CN105032189A - New method and apparatus of membrane-method calcium chloride mother liquid concentration - Google Patents
New method and apparatus of membrane-method calcium chloride mother liquid concentration Download PDFInfo
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- CN105032189A CN105032189A CN201410173977.3A CN201410173977A CN105032189A CN 105032189 A CN105032189 A CN 105032189A CN 201410173977 A CN201410173977 A CN 201410173977A CN 105032189 A CN105032189 A CN 105032189A
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Abstract
The invention relates to a new method and an apparatus of membrane-method calcium chloride mother liquid concentration. The method includes the following particular steps: (1) regulating the pH of a to-be-concentrated low-concentration calcium chloride mother liquid to 6.0-6.5 with hydrochloric acid; (2) adding 0.01-0.5% of a chelating agent R; (3) in a liquid storage tank 1, performing temperature-constant treatment to the to-be-concentrated low-concentration calcium chloride mother liquid to 65 +/- 2 DEG C; (4) pumping the material liquid through a liquid transportation pump 2, enabling the material liquid to flow through a membrane core of a hydrophobic membrane assembly 7, feeding the material liquid to a pump body, and finally enabling the material liquid to flow through a rotor flow meter 3, a pressure meter 4 and a temperature meter 5 and then feeding the material liquid back to the liquid storage tank 1 for further circulation; (5) when a vacuum pump 9 is started, pumping one part of evaporated material liquid into a condenser 8 through the vacuum pump 9 through micropores on the hydrophobic membrane assembly 7, and cooling the evaporated material liquid and feeding the evaporated material liquid into a collection bottle 6; and (6) enabling the other part of the material liquid to flow out through the hydrophobic membrane assembly 7 back into the liquid storage tank 1, thereby concentrating the material liquid in the liquid storage tank 1 and finally reaching the concentration of not less than 30%.
Description
Technical field
The present invention relates to the concentrated field of industrial chlorinations mother liquor of calcium, specifically, is the concentrated new method of a kind of embrane method calcium chloride and device.
Background technology
Calcium chloride mother liquor for low concentration concentrates, and usually adopt the method for evaporating such as single vaporization, multiple-effect evaporation to reclaim wherein calcium chloride, but concentration is lower, energy consumption is larger, must be concentrated into more than 30% and carry out multiple-effect evaporation just economically feasible again.
The technology that can be used for carrying out concentrated salting liquid is at present more, as heat pump techniques, infiltration evaporation, film distillation technology etc. that electrodialysis, counter-infiltration, nanofiltration, ion-exchange and development in recent years are got up.Method is different, energy consumption and thickening efficiency different.
Electrodialysis, counter-infiltration, nanofiltration, ion exchange process require comparatively strict to stoste salinity, be only applicable to the lower solution concentration of salinity, otherwise there will be concentration polarization formation fouling membrane, affect the performance of film.The salt content of electrodialytic technique General Requirements stoste is both economical at below 5000ppm; Counter-infiltration requires that stoste salt content is both economical at below 1500ppm; Often need to adopt multiple-effect evaporation technology in the stoste process of 5000ppm for salt content, multiple-effect evaporation technology will make a large amount of water in processing procedure, and energy consumption is large, and processing cost is high, and economy is poor.
Film distillation technology is the new technology of brine concentration, and its principle is combined with still-process by membrane technology, utilizes film to carry out strengthening transfer process, promotes gas-liquid phase equilibrium separation process, and film distillation technology realizes realizing fresh water that is concentrated and salt water.
Compared with other method, the technical advantage of film distillation technology is: 1. operating temperature is low; 2. distillation device has larger gas-liquid contact interface and mass-and heat-transfer area; 3. distillation device adopts the nonmetal equipment not high to temperature requirement, has good preservation antioxidation performance, better can resist the corrosivity of high-temperature bittern, reduces equipment cost, can avoid the employing of series of anticorrosion measure; 4. equipment volume is little, and floor space is little; 5. when membrane area is larger, volatile organic matter can be removed more up hill and dale, improve product purity; 6. not high to the mechanical property requirements of equipment and film; 7. be easy to operation and management, be easy to adjust at any time production scale, easily be automated and on-line monitoring.As can be seen here, utilize membrane distillation method while improving the quality of products, effectively can also save energy consumption, improve efficiency of energy utilization, reduce manufacturing cost.
This patent adopts film distillation technology, is separating medium, film distillation technology is applied to CaCl with hydrophobic hollow fiber membrane
2concentrating of waste liquid, is concentrated into more than 30% and carries out multiple-effect evaporation again, make whole technique economical by calcium chloride.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the new method providing a kind of embrane method calcium chloride concentrated and device.The present invention is that concrete grammar is as follows by adopting film device as shown in Figure 1 to realize the concentrated of calcium chloride mother liquor by the following method:
First the low concentration calcium chloride mother liquor pH value that will concentrate is regulated, then a certain amount of chelating agent is added, the low concentration calcium chloride mother liquor constant temperature that will concentrate in reservoir 1, feed liquid is through the suction of circulating pump 2, flow through the film core of hydrophobic film assembly 7, then the pump housing is entered, eventually pass spinner flowmeter 3, Pressure gauge 4, thermometer 5, get back to fluid reservoir 1 to circulate further, after vavuum pump 9 is opened, a part through the micropore of hydrophobic membrane, by vavuum pump 9 suction condenser 8, is entered feeder 6 by the feed liquid of evaporating after cooling; Another part feed liquid is flowed out by membrane module 7, gets back in reservoir 1, and feed liquid in reservoir is thickened.
Fig. 1 embrane method calcium chloride enrichment facility figure
1 reservoir, 2 circulating pumps, 3 spinner flowmeters, 4 Pressure gauges, 5 thermometers, 6 feeders, 7 membrane modules, 8 condensers, 9 vavuum pumps
The present invention is achieved through the following technical solutions:
(1) the low concentration calcium chloride mother liquor pH value hydrochloric acid that first will concentrate is adjusted to 6.0 ~ 6.5; By regulating the mode such as pH, pre-filtering of mother liquor to be concentrated, fouling membrane can be reduced;
(2) in order to prevent the precipitation of calcium salt, adopting a kind of polyocarboxy acid type chelating agent R, carrying out complex reaction with calcium, making not separate out calcium salt in feed liquid, the addition of chelating agent is between 0.01% ~ 0.5%, and preferred addition is 0.05%;
(3) low concentration calcium chloride mother liquor constant temperature to 65 ± 5 DEG C that will concentrate in reservoir 1;
(4) film adopts hydrophobic microporous membrane, and aperture is between 0.1um ~ 2um, and preferred aperture is 0.8um; Film is hollow-fibre membrane, also can Flat Membrane, tubular membrane or rolled film, preferred hollow-fibre membrane, obtains maximum membrane module filling area like this.
(5) innovation of this patent most critical is to utilize the suction of pump inlet by mother liquor sucking-off from film core, larger face cross-flow flow velocity can be obtained like this, greatly reduce film surface contamination, assembly can also be prevented in addition because of the leakage of the excessive generation of pressure, the service life of membrane component and prolong greatly;
(6) feed velocity flowing through film core controls between 0.05 ~ 1.0m/s, then enter the pump housing, eventually pass spinner flowmeter 3, Pressure gauge 4, thermometer 5 (entering the flow velocity after membrane module, pressure and temperature for recording feed liquid) get back to fluid reservoir 1 and circulate further;
(7), after vavuum pump 9 is opened, a part through the micropore of hydrophobic membrane, by vavuum pump 9 suction condenser 8, is entered feeder 6 by the feed liquid of evaporating after cooling; Another part feed liquid is flowed out by membrane module 7, gets back in reservoir 1, and feed liquid in reservoir is thickened.
(8) after the Membrane Materials that further circulates, calcium chloride mother liquor lower for initial concentration can be concentrated into more than 30%.
(9) material liquid supplemented carries out heat exchange through condenser, reclaims heat, reduces energy consumption, decreases the consumption of cooling water simultaneously.
(10) by plural serial stage and the parallel connection of this device, continuous concentration process can be realized.
Some leading indicators of embrane method calcium chloride concentration process can be obtained by following calculating: (1) membrane flux
Collect the condensate liquid of a period of time, measure its quality, calculate the flux J of Membrane Materials process with formula (1):
J＝W/(S·t)(1)
In formula: W is condensate liquid quality (g); S is the effective area (m of film
2); T is running time (h).
(2) salt rejection rate
Stoste calcium chloride concentration and condensate liquid calcium chloride concentration can be obtained by electrical conductivity or chemical analysis (GB23941-2009), can calculate salt rejection rate R by (2).
R＝(C
F-C
P)/C
F(2)
Wherein, R is salt rejection rate, %; C
ffor calcium chloride original liquid concentration, unit is g/L; C
pfor condensate liquid calcium chloride concentration, unit is g/L.
(3) calcium chloride enrichment factor
The enrichment factor of stoste calcium chloride can be obtained by the ratio of the calcium chloride concentration of following formula (3) concentrate calcium chloride concentration and stoste.
P＝C
R/C
F(3)
Wherein, P is enrichment factor, %; C
ffor original liquid concentration, unit is g/L; C
rfor concentrate concentration, unit is g/L.
Compared with prior art, good effect of the present invention is:
(1) present invention process is comparatively simple, adopt pumping hole suction as the power of membrane module liquid-circulating, can prevent assembly because of in press through large generation run-down or leakage, in addition large as far as possible acquisition face cross-flow flow velocity, reduce film surface contamination, the service life of membrane component and prolong greatly;
(2) by adding polyocarboxy acid type chelating agent R, regulate the mode such as pH, pre-filtering of calcium chloride mother liquor, can reduce fouling membrane, the cycle of operation of this device can be made to extend significantly, the life-span of film is also extended greatly;
(3) carry out heat exchange by supplementary material liquid and condenser, the feed liquid that preheating supplements, can heat be reclaimed, reduce energy consumption, decrease the consumption of cooling water simultaneously;
(4) by plural serial stage and the parallel connection of this device, continuous concentration process can be realized, be suitable for industrialization and run.
As can be seen here, utilize the method and apparatus of this patent, can fouling membrane be reduced, realize the effectively concentrated of rare calcium chloride, save energy consumption simultaneously, reduce manufacturing cost.
The detailed description of the invention of the present invention's new method that a kind of embrane method calcium chloride concentrates and device is below provided.
Embodiment
(1) as Fig. 1, in mother liquor, add polyocarboxy acid type chelating agent R, regulate the pH to 6.5 of calcium chloride mother liquor, heat pending feed liquid, temperature is 65 DEG C, preset temperature to be achieved stablizes about 10min, ON cycle pump, realizes the circulation of feed liquid between membrane module and reservoir, by cmf record charging flow velocity, thermometer record temperature, Pressure gauge record discharge pressure, and the recirculated water of open cold condenser;
(2) open vavuum pump, record Vacuum Pressure, now Membrane Materials process formally starts.Part feed liquid is evaporated to gas, through the micropore of hydrophobic hydrophobic membrane, is extracted enter condenser by vavuum pump, collect after cooling, another part feed liquid loops back in reservoir and forms strong brine, the time of the initial time that record condensate liquid generates and sampling, calculates the flux of Membrane Materials process;
(3) utilize conductivity meter to measure the condensate liquid collected, and measure the electrical conductivity of material liquid, calculate the salt rejection rate of Membrane Materials process;
(4) change input concentration, temperature, flow velocity and vacuum, repeat step (1) ~ (4);
When feeding temperature is 65, DEG C flow velocity is 0.1m/s, and vacuum is-0.095Mpa, and when input concentration is 10.2%, measuring film average flux is 15.6kg/m
2h, salt rejection rate is the concentration of mother liquor can be concentrated to more than 30.0% after more than 99.0%, 7h, and the life-span of film at least can obtain more than 3 months.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise; can also make some improvements and modifications, these improvements and modifications also should be considered within the scope of protection of the present invention.
Claims (2)
1. the new method that embrane method calcium chloride is concentrated and a device, is characterized in that:
(1) pending calcium chloride mother liquor concentration is between 2% ~ 30%;
(2) addition of chelating agent is between 0.01% ~ 0.5%, and preferred addition is 0.05%;
(3) regulate the pH of mother liquor to be concentrated to be less than 7, preferred pH is 6.0 ~ 6.5;
(4) film adopts hydrophobic microporous membrane, and aperture is between 0.1um ~ 2um, and preferred aperture is 0.8um; Film is hollow-fibre membrane, also can Flat Membrane, tubular membrane or rolled film, preferred hollow-fibre membrane.
2.(1) calcium chloride mother liquor flows through from the film core of hollow-fibre membrane, also can flow through from core, preferably flow through from film core, can obtain larger face cross-flow flow velocity like this, greatly reduces film surface contamination; The feed velocity flowing through film core controls between 0.05 ~ 1.0m/s, and preferable flow rate is 0.7m/s;
(2) utilize the suction of pump inlet by mother liquor sucking-off from film core, assembly can be prevented like this because of the leakage of the excessive generation of pressure, the service life of membrane component and prolong greatly;
(3) material liquid supplemented carries out heat exchange through condenser, reclaims heat, reduces energy consumption, reduces the consumption of cooling water simultaneously.
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| CN201410173977.3A CN105032189A (en) | 2014-04-29 | 2014-04-29 | New method and apparatus of membrane-method calcium chloride mother liquid concentration |
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| CN201410173977.3A CN105032189A (en) | 2014-04-29 | 2014-04-29 | New method and apparatus of membrane-method calcium chloride mother liquid concentration |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108704484A (en) * | 2018-06-06 | 2018-10-26 | 大连理工大学 | A kind of membrane contactor separation method for polynary pollutant aqueous solution |
| CN111302422A (en) * | 2020-03-12 | 2020-06-19 | 上一环保科技（杭州）有限公司 | Concentration and reduction device and method for high-salt high-concentration organic wastewater |
-
2014
- 2014-04-29 CN CN201410173977.3A patent/CN105032189A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108704484A (en) * | 2018-06-06 | 2018-10-26 | 大连理工大学 | A kind of membrane contactor separation method for polynary pollutant aqueous solution |
| CN111302422A (en) * | 2020-03-12 | 2020-06-19 | 上一环保科技（杭州）有限公司 | Concentration and reduction device and method for high-salt high-concentration organic wastewater |
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