CN1019291B - Synthetic glass factory cyanide wastewater treatment process method - Google Patents
Synthetic glass factory cyanide wastewater treatment process methodInfo
- Publication number
- CN1019291B CN1019291B CN87103664.9A CN87103664A CN1019291B CN 1019291 B CN1019291 B CN 1019291B CN 87103664 A CN87103664 A CN 87103664A CN 1019291 B CN1019291 B CN 1019291B
- Authority
- CN
- China
- Prior art keywords
- waste water
- waste
- wastewater treatment
- crystallization
- synthetic glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000011521 glass Substances 0.000 title claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 6
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 title claims description 12
- 239000002351 wastewater Substances 0.000 claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000002699 waste material Substances 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 239000002817 coal dust Substances 0.000 claims abstract description 11
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 5
- 239000002594 sorbent Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000003463 adsorbent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 14
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 13
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000012452 mother liquor Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000012141 concentrate Substances 0.000 abstract description 3
- 239000010881 fly ash Substances 0.000 abstract description 3
- 239000002893 slag Substances 0.000 abstract description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical class [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 2
- 229960000892 attapulgite Drugs 0.000 abstract description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 abstract description 2
- 239000004927 clay Substances 0.000 abstract description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007599 discharging Methods 0.000 abstract description 2
- 229910052625 palygorskite Inorganic materials 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000010457 zeolite Substances 0.000 abstract description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000012535 impurity Substances 0.000 description 11
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 239000002910 solid waste Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000010808 liquid waste Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MWFMGBPGAXYFAR-UHFFFAOYSA-N 2-hydroxy-2-methylpropanenitrile Chemical compound CC(C)(O)C#N MWFMGBPGAXYFAR-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003621 irrigation water Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000013327 media filtration Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Removal Of Specific Substances (AREA)
Abstract
The method of wastewater treatment of cyanidation technology during synthetic glass is produced, carry out purifying treatment through sorbent material, sorbent material is selected gac for use, coke powder, coal dust, flyash, slag, diatomite, zeolite, wilkinite, attapulgite clay, activated magnesia, active silica etc., sodium sulfate in the waste liquid is reclaimed in crystallization, can concentrate earlier before the crystallization, but mother liquor reuse after the structure, purification process mud can be made burn processing, when concentrated also to being furnished with the alkali absorption technique, eliminated the enormous expenditure of handling discharging institute palpus behind the waste water with this method, not only do not have waste liquid and discharge, and be recoverable to a large amount of sodium sulfate, have very great society economic benefit.
Description
The present invention relates to the processing method of cyaniding liquid waste disposal in the chemical field and utilization thereof, be used in particular for synthetic glass production.
Industrial production polymethylmethacrylate (synthetic glass) is to be raw material with acetone and sodium cyanide, makes acetone cyanohydrin earlier, and again by its synthesizing methylmethacrylate, China more than 60 tame synthetic glass factory all adopts this technology.The main waste water of this production process occurs in the prussic acid production of cyaniding operation.Prussic acid production is to be raw material with sodium cyanide and sulfuric acid, and the distillation of reaction back is produced the prussic acid reaction formula and is:
Sodium cyanide often is made into 25% left and right sides aqueous solution, and sulfuric acid is made into the aqueous solution of 28 ± 2% concentration, waste discharge during this is produced, and it is blue that outward appearance is, and includes the sulfuric acid about 5%, water-soluble cyanogen root 20～1000PPm, and suspended state impurity prussiate, Na
2SO
4Content about about 25%.This waste water never has suitable technology governance, mainly be that the neutralization alkalization is acid now, destroy prussiate with common way again, and then discharging, but shortcoming is apparent: the harm to environment is very big, it is too high to administer investment and process cost, can't reclaim a large amount of industrial chemicals-sodium sulfate, discharges 5 tons of waste water every day as certain factory, cause farmland irrigation water acidifying (pH4～2), have a strong impact on the life of farm crop and fish, sodium sulfate effluxes annual nearly 100,000 tons of the whole nation, is worth up to ten million units.
The objective of the invention is fundamentally to effect a radical cure waste water, design a kind of pollution-free cyanidation technology, and recyclable resource.
Technical solution of the present invention is: process for purifying waste water, promptly adopt the sorbent material purification and filter suspended state and portion water solubility impurity in the removal waste water, also but direct filtration is removed impurity, (contain foreign matter contents such as prussiate when the sulfate crystal composition can meet the demands time), handle the back waste liquid and carry out the sodium sulfate recovery, but also reuse spent acid solution and part prussiate, water cycle is used again.
Utilize processing method of the present invention to realize not having useless cyaniding production, can reclaim high-quality sodium sulfate, while whole sulfuric acid of reuse and water, reuse part sodium cyanide no longer effluxes poisonous and harmful waste water, has reduced a large amount of costs of production cost and processing waste water.Also can be used for liquid waste disposal behind other cyanidation technology.
Below the invention will be further described by drawings and Examples: Fig. 1 is a process flow diagram.
The purification of waste water:
Except containing residual sulfuric acid, sodium sulphate, also have part cyanide, raw material impurity and other impurity in the waste water, in order to guarantee a reclaim sulfuric acid sodium quality (not being recrystallized) and again reuse of waste liquid, these impurity should be removed.
Filtration, purification technique can adopt and add cleanser purification part soluble impurity, and by removing by filter suspension, the operation of two steps can be carried out simultaneously again. Adsorbent can be used active carbon, coke blacking, petroleum cracking residue solid powder, coal dust, flyash, slag, diatomite, zeolite, bentonite, Concave-convex clay rod, active silica, activated magnesia etc., but consider economy, do not introduce in the adsorption cleaning process sodium sulphate is reclaimed and sulfuric acid reuse disadvantageous impurity, particularly Ca+Plasma, and the rear solid waste of purifying liquid waste easily processes, and do not cause secondary pollution.
Therefore, sorbent material is to select for use coal dust for well, and material economy is easy to get, and advantages of good adsorption effect.Coal is crossed 80 orders after crushed with top sieve, and coal dust is thinner, adsorption effect better, also available organic fibre.
Coal dust adds waste water, and dosage is 0.5～1% waste water weight percent, and waste water becomes colourless, cyanogen root clearance from blueness and reaches about 80%, after filtering, absorption waste water coal dust contains mud, still can make fuel, it is destroyed through burning to be contained in the coal dust pollutent, does not produce secondary pollution.
Time 10-30 minute of coal dust absorption, absorption is after mechanical filter or media filtration carry out solid-liquid separation.
Consider and filter back mother liquor clarification, safe ready on the good and technology of filtering velocity, solid-liquid separator can adopt slag tap automatically whizzer or other pressurization or the close filter that reduces pressure.
To the producer that equipment anticorrosion well also can satisfy processing condition, also can be without absorption, the waste water direct filtration is removed suspended substance.
For preventing the evaporation of prussic acid in the solid waste, can be to solid waste sprinkle diluted alkaline water, or in solid waste, mix calcium oxide, so that prussic acid is converted into prussiate, solid waste is burnt and is advisable to drop into boiler.
The recovery of sodium sulfate must be considered the temperature curve of sodium sulfate solubleness, and 10 ℃ of following solubleness are reduced to below 10%, therefore can be by crystallisation by cooling sodium sulfate in the mother liquor of purifying treatment.Contained sulfate crystal more better in the mother liquor.Can before crystallisation by cooling, mother liquor be carried out vacuum concentration earlier, help crystallization and reach water yield reuse balance fully.Then the temperature of crystallisation by cooling is at 0-5 ℃.Also can be with waste water, earlier through concentration.
Waste water gained waste liquid after purifying treatment has been removed impurity, can satisfy complex acid and preparation liquid sodium cyanide solution, for guaranteeing the balance of the reuse water yield, to using the factory of 35% left and right sides sodium cyanide as raw material, purifying waste can carry out concentrating under reduced pressure before crystallisation by cooling, can be furnished with the alkali absorption technique when concentrated, referring to accompanying drawing, make prussic acid be converted into sodium cyanide, but reuse prepares certain density sodium cyanide usefulness, concentrate back waste liquid crystallisation by cooling.
(1) is waste water treatment tank, (a) be waterwater entrance, discontinuous interval is produced can two waste water tank arranged side by side, coal dust dropped in the jar through 10～30 minutes, stir simultaneously, through solid-liquid separator (2) solid purificant and mud are leached (A), waste water is hot wastewater, corrosion resistant jar and solid-liquid separating machine must be selected for use, also a jar processing can be after the waste water cooling, reentered.Purify back waste drains pump (3) go into concentration tank (4) reduce pressure or reduce pressure heat concentrated, consider the evaporation of HCN, is furnished with the alkali absorption technique, concentration tank has outlet (b) through absorbing the inlet (d) of pot (5), and alkali lye absorbs in absorption tower (6) and absorption pot (5) again, and cooling tower (7) cools off, water-ring pump (8) provides the gas-liquid driving power, the gas HCN that has not absorbed through air water separator (9) again admission port (c) go into concentration tank, constitute one and close circulating system, no HCN is excessive.The prussiate (NaCN) that absorbs pot (5) absorption reclaims joins NaCN(D), waste liquid is evaporated to 4/5～1/2 of original volume, concentrate the back waste liquid and go into crystallizer (10), (with solid NaCN and liquid NaCN is that the spissated volume of factory of raw material is different, main consideration does not have useless discharge, water balance), through cooling and stirring, carry out solid-liquid separation by solid-liquid separator (11) after the crystallization, can use whizzer.(C) be sodium sulfate, waste liquid flows into basin (12) reuse complex acid (B) after the crystallization.
For guaranteeing the process pipe cleaning,, before each the parking, use bypass fresh water pipe blow-through, to avoid residual sodium sulfate in the pipeline to the periodical operation production technique.
Example one, tower waste water (not aeration) takes place in chemical plant, Yongfeng HCN, and it is blue that this water is, and contains H
2SO
4～5%, Na
2SO
4～25%, solubility CN
-, 248PPm, prussiate and other impurity in addition suspend.
Handle waste water with 120 order coal dusts (1% weight percent), the clarification time 20, filtering separation, it is colourless to handle the back waste liquid, CN
-Concentration 26PPm, water is limpid, does not contain suspended substance, and this liquid is concentrated into 2/3 of original volume, and vaporised gas absorbs by 0.5%NaOH, gets alkaline evaporated liquor, and distillation back waste liquid is cooled to 2 ℃, a large amount of Na
2SO
410H
2O separates out, and product analysis shows Na
2SO
4Meet primary standard, waste liquid contains cyanogen root 0.8PPm after the crystallization.
Tower waste water takes place behind aeration with the HCN of factory in example two, and it is blue that waste water is, and contains H
2SO
4～5%, Na
2SO
4～25%, solubility cyanogen root～20PPm contains impurity such as suspended substance, with 120 orders, 0.5% coal dust, (as the same with coke powder, gac, attapulgite, flyash etc.) purifies 20 minutes after-filtration and separates, and it is colourless to handle the back waste liquid, cyanogen root concentration～2PPm operates equally with example one, gets one-level Na
2SO
4
Claims (2)
1, cyanide wastewater treatment process method during a kind of synthetic glass is produced adopts sorbent material to the waste water adsorption cleaning, it is characterized in that waste water after adsorbents adsorb such as coal dust, purifies recrystallize reclaim(ed) sulfuric acid sodium, crystallization waste liquid reuse preparation acid solution after filtration.
2,, it is characterized in that elder generation's process concentrating under reduced pressure before crystallization is reclaimed, and be furnished with the alkali absorption technique by the described cyanide wastewater treatment process of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103664.9A CN1019291B (en) | 1987-05-15 | 1987-05-15 | Synthetic glass factory cyanide wastewater treatment process method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87103664.9A CN1019291B (en) | 1987-05-15 | 1987-05-15 | Synthetic glass factory cyanide wastewater treatment process method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87103664A CN87103664A (en) | 1987-12-02 |
| CN1019291B true CN1019291B (en) | 1992-12-02 |
Family
ID=4814539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87103664.9A Expired CN1019291B (en) | 1987-05-15 | 1987-05-15 | Synthetic glass factory cyanide wastewater treatment process method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019291B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1312047C (en) * | 2004-08-20 | 2007-04-25 | 沈阳戴维环保节能设备有限公司 | Comprehensive treating method for industrial waste water and sludge using coke powder |
| CN100387532C (en) * | 2005-08-26 | 2008-05-14 | 南京工业大学 | Coagulant for disposing dying waste water and its production method |
| CN101704563B (en) * | 2009-11-19 | 2011-09-28 | 杨祺 | Method for treating sewage by industrial solid wastes |
| CN101857326B (en) * | 2010-07-05 | 2011-09-07 | 天津天达联合工程技术有限公司 | Comprehensive treatment method of high-concentration cyanogens-containing and thiocyanate-containing waste liquid |
| CN106268662A (en) * | 2016-08-25 | 2017-01-04 | 贵州万山兴隆锰业有限公司 | A kind of manganese ore waste water adsorbing material and preparation method thereof |
| CN106693930A (en) * | 2017-01-20 | 2017-05-24 | 福州市天伟达电子科技有限公司 | Environmentally-friendly material for treating large-particle pollution of water body, and manufacturing method thereof |
| CN108264065A (en) * | 2018-03-16 | 2018-07-10 | 邯郸市同俊达矿山设备股份有限公司 | A kind of hopcalite agent waste water utilization device |
| CN108773924B (en) * | 2018-05-03 | 2021-08-03 | 国药集团威奇达药业有限公司 | Comprehensive recovery method of effective components in clavulanic acid extraction raffinate |
| CN112973651B (en) * | 2021-02-20 | 2022-07-29 | 武汉绿知行环保科技有限公司 | Cyclic regeneration water treatment adsorption material and preparation method thereof |
-
1987
- 1987-05-15 CN CN87103664.9A patent/CN1019291B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN87103664A (en) | 1987-12-02 |
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