CN101717164B - Method for treating and recycling waste water of cyanation technique and device thereof - Google Patents
Method for treating and recycling waste water of cyanation technique and device thereof Download PDFInfo
- Publication number
- CN101717164B CN101717164B CN2009102131800A CN200910213180A CN101717164B CN 101717164 B CN101717164 B CN 101717164B CN 2009102131800 A CN2009102131800 A CN 2009102131800A CN 200910213180 A CN200910213180 A CN 200910213180A CN 101717164 B CN101717164 B CN 101717164B
- Authority
- CN
- China
- Prior art keywords
- waste water
- cyanation
- technique
- processing
- acid
- 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.)
- Active
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 111
- 238000007333 cyanation reaction Methods 0.000 title claims abstract description 59
- 238000004064 recycling Methods 0.000 title abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 42
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 230000003647 oxidation Effects 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000004087 circulation Effects 0.000 claims abstract description 6
- 229910000575 Ir alloy Inorganic materials 0.000 claims abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 4
- 239000010936 titanium Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 37
- 239000002253 acid Substances 0.000 claims description 32
- 238000004821 distillation Methods 0.000 claims description 30
- 238000007743 anodising Methods 0.000 claims description 28
- 238000001179 sorption measurement Methods 0.000 claims description 27
- 238000005194 fractionation Methods 0.000 claims description 26
- 238000011084 recovery Methods 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005516 engineering process Methods 0.000 claims description 16
- 230000033228 biological regulation Effects 0.000 claims description 13
- 239000000460 chlorine Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000005292 vacuum distillation Methods 0.000 claims description 7
- 239000002594 sorbent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- CJTCBBYSPFAVFL-UHFFFAOYSA-N iridium ruthenium Chemical compound [Ru].[Ir] CJTCBBYSPFAVFL-UHFFFAOYSA-N 0.000 claims description 3
- 230000003472 neutralizing effect Effects 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910000929 Ru alloy Inorganic materials 0.000 abstract 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- DFJYZCUIKPGCSG-UHFFFAOYSA-N decanedinitrile Chemical compound N#CCCCCCCCCC#N DFJYZCUIKPGCSG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- -1 aliphatic diamine Chemical class 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000998 batch distillation Methods 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 230000001839 systemic circulation Effects 0.000 description 1
Images
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a method for treating and recycling waste water of cyanation technique. The method comprises ammonia recycling procedure, acidizing separation procedure, absorbing separation procedure and electrode oxidation procedure; the waste water of cyanation technique is first distilled to recycle the ammonia therein, is acidized to precipitate organic matters and separate out, is subject to absorbing separation to further reduce content of organic matters and finally enters into an electrode oxidation tank for treatment, so that the contents of ammonia nitrogen and COD can meet Grade I national discharge standard. The electrode oxidation tank in the electrode oxidation procedure comprises inert electrode plates, a DC stabilized power supply, an oxidation tank and a circulation pump, wherein, the inert positive electrode plate is made by coating ruthenium and iridium alloy on titanium substrate, and is of a mesh or plate shape, and the distance between the positive electrode plate and the negative electrode plate is kept between 3mm and 25mm. The method for treating and recycling waste water of cyanation technique and a device thereof in the invention have simple treatment process, stable operation and lower cost.
Description
Technical field
The present invention relates to the method for a kind of wastewater treatment and recycling, comprise its equipment, specifically a kind of processing of waste water of cyanation technique and recoverying and utilizing method and specific equipment thereof.
Background technology
Long carbochain fat dintrile is the important source material of synthetic long carbochain aliphatic diamine, is class purposes fine-chemical intermediate comparatively widely.Generally, with grow the carbochain fat diacid, liquefied ammonia is raw material, make by aminating reaction.In its aminating reaction process, produce a considerable amount of processing wastewaters, and smell is heavier, component is many, and with regard to generalized case, its TAN is 10～200,000 mg/L and numerous and jumbled, and the COD value is 8～150,000 mg/L.Ready-made treatment process all adopts distillation+biochemistry combination process, and concrete operations are by the wherein most of ammonia of fractionation by distillation, and residue ammonia nitrogen and organism are handled by biochemical process.But from practical operation situation, unsatisfactory, mainly show three aspects: 1, because of original water quality not only contains ammonia nitrogen but also contain organism, and component is many, and biochemical load is heavy and numerous and jumbled, the processing cost height.2, peculiar smell is difficult for removing.3, original capital is relatively large.So be necessary to seek a kind of more effective practical art treatment.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, provide that a kind for the treatment of processes is succinct, stable, the processing of lower-cost waste water of cyanation technique and recoverying and utilizing method, and specific equipment.
According to technical scheme provided by the invention, the processing of described a kind of waste water of cyanation technique and recoverying and utilizing method, comprise ammonia recovery process, acidifying separation circuit, fractionation by adsorption operation and anodizing operation, it is characterized in that: in described ammonia recovery process, waste water of cyanation technique is at first by distillation recovery ammonia wherein; In acidifying separation circuit subsequently, separate out organism and separation by acidification with having reclaimed the waste water of cyanation technique behind the ammonia; In ensuing fractionation by adsorption operation, further reduce organic content by fractionation by adsorption with having separated the waste water of cyanation technique behind the organism; In last anodizing operation, the waste water of cyanation technique after the fractionation by adsorption is added the anodizing groove, do further oxide treatment, make ammonia nitrogen and COD content reach the first discharge standard of national regulation.
In described ammonia recovery process: waste water of cyanation technique is added distillation tower, adopt alkali lye to regulate between its pH value to 8～14, under 40～100 ℃ condition, carry out negative pressure or air distillation, when TAN＜500mg/L, finish the ammonia recovery process, send next process;
In described acid out separation circuit: will add neutralizing well through the processing wastewater that the ammonia recovery process was handled, be acidified with acid, regulate its pH value between 2～3, acid organism in the water is fully separated out, adopt filtration or centrifugal mode to be separated then, the restored acid organic matter can continue to recycle after handling by process for refining such as washing desalinations, after this operation finishes, the COD value is generally at 3000～5000mg/L, and the highest 10000mg/L that is no more than enters next process;
In described fractionation by adsorption operation: will add the fractionation by adsorption groove through the processing wastewater that the acid out separation circuit was handled, and add sorbent material, and open and stir, and under normal temperature condition, further remove the organism in the waste water; Meanwhile, the pH value of the hierarchy of control is looked particular case between 3～7, repeat described adsorption operations, and the COD value in the control waste water is no more than 800mg/L, enters next process;
In described anodizing operation: will add the anodizing groove through the processing wastewater after the fractionation by adsorption operation is handled, and open the dc constant voltage power supply, control voltage is between 2～6v; Start recycle pump, allow the waste water dynamic circulation; To keep C1 in the waste water simultaneously
-Concentration after 1.5～3.5 hours, finishes the anodizing operation between 0.05%～1%, but the waste water qualified discharge.
According to the waste water in the treatment process of the present invention, be meant the processing wastewater in the production of long carbochain fat dintrile, in particular, be meant that carbon number is C
8～C
18Processing wastewater during fatty dintrile in the scope is produced, preferred carbon number is C
9~ C
14Processing wastewater during fatty dintrile in the scope is produced.
Be meant the anodizing groove according to the specific equipment that the invention provides in the technical scheme, it is made of noble electrode plate, D.C. regulated power supply, oxidation trough and recycle pump; It is characterized in that: the noble electrode plate is positioned at oxidation trough, and recycle pump is used to make the treatment solution that is positioned at oxidation trough to circulate, and D.C. regulated power supply provides power supply for the noble electrode plate; Inert anode pole plate in the noble electrode plate adopts the titanium base to be coated with the ruthenium iridium alloy and is made, and is shaped as net or tabular; The cathode and anode distance between plates is from remaining on 3～25mm.
Aforesaid anodizing method is handled nitrilation waste water, and its technological principle is: in the anodizing groove of customization, keep Cl
-Suitable concentration, electrolysis under volts DS, at this moment, anode is mainly analysed the chlorine reaction, secondly is oxygen evolution reaction, so main oxides such as very fast generation chlorine, hypochlorous acid, hypochlorite in system, simultaneously, also produce dissolved oxygen in the system, ozone and other living radical are (as hydroxyl radical free radical, atomic oxygens etc.), its content is along with the prolongation of time is progressively increasing.
Chlorine, oxide compounds such as hypochlorous acid can react with ammonia very soon, generate nitrogen; Simultaneously also can be oxidized to carbonic acid gas and water to most organic in the system; On the other hand, the ozone in the system and other living radical also can be fast and effeciently most organism exhaustive oxidations.
The present invention compared with prior art has the following advantages:
1, technology of the present invention can realize recycling of material to greatest extent, as: ammonia reclaims the ammonia that reclaims in the technology and can dynamically recycle, and the organic efficiency height, and residual rate is low; The organism that reclaims in the acidifying separation circuit can continue to use after handling by process for refining such as desalination, washings;
2, the anodizing technology among the present invention is to ammonia nitrogen and COD decreasing ratio height, and effect stability, in allowing fluctuation range, is subjected to environmental factors and conditionality hardly, and ammoniacal liquor and the organism of handling lower concentration as process matched therewith are most suitable.
3, combination process of the present invention, less investment, flexible and convenient operation, and the saving energy that is in operation have reduced cost greatly, especially are fit on a small scale the processing of waste water in batches.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Each step of the processing of described waste water of cyanation technique and recoverying and utilizing method is as follows:
(1) ammonia recovery process:
Waste water of cyanation technique is at first by the ammonia in the distillation recovery system, distillation can be a vacuum distillation, also can adopt air distillation, no matter adopt any distillation mode, all will regulate the pH value of waste water, maintain in 8～14 scopes with alkali lye, to control suitable temperature and pressure simultaneously, the highest to guarantee distillation efficiency, when ammonia nitrogen concentration＜500mg/L, send next procedure to handle.
As mentioned above, distillation can be a vacuum distillation, also can be air distillation, but preferably adopt vacuum distillation, and reason has two: one, and under synthermal condition, the solubleness of ammonia in water obviously reduces, so adopt vacuum distillation to be more conducive to the separation that removes of ammonia; The 2nd, pressure descends, and the energy consumption of handling unit waste water descends, and therefore adopts vacuum distillation, and working cost reduces.
As mentioned above, the pH value will be controlled at 8～14, and optimum value should be controlled at 10～12 because ammonia water-soluble after, mostly with ammonium ion (NH
4 +) the form existence, make NH
4 +Change free ammonia into, just must change equilibrium relationship, improve the pH value of system, balance just can constantly move to the direction that generates ammonia, and the concentration of free ammonia is high more, and the effect of volatile matter distillation is just good more.But, be not that the pH value is high more good more, because the pH value is too high, system viscosity obviously increases, and is unfavorable for heat and mass.
As mentioned above, regulate the alkali lye of pH value, can adopt sodium hydroxide solution, potassium hydroxide solution, barium hydroxide solution, yellow soda ash or sodium hydrogen carbonate solution, preferred sodium hydroxide solution; Regulative mode can be a dynamic adjustments, also can be once to regulate, preferred dynamic adjustments.
As mentioned above, distillation temperature is controlled at 40～100 ℃, and preferred 60～70 ℃, obviously, temperature is high more, and the dissolving power of ammonia in system descends, and when vacuum distillation, velocity of evaporation is along with the rising of temperature is obviously accelerated.But after surpassing 70 ℃, it is not fairly obvious that the temperature rising removes influence to ammonia, and this point is verified in practice repeatedly, so preferred temperature is 60～70 ℃.
As mentioned above, distillation deamination pressure-controlling is at-0.09～0Mpa, preferred-0.07～-0.05Mpa, with regard to generalized case, negative pressure is high more, helps the ammonia volatilization more, can accelerate the speed that removes of ammonia nitrogen.But and non-linear rising, find in the test: when negative pressure further increases, fail obviously to accelerate removing of ammonia nitrogen, on the contrary, undue gas clean-up can increase the energy expenditure for the treatment of processes.
(2) acid out separation circuit:
Processing wastewater through the ammonia recovery process was handled need be acidified with acid, and the pH value is controlled at 2～3 and is advisable, and could guarantee that so the acid organism in the water is fully separated out, and is separated with filtration or centrifugal mode.
As mentioned above, acidifying can be hydrochloric acid, sulfuric acid with acid, and preferred hydrochloric acid is because hydrochloric acid is favourable to subsequent disposal.
As mentioned above, isolating acid organism further can return systemic circulation and use based on lipid acid after the refinement treatment.
(3) fractionation by adsorption operation:
The processing wastewater of handling through the acid out separation circuit, the COD value is generally at 3000～5000mg/L, the highlyest can not surpass 10000mg/L yet, to its little adjust pH in 5～7 scopes, the interpolation sorbent material further removes the organism in the waste water, at normal temperatures, and repetitive operation 2～3 times, certainly specifically decide on COD value size, sorbent material can be applied mechanically step by step.After the processing of this operation finished, the COD value was usually less than 500mg/L, the highlyest was no more than 800mg/L.
As mentioned above, sorbent used is powdered carbon or particulate resins, preferred gac, and consumption is few on the one hand, and consumption is generally 1～2% (weight ratio) of waste water of cyanation technique, and cost is lower; Be to apply mechanically conveniently on the other hand.
(4) anodizing operation:
The waste water of cyanation technique of handling through the fractionation by adsorption operation, COD value＜500mg/L, ammonia nitrogen value＜300mg/L, this moment is also below standard, can not directly discharge, need to continue to handle, concrete grammar is: the waste water of cyanation technique that the fractionation by adsorption operation was handled pumps into the anodizing groove, open the dc constant voltage power supply, and allow voltage be stabilized in 2～6v scope; Then start recycle pump, allow waste water be in the dynamic circulation state, simultaneously with hydrochloric acid or sodium hydroxide regulation system pH value between 6～7, and keep Cl in the waste water
-Concentration is in 0.05%～1% scope, and deficiency needs to add sodium-chlor, generally, after 1.5～3.5 hours, TAN＜5mg/L in the waste water, COD value＜50mg/L, but qualified discharge.
Aforesaid anodizing technology, the Cl in the waste water
-Concentration must maintain 0.05%～1%, and is preferred 0.1%～0.3%, because current efficiency is directly proportional with electrolyte concentration, so Cl
-Concentration is high more, and chlorine evolution potential is just low more, and energy consumption also just descends.But, Cl
-Concentration also should not be too high, otherwise can appear under the equal voltage conditions, increases the heat effect of bringing because of current density.Meanwhile, the too high environmental friendliness that also is unfavorable for of salinity.
Aforesaid anodizing technology, voltage should be controlled and be 2～6v, more particularly, should be controlled at 3～5v, can guarantee that like this under the condition of equal amount of oxidation, the energy loss-rate is lower.
What need further emphasize is: all oxides is dynamic generation in the system, dynamic oxidation, and utilization ratio improves greatly, compares with technologies such as the break point chlorination method of routine, ozone oxidation methods, and efficient is much higher.
As mentioned above, the anodizing groove is the specific equipment in the wastewater treatment, comprise noble electrode plate, D.C. regulated power supply, oxidation trough and recycle pump, core component is the inert anode pole plate, it consists of the titanium base and is coated with the ruthenium iridium alloy, and it is strong that it analyses the chlorine ability, and the making form is netted or tabular, but netted higher than tabular efficient, the cathode and anode distance between plates is from remaining on 3～25mm.
Following mask body is described further the present invention in conjunction with the accompanying drawings and embodiments.
Embodiment 1 ~ 3 is the processing wastewater disposition in the sebaconitrile production, but original COD value and ammonia-nitrogen content difference
Embodiment 1
(1) ammonia recovery process: the waste water of cyanation technique that produces in the sebaconitrile production is pumped into distillation tower (1 ton of weight), COD value 9.5 ten thousand mg/L of waste water of cyanation technique, TAN 120,000 mg/L.Adopt the mode of batch distillation to reclaim ammonia, the distillation pressure-controlling is at-0.07Mpa, and distillation temperature is controlled at 65 ℃, and the pH value employing sodium hydroxide dynamic adjustments of system is controlled between 10～12, and distillation time is 3 hours; Detect then, the TAN in the waste water of cyanation technique enters next procedure and handles during less than 500mg/L;
(2) acid out separation circuit: will pump into neutralizing well through the waste water of cyanation technique that the ammonia recovery process was handled, start and stir,, treat that the pH value is at 3 o'clock with the acidifying of salt slow acid, stop to add acid, and continue to stir 15～30 minutes, observing the pH value has no change, high if the pH value is run, can continue to add acid and pull back to 3, and continue to stir several minutes, the acid organism in the waste water is fully separated out, the acid organism that then adopts the press filtration mode to separate to separate out; Detect the COD value of waste water of cyanation technique then, the COD value is 4500mg/L, meets the requirements, and enters next procedure and handles; After the restored acid organic matter washs the salinity of removing wherein with clear water, recycling, handle in the bath water adding system in the lump.
(3) fractionation by adsorption operation: will pump into the fractionation by adsorption groove through the waste water of cyanation technique that the acid out separation circuit was handled, by weight 2% adding powdered carbon, to open and stir, hierarchy of control temperature is at 25～30 ℃, the pH value is 3～5,30 minutes adsorption treatment time further removed the organism in the waste water, isolated gac then, operate (gac can be applied mechanically step by step) 2 times by same mode, the COD value that detects in the waste water of cyanation technique is 550mg/L, meets the requirements, and sends into next procedure and handles.
(4) anodizing operation: will pump into the anodizing groove through the waste water of cyanation technique after the fractionation by adsorption operation is handled, start recycle pump, and allow waste water be in the dynamic circulation state, simultaneously with hydrochloric acid or sodium hydroxide regulation system pH value between 6～7, keep Cl
-Concentration is opened the dc constant voltage power supply in 0.1%～0.3% scope, control voltage is about 4v, ammonia nitrogen in the waste water and organism are carried out deep oxidation, 1.5 after hour, voltage is transferred to 5v, continued oxide treatment 70 minutes, TAN in the detection of end waste water of cyanation technique and COD value, after testing, TAN is 2mg/L, and the COD value is 40mg/L, reach the wastewater discharge standard of national regulation fully, can discharge.
Embodiment 2
Handle the waste water of cyanation technique that produces in the sebaconitrile production, original TAN is 140,000 mg/L in this waste water, the COD value is that 10.5 ten thousand mg/L are (than embodiment 1 height, its value is relevant with manufacturing condition), adopt technology and the operational condition identical to handle, after testing with embodiment 1, TAN is 2mg/L in the waste water of cyanation technique after the processing, the COD value is 42mg/L, reaches the wastewater discharge standard of national regulation fully, can discharge.
Real embodiment 3
Handle the waste water of cyanation technique that produces in the sebaconitrile production, original TAN is 170,000 mg/L in this waste water, the COD value is that 120,000 mg/L are (than embodiment 2 height, its value is relevant with manufacturing condition), adopt technology and the operational condition identical to handle, after testing with embodiment 1, TAN is 5mg/L in the waste water of cyanation technique after the processing, the COD value is 49mg/L, reaches the wastewater discharge standard of national regulation fully, can discharge.
Embodiment 4～6 is the processing wastewater disposition during different fatty dintrile are produced
Execute example 4
Handle the waste water of cyanation technique that produces in the production of 11 carbon dintrile, original TAN is 130,000 mg/L in this waste water, the COD value is 110,000 mg/L, adopt technology and the operational condition identical to handle with embodiment 1, after testing, TAN is 3mg/L in the waste water of cyanation technique after the processing, and the COD value is 44mg/L, reach the wastewater discharge standard of national regulation fully, can discharge.
Embodiment 5
Handle the waste water of cyanation technique that produces in the production of 12 carbon dintrile, original TAN is 13.5 ten thousand mg L/ in this waste water, the COD value is 100,000 mg/L, adopt technology and the operational condition identical to handle with embodiment 1, after testing, TAN is 4mg/L in the waste water of cyanation technique after the processing, and the COD value is 39mg/L, reach the wastewater discharge standard of national regulation fully, can discharge.
Embodiment 6
Handle the waste water of cyanation technique that produces in the production of 13 carbon dintrile, original TAN is 11.5 ten thousand mg/L in this waste water, the COD value is 90,000 mg/L, adopt technology and the operational condition identical to handle with embodiment 1, after testing, TAN is 3mg/L in the waste water of cyanation technique after the processing, and the COD value is 42mg/L, reach the wastewater discharge standard of national regulation fully, can discharge.
Embodiment 7～8 is the result of processing wastewater under different technology conditions of water quality of the same race, COD value 9.5 ten thousand mg/L of waste water of cyanation technique wherein, TAN 120,000 mg/L.
Embodiment 7
(1) ammonia recovery process: the waste water of cyanation technique that produces in the sebaconitrile production is pumped into distillation tower (1 ton of weight), adopt the mode of batch distillation to reclaim ammonia, wherein, the distillation pressure-controlling is at-0.08Mpa, distillation temperature is controlled at 60 ℃, the pH value of system adopts the sodium hydroxide dynamic adjustments, is controlled between 10～12, and distillation time is 5 hours; Detect then, the TAN in the waste water of cyanation technique enters next procedure and handles during less than 480mg/L;
(2) acid out separation circuit: with identical among the embodiment 1;
(3) fractionation by adsorption operation: with identical among the embodiment 1;
(4) anodizing operation: with identical among the embodiment 1;
End and detect: TAN is 2mg/l, and the COD value is 38mg/l, reaches the wastewater discharge standard of national regulation fully, can discharge.
Embodiment 8
(1) ammonia recovery process: with identical among the embodiment 1;
(2) acid out separation circuit: with identical among the embodiment 1;
(3) fractionation by adsorption operation: with identical among the embodiment 1;
(4) will pump into the anodizing groove through the waste water of cyanation technique after the fractionation by adsorption operation is handled, start recycle pump, and allow waste water be in the dynamic circulation state, simultaneously with hydrochloric acid or sodium hydroxide regulation system pH value between 6～7, keep Cl
-Concentration is opened the dc constant voltage power supply in 0.1%～0.3% scope, control voltage is about 4.5v, ammonia nitrogen in the waste water and organism are carried out deep oxidation, 1.5 after hour, voltage is transferred to 5.5v, continued oxide treatment 50 minutes, detection of end: TAN in the waste water of cyanation technique and COD value, after testing, TAN is 1mg/L, and the COD value is 31mg/L, reach the wastewater discharge standard of national regulation fully, can discharge.
Take a broad view of embodiment 1～8, adopt processing method described in the invention to handle the processing wastewater of long carbochain fat dintrile in producing, no matter be water quality of the same race, or different quality, as long as in allowing fluctuation range, treatment effect is subjected to environmental factors and conditionality hardly, and stable, reliable.
In addition, content of the present invention is not limited in the above embodiments, and the technician in the same area can propose other embodiment easily under the present invention inspires, still fall within the scope of the present invention.
Claims (11)
1. the processing of a waste water of cyanation technique and recoverying and utilizing method, comprise ammonia recovery process, acid out separation circuit, fractionation by adsorption operation and anodizing operation, it is characterized in that: in described ammonia recovery process, waste water of cyanation technique is at first by distillation recovery ammonia wherein; In acid out separation circuit subsequently, separate out organism and separation by acidification with having reclaimed the waste water of cyanation technique behind the ammonia; In ensuing fractionation by adsorption operation, further reduce organic content by fractionation by adsorption with having separated the waste water of cyanation technique behind the organism; In last anodizing operation, the waste water of cyanation technique after the fractionation by adsorption is sent into the anodizing groove handle, make ammonia nitrogen and COD content reach national specified discharge standard.
2. according to the processing and the recoverying and utilizing method of the described waste water of cyanation technique of claim 1, it is characterized in that,
(1) ammonia recovery process: waste water of cyanation technique is added distillation tower, adopt alkali lye to regulate between its pH value to 8～14, under 40～100 ℃ condition, carry out negative pressure or air distillation, when TAN＜500mg/L, finish the ammonia recovery process, enter next process;
(2) acid out separation circuit: will add neutralizing well through the processing wastewater after the ammonia recovery process is handled, be acidified with acid, regulate its pH value between 2～3, the acid organism in the water is fully separated out, adopt filtration or centrifugal mode to separate the acid organism of separating out then, enter next process;
(3) fractionation by adsorption operation: will add the fractionation by adsorption groove through the processing wastewater after the acid out separation circuit is handled, and add sorbent material, and open and stir, and further remove the organism in the waste water; Wherein, the pH value of system is controlled between 3～7, under normal temperature condition, repeats described fractionation by adsorption operation 2～3 times, and the COD value in the control waste water is no more than 800mg/L, enters next process;
(4) anodizing operation: will add the anodizing groove through the processing wastewater after the fractionation by adsorption operation is handled, and start recycle pump, and allow the waste water dynamic circulation; Then open the dc constant voltage power supply, control voltage is between 2～6v; Use hydrochloric acid and sodium hydroxide regulation system pH value simultaneously between 6～7, keep Cl-concentration in 0.05%～1% scope, insufficient section need be added sodium-chlor; In 1.5～3.5 hours treatment times, when the TAN in the waste water and COD value are qualified, finish the anodizing operation, discharged wastewater met the national standard.
3. according to the processing and the recoverying and utilizing method of claim 1 or 2 described waste water of cyanation technique, its feature also is: in the described ammonia recovery process, the alkali lye of adjusting pH value adopts one or more in sodium hydroxide solution, potassium hydroxide solution, barium hydroxide solution, sodium carbonate solution, the sodium hydrogen carbonate solution.
4. according to the processing and the recoverying and utilizing method of the described waste water of cyanation technique of claim 1, its feature also is: in the described ammonia recovery process, distillation is air distillation, or vacuum distillation.
5. according to the processing and the recoverying and utilizing method of claim 1 or 2 described waste water of cyanation technique, its feature also is: in the described ammonia recovery process, the distil process preferred parameter is: distillation temperature is controlled between 60～70 ℃, the distillation pressure-controlling-0.07～-0.05MPa between, the pH value is controlled between 10～12.
6. according to the processing and the recoverying and utilizing method of claim 1 or 2 described waste water of cyanation technique, its feature also is: acidifying acid is hydrochloric acid or sulfuric acid in the described acid out separating technology.
7. according to the processing and the recoverying and utilizing method of claim 1 or 2 described waste water of cyanation technique, its feature also is: separate can be recycled after the organism that obtains is further made with extra care in the described acid out separating technology.
8. according to the processing and the recoverying and utilizing method of claim 1 or 2 described waste water of cyanation technique, its feature also is: the sorbent material in the described fractionation by adsorption operation is gac or resin.
9. according to the processing and the recoverying and utilizing method of claim 1 or 2 described waste water of cyanation technique, its feature also is: in the described anodizing operation, optimizing technology parameters is: voltage control between 3～5v, the Cl in the waste water of cyanation technique
-Concentration is controlled at 0.1～0.3%.
10. according to the processing and the recoverying and utilizing method of the described waste water of cyanation technique of claim 1, its feature also is: described nitrilation waste water is meant that carbon number is C
8～C
18Processing wastewater during fatty dintrile in the scope is produced.
11. used equipment in the processing of the described waste water of cyanation technique of claim 1 and the recoverying and utilizing method, it is characterized in that: the anodizing groove in the described anodizing operation comprises noble electrode plate, D.C. regulated power supply, oxidation trough and recycle pump; The noble electrode plate is positioned at oxidation trough, and recycle pump is used to make the treatment solution that is positioned at oxidation trough to circulate, and D.C. regulated power supply provides power supply for the noble electrode plate; Inert anode pole plate in the noble electrode plate adopts the titanium base to be coated with the ruthenium iridium alloy and is made, and is shaped as netted or tabular; The cathode and anode distance between plates is from remaining on 3～25mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102131800A CN101717164B (en) | 2009-10-20 | 2009-10-20 | Method for treating and recycling waste water of cyanation technique and device thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009102131800A CN101717164B (en) | 2009-10-20 | 2009-10-20 | Method for treating and recycling waste water of cyanation technique and device thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101717164A CN101717164A (en) | 2010-06-02 |
| CN101717164B true CN101717164B (en) | 2011-08-03 |
Family
ID=42431812
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009102131800A Active CN101717164B (en) | 2009-10-20 | 2009-10-20 | Method for treating and recycling waste water of cyanation technique and device thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101717164B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120323367A1 (en) * | 2011-06-16 | 2012-12-20 | Honeywell International Inc. | APPARATUS AND METHOD FOR pH CONTROL IN WASTEWATER TREATMENT PLANTS AND OTHER SYSTEMS |
| CN103739136B (en) * | 2014-01-06 | 2015-01-21 | 甘肃银光聚银化工有限公司 | Method for processing hyper-saline organic wastewater |
| CN112408664A (en) * | 2020-11-16 | 2021-02-26 | 广东石油化工学院 | Catalytic cracking catalyst production wastewater pretreatment system and method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3940332A (en) * | 1974-09-06 | 1976-02-24 | Sumitomo Heavy Industries, Ltd. | Treating waste water containing nitriles and cyanides |
| CN1167089A (en) * | 1996-06-03 | 1997-12-10 | 标准石油公司 | Treatment process for acrylonitrile plant wastewater streams |
| CN1911837A (en) * | 2006-08-23 | 2007-02-14 | 重庆紫光化工有限责任公司 | Treatment method of high concentration undegradable nitrile containing organic waste water |
| CN101492391A (en) * | 2008-01-25 | 2009-07-29 | 天津普莱化工技术有限公司 | Process for separating ethane nitrile wastewater with combination of abstraction and distillation |
-
2009
- 2009-10-20 CN CN2009102131800A patent/CN101717164B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3940332A (en) * | 1974-09-06 | 1976-02-24 | Sumitomo Heavy Industries, Ltd. | Treating waste water containing nitriles and cyanides |
| CN1167089A (en) * | 1996-06-03 | 1997-12-10 | 标准石油公司 | Treatment process for acrylonitrile plant wastewater streams |
| CN1911837A (en) * | 2006-08-23 | 2007-02-14 | 重庆紫光化工有限责任公司 | Treatment method of high concentration undegradable nitrile containing organic waste water |
| CN101492391A (en) * | 2008-01-25 | 2009-07-29 | 天津普莱化工技术有限公司 | Process for separating ethane nitrile wastewater with combination of abstraction and distillation |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2005-7275A 2005.01.13 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101717164A (en) | 2010-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105776765A (en) | Cyanide-containing wastewater treatment method | |
| CN113737205B (en) | Method for directly preparing ammonia gas by electrochemical reduction of nitrite | |
| CN109761412A (en) | The electrolysis treatment process and device of low content organic pollutant in a kind of high salinity rare-earth wet method smelting wastewater | |
| CN108101163A (en) | It is a kind of that valuable metal is recycled from industrial wastewater and drops ammonia nitrogen and the method for COD | |
| CN101717164B (en) | Method for treating and recycling waste water of cyanation technique and device thereof | |
| CN101973668B (en) | Acrylic acid industry wastewater treatment process | |
| CN202369461U (en) | Deep treatment device for garbage leachate | |
| CN103951017A (en) | Method for treating cyanogen-containing copper-containing electroplating wastewater by electrolysis and recycling copper | |
| CN104529049A (en) | Treatment method for using ketazine process hydrazine hydrate brine waste in ion exchange membrane electrolysis | |
| CN106244811A (en) | The recoverying and utilizing method of the electroplating sludge that a kind of copper iron content is low, stannum nickel content is high | |
| CN107200422B (en) | Method for electrochemically pretreating gold ore dressing and smelting residual organic matters and cyanide-containing wastewater | |
| CN110219020B (en) | Method for improving conductivity of lead electrolyte | |
| CN115432870B (en) | System and method for electrochemically recycling ammonia aiming at high ammonia nitrogen or nitrate nitrogen wastewater | |
| CN109179801B (en) | Treatment method of trivalent chromium electroplating waste liquid | |
| CN103058329A (en) | Method for treating trifluralin pesticide wastewater by diamond film electrode | |
| CN102660756B (en) | High-purity manganese metal and preparation method thereof | |
| WO2019071642A1 (en) | Method for recovering lead from waste lead-acid battery lead paste in wet process | |
| CN114538690A (en) | Electrochemical combined treatment method for 2,4-D high-salt pesticide organic wastewater | |
| CN106966469A (en) | A kind of processing method of containing sulfate radicals waste water | |
| CN114016034A (en) | Recycling treatment method of etching waste liquid mixed acid | |
| CN204058604U (en) | The device of ammonia and urea soln gas cleaning absorption liquid ammonium persulphate | |
| CN102321890A (en) | Method for preparing thiram by direct-electrochemical-oxidation | |
| CN202170259U (en) | Reverse osmosis system electrolyzing device with high recovery rate | |
| CN1321224C (en) | Method for separating and purifying zinc and manganese dioxide in comprehensive treatment of waste batteries | |
| CN220317574U (en) | Microalgae wastewater treatment device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for treating and recycling waste water of cyanation technique and device thereof Effective date of registration: 20140110 Granted publication date: 20110803 Pledgee: Wuxi rural commercial bank Limited by Share Ltd Pledgor: Xingda Wuxi nylon Co., Ltd.|Wuxi Yin Da nylon Co., Ltd. Registration number: 2014990000026 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20151229 Granted publication date: 20110803 Pledgee: Wuxi rural commercial bank Limited by Share Ltd Pledgor: Xingda Wuxi nylon Co., Ltd.|Wuxi Yin Da nylon Co., Ltd. Registration number: 2014990000026 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for treating and recycling waste water of cyanation technique and device thereof Effective date of registration: 20151229 Granted publication date: 20110803 Pledgee: Wuxi rural commercial bank Limited by Share Ltd Pledgor: Xingda Wuxi nylon Co., Ltd.|Wuxi Yin Da nylon Co., Ltd. Registration number: 2015990001196 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20181123 Granted publication date: 20110803 Pledgee: Wuxi rural commercial bank Limited by Share Ltd Pledgor: Xingda Nylon Co., Ltd., Wuxi City|Wuxi Yinda Nylon Co., Ltd. Registration number: 2015990001196 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Method for treating and recycling waste water of cyanation technique and device thereof Effective date of registration: 20181123 Granted publication date: 20110803 Pledgee: Wuxi rural commercial bank Limited by Share Ltd Pledgor: Wuxi Yinda Nylon Co., Ltd.|Xingda Nylon Co., Ltd., Wuxi City Registration number: 2018990001110 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20211208 Granted publication date: 20110803 Pledgee: Wuxi rural commercial bank Limited by Share Ltd. Pledgor: WUXI YINDA NYLON Co.,Ltd. Registration number: 2018990001110 |