The purification of H acid producing waste water and the method for resource recycling
One, technical field
The present invention relates to the recoverying and utilizing method of useful resources in the purification of waste water of being discharged in a kind of H acid production process and the waste water.Specifically, be exactly a kind of from the H acid producing waste water separating and recovering sodium sulfate saturated solution, from waste water, reclaim the method for useful resources H acid and T acid simultaneously.
Two, background technology
H acid is 1-amino-8-naphthol-3, the 6-disulfonic acid (chemical structural formula is:
), be important naphthalene series dye intermediate, it is mainly used in and produces directly, acid, reactive dyestuffs and azoic dyestuff intermediate, as acid day blue, direct kind surplus the black Reactive Brilliant Red K-2BP etc. 90, also can be used for pharmaceutical industry.At present, the production technique of domestic H acid generally is to be raw material with the refined naphthalene, makes through operations such as sulfonation, nitrated, neutralization, reduction, alkali fusion and acid outs.Produced COD in the production process
CrUp to the waste water of 20000~30000mg/L, contain the sodium sulfate of saturation concentration in the waste water, wherein organic composition is mainly product H acid and intermediate T acid.Because it is very high that H acid and T acid are difficult in biological degradation, the water-soluble very big again and waste water sodium sulphate content, thereby the cost-effective improvement of H acid producing waste water is the generally acknowledged difficult problem of domestic and international environmental protection circle always.The manufacturing enterprise of H acid both at home and abroad at present mainly adopts this waste water of dilution-biochemical treatment, and H acid and the T acid in the water body at this moment is broken to small-molecule substance and causes the wasting of resources in treating processes.
Three, summary of the invention
The purpose of this invention is to provide a kind of purification of H acid producing waste water and the method for resource recycling, this method can make waste water after resin absorption is separated, in reuse sodium sulfate saturated solution, reclaim wherein T acid, H acid, realize the combination of waste water treatment and resource recycling.
The objective of the invention is to be achieved through the following technical solutions:
A kind of purification of H acid producing waste water and the method for resource recycling is characterized in that it may further comprise the steps:
A) the H acid producing waste water is filtered, remove suspended substance wherein; Raw wastewater among the present invention is the sodium sulfate saturated solution that slightly is muddy shape, and wherein, the H acid concentration is 2000~4000mg/L, and the T acid concentration is 14000~17000mg/L, COD
CrBe 20000~30000mg/L.
B) with steps A) filtrate that obtains is by being filled with the macroporous resin absorption tower, and H acid and T acid in the waste water optionally are adsorbed on the resin, and absorption effluent is water white sodium sulfate saturated solution; The present invention can be at 5~45 ℃ with steps A) filtrate that obtains with the flow of 0.5~3BV/h (BV is the resin bed volume) by being filled with the macroporous resin absorption tower.Described resin is to be the macroporous resin of basic framework with the polystyrene, it can be ND-910 complexing polymeric adsorbent, NDA-99 and NDA-88 composite function resin (Jiangsu Nanda Gede Environmental Protection Technology Co., Ltd's production) and D301 resin (production such as Langfang, Hebei electric power resin processing plant), also can be the macroporous resins such as Amberlite IRA96, IRA93 that U.S. RohmHaas company produces, ND-910 complexing polymeric adsorbent preferably wherein.Water white sodium sulfate saturated solution can be back to T acid, the H acidleach of original production process among the present invention
Cake flushing operation.
C) when absorption reaches leakage point, stop absorption, as desorbing agent, carry out desorption and regeneration, obtain the sodium salt solution of high density H acid, T acid with aqueous sodium hydroxide solution; Naoh concentration of the present invention can be 2%~10%, carries out desorption and regeneration at 30~55 ℃ of flows with 0.5~2BV/h.For guaranteeing the quality of desorption and regeneration, for saving cost, the present invention carries out the resin desorption and regeneration after polymeric adsorbent has been handled 5~10BV/ batch waste water on the other hand on the one hand.
D) will be by step C) the desorption high density H acid of getting off, the sodium salt solution of T acid returns the alkali fusion procedure of original production process, and light concentration desorption liquid is used to prepare the aqueous sodium hydroxide solution cover and is used for the next batch desorption manipulation.
The present invention is at step B) described in adsorption tower can adopt the operation scheme of double-column in series absorption, single tower desorption; I, II, three adsorption towers of III are set, and with I, II tower series connection following current absorption, the I tower is as first post earlier, the II tower after the absorption of I tower is saturated, switches to II, III tower series connection following current absorption as stern post, the II tower is as first post, and the III tower is as stern post, and the I tower carries out desorption and regeneration with desorbing agent simultaneously.
According to method provided by the invention, (slightly muddy, the H acid concentration is 2000~4000mg/L to raw wastewater, and the T acid concentration is 14000~17000mg/L, COD
CrBe the sodium sulfate saturated solution of 20000~30000mg/L) after resin absorption was separated, water outlet was water white sodium sulfate saturated solution, H acid concentration<20mg/L, T acid concentration<30mg/L, COD
Cr<650mg/L, T acid, the H acidleach cake that can be back to original production process wash operation; Can from every cubic metre of waste water, reclaim simultaneously about 2 kilograms of H acid, about 10 kilograms of T acid.The present invention has realized the separation and the recycling of pollutent when administering waste water.
Resin absorption operation among the present invention can be adopted the operation scheme of double-column in series absorption, single tower desorption, moves continuously to guarantee whole waste water treatment device.Compared with prior art, beneficial effect of the present invention is: 1, the water outlet after fractionation by adsorption of H acid producing waste water is water white sodium sulfate saturated solution, H acid concentration<20mg/L, T acid concentration<30mg/L, COD
Cr<650mg/L, T acid, the H acidleach cake that can be back to original production process wash operation; 2, most H acid and T acid in the separable recovery raw wastewater realizes the resource recycling; 3, the polymeric adsorbent regenerability is good, and is reusable.
Four, embodiment
By the following examples the present invention is further described:
Embodiment 1
10mL (about 6.8 gram) macropore complexing polymeric adsorbent NDA-910 packed in the glass adsorption column of strap clamp cover, and (Φ 12 * 160mm).Waste water COD
CrBe 23000mg/L, after the filtration, in 15 ± 5 ℃, by resin bed, treatment capacity is that 70mL/ criticizes with the flow of 10mL/h with it.After resin absorption, the water outlet water white transparency, the H acid concentration is 14mg/L, the T acid concentration is 25mg/L, COD
CrBe 550mg/L.
The 20mL4% aqueous sodium hydroxide solution under 45 ± 5 ℃ temperature, is carried out desorption with the flow following current of 5mL/h by resin bed.The high density H acid that desorption gets off, the sodium salt solution of T acid can return the alkali fusion procedure of original production process.Light concentration desorption liquid is used to prepare the used aqueous sodium hydroxide solution of next batch desorption.
Embodiment 2
100mL (about 68 gram) NDA-910 resin packed in the glass adsorption column of strap clamp cover, and (Φ 32 * 260mm).Waste water COD
CrBe 22000mg/L, after the filtration, in 40 ± 5 ℃, by resin bed, treatment capacity is that 700mL/ criticizes with the flow of 150mL/h with it.After resin absorption, the water outlet water white transparency, the H acid concentration is 15mg/L, the T acid concentration is 23mg/L, COD
CrBe 500mg/L.
The 100mL10% aqueous sodium hydroxide solution under 35 ± 5 ℃ temperature, is carried out desorption with the flow following current of 50mL/h by resin bed.The high density H acid that desorption gets off, the sodium salt solution of T acid can return the alkali fusion procedure of original production process.Light concentration desorption liquid is used to prepare the used aqueous sodium hydroxide solution of next batch desorption.
Embodiment 3
1000mL (about 680 gram) ND-910 resin packed in the glass adsorption column of strap clamp cover, and (Φ 70 * 500mm).Waste water COD
CrBe 24000mg/L, after the filtration, in 15 ± 5 ℃, by resin bed, treatment capacity is that 6000mL/ criticizes with the flow of 2500mL/h with it.After resin absorption, the water outlet water white transparency, the H acid concentration is 18mg/L, the T acid concentration is 27mg/L, COD
CrBe 620mg/L.
The 1500mL6% aqueous sodium hydroxide solution under 40 ± 5 ℃ temperature, is carried out desorption with the flow following current of 1000mL/h by resin bed.The high density H acid that desorption gets off, the sodium salt solution of T acid can return the alkali fusion procedure of original production process.Light concentration desorption liquid is used to prepare the used aqueous sodium hydroxide solution of next batch desorption.
Embodiment 4
Select that three specifications are identical, material is 316L stainless steel adsorption tower for use (Φ 550 * 3500mm), compile Shang number be respectively I, II and III, every tower loads 340 kilograms of (about 0.5m of NDA-910 polymeric adsorbent
3).Waste water COD
CrBe 24000mg/L, after the filtration, with it in 20 ± 5 ℃, with 0.5m
3The flow of/h is squeezed into adsorption tower with pump, and the mode of I, II tower double-column in series following current absorption is adopted in absorption, and treatment capacity is 3.5m
3/ batch.After resin absorption, the water outlet water white transparency, the H acid concentration is 15mg/L, the T acid concentration is 25mg/L, COD
CrBe 550mg/L.
To adsorb 3.5m
3The first post I adsorption tower of waste water breaks away from absorption system and carries out desorption manipulation; And the next batch adsorption operations changes II, the series operation of III tower into, post headed by the II tower becomes.
Earlier raffinate in the I adsorption tower is drained, again with 0.75m
38% aqueous sodium hydroxide solution is under 35 ± 5 ℃ temperature, with 0.25m
3The flow following current of/h is carried out desorption by resin bed.The high concentration desorption liquid that desorption gets off is back to the alkali fusion procedure of original production process.Light concentration desorption liquid is used to prepare the aqueous sodium hydroxide solution cover and is used for the next batch desorption manipulation.
I adsorption tower after desorption finishes will be as the stern post of the 3rd batch of adsorption operations.Can guarantee that by the present invention whole waste water treatment device moves continuously.
Embodiment 5
Change the NDA-910 resin among the embodiment 1 domestic resins such as into NDA-99, NDA-88, NDA-100 and D301, or resin and macroporous weak such as U.S. AmberliteIRA93, IRA96, other operational conditions remain unchanged, except that every batch processing volume and absorption effluent water quality decreased, other effects substantially roughly the same.