CN105565342B - Refining agent and its application for primary refined brine in chlorine industry - Google Patents
Refining agent and its application for primary refined brine in chlorine industry Download PDFInfo
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- CN105565342B CN105565342B CN201510944051.4A CN201510944051A CN105565342B CN 105565342 B CN105565342 B CN 105565342B CN 201510944051 A CN201510944051 A CN 201510944051A CN 105565342 B CN105565342 B CN 105565342B
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- refining agent
- brine
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Treatment Of Water By Ion Exchange (AREA)
Abstract
The present invention relates to chemical industry for making chlorine and alkali field, specifically a kind of new refining agent for substituting existing refining agent in primary refined brine process in chlorine industry.The technical problem to be solved in the present invention is in current chemical industry for making chlorine and alkali technique, and the brine quality into resin tower is still not high enough.The technical scheme that the present invention solves the technical problem is in a kind of new refining agent for being used for salt refining process in chlorine industry of offer, to substitute former " two alkali " refining agent used.The refining agent, it is using phosphate as active ingredient.The new refining agent strong adaptability, substituting original refining agent can make the total content of magnesium and calcium in primary brine reduce by 10 times, so as to reduce resin tower operating load, extend the resin tower recovery time, and then reduce manufacturing cost, have good application prospect.
Description
Technical field
It is specifically a kind of to substitute in chlorine industry in primary refined brine process the present invention relates to chemical industry for making chlorine and alkali field
The new refining agent of existing refining agent.
Background technology
In ion chemical industry for making chlorine and alkali industry, entering groove salt solution has very high quality requirement.Salt solution is adding sodium hydroxide and carbonic acid
After sodium refining agent precipitation calcium and magnesium, by pretreatment, it is also necessary to further cleaned into filter and exchange resin tower, to obtain
The salt solution of ionic membrane method alkali-making process requirement must be met.
The flow chart of existing typical production technology is as shown in Figure 1.Its main step is：
Salt solution is a closed circuit circulatory system, and the dechlorination light salt brine from electrolysis process, a portion is in baffling groove (one
As be referred to as 1# bafflings groove) in after barium chloride solution (typical concentrations 20%) hybrid reaction flow into settling tank sulfate radical, clarification
Rear light salt brine, which flows into, matches somebody with somebody bucket, filtrate water, industry water, recovered brine with filter press and the dechlorination light salt brine of sulfate radical
Carry out water distribution.With the water prepared in bucket, heat exchanger is pumped into by salt dissolving feed, salt dissolving pond is arrived after controlling preference temperature, it is molten
Saturation crude brine is obtained after solution Nacl.Crude brine flows into baffling groove (commonly referred to as 2# bafflings groove), is separately added into sodium hydroxide
Solution (typical concentrations 30%) and liquor natrii hypochloritis's (typical concentrations 1%) enter preceding reactive tank, the crude salt in preceding reactive tank afterwards
Magnesium ion in water is with the sodium hydroxide reaction generation organic matter such as magnesium hydroxide, Homonemeae, humic acid then by hypochlorite oxidation
It is decomposed into small organic molecule.The crude brine in preceding reactive tank is delivered in gas-water mixer with force (forcing) pump and mixed with air,
Into the molten gas of pressure air-dissolving tank, preprocessor is entered back into, and add FeCl in preprocessor import3Solution (conventional 1%).By pre-
The salt solution of processing enters rear reactive tank, while adds sodium carbonate (typical concentrations 20%) solution, calcium ion and carbon in salt solution
Sour sodium reacts to form calcium carbonate, and fully reacted salt solution gravity flow enters medial launder, and is pumped into feed liquor surge tank by centre, leads to
Cross feed liquor surge tank and filtered from HVMTM membrane filter is flowed into.Salt solution adds sodium sulfite solution (typical concentrations 5%) and removed after filtering
Enter a clarified brine storage tank after free chlorine in salt solution, heat exchanger is pumped into refined brine, after heating (conventional 65 DEG C of temperature)
Into resin tower, impurity cationic is further removed through exchange adsorption, electrowinning process is sent into and is electrolysed, the light salt brine after electrolysis
Primary brine saturation again is returned again to after physics and chemical dechlorination, entirely forms a recyclable process.
Wherein, resin tower is a kind of salt water purification installation of renewable recycling, typically uses ion exchange resin tower.
There is close relation its regeneration period with the brine quality for entering resin tower.If poor quality, especially the total content of magnesium and calcium is high,
The operating load of resin tower can be increased, secondary brine quality may be influenceed and shorten the regeneration period of resin tower, this can cause with
The influence of lower two aspects：(1) tank voltage is caused rapidly to raise, electrolytic efficiency reduces；(2) cause frequent regeneration resin tower, increase
While having added the discharge of waste liquid, the life-span of resin is also reduced.What is now used is " two alkali " refining agent, i.e., by sodium hydroxide with
Sodium carbonate adds in 2# bafflings groove when in use collectively as refining agent, sodium hydroxide, and sodium carbonate then adds in rear reactive tank
Enter.Refining agent is wherein added, is commonly referred to as primary brine with caused salt solution after filter by pre-processing, at present PROCESS FOR TREATMENT
The calcium ions and magnesium ions total amount (the total content of magnesium and calcium) in primary brine can be made to be slightly below 1ppm, the space also further improved.
The content of the invention
The technical problem to be solved in the present invention is in current chemical industry for making chlorine and alkali technique, into resin tower brine quality still not
Enough height.The present invention solve the technical problem technical scheme be in provide it is a kind of be used for chlorine industry in salt refining process it is new
Type refining agent, to substitute former " two alkali " refining agent used.This be used for chlorine industry in salt refining process refining agent, be with
Phosphate is active ingredient.
Further, the phosphate described in above-mentioned refining agent is in sodium phosphate, disodium-hydrogen or sodium dihydrogen phosphate
It is at least one.
The present invention additionally provides the application method of above-mentioned refining agent simultaneously.This method is to add refining agent in salt dissolving pond
In baffling groove afterwards, with substitute used in existing chemical industry for making chlorine and alkali with sodium hydroxide NaOH and sodium carbonate Na2 CO3Collectively constitute
Refining agent.
Further, the dosage of refining agent described in the above method is by addition 0.08~0.12g/l of concentration excess.It is preferred that
, the dosage of the refining agent is excessive 0.01g/l.
The present invention additionally provides a kind of process for purification of the primary brine in chemical industry for making chlorine and alkali simultaneously.Including for this method is following
Step：The crude brine for obtaining salt dissolving pond flows into baffling groove, is separately added into phosphate in baffling groove and liquor natrii hypochloritis is laggard
After reaction channelization is fully reacted before entering, then carry out molten gas process；FeCl is added subsequently into preprocessor3Solution is located in advance
Reason；Pretreated salt solution enters rear reactive tank, does not add sodium carbonate liquor；Filtered after going out reactive tank, then add sulfurous
Acid sodium solution removes the free chlorine in salt solution, obtains the refined brine available for follow-up resin tower treatment process.
Wherein, the phosphate described in the above method is at least one in sodium phosphate, disodium-hydrogen or sodium dihydrogen phosphate
Kind.
Further, the dosage of refining agent described in the above method is by addition 0.08~0.12g/l of concentration excess.It is preferred that
, the dosage of the refining agent is excessive 0.01g/l.The determination method of the excessive value of refining agent be question response it is complete after measuring
HVMTM membrane filter filtering after salt solution in phosphate content be its excessive value.
Obviously, present invention also offers new application of the phosphate as primary refined brine agent.Further, described phosphorus
Hydrochlorate is at least one of sodium phosphate, disodium-hydrogen or sodium dihydrogen phosphate.
Beneficial effects of the present invention are：The present invention creatively uses phosphate as primary refined brine agent.This is new
Type refining agent is added to former chemical industry for making chlorine and alkali primary brine process 2# baffling grooves, is not only only capable of substituting original " two alkali " refining agent,
The total content of magnesium and calcium in primary brine can also be unexpectedly set to decrease below 0.1ppm less than 1ppm by original.This is new refined
Agent strong adaptability, substituting original refining agent can make the total content of magnesium and calcium in primary brine reduce by 10 times, negative so as to reduce resin tower operation
Lotus, extend the resin tower recovery time, and then reduce manufacturing cost, there is good application prospect.
Brief description of the drawings
Fig. 1 is refining agent species and addition point schematic diagram in the industrial primary brine process of former chemical industry for making chlorine and alkali；
Fig. 2 is the feed postition schematic diagram of refining agent of the present invention.
Embodiment
The present invention creatively uses phosphate as primary refined brine agent.The new refining agent is mainly added to chlorine
The 2# bafflings groove (process charts are referring to Fig. 1, Fig. 2) of alkalization work primary brine process, substitutes original " two alkali " refining agent, not only
Only with a kind of composition, and only need addition once, reduce workload, improve effect.Refining agent of the present invention is with phosphoric acid
Salt is active ingredient.The phosphate used can be at least one of sodium phosphate, disodium-hydrogen or sodium dihydrogen phosphate.It is described
The dosage of refining agent is by addition 0.08~0.12g/l of concentration excess.Preferably excessive 0.01g/l.The excessive value of refining agent
The method of determination is to measure the content of phosphate radical in the salt solution after HVMTM membrane filter filters, that is, is considered as its excessive value.
The present invention comprises the following steps：The crude brine for obtaining salt dissolving pond flows into baffling groove, and phosphorus is separately added into baffling groove
Enter after hydrochlorate and liquor natrii hypochloritis after preceding reaction channelization fully reacts, then carry out molten gas process；Subsequently into preprocessor
Add FeCl3Solution is pre-processed；Pretreated salt solution enters rear reactive tank, does not add sodium carbonate liquor；Go out reaction
Filtered after groove, the free chlorine then added in sodium sulfite solution removing salt solution, obtain and can be used for follow-up resin tower processing work
The refined brine of sequence.Described phosphate is at least one of sodium phosphate, disodium-hydrogen or sodium dihydrogen phosphate.Described phosphorus
The addition of hydrochlorate is 0.08~0.12g/l.Preferably, phosphatic addition is 0.1g/l.
Embodiment one prepares primary brine using refining agent of the present invention
Salt dissolving pond water flow is 21.5m per hour3, its calcium ions and magnesium ions total amount is 74ppm, is added per hour in 2# bafflings groove
Enter the phosphorous acid group 40.18g/l of 54L sodium radio-phosphate,P-32 solution, salt solution phosphate radical excessive value is determined after sodium phosphate fully reacts is
0.13g/l, by process shown in Fig. 1, primary brine is obtained after triumphant membrane filtration.After measured after triumphant membrane filtration, gained one
The total content of magnesium and calcium is 0.0879ppm in secondary salt solution, the resin tower treatment process available for next step
Embodiment two prepares primary brine using refining agent of the present invention
Salt dissolving flow is 43m per hour3, its calcium ions and magnesium ions total amount is 78ppm.110L is added per hour in 2# bafflings groove to contain
Phosphate radical 39.75g/l sodium radio-phosphate,P-32 solution, it is 0.11g/l to determine salt solution phosphate radical excessive value after sodium phosphate fully reacts, warp
Process shown in Fig. 1 is crossed, primary brine has been obtained after triumphant membrane filtration.After measured, the total content of magnesium and calcium is in gained primary brine
0.0792ppm.Resin tower treatment process available for next step
Comparative example prepares primary brine using original " two alkali " refining agent
Salt dissolving flow is 43m per hour3, its calcium ions and magnesium ions total amount is 72ppm.30% hydrogen is added per hour in 2# bafflings groove
Sodium oxide molybdena, addition 5l/h, excessive 0.28g/l, after the step such as preceding reactive tank and pretreatment separation, in rear reactions steps
10% sodium carbonate, addition 250l/h, excessive 0.42g/l are added before.
Then after reactive tank fully reacts after, with having obtained primary brine after triumphant membrane filtration.After measured, gained is once
The total content of magnesium and calcium is 0.92ppm in salt solution.The resin tower treatment process of next step can be entered.
Claims (2)
1. the primary refined brine method in chemical industry for making chlorine and alkali, it is characterised in that comprise the following steps：The crude salt for obtaining salt dissolving pond
Water flows into baffling groove, after entering preceding reaction channelization after baffling groove is separately added into phosphate and liquor natrii hypochloritis and fully reacting,
Molten gas process is carried out again；FeCl is added subsequently into preprocessor3Solution is pre-processed；Pretreated salt solution is anti-after entering
Groove is answered, does not add sodium carbonate liquor；Triumphant membrane filtration is carried out after going out reactive tank, sodium sulfite solution is then added and removes in salt solution
Free chlorine, obtain available for follow-up resin tower treatment process refined brine；Described phosphate is sodium phosphate, phosphoric acid one
At least one of hydrogen sodium or sodium dihydrogen phosphate；Described phosphatic addition is 0.08~0.12g/l.
2. salt refining method according to claim 1, it is characterised in that described phosphatic addition is 0.1g/
l。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107585903B (en) * | 2017-08-16 | 2020-10-30 | 上海氯碱化工股份有限公司 | Method for treating and recycling dilute brine containing sodium carbonate and sodium hypochlorite |
| CN107804925B (en) * | 2017-09-28 | 2020-06-19 | 枣庄学院 | Chlor-alkali brine purification device and purification process thereof |
| CN108517535A (en) * | 2018-04-20 | 2018-09-11 | 上海海节环保科技有限公司 | Extend the method for ion film caustic soda resin tower regeneration period and the device using the method |
| CN108675499A (en) * | 2018-05-30 | 2018-10-19 | 龙蟒佰利联集团股份有限公司 | A kind of method of chloride slag mashing waste water integrated treatment |
| CN111453905A (en) * | 2020-03-20 | 2020-07-28 | 鲁西化工集团股份有限公司氯碱化工分公司 | Recycling treatment process and device for regenerated acid-base wastewater |
| CN112028090A (en) * | 2020-09-15 | 2020-12-04 | 诸城泰盛化工股份有限公司 | Deep treatment system and process for chlor-alkali recovered salt |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1156599A (en) * | 1977-10-13 | 1983-11-08 | Shigeaki Fuseya | Process for purifying aqueous solution of alkali metal halide for electrolysis |
| CN103449479A (en) * | 2013-09-12 | 2013-12-18 | 山东东岳氟硅材料有限公司 | Method for reducing content of calcium and magnesium ions in primary brine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN204198435U (en) * | 2014-09-03 | 2015-03-11 | 江苏梅兰化工有限公司 | A kind of device adopting phosphoric acid and sodium salt refined brine thereof |
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2015
- 2015-12-16 CN CN201510944051.4A patent/CN105565342B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1156599A (en) * | 1977-10-13 | 1983-11-08 | Shigeaki Fuseya | Process for purifying aqueous solution of alkali metal halide for electrolysis |
| CN103449479A (en) * | 2013-09-12 | 2013-12-18 | 山东东岳氟硅材料有限公司 | Method for reducing content of calcium and magnesium ions in primary brine |
Non-Patent Citations (1)
| Title |
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| 电解用盐水精制剂改用磷酸及其钠盐的探讨;魏以勉;《氯碱工业》;19941231;全文 * |
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