CN103058427A - Treatment method of brine waste in production process of toluene-2,4-diisocyanate (TDI) - Google Patents
Treatment method of brine waste in production process of toluene-2,4-diisocyanate (TDI) Download PDFInfo
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- CN103058427A CN103058427A CN2013100294161A CN201310029416A CN103058427A CN 103058427 A CN103058427 A CN 103058427A CN 2013100294161 A CN2013100294161 A CN 2013100294161A CN 201310029416 A CN201310029416 A CN 201310029416A CN 103058427 A CN103058427 A CN 103058427A
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Abstract
The invention relates to a treatment method of brine waste in a production process of toluene-2,4-diisocyanate (TDI). The treatment method comprises the following steps of a, carrying out acid neutralization on the brine waste by hydrochloric acid or hydrogen chloride, removing carbonate and generating decarbonized silicate saline water; b, filtering the decarbonized silicate saline water through a coalesce or a tilted plate separator to separate micro oil drops in water; c, mixing the processed brine waste with sodium hypochlorite to oxidize and remove organic pollutant; d, filtering the oxidized waste water, and removing a trace of organic matter by active carbon, and then entering an electrolysis process. By adopting the treatment method, the brine waste generated in production of toluene diisocynate by a phosgene method is cyclically used in production after being processed; cyclic utilization of the entire production process is finished; zero discharge standard of the waste water is achieved; significant economic benefit is brought about, and harmonious sustainable development of economics and environmental protection is also achieved.
Description
Technical field
The invention belongs to technical field of waste water processing, particularly phosgenation is produced the treatment process of brine waste in the TDI production process.
Background technology
Tolylene diisocyanate (TDI) is the main raw material(s) of material polyurethane (PU), is widely used in to produce polyurethane foam, plastics, coating, elastomerics and bonding agent etc.Its production process is disclosed.Description is arranged, such as patent CN200710106678.8 number, CN1149579A number and CN201010115308.2 number etc. in Chinese invention patent.Produce in the tolylene diisocyanate at phosgenation, wherein excessive phosgene is destroyed by alkali lye, the waste liquid of discharging is the effluent brine that contains the inorganicss such as sodium hydroxide of 1～3% sodium-chlor, 5～10% yellow soda ash and 1～5%, is wherein inevitably carrying various organic impuritys secretly.Effluent brine biological oxygen demand (BOD
5) be 2～5mg/L, total content of organic carbon (TOC) is 50～200mg/L.Organism is complicated in the waste water, wherein mainly contains just like aniline＜50mg/L diethyl phthalate＜10mg/L, straight-chain paraffin＜20mg/L, total organic content＜200mg/L.Process the waste water of this high content of salt, biochemical system is inapplicable, unless reduce the saltiness concentration in the waste water.At present, the processing that contains the high-concentration chlorine ion wastewater from chemical industry is one of difficult point of environment protection, reduces or removes chloride content in the waste water, and its processing costs is very expensive, and this has aggravated the burden of enterprise greatly.
Present stage country " integrated wastewater discharge standard " (GB8978-1996) and in some other discharge standard does not all carry out standard to this index of saltiness.So more enterprise controls mainly for indexs such as chemical oxygen demand (COD) (COD), and the muriate in the waste water is not processed according to " integrated wastewater discharge standard " relevant regulations in (GB8978-1996).When chloride content is high in the waste water, can destroy the balance of nature of water body, make water quality deterioration, also can polluted underground water when serious and drink origin.In addition, the too high meeting of chloride concentration makes the pedogenesis salinization in the water. and have a strong impact on the growth of plant.
The begin one's study processing of brine waste of existing increasing enterprise, hope can be found a kind of economically viable method, reduces the muriate of waste water.More advanced theory is to make this part brine waste recycle in the middle of production.Recycling of various effluent brines has many reports, and for example US Patent No. 7,858, introduces among the 727B2, and the sodium chloride waste water that produces in the polycarbonate production process is used for electrolysis with ion-exchange film, and the chlorine that electrolysis produces and alkali lye recycle are to polycarbonate production.And for organism in the sodium chloride waste water, such as the removal of residual solvent and catalyzer, just simply distill with steam, adsorb with gac again.The ionic membrane assembly is highstrung to the contained organic impurities of electrolytic solution in electrolytic process, and the salt solution that particularly purifies for any regeneration will be noted its security more, must guarantee that organic content is up to standard in the salt solution.And contained organic constituents is comparatively complicated in the most brine waste, only utilizes the method for distillation and charcoal absorption, is difficult to satisfy the requirement of ionic membrane, and its security must not get and guaranteed.
Chinese patent CN 1402749A discloses " method and apparatus of the preparation polycarbonate under brine recycling ".The method comprises: (a) the abraum salt current are mixed to reduce organic impurities concentration in the effluent brine with ozone; (b) the above-mentioned ozonize salt solution of acidifying is to remove carbonate; (c) concentrated above-mentioned salt solution is to form wherein NaCl concentration as the processing salt solution of at least 10～20% (weight); (d) 20～30%NaCl salt brine solution electrolytic preparation chlorine.Organic pollutant in the salt solution is completely oxidized to CO by the oxidation of ozone
2, H
2O and NO
3And intermediate product, reduce organic content in the effluent brine.Ozone has extremely strong oxidation capacity, inorganics in can oxidizing water, reduce COD content, this is comparatively desirable treatment process, but shortcoming also is comparatively obvious, its processing costs is very high, so that the economy of this method reduces greatly, causes this method to fail extensively to be promoted.
Summary of the invention
The object of the invention is to avoid the defective of prior art, a kind of reliable secondary salt treatment process is provided, the method running cost is low, non-wastewater discharge, free from environmental pollution, the most key is the effluent brine recycle, and the starting material of producing TDI are provided, optimize the structure of production.
For achieving the above object, the technical scheme that the present invention takes is: the treatment process of brine waste in a kind of TDI production process is characterized in that comprising the steps:
A. the brine waste that produces in the production of toluene diisocyanate process is carried out acidizing neutralization with hydrochloric acid or hydrogenchloride, adjust pH less than 7, remove carbonate and produce decarburization hydrochlorate salt solution;
B. remove the small oil droplet of lubricating oil that contains in the decarburization hydrochlorate salt solution;
C. the effluent brine of step b processing contains the chemical pollutants such as organism aniline, diethyl phthalate, effluent brine after the step b processing is fully mixed with clorox, remove organic pollutant with oxidation, effluent brine and sodium hypochlorite reaction time are not less than 20min;
D. the effluent brine of oxide treatment being crossed is removed impurity by metallic filter, and the equipment by the filling gac makes total organic carbon (TOC) content of the salt solution of crossing through activated carbon treatment＜30 mg/L to remove the organism of trace again, then enters electrowinning process;
E. the clorox of electrowinning process production returns step c as the raw material of processing effluent brine; The sodium hydroxide that electrowinning process is produced, chlorine, hydrogen return in the required operation of producing tolylene diisocyanate as the raw material of producing tolylene diisocyanate, realize complete closed cycle utilization.
Described step b removes the small oil droplet of lubricated wet goods that contains in the decarburization hydrochlorate salt solution, adopt fiber coalescer or tilted plate separator to fall little oil droplet and be agglomerated into larger oil droplet, carry out static separation and remove oil droplet, the residence time of decarburization hydrochlorate salt solution static separation is not less than 120min.
The invention has the beneficial effects as follows: be used for electrolytic brine after the effluent brine that produces in the phosgenation production of toluene diisocyanate process is processed, electrolysate is cycled to used in the middle of the production of toluene diisocyanate, starting material as production of toluene diisocyanate, finish the recycle of whole production technique, this theory has not only solved the emission problem of waste water, and optimized the industrial structure, greatly reduce the cost of producing tolylene diisocyanate (TDI).
Description of drawings
Fig. 1 is production of toluene diisocyanate device circulation synoptic diagram;
Fig. 2 is schematic flow sheet of the present invention.
Embodiment
Below in conjunction with accompanying drawing principle of the present invention and feature are described, institute gives an actual example and only is used for explaining the present invention, is not be used to limiting scope of the present invention.
Embodiment 1: see Fig. 2, the treatment process of brine waste is characterized in that comprising the steps: in a kind of TDI production process
A, the brine waste that produces in the production of toluene diisocyanate process is neutralized with 12% hydrochloric acid by line mixer, adjusting pH is 5～6, removes carbonate;
B, with waste water by the fibre bed coalescer, the small-particle oil droplet is coalescent, lead to the static separation device and separate, the residence time is 120min;
The water of c, static separation device bottom mixes with clorox, reacts, and the reaction times is 20min;
D, the effluent brine that oxide treatment is crossed pass through metallic filter, and filter material is 316L, and filter core is polypropylene, through behind the activated carbon adsorber, enters electrolysis plant salt operation, then enters electrowinning process;
The clorox that e, electrowinning process are produced is as the raw material of processing effluent brine, return step c, the sodium hydroxide that electrowinning process is produced, chlorine, hydrogen are as the raw material of producing tolylene diisocyanate, return in the required operation of producing tolylene diisocyanate, realize complete closed cycle utilization (as shown in Figure 1).
Table (one) has been listed the effluent brine indices value of processing.According to the electrowinning process processing requirement, Inorganic Ammonium＜0.4mg/L, total ammonium amount＜1.0mg/L, TOC＜30mg/L.Drawn by table (), treated effluent brine reaches the electrowinning process processing requirement fully.
Table (one)
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. the treatment process of brine waste in the TDI production process is characterized in that comprising the steps:
A, the brine waste that produces in the production of toluene diisocyanate process is carried out acidizing neutralization with hydrochloric acid or hydrogenchloride, adjust pH less than 7, remove carbonate and produce decarburization hydrochlorate salt solution;
B, remove the small oil droplet of lubricating oil that contains in the decarburization hydrochlorate salt solution;
C, the effluent brine after step b processed fully mix with clorox, remove organic pollutant with oxidation, and effluent brine and sodium hypochlorite reaction time are not less than 20min;
D, the effluent brine that oxide treatment is crossed are removed impurity by metallic filter, again by the filling gac equipment with remove the trace organism, make total organic carbon (TOC) content of the salt solution of crossing through activated carbon treatment＜30 mg/L, then enter electrowinning process.
2. the treatment process of brine waste in the TDI production process as claimed in claim 1 characterized by further comprising step e: the clorox that electrowinning process is produced returns step c as the raw material of processing effluent brine; The sodium hydroxide that electrowinning process is produced, chlorine, hydrogen return in the required operation of producing tolylene diisocyanate as the raw material of producing tolylene diisocyanate, realize complete closed cycle utilization.
3. the treatment process of brine waste in the TDI production process as claimed in claim 1, it is characterized in that described step b removes the small oil droplet of lubricating oil that contains in the decarburization hydrochlorate salt solution, adopt fiber coalescer or tilted plate separator to fall little oil droplet and be agglomerated into larger oil droplet, carry out static separation and remove oil droplet, the residence time of decarburization hydrochlorate salt solution static separation is not less than 120min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864246A (en) * | 2014-04-02 | 2014-06-18 | 青岛科技大学 | Treatment method of effluent brine generated in alkyl ketene dimer production process |
| CN107298494A (en) * | 2017-07-04 | 2017-10-27 | 聊城鲁西聚碳酸酯有限公司 | A kind of system and method for handling the waste water produced in makrolon technique |
| CN109293089A (en) * | 2018-10-29 | 2019-02-01 | 甘肃银光聚银化工有限公司 | A kind of processing method of TDI production neutral and alkali brine waste |
| CN109678760A (en) * | 2019-01-31 | 2019-04-26 | 甘肃利亨新材料有限公司 | A method of it recycling TDI and produces waste residue |
| CN111870862A (en) * | 2020-07-29 | 2020-11-03 | 沈阳有研矿物化工有限公司 | Harmless treatment method for waste salt in production of alkylxanthate beneficiation reagent |
| CN112499817A (en) * | 2020-11-26 | 2021-03-16 | 中化环境科技工程有限公司 | Pretreatment method for treating TDI (toluene diisocynate) comprehensive wastewater containing foaming agent |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103864246A (en) * | 2014-04-02 | 2014-06-18 | 青岛科技大学 | Treatment method of effluent brine generated in alkyl ketene dimer production process |
| CN107298494A (en) * | 2017-07-04 | 2017-10-27 | 聊城鲁西聚碳酸酯有限公司 | A kind of system and method for handling the waste water produced in makrolon technique |
| CN109293089A (en) * | 2018-10-29 | 2019-02-01 | 甘肃银光聚银化工有限公司 | A kind of processing method of TDI production neutral and alkali brine waste |
| CN109678760A (en) * | 2019-01-31 | 2019-04-26 | 甘肃利亨新材料有限公司 | A method of it recycling TDI and produces waste residue |
| CN111870862A (en) * | 2020-07-29 | 2020-11-03 | 沈阳有研矿物化工有限公司 | Harmless treatment method for waste salt in production of alkylxanthate beneficiation reagent |
| CN112499817A (en) * | 2020-11-26 | 2021-03-16 | 中化环境科技工程有限公司 | Pretreatment method for treating TDI (toluene diisocynate) comprehensive wastewater containing foaming agent |
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Effective date of registration: 20170905 Address after: 730900 chemical industry park, Baiyin hi tech Industrial Park, Gansu Patentee after: Gansu North Santai Chemical Co. Ltd. Address before: 730900 Gansu province Baiyin District Silver Road No. 1-1 Patentee before: Gansu Yinguang Juyin Chemical Industry Co., Ltd. |