CN206580666U - The advanced treatment system of mercury-containing waste water in vinyl chloride production - Google Patents
The advanced treatment system of mercury-containing waste water in vinyl chloride production Download PDFInfo
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- CN206580666U CN206580666U CN201720103735.6U CN201720103735U CN206580666U CN 206580666 U CN206580666 U CN 206580666U CN 201720103735 U CN201720103735 U CN 201720103735U CN 206580666 U CN206580666 U CN 206580666U
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Abstract
The utility model is related to mercury-containing waste water process field, the advanced treatment system of mercury-containing waste water in specifically a kind of vinyl chloride generating process, specific to be low concentration mercury-containing waste water after coagulation (sulfide precipitation+filtering), system mainly includes second reactor, suspended filter, pans, purpose ceramic-film filter and two-stage depth absorber.The problems such as systems approach of the present utility model solves the fluctuation of service of existing mercury-containing waste water handling process presence, aqueous concentration is not up to standard; aqueous concentration is remained permanently in below 1ppb; and operation and maintenance cost is very low; the purpose of energy-saving and emission-reduction and environmental protection is have effectively achieved, this system can be used in the transformation of existing mercury-containing waste water processing unit or newly-built mercury-containing waste water handling process.
Description
Technical field
The utility model is related to mercury-containing waste water process field, specifically, is mercurous useless in a kind of vinyl chloride generating process
The advanced treatment system of water.
Background technology
All it is to use mercuric chloride catalyst in domestic production of vinyl chloride by calcium carbide method production technology, can produces in process of production a small amount of
Mercury-containing waste water, mercury content is between 500~1000ppb.In view of significant damage of the mercury to the mankind, country is to draining mercury content
Requirement it is increasingly stricter (<3ppb), each chlor-alkali enterprises take the processing of all kinds of handling process progress mercury-containing waste waters one after another.
The processing method of mercury-containing waste water mainly includes following several：The traditional chemical precipitation method, ion-exchange, reducing process,
Absorption method, electrolysis, amalgam extraction method, microorganism treatment etc..At present, in most of vinyl chloride industry mercury-containing waste water processing
Use what " sulfide precipitation+filtering " technique based on sulfide and mercury ion formation HgS precipitations was realized.
Chinese patent literature CN1673117A discloses " a kind of processing method of mercury-containing waste water ", and its method is：To mercurous
Na is sequentially added in waste water2After S and organic flocculant, generation HgS precipitations, flocculent deposit is separated with separated water, obtained
The qualified water of processing, this method is difficult to grasp the usage amount of vulcanized sodium, easily forms soluble complexes, effluent quality is by water inlet water
The interference of matter is larger, and effluent quality is unstable, there is exceeded possibility；Chinese patent literature CN102010086A discloses " one
Plant the method that three sections of continuous processings handle mercury-containing waste water ", its method is：Mercury-containing waste water pH is adjusted to 9-10, Na is sequentially added2S
And inorganic flocculating agent, after generation HgS precipitations, supernatant qualified discharge after filtering, this method lacks advanced treatment process, processing
The still mercury containing low concentration, and effluent quality is larger by the interference of influent quality in waste water afterwards, effluent quality is unstable, deposits
In exceeded possibility；Chinese patent literature CN102145930B discloses " a kind of processing method of mercury-containing waste water ", and its method is：
PH is adjusted to neutrality, vulcanizing agent and composite assistant is added, separated supernatant after forming precipitation, then using sand filtration, fiber mistake
Filter, accurate filter or film enter water-filling and the separation of particulate matter, although the above method adds advanced treating step, simultaneously
The mercury for not forming precipitation can not be removed, still there is risk of exceeding criterion in water outlet.Therefore, it is existing mercurous useless based on sulfide precipitation
There are problems in water technology, such as, and operating difficulties, batch-type react, effluent quality is unstable, there is exceeded danger
(being extremely difficult to below 5ppb), shortage thoroughly remove deep treatment method of the removal of mercury etc..
Increasing with country to environmentally friendly attention dynamics, is mostly based on the mercury-containing waste water of " sulfide precipitation+filtering " technique
Handling process is difficult to meet the standard requirement of country, and the discharge of the mercury-containing waste water after processing causes the waste of water resource, because
This apparatus and process need to improve.On a kind of advanced treating low concentration mercury-containing waste water, (early stage uses " sulfide precipitation+filtering " at present
The waste water of PROCESS FOR TREATMENT) processing system (mercury concentration is maintained at below 1ppb after processing) have not been reported.
The content of the invention
The purpose of this utility model is by transforming original mercury-containing waste water processing system, advanced treating vinyl chloride production industry
The concentration of the mercury-containing waste water of middle generation, further reduction mercury, it is ensured that the continual and steady super low concentration of effluent quality (<1ppb) discharge,
And then protect water environment.The utility model is mainly used in early stage and contained using the low concentration after " sulfide precipitation+filtering " PROCESS FOR TREATMENT
The advanced treating of mercury waste water.
Workflow and principle of the present utility model：
Sulfurization-precipitation method is most ripe treatment of mercury-containing wastewater, and mercury ion sinks with sulphion reaction generation mercuric sulphide
Form sediment.《Caustic soda PVC industry pollution discharge standard (GB15581-1995)》Limiting the highest of total mercury allows discharge dense
Spend for 5ppb, " sulfide precipitation+filtering " technique nowadays generally used is difficult the requirement for the standard that meets, although many factories are to sulphur
Change depositing technology to be improved, such as add active carbon absorption technology, membrane filtration process etc., but it is unstable there are still water outlet
Fixed, not up to standard the problems such as.
Processing of the utility model to mercury-containing waste water is that the depth combination added after " sulfide precipitation+filtering " technique is set
It is standby, mainly for traditional sulfide precipitation technique exist go out water unstable, it is not up to standard the problems such as, be high-efficient mercury precipitation+filtering+
The integrated application of absorption.The mercury content for first passing around the mercury-containing waste water of early stage " sulfide precipitation+filtering " equipment processing is down to 20~
100ppb, then waste water is into advanced treating combination unit, using the reaction of heavy metal chelating agent and mercury in second reactor,
The water insoluble chelate of generation, the completely rear waste water of precipitation enters fiber bundle filter, filters out suspension, clear liquid is sequentially entered
Purpose ceramic-film filter and mercury chelating resin absorber, the remaining mercury of further Adsorption.
To achieve these goals, the utility model provides a kind of advanced treating of mercury-containing waste water in vinyl chloride generating process
System (see Fig. 1), including pass sequentially through second reactor, suspended filter, pans, the purpose ceramic-film filter of pipeline connection
With two-stage depth absorber；The delivery port of described second reactor and the water inlet of suspended filter are connected, and described is outstanding
The delivery port of float filter and the water inlet of pans are connected, the described delivery port of pans and entering for purpose ceramic-film filter
The mouth of a river is connected, and the delivery port of described purpose ceramic-film filter is connected with the water inlet of two-stage depth absorber.
It is preferred that, described two-stage depth absorber includes the level deep absorber being used in series and two grades of depth absorption
It is provided with renewable removal of mercury chelating resin, two grades of depth absorbers and is removed provided with non-renewable in device, wherein level deep absorber
Mercury chelating resin.It is to go out on bottom is entered that described level deep absorber and two grades of depth absorbers, which are flowed to, wherein level deep
Absorber uses renewable resin, quarterly regenerates once, and regeneration liquid waste returns to front end coagulation system processing in the lump,
Two grades of depth absorbers use non-renewable resin.In addition, partial period is without using two grades of depth absorbers, two grades of depth
Absorber is only used under accident conditions.
It is furthermore preferred that described level deep absorber uses renewable removal of mercury chelating resin Tulsion CH-97,
Two grades of described depth absorbers use non-renewable removal of mercury chelating resin Tulsion CH-95.
It is preferred that, it is also associated with storing the heavy metal chelating agent storage tank of heavy metal chelating agent on described second reactor.
It is preferred that, the polypropylene fibre bundle as filtering material is provided with described suspended filter.It is furthermore preferred that described
Polypropylene fibre bundle characteristic parameter be 1.5m length, 280g/ roots, be purchased from Henan Hua Xin Environmental Protection Technology Co., Ltd.
It is preferred that, porous nano ceramic membrane is provided with described purpose ceramic-film filter.It is furthermore preferred that described porous nano
The Sen Meisi of the environmentally friendly Co., Ltd of ceramic 20~50nm of membrane aperture, optional Hunan Sen MeisiType.
The use of described advanced treatment system need to be carried out according to the following steps：
The first step, second reactor is flowed into by the low concentration mercury-containing waste water of coagulation, while adding heavy metals trapping
Flow into second reactor bottom after agent, Precipitation, sediment returns to coagulation system, liquid is from second reactor overhead stream
Go out；Second step, second reactor water outlet flows into suspended filter, filters suspension, and filtrate enters pans；3rd step, in
Between middle waste water in tank flow into purpose ceramic-film filter and carry out filtering absorption, further go the removal of mercury；4th step, purpose ceramic-film filter
In water outlet flow into two-stage depth absorber, can be discharged after water outlet detection is up to standard or into the recycling ring of next step
Section, detects that waste water not up to standard is discharged into pans (see Fig. 2).
It is preferred that, it is mercurous that the low concentration mercury-containing waste water of described process coagulation comes from one-level " sulfide precipitation+filtering "
Waste Water Treatment, waste water mercury content has been lowered to 20~100ppb.
It is preferred that, described heavy metal chelating agent is to add in second reactor after liquid, 50~100 times of dissolved dilution,
Total addition of heavy metal chelating agent is 5~15mg/L mercury-containing waste waters.It is furthermore preferred that described heavy metal chelating agent uses Wuhan
The TNT-18F heavy metal chelating agents of Bo Ren enlightening Science and Technology Ltd..
It is preferred that, described deep treatment method can continue water inlet, continue water outlet, keep continuous operation, and typically
Operating flux is in 5~10m3/ hour.
The utility model has the advantage of：
1st, after the processing of one-level " sulfide precipitation+filtering " mercury-containing waste water, the reduction of mercury-containing waste water concentration is obvious, and waste water is mercurous
Amount has been lowered to 20~100ppb, but there are problems that aqueous concentration it is high, the utility model is mainly for passing through one
Low concentration mercury-containing waste water after level processing, is targetedly combined with various technologies, can further reduce mercury in mercury-containing waste water
Concentration, reaches continual and steady purpose up to standard, and aqueous concentration is less than 1ppb for a long time, far below national standard requirement.
2nd, the utility model solves the fluctuation of service of existing mercury-containing waste water handling process presence, aqueous concentration and not reached
The problems such as mark, not only treatment effeciency is high, and simple to operate, service life of equipment length, operation and maintenance cost are extremely low, significantly drop
Low production cost.
3rd, the utility model be targetedly additionally added on the basis of traditional " sulfide precipitation+filtering " technique it is multiple
Equipment, be particularly suitable for use in traditional mercury-containing waste water handling process transformation, available for existing mercury-containing waste water processing unit transformation or new
In the mercury-containing waste water handling process built.
4th, mercury content is extremely low in the waste water after handling, and salt content is high, can be used for as haline water in other techniques, realizes true
Mercury-containing waste water zero-emission in positive meaning, it is to avoid the waste of water resource, have effectively achieved energy-saving and emission-reduction and environmental protection
Purpose.
Brief description of the drawings
The structural representation of the advanced treatment system of mercury-containing waste water in Fig. 1 vinyl chloride generating process of the present utility model.
The use flow chart of the advanced treatment system of mercury-containing waste water in Fig. 2 the utility model vinyl chloride generating process.
The reference and part being related in accompanying drawing are as follows：
1- second reactors, 2- heavy metal chelating agent storage tanks, 3- suspended filters, 4- pans, 5- ceramic membrane filters
Device, 6- level deep absorbers, bis- grades of depth absorbers of 7-.
Embodiment
The embodiment provided with reference to embodiment and accompanying drawing the utility model elaborates.
Embodiment 1
In Shandong Province Chiping County, letter hair chemical industry uses the advanced treatment system in the utility model to arrange VCM process units
The mercury-containing waste water gone out has carried out advanced treating.
1st, mercury-containing waste water index after coagulation：
Mercury content is between 10~50ppb in mercury-containing waste water after one-level sulfide precipitation+filtration treatment, pH between
Between 6~9.
2nd, advanced treatment process condition：
System diagram and flow chart are as depicted in figs. 1 and 2.The first step, is flowed into by the low concentration mercury-containing waste water of coagulation
In second reactor 1, the bottom of second reactor 1 is flowed into after heavy metal chelating agent, Precipitation while adding, sediment returns to one
Level processing system, liquid flows out from the top of second reactor 1；Second step, the water outlet of second reactor 1 flows into suspended filter 3
In, suspension is filtered, filtrate enters pans 4；Middle waste water in 3rd step, pans 4 flows into purpose ceramic-film filter 5 and carried out
Filtering absorption, further goes the removal of mercury；Water outlet in 4th step, purpose ceramic-film filter 5 flows into two-stage depth absorber (level deep
Absorber 6 and two grades of depth absorbers 7) in, it can be discharged or into the recycling link of next step after water outlet detection is up to standard,
Detection waste water not up to standard is discharged into pans 4.Heavy metal chelating agent is the TNT-18F liquid of Wuhan Bo Ren enlightening Science and Technology Ltd.
Added after heavy metal chelating agent, 75 times of dissolved dilution in second reactor 1, the addition of heavy metal chelating agent is mercurous for 10mg/L
Waste water；Filtering material in suspended filter 3 is polypropylene fibre bundle, and fibre bundle characteristic parameter is 1.5m length, 280g/ roots, purchase
In Henan Hua Xin Environmental Protection Technology Co., Ltd.Ceramic membrane in purpose ceramic-film filter 5 is porous nano ceramic membrane, porous nano pottery
20~50nm of porcelain membrane aperture.
Two-stage depth absorber has two absorbers (level deep absorber 6 and two grades of depth absorbers 7) to be used in series,
Flow direction is to go out on bottom is entered, and is removal of mercury chelating resin using resin, and wherein level deep absorber 6 uses renewable tree
Fat, is quarterly regenerated once, and regeneration liquid waste returns to front end first class reaction pot processing in the lump, and two grades of depth absorbers 7 are used
Non-renewable resin, in addition, partial period is without using two grades of depth absorbers 7.Level deep absorber 6 uses renewable
The removal of mercury chelating resin Tulsion CH-97, the non-renewable removal of mercury chelating resin Tulsion that two grades of depth absorbers 7 are used
CH-95.Advanced treating can keep continuous operation, and operating flux is in 7.5m3Or so/hour.
3rd, using result：
The mercury-containing waste water advanced treatment system of letter hair chemical industry averagely can monthly handle 2600m3Mercury-containing waste water.Advanced treating system
System was succeeded in the test run from November 27th, 2013, and running situation is good.Sequentially determining water inlet, the water outlet of second reactor 1, suspension mistake
The water outlet of filter 3, the water outlet of purpose ceramic-film filter 5 and two-stage resin absorber (level deep absorber 6 and two grades of depth absorbers 7)
The mercury content of water outlet.Table 1 below is listed from operation is driven in two years, and the mercury in the once each Process for Effluent monthly randomly selected contains
Amount.
Mercury content in once each equipment water outlet that table 1 is monthly randomly selected
Shown by data statistics, the mercury-containing waste water mercury content after level deep adsorption treatment<0.5ppb accounts for 95%,
<1ppb accounts for 100%, and its result all meets national standard requirement.And can also be seen that after two grades of depth adsorption treatments
Water outlet can all reach the class standard mercury content of water environment quality standard III<0.1ppb.Importantly, useless after processing
Water enters high-salt wastewater processing system, eventually enters into generator and reuses, and realizes mercury-containing waste water zero-emission truly.
Embodiment 2
Mountain of papers city of Zhuang-Miao Autonomous Prefecture of Wenshan of Yunnan Province Ma Tang industrial parks, Yunnan Tian Ye Chemical Co., Ltd.s intend going into operation
The annual capacities of PVC devices be 120,000 tons/year, the processing of the mercury-containing waste water of the said firm uses the technique in the utility model,
The advanced treatment system in the utility model is used to carry out removal of mercury experiment before test run.
1st, mercury-containing waste water index is used in experiment：
Mercury content is 40ppb in mercury-containing waste water, and pH is 8.
2nd, advanced treatment process：
System diagram and flow chart are equally as illustrated in fig. 1 and 2.The first step, two grades are added by the low concentration mercury-containing waste water of configuration
In reactor 1, add and the bottom of second reactor 1 is flowed into after heavy metal chelating agent, Precipitation, sediment returns to coagulation system
System, liquid flows out from the top of second reactor 1；Second step, the water outlet of second reactor 1 is flowed into suspended filter 3, and filtering is outstanding
Float, filtrate enters pans 4；Middle waste water in 3rd step, pans 4 flows into purpose ceramic-film filter 5 and carries out filtering absorption,
Further go the removal of mercury；Water outlet in 4th step, purpose ceramic-film filter 5 flows into the two-stage depth absorber (He of level deep absorber 6
Two grades of depth absorbers 7) in, it can be discharged after water outlet detection is up to standard or into the recycling link of next step, detection does not reach
Mark waste water is discharged into pans 4.Low concentration mercury-containing waste water mercury content is 40ppb；Heavy metal chelating agent is Wuhan Bo Ren enlightening science and technology
Added after the TNT-18F liquid heavy metal chelating agents of Co., Ltd, 50 times of dissolved dilution in second reactor 1, heavy metals trapping
The addition of agent is 10mg/L；Filtering material in suspended filter 3 is polypropylene fibre bundle, and fibre bundle characteristic parameter is 1.5m
Long, 280g/ roots, are purchased from Henan Hua Xin Environmental Protection Technology Co., Ltd.Ceramic membrane in purpose ceramic-film filter 5 is porous nano ceramics
Film, 20~50nm of porous nano ceramics membrane aperture.
Two-stage depth absorber has two absorbers (level deep absorber 6 and two grades of depth absorbers 7) to be used in series,
Flow direction is to go out on bottom is entered, and is removal of mercury chelating resin using resin, and wherein level deep absorber 6 uses renewable tree
Fat, is quarterly regenerated once, and regeneration liquid waste returns to front end first class reaction pot processing in the lump, and two grades of depth absorbers 7 are used
Non-renewable resin, in addition, two grades of depth absorbers 6 are in and continue use state.Level deep absorber 6 is used can be again
Raw removal of mercury chelating resin Tulsion CH-97, the non-renewable removal of mercury chelating resin Tulsion that two grades of depth absorbers 7 are used
CH-95.Advanced treating can keep continuous operation, and operating flux is in 5m3Or so/hour.
3rd, experimental result：
According to designed process conditions, repeat the removal of mercury experiment, sequentially determining water inlet, the water outlet of second reactor 1, hang
(level deep absorber 6 and two grades of depth are inhaled for the water outlet of float filter 3, the water outlet of purpose ceramic-film filter 5 and two-stage resin absorber
Adnexa 7) water outlet mercury content, experimental result see the table below 2.
The mercury-containing waste water advanced treating experimental result of table 2
Shown by data statistics, the mercury-containing waste water mercury content after level deep adsorption treatment<0.5ppb accounts for 90%,
<1ppb accounts for 100%, the water outlet whole mercury content after two grades of depth adsorption treatments<0.1ppb, reaches surface water environment quality mark
Accurate III class standard.Examples 1 and 2 prove that mercury-containing waste water advanced treatment process of the present utility model is especially suitable for the depth of mercury-containing waste water
Degree processing.
Described above is only preferred embodiment of the present utility model, it is noted that for the common skill of the art
Art personnel, on the premise of the utility model principle is not departed from, can also make some improvement and supplement, and these improve and supplemented
Also it should be regarded as protection domain of the present utility model.
Claims (7)
1. the advanced treatment system of mercury-containing waste water in vinyl chloride generating process, it is characterised in that including passing sequentially through pipeline connection
Second reactor, suspended filter, pans, purpose ceramic-film filter and two-stage depth absorber；Described second order reaction
The water inlet of the delivery port of device and suspended filter is connected, the water inlet of the delivery port and pans of described suspended filter
Mouthful connection, the delivery port of described pans and the water inlet of purpose ceramic-film filter are connected, and described purpose ceramic-film filter goes out
The mouth of a river is connected with the water inlet of two-stage depth absorber.
2. the advanced treatment system of mercury-containing waste water in vinyl chloride generating process according to claim 1, it is characterised in that institute
The two-stage depth absorber stated includes the level deep absorber and two grades of depth absorbers being used in series, and wherein level deep is inhaled
It is provided with adnexa in renewable removal of mercury chelating resin, two grades of depth absorbers and is provided with non-renewable removal of mercury chelating resin.
3. the advanced treatment system of mercury-containing waste water in vinyl chloride generating process according to claim 1, it is characterised in that institute
It is also associated with storing the heavy metal chelating agent storage tank of heavy metal chelating agent on the second reactor stated.
4. the advanced treatment system of mercury-containing waste water in vinyl chloride generating process according to claim 1, it is characterised in that institute
The polypropylene fibre bundle as filtering material is provided with the suspended filter stated.
5. the advanced treatment system of mercury-containing waste water in vinyl chloride generating process according to claim 4, it is characterised in that institute
Long 1.5m, 280g/ root of polypropylene fibre bundle stated.
6. the advanced treatment system of mercury-containing waste water in vinyl chloride generating process according to claim 1, it is characterised in that institute
Porous nano ceramic membrane is provided with the purpose ceramic-film filter stated.
7. the advanced treatment system of mercury-containing waste water in vinyl chloride generating process according to claim 6, it is characterised in that institute
20~the 50nm of the ceramic membrane aperture of porous nano stated.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830421A (en) * | 2017-01-25 | 2017-06-13 | 内蒙古睿达鑫科技有限责任公司 | The advanced treatment system and method for mercury-containing waste water in vinyl chloride production |
| CN108503073A (en) * | 2017-12-28 | 2018-09-07 | 新疆华泰重化工有限责任公司 | A kind of device and method of the mercurous waste hydrochloric acid removal of mercury |
-
2017
- 2017-01-25 CN CN201720103735.6U patent/CN206580666U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106830421A (en) * | 2017-01-25 | 2017-06-13 | 内蒙古睿达鑫科技有限责任公司 | The advanced treatment system and method for mercury-containing waste water in vinyl chloride production |
| CN108503073A (en) * | 2017-12-28 | 2018-09-07 | 新疆华泰重化工有限责任公司 | A kind of device and method of the mercurous waste hydrochloric acid removal of mercury |
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