utilization of the present invention removes agent and absorbs, and removing agent can recycle, so consume few), do not add the alkali step, solved and added in the alkali and the discharging sour water, the waste resource, and cause secondary pollution problem.Advanced technology, the thickening efficiency height.The initial condition of water quality design quantity of osmotic distillation membrane module basis how much, is modular design.Remove agent through reuse after the evaporation concentration, reduce running cost, it is few to concentrate sour water impurity; The present invention can be used in pickling iron and steel industry and the Chemical Manufacture, creates economic benefit.
Description of drawings
Fig. 1 is a low-concentration industrial waste acid concentrate recovery process schema of the present invention;
Fig. 2 is that low-concentration industrial waste acid concentrates the recovery system structural representation, wherein: 1 spent acid collecting tank; 2 aeration tanks; 3 feed pump A; 4 high-efficiency fiber filters; The sour pond of 5 storages; 6 feed pump B; 7 osmotic distillation membrane modules; 8 remove agent pump A; 9 remove the developing agent storage pond; 10 remove agent pump B; 11 evaporation concentration devices; 12 high-pressure pump; 13 anti-strong acid nanofiltration membrane components; 14 valve A; 15 valve B; 16 valve C; 17 valve D; 18 valve E.
Embodiment
A kind of concentrated recovery method of low-concentration waste acid water comprises the steps:
(1) pre-treatment of waste acid water: with aeration method dissolved difficulty in the waste water is removed material earlier and separate out, remove macromolecular substance in the water by high-efficiency fiber filter then;
(2) osmotic distillation: the waste acid water after step (1) is handled enters the osmotic distillation membrane module, in a side of osmotic distillation membrane module is waste acid water after step (1) is handled, opposite side at the osmotic distillation membrane module is to contain the aqueous solution that removes agent, remove agent and select the lower inorganic salt solution of infiltration activity ratio, this example is chosen as magnesium chloride, and concentration is 34%; Carry out the osmotic distillation dehydration at 20 ℃, the sulfur waste acid concentration is increased to 41% from 8% after the osmotic distillation dehydration concentrates; Osmotic distillation membrane module modularized design is according to what of the size design membrane module of handling the water yield, promptly when treatment capacity increases, can improve processing power by adding membrane module, invest for a short time, the interpolation of membrane module is simple to operate, equipment takes up an area of province in addition, according to the domain size, installs flexibly; And traditional thickening equipment floor space is big, and equipment is once definite, and processing power is just fixing, and increasing treatment capacity can only invest bigger by increasing new equipment.
(3) remove the agent evaporation concentration: diluted remove agent with what step (2) obtained, carry out evaporation concentration, be concentrated into saturated the salts contg that removes agent or supersaturation, be back to use osmotic distillation, recycle;
(4) the gelled acid water purification is handled: (nanofiltration membrane component of anti-strong acid can be held back the impurity such as iron ion in the acid to the sour water after will concentrating with the nanofiltration membrane component of anti-strong acid, nanofiltration membrane component generally adopts the two-stage setting, be that the water outlet of one-level nanofiltration membrane component enters the secondary nanofiltration membrane component, the water outlet of secondary nanofiltration membrane component is the low-down sour water of foreign matter content) filter, remove the impurity such as iron ion in the sour water, reach the technical grade standard.
In the step (3), directly discharging or of the water that is evaporated through evaporation concentration device as the wash-down water reuse.
In the step (4), contain ferrous sulfate in the impurity that nanofiltration membrane is held back, can be used as the raw material of producing water conditioner.
Embodiment 2:
Substance is with embodiment 1, and its difference is, removes agent and selects sal epsom, and concentration is carried out the osmotic distillation dehydration 25% at 25 ℃; The abraum salt acid concentration is increased to 17% from 2% after the osmotic distillation dehydration concentrates, osmotic distillation membrane module modularized design, according to what of the size design membrane module of handling the water yield, promptly when treatment capacity increases, can improve processing power by adding membrane module, the interpolation of membrane module is simple to operate, and equipment takes up an area of province in addition, according to the domain size, install flexibly; And traditional thickening equipment floor space is big, and equipment is once definite, and processing power is just fixing, and increasing treatment capacity can only invest bigger by increasing new equipment.(nanofiltration membrane component of anti-strong acid can be held back the impurity such as iron ion in the acid through nanofiltration membrane component to concentrate sour water, nanofiltration membrane component generally adopts the two-stage setting, be that the water outlet of one-level nanofiltration membrane component enters the secondary nanofiltration membrane component, the water outlet of secondary nanofiltration membrane component is the low-down sour water of foreign matter content) filtration, purification reaches technical grade standard GB 320-2006 after handling.
Embodiment 3:
Substance is with embodiment 1, and its difference is, removes agent selective chlorination calcium, and concentration is carried out the osmotic distillation dehydration 32% at 27 ℃; The abraum salt acid concentration is increased to 21% from 5% after the osmotic distillation dehydration concentrates, osmotic distillation membrane module modularized design, according to what of the size design membrane module of handling the water yield, promptly when treatment capacity increases, can improve processing power by adding membrane module, the interpolation of membrane module is simple to operate, and equipment takes up an area of province in addition, according to the domain size, install flexibly; And traditional thickening equipment floor space is big, and equipment is once definite, and processing power is just fixing, and increasing treatment capacity can only invest bigger by increasing new equipment.(nanofiltration membrane component of anti-strong acid can be held back the impurity such as iron ion in the acid through nanofiltration membrane component to concentrate sour water, nanofiltration membrane component generally adopts the two-stage setting, be that the water outlet of one-level nanofiltration membrane component enters the secondary nanofiltration membrane component, the water outlet of secondary nanofiltration membrane component is the low-down sour water of foreign matter content) filtration, purification reaches technical grade standard GB 320-2006 after handling.
Embodiment 4:
Substance is with embodiment 1, and its difference is, removes agent and selects dipotassium hydrogen phosphate, and concentration is carried out the osmotic distillation dehydration 43% at 27 ℃; The sulfur waste acid concentration is increased to 52% from 10% after the osmotic distillation dehydration concentrates; (nanofiltration membrane component of anti-strong acid can be held back the impurity such as iron ion in the acid through nanofiltration membrane component to concentrate sour water, nanofiltration membrane component generally adopts the two-stage setting, be that the water outlet of one-level nanofiltration membrane component enters the secondary nanofiltration membrane component, the water outlet of secondary nanofiltration membrane component is the low-down sour water of foreign matter content) filtration, purification reaches technical grade standard GB/T534-2002 after handling.
Embodiment 5:
Substance is with embodiment 1, and its difference is, removes agent selective chlorination magnesium and sal epsom, and its total concn is carried out the osmotic distillation dehydration 30% at 28 ℃; The weight ratio of magnesium chloride and sal epsom is 1: 1: the abraum salt acid concentration is increased to 20% from 6% after the osmotic distillation dehydration concentrates, (nanofiltration membrane component of anti-strong acid can be held back the impurity such as iron ion in the acid through nanofiltration membrane component to concentrate sour water, nanofiltration membrane component generally adopts the two-stage setting, be that the water outlet of one-level nanofiltration membrane component enters the secondary nanofiltration membrane component, the water outlet of secondary nanofiltration membrane component is the low-down sour water of foreign matter content) filtration, purification reaches technical grade standard GB 320-2006 after handling.
Embodiment 6:
Substance is with embodiment 1, and its difference is, removes agent selective chlorination calcium and magnesium chloride, and total concn is 35%, and calcium chloride and magnesium chloride weight ratio are 1: 1, carry out the osmotic distillation dehydration at 30 ℃; The sulfur waste acid concentration is increased to 40% from 5% after the osmotic distillation dehydration concentrates; (nanofiltration membrane component of anti-strong acid can be held back the impurity such as iron ion in the acid through nanofiltration membrane component to concentrate sour water, nanofiltration membrane component generally adopts the two-stage setting, be that the water outlet of one-level nanofiltration membrane component enters the secondary nanofiltration membrane component, the water outlet of secondary nanofiltration membrane component is the low-down sour water of foreign matter content) filtration, purification reaches technical grade standard GB/T534-2002 after handling.
Fig. 2 is the concentrated recovery system structural representation of low-concentration industrial waste acid, comprises as lower device: spent acid collecting tank 1 is communicated with aeration tank 2 by pipeline; The water-in of feed pump A3 inserts in the aeration tank 2, and the water outlet of feed pump A3 is by the water-in of pipe connection to efficient fabric filter 4; The water outlet of high-efficiency fiber filter 4 inserts the sour pond 5 of storage by pipeline; The water-in of feed pump B 6 inserts the sour pond 5 of storage, the water outlet of feed pump B 6 is by the liquor inlet of pipe connection to osmotic distillation membrane module 7, in parallel or series connection between the osmotic distillation membrane module, the material liquid outlet of osmotic distillation membrane module 7 inserts the sour pond 5 of storage by pipeline; To removing developing agent storage pond 9, what the water outlet that removes agent pump A 8 inserted osmotic distillation membrane module 7 removes the agent import to the water-in that removes agent pump A 8 by pipe connection, and the agent outlet that removes of osmotic distillation membrane module 7 inserts by pipeline and removes developing agent storage pond 9; The water-in that removes agent pump B 10 inserts and to remove developing agent storage pond 9, removes the import of the water outlet of agent pump B 10 by pipe connection evaporation concentration device 11, the outlet of evaporation concentration device 11 by pipe connection to removing developing agent storage pond 9; The water-in of high-pressure pump 12 inserts the sour pond 5 of storage, and the water outlet of high-pressure pump 12 is by the nanofiltration membrane component 13 of the anti-strong acid of pipe connection.
All insert valve in aforesaid device before the water-in of all pumps, be used for the flooding velocity of control pump.As: insert valve A 14 before the feed pump A 3, insert valve B15 before the feed pump B 6, remove the agent pump A 8 preceding valve C16 that insert; Insert valve D17 before removing agent pump B 10; Insert valve E18 before the high-pressure pump 12.
Described high-efficiency fiber filter material is the polypropylene fibre pompon, and filtering accuracy is at 100 μ m.
The mould material of described osmotic distillation membrane module is polypropylene or polyvinylidene difluoride (PVDF) or tetrafluoroethylene.
Described osmotic distillation membrane module adopts tubular fibre formula assembly or plate and frame assembly.
The membrane pore size of described osmotic distillation membrane module is 0.1～1.0 μ m; Described osmotic distillation membrane module length-to-diameter ratio is 3～5, and the packing factor of membrane module is 10～40%.For example select for use length-to-diameter ratio to be respectively 3,4,5, the packing factor of membrane module is respectively 10%, 20%, 30%, 40%.
The quantity of described osmotic distillation membrane module can design according to handling the water yield, in parallel or series connection use between the assembly.Series connection is meant that waste water passes through every membrane module successively, promptly enter the water-in of second assembly from the water outlet of first assembly, enter the water-in of the 3rd assembly from the water outlet of second assembly, by that analogy, the water outlet of last assembly is to reach the concentrated acid water that acid concentration requires.Parallel connection is that waste water is distributed by pipeline, enter every membrane module simultaneously, concentrate to come out again from outlet conduit, the water-in that is every membrane module is connected on the inlet channel, the water outlet of every membrane module is connected on the outlet conduit, the waste water circulation concentrates, and finally reaches concentration requirement, comes out from outlet conduit.Two kinds of methods of attachment respectively have relative merits, but can both reach the expection treatment effect.Need membrane module few when being connected in parallel, power consumption is low, be convenient to control, but waste water needs circular treatment, influences the continuity of wastewater treatment; Waste water once passes through when being connected in series, and reaches concentrated purpose, but needs membrane module many, the power consumption height.
In the described osmotic distillation membrane module, one side of film is a waste acid water, the opposite side of film is for removing agent, remove agent and select the lower inorganic salt solution of infiltration activity ratio, as concentration is the calcium chloride of 25%-43%, any or several mixing (referring to embodiment 1～6) of magnesium chloride, sal epsom or dipotassium hydrogen phosphate; Service temperature is at 20～30 ℃.
Described evaporation equipment is a falling-film evaporator, adopts steam heating.
Described anti-strong acid nanofiltration membrane component is the anti-strong acid nanofiltration membrane of SELRO series, the Impurity removals such as iron ion in the spent acid can be put forward highly acid purity.
Industrial waste acid water is sent into aeration tank 2 from spent acid collecting tank 1, after in aeration tank 2, passing through aeration, deliver to high-efficiency fiber filter 4 by feed pump A 3 and carry out pre-treatment, insert valve A 14 before the feed pump A 3, the industrial waste acid water after the processing injects the sour pond 5 of storage and prepares to concentrate.Treat that spissated waste acid water is pumped into the liquor inlet of osmotic distillation membrane module 7 by feed pump B 6, insert valve B 15 before the feed pump B 6, waste water flows at the inner chamber of polypropylene hollow fiber membrane silk, flow out from the material liquid outlet of assembly, be back to the sour pond 5 of storage, pump into the assembly liquor inlet from storing sour pond 5 by feed pump B 6 again, so circulation is carried out.Meanwhile, remove agent and remove the agent import from what remove that developing agent storage pond 9 pumps into osmotic distillation membrane module 7 by removing agent pump A 8, insert valve C 16 before removing agent pump A 8, remove the flows outside of agent at the hollow-fibre membrane silk, the agent outlet that removes at assembly is flowed out, be back to and remove developing agent storage pond 9, this process also circulates and carries out.Be diffused into by film and remove in the agent along with the water molecules in the waste acid water constantly becomes water vapour, waste acid water is concentrated, and it is diluted to remove agent, therefore needs to improve remove the carrying out that agent concentration guarantees sour concentration process.When removing agent concentration and be not enough to carry out osmotic distillation, utilize to remove agent pump B 10 it is sent into evaporation concentration device 11, insert valve D 17 before removing agent pump B 10, treat that strength of solution when saturated, send back to and remove developing agent storage pond 9, recycle.After acid-spending strength reaches requirement, need further purifying treatment, utilize high-pressure pump 12 that spissated sour water is pumped into the nanofiltration membrane component 13 of anti-strong acid by the sour pond 5 of storage, insert valve E 18 before the high-pressure pump 12, remove impurity wherein, obtain purified concentrated acid.
Claims (10)
1, the concentrated recovery method of low-concentration industrial waste acid water is characterized in that, comprises the steps:
(1) pre-treatment of waste acid water: with aeration method dissolved difficulty in the waste water is removed material earlier and separate out, use macromolecular substance in the high-efficiency fiber filter filtering water then;
(2) osmotic distillation: the waste acid water after step (1) is handled enters the osmotic distillation membrane module, in a side of osmotic distillation membrane module is waste acid water after step (1) is handled, opposite side at the osmotic distillation membrane module is to contain the aqueous solution that removes agent, remove agent and select the lower inorganic salt solution of infiltration activity ratio, concentration is at 25%-43%; Between 20～30 ℃, carry out the osmotic distillation dehydration;
(3) remove the agent evaporation concentration: diluted remove agent with what step (2) obtained, carry out evaporation concentration, be concentrated into saturated the salts contg that removes agent or supersaturation, be back to use osmotic distillation, recycle;
(4) the gelled acid water purification is handled: the sour water after will concentrating filters with the nanofiltration membrane component of anti-strong acid, removes the impurity such as iron ion in the sour water.
2, the concentrated recovery method of low-concentration industrial waste acid water according to claim 1 is characterized in that, described to remove agent be magnesium chloride, sal epsom, calcium chloride, any one or a few mixing of dipotassium hydrogen phosphate.
3, the concentrated recovery system of low-concentration industrial waste acid water is characterized in that, comprise as lower device: the spent acid collecting tank is communicated with the aeration tank by pipeline; The water-in of feed pump A inserts in the aeration tank, and the water outlet of feed pump A is by the water-in of pipe connection to efficient fabric filter; The water outlet of high-efficiency fiber filter inserts the sour pond of storage by pipeline; The water-in of feed pump B inserts the sour pond of storage, and the water outlet of feed pump B is by the liquor inlet of pipe connection to the osmotic distillation membrane module, in parallel or series connection between the osmotic distillation membrane module, and the material liquid outlet of osmotic distillation membrane module inserts the sour pond of storage by pipeline; To removing the developing agent storage pond, what the water outlet that removes agent pump A inserted the osmotic distillation membrane module removes the agent import to the water-in that removes agent pump A by pipe connection, and the agent outlet that removes of osmotic distillation membrane module inserts by pipeline and removes the developing agent storage pond; The water-in that removes agent pump B inserts and to remove the developing agent storage pond, removes the import of the water outlet of agent pump B by the pipe connection evaporation concentration device, the outlet of evaporation concentration device by pipe connection to removing the developing agent storage pond; The water-in of high-pressure pump inserts the sour pond of storage, and the water outlet of high-pressure pump is by the nanofiltration membrane component of the anti-strong acid of pipe connection.
4, the concentrated recovery method of low-concentration industrial waste acid water according to claim 3 is characterized in that, described high-efficiency fiber filter material is the polypropylene fibre pompon, and filtering accuracy is at 100 μ m.
5, the concentrated recovery system of low-concentration industrial waste acid water according to claim 3 is characterized in that, the material of described osmotic distillation membrane module is polypropylene, polyvinylidene difluoride (PVDF) or tetrafluoroethylene, and the aperture is 0.1～1.0 μ m.
6, the concentrated recovery system of low-concentration industrial waste acid water according to claim 3 is characterized in that, described osmotic distillation membrane module adopts tubular fibre formula assembly or plate and frame assembly.
7, the concentrated recovery system of low-concentration industrial waste acid water according to claim 3 is characterized in that, in parallel or series connection use between the described osmotic distillation membrane module.
8, the concentrated recovery system of low-concentration industrial waste acid water according to claim 3 is characterized in that, described evaporation concentration equipment is a falling-film evaporator, adopts steam heating.
9, the concentrated recovery system of low-concentration industrial waste acid water according to claim 3 is characterized in that, described anti-strong acid nanofiltration membrane component is the anti-strong acid nanofiltration membrane of SELRO series.
10, the concentrated recovery system of low-concentration industrial waste acid water according to claim 3 is characterized in that, all inserts valve before described all water-ins of " pumps ", is used for the flooding velocity of control pump.
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| CN104743694A (en) * | 2013-12-30 | 2015-07-01 | 北京有色金属研究总院 | Recycling processing method and device of heavy metal ion-containing organic acid wastewater |
| CN105601012A (en) * | 2015-12-23 | 2016-05-25 | 韦建初 | Method for treating acid-containing waste liquid by condensation and distillation purification |
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| GB9705349D0 (en) * | 1997-03-14 | 1997-04-30 | Ici Plc | Treatment of effluent streams |
| ZA200600753B (en) * | 2003-07-24 | 2007-05-30 | Otv Sa | System and method for treatment of acidic wastewater |
| CN101323491A (en) * | 2007-06-12 | 2008-12-17 | 北京富特斯化工科技有限公司 | Acidic industrial waste water processing method and system |
| CN101434442A (en) * | 2008-12-22 | 2009-05-20 | 冯圣君 | Comprehensive utilization method for industrial waste acid containing cupric ion and special equipment therefor |
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| CN105601012A (en) * | 2015-12-23 | 2016-05-25 | 韦建初 | Method for treating acid-containing waste liquid by condensation and distillation purification |
| CN106578782A (en) * | 2016-12-19 | 2017-04-26 | 甘肃农业大学 | Soft pear juice concentration device and soft pear juice production method |
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