CN102295384B - 1,4-butanediol chemical waste water treatment technology - Google Patents
1,4-butanediol chemical waste water treatment technology Download PDFInfo
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- CN102295384B CN102295384B CN 201110162235 CN201110162235A CN102295384B CN 102295384 B CN102295384 B CN 102295384B CN 201110162235 CN201110162235 CN 201110162235 CN 201110162235 A CN201110162235 A CN 201110162235A CN 102295384 B CN102295384 B CN 102295384B
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- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 16
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 title abstract description 31
- 239000002894 chemical waste Substances 0.000 title abstract 4
- 239000010802 sludge Substances 0.000 claims abstract description 54
- 239000002351 wastewater Substances 0.000 claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 235000016709 nutrition Nutrition 0.000 claims description 7
- 230000035764 nutrition Effects 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- -1 nitrogenous compound Chemical class 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000010525 oxidative degradation reaction Methods 0.000 claims description 2
- 150000003016 phosphoric acids Chemical class 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 238000005842 biochemical reaction Methods 0.000 claims 1
- 230000001376 precipitating effect Effects 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract 2
- 238000000265 homogenisation Methods 0.000 abstract 1
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- 244000005700 microbiome Species 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 230000002906 microbiologic effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007483 microbial process Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002417 nutraceutical Substances 0.000 description 1
- 235000021436 nutraceutical agent Nutrition 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Purification Treatments By Anaerobic Or Anaerobic And Aerobic Bacteria Or Animals (AREA)
- Activated Sludge Processes (AREA)
Abstract
The invention relates to a 1,4-butanediol chemical waste water treatment technology, and belongs to the technical field of environment engineering. The 1,4-butanediol chemical waste water treatment technology comprises that high-density 1,4-butanediol production waste water is fed into a homogenization pond; the high-density 1,4-butanediol production waste water is fed into a two-stage aerobic reaction pond through an elevator pump; the high-density 1,4-butanediol production waste water treated by an aerobic reaction flows automatically into a settling pond; after muddy water is separated from the high-density 1,4-butanediol production waste water in the settling pond, the high-density 1,4-butanediol production waste water is discharged; and a part of the muddy water flows back to the two-stage aerobic reaction pond and the rest of the muddy water is dehydrated and then discharged, wherein a first section of the two-stage aerobic reaction pond is added with a biological carrier filling material and a second section of the two-stage aerobic reaction pond does not need a carrier filling material and is added only with sludge. The 1,4-butanediol chemical waste water treatment technology has the advantages of device work stabilization, high efficiency, stable quality of yielding water, convenience of automatic control, management and operation, and low operating cost.
Description
Technical field
The present invention relates to a kind of BDO chemical wastewater treatment technique, belong to field of environment engineering technology.
Background technology
The processing wastewater Pollutant levels that produce during BDO is produced are high, toxicity large, the pollutent complicated, have the bio-refractory material, and waste water typical case COD value is at 20,000-30,000 mg/L.The method of processing at present the BDO wastewater from chemical industry mainly contains: anaerobism+anoxic+aerobic, SBR technique etc., and take process COD at the following waste water of 1000mg/L as main, process then to have no report for the high density processing wastewater of COD more than 5000mg/L.Anaerobic technique is complicated, and the reference mark is more, and anaerobism, anaerobic treatment DeGrain.And SBR technique is periodical operation, and wastewater treatment continuous for the water yield and that concentration is higher is improper.The present invention is intended to process the processing wastewater in the above high density BDO production process of 10,000mg/L.
Chinese patent application 200710077937.9 discloses a kind of 1, the treatment process of 4-butyleneglycol factory effluent, but the method biochemical treatment water inlet (equalizing tank water outlet) COD can not be greater than 1000mg/L, must dilute or enter accident pool when concentration is higher regulates, and this technique is batch technology, and impact is produced continuously.
Summary of the invention
For overcoming defects, technical purpose of the present invention is to provide a kind of 1,4-butyleneglycol wastewater from chemical industry is decomposed into main treatment process with microorganism, thereby so that this technology can be decomposed removal COD by microorganism with the BDO wastewater of chemical industry with high concentration under aerobic condition sewage is purified; And the process efficiency of using this technology is high, production equipment is compact, stable effluent quality, simple to operate and easily be automated control, can solve well 1, the unmanageable problem of high-concentration waste water that produces in the 4-butyleneglycol production process, and cost for wastewater treatment is reasonable.
For realizing technical purpose of the present invention, technical solution of the present invention is:
A kind of BDO chemical wastewater treatment technique is characterized in that may further comprise the steps:
(1) waste water is regulated: high density BDO wastewater from chemical industry is entered homogeneous pond modified evenly; The waste water that produces during to overstandard waste water or production start-stop car stage or accident enters accident pool and temporarily stores, and then slowly pumps into homogeneous pond; Waste water ph, temperature and interpolation nutritive substance are regulated in homogeneous pond.
Wherein, homogeneous pond has concurrently regulates pH value and nutraceutical function, establishes the system of mixing in it.Factory effluent COD value, pH are in relatively stable, regulate simultaneously nutrient balance.
(2) one sections bio-oxidations: with 1 in the homogeneous pond, 4-butyleneglycol wastewater from chemical industry is delivered to one section aerobe carrier current movable bed reaction tank and carries out the biochemical oxidation processing, so that most of pollutent oxygenolysis under the microbial process of carrier biofilm and active sludge in the waste water.
(3) two sections bio-oxidations: the wastewater sludge mixed solution of step (2) enters two sections active sludge biological oxidation ponds again, so that the further oxidative degradation under the active sludge microorganism effect of the residual contamination thing in the waste water, active sludge microorganism also obtains effective activation recovering and stable performance simultaneously.
(4) precipitate and separate: the wastewater sludge mixed solution that step (3) obtains enters the second pond precipitate and separate, the supernatant liquor discharging, and sludge reflux is to one section aerobe carrier current movable bed reaction tank of step (2); Excess sludge discharge to the sludge storage pool that produces in the waste water microbiological treatment engineering stores.
(5) sludge dewatering: the excess sludge that the storage pond of step (4) stores is after sludge dewatering system (plate-and-frame filter press) carries out processed, and filtrate is returned the homogeneous pond of step (1), and the mud cake outward transport is disposed.
The whole process temperature of biochemical process of the present invention is 10～40 ℃, and one section aerobe carrier current movable bed reaction tank and two sections active sludge biological oxidation pond pH values are 6～9.
Step of the present invention (1) adds nutrition and regulates in homogeneous pond; And regulate the pH value in homogeneous pond.Wherein said nutrition is nitrogenous compound (urea, ammoniacal liquor or ammonium salt etc.) and phosphoric acid salt; PH adjusting agent is acid or alkali.
The homogeneous pond water outlet of step of the present invention (1) pH is 5～8,10～45 ℃ of temperature.
(2) one sections aerobe carrier current movable beds of step of the present invention reaction tank DO value is 2～6 mg/L, and the carrier dosage is volume ratio 25～67%, sludge concentration 1～16 g/L, total hrt 0.5～20 day.
(3) two sections active sludge biological oxidation pond DO of step of the present invention value is 1～6 mg/L, sludge concentration 1～8 g/L, total hrt 0.5～20 day.
The return sludge ratio 50～200% of step of the present invention (4) settling tank, settling tank surface load 0.2～1.0m
3/ m
2H.
Beneficial effect of the present invention is:
The present invention has adopted equalizing tank, secondary aerobic enhanced biological art breading waste water, utilize one section aerobe carrier current movable bed reaction tank technique to decompose and remove organism in the waste water, effective microbe sludge concentration and biological treatment performance have been improved, and make microorganism active effectively be recovered and stablize at two sections active sludge biological oxidation ponds, water outlet COD is low.The present invention is take biotechnology as the basis, and technical process is reasonable, operating performance is stable, treatment effect is good, investment and running cost are low.。The present invention is equally applicable to the biological treatment of other similar high density toxicity organic waste waters.
The BDO processing wastewater mainly contains the pollutents such as alcohol, fat, toluene and 2-methoxyl group tetrahydrofuran (THF), and Process for Effluent COD value is high, usually 20,000～30, and 000mg/L, during abnormal accident even up to 150,000mg/L.Because of waste strength high, the impacts such as bio-toxicity is large, the hi-tech means that take full advantage of bio-carrier enriched microorganism species when employing is of the present invention make reaction tank process high loading COD, simultaneously the second pond sludge reflux improves active sludge microorganism concentration, improves the recovery of its activity and stable, makes waste water efficiently be removed and administer at reaction tank.
The present invention is based on the microbiological treatment technology, technical process is reasonable, succinct, and investment and running cost are low, are convenient to industrial applications.
Description of drawings
Fig. 1 is the schematic flow sheet of technique of the present invention.
Embodiment
Embodiment 1
The BDO wastewater from chemical industry at first enters homogeneous distribution reservoir.Distribution reservoir waste water is through one section aerobe carrier current movable bed reaction tank+two sections active sludge biological oxidation pond+settling tank of lift pump input, reaction tank volume 26L.Homogeneous pond wastewater outlet flow 5L/d, COD 20, and 231mg/L adds nutrition urea in the homogeneous pond and SODIUM PHOSPHATE, MONOBASIC is regulated; And regulate the pH value 7 in homogeneous pond.One section aerobe carrier current movable bed reaction tank bio-carrier (the composite modified carrier P15 of Bo Ruide (Nanjing) purification techniques company limited type) adds 50%, one section microorganism sludge concentration 10g/L, DO3.5mg/L, hydraulic detention time 5 days.Two sections activated sludge tank sludge concentration 4g/L, DO3.0mg/L, hydraulic detention time 5 days.Two sections outputted aerobic water enter second pond, carry out solid-liquid separation, and waste water drains into the discharging pond, second pond return sludge ratio 100%, and excess sludge is regularly got rid of, second pond surface load 0.7 m
3/ m
2H.
The waste water whole process operating temperature of the present embodiment is at 25～30 ℃.Settling tank discharging water outlet pH7.8 during steady running, COD 116mg/L, SS 40mg/L.
Embodiment 2
The BDO wastewater from chemical industry at first enters homogeneous pond.Homogeneous pond waste water is through one section carrier biofilm Aerobic Pond of lift pump input, homogeneous pond wastewater outlet flow 60m
3/ d, COD 21, and 890mg/L adds nutrition urea and Sodium phosphate dibasic and regulates in the homogeneous pond, and to regulate the pH value with alkali be 5～7.One section Aerobic Pond carrier filler (the composite modified filler P15 of Bo Ruide (Nanjing) purification techniques company limited type) adds 40%, one section carrier biofilm reaction tank sludge concentration 12g/L, DO2.0mg/L, hydraulic detention time 2 days.Two sections activated sludge tank sludge concentration 4g/L, DO2.5mg/L, hydraulic detention time 3.5 days.Two sections outputted aerobic water enter second pond, carry out solid-liquid separation, and waste water drains into the discharging pond, and second pond return sludge ratio 100%, excess sludge be to sludge dewatering system, second pond surface load 0.6 m
3/ m
2H.
The waste water whole process operating temperature of the present embodiment is at 35～39 ℃.Finally discharge after testing water outlet pH8.2, COD 248mg/L, SS 53mg/L.
Embodiment 3
The BDO processing wastewater at first is placed on homogeneous pond through grid filtration.Homogeneous pond waste water is through one section carrier biofilm Aerobic Pond of lift pump input, homogeneous pond wastewater outlet flow 50m
3/ d, COD 23, and 538mg/L adds nutrition ammoniacal liquor in the homogeneous pond and SODIUM PHOSPHATE, MONOBASIC is regulated; And regulate the pH value 5.0～6.0 in homogeneous pond with mineral acid or alkali.One section Aerobic Pond carrier filler (the composite modified filler P15 of Bo Ruide (Nanjing) purification techniques company limited type) adds 65%, one section carrier biofilm reaction tank sludge concentration 9g/L, DO3.0mg/L, hydraulic detention time 5 days.Two sections activated sludge tank sludge concentration 3g/L, DO4.0mg/L, hydraulic detention time 5 days.Two sections outputted aerobic water enter second pond, carry out solid-liquid separation, and waste water drains into the discharging pond, and second pond return sludge ratio 50%, excess sludge be to sludge dewatering system, second pond surface load 0.7 m
3/ m
2H.
The waste water whole process operating temperature of the present embodiment is at 32～35 ℃.Finally discharge after testing water outlet pH8.2, COD 317mg/L, SS 63mg/L.
Claims (7)
1. BDO chemical wastewater treatment technique is characterized in that may further comprise the steps:
(1) waste water is regulated: high density BDO processing wastewater is entered homogeneous pond; When producing start-stop car stage or accident, waste water enters accident pool, and accident pool waste water is slowly regulated and entered homogeneous pond; Waste water ph and temperature are regulated in homogeneous pond;
(2) one sections bio-oxidations: with 1 in the homogeneous pond, 4-butyleneglycol processing wastewater is delivered to one section aerobe carrier current movable bed reaction tank and carries out the efficient biochemical processing, so that most of pollutent oxygenolysis under the effect of carrier biofilm and active sludge in the waste water;
Wherein, one section aerobe carrier current movable bed reaction tank DO value is 2～6 mg/L, and the carrier dosage is volume ratio 25～67%, sludge concentration 1～16 g/L, total hrt 0.5～20 day;
(3) two sections bio-oxidations: the waste water of step (2) enters two sections active sludge biological oxidation ponds again, so that the further oxidative degradation under the effect of active sludge of the residual contamination thing in the waste water;
Wherein, two sections active sludge biological oxidation pond DO values are 1～6 mg/L, sludge concentration 1～8 g/L, total hrt 0.5～20 day;
(4) precipitating sludge: the waste water that step (3) obtains enters the second pond precipitation, the supernatant liquor that obtains discharging, and sludge part is back to one section aerobe carrier current movable bed reaction tank of step (2), and excess sludge discharge is to sludge dewatering system;
Wherein, the return sludge ratio 50～200% of settling tank, settling tank surface load 0.2～1.0 m
3/ m
2H;
(5) sludge dewatering: the excess sludge of step (4) is after sludge dewatering system carries out processed, and filtrate is returned the homogeneous pond of step (1), and the mud cake outward transport is processed and put.
2. BDO chemical wastewater treatment technique according to claim 1 is characterized in that the omnidistance temperature of the biochemical section of described technique is 10～40 ℃, and biochemical reaction section pH value is 6～9.
3. BDO chemical wastewater treatment technique according to claim 1 is characterized in that described step (1) adds nutrition and regulates in homogeneous pond; And regulate the pH value in homogeneous pond.
4. BDO chemical wastewater treatment technique according to claim 3 is characterized in that wherein said nutrition is nitrogenous compound and phosphoric acid salt.
5. BDO chemical wastewater treatment technique according to claim 4 is characterized in that described nitrogenous compound is urea, ammonium salt or ammoniacal liquor.
6. BDO chemical wastewater treatment technique according to claim 3 is characterized in that described pH regulator is for regulating with acid or alkali.
7. BDO chemical wastewater treatment technique according to claim 1 is characterized in that the homogeneous pond water outlet of described step (1) pH is 5～8,10～45 ℃ of temperature.
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| CN 201110162235 CN102295384B (en) | 2011-06-16 | 2011-06-16 | 1,4-butanediol chemical waste water treatment technology |
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| CN 201110162235 CN102295384B (en) | 2011-06-16 | 2011-06-16 | 1,4-butanediol chemical waste water treatment technology |
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| CN102674627B (en) * | 2012-05-02 | 2014-12-17 | 国电宁夏英力特宁东煤基化学有限公司 | Method for biochemical treatment and standard discharge of sewage of coal chemical industry |
| CN103253827B (en) * | 2013-05-13 | 2014-05-21 | 同济大学 | Combined treatment method of 1,4-butanediol production wastewater |
| WO2014193889A1 (en) | 2013-05-31 | 2014-12-04 | Shell Oil Company | Glycol recovery with solvent extraction |
| CN105209415B (en) | 2013-05-31 | 2017-05-03 | 国际壳牌研究有限公司 | Process for the separation of an alkylene glycol |
| BR112015021060A2 (en) | 2013-05-31 | 2017-07-18 | Shell Int Research | process for the recovery of 1,4-butanediol and at least one selected co-product |
| US20160096790A1 (en) * | 2013-05-31 | 2016-04-07 | Shell Oil Company | Process for the separation of 1,4-butanediol |
| CN104291524B (en) * | 2014-09-22 | 2016-08-24 | 中国石化仪征化纤有限责任公司 | BDO oxidized waste water continuous treatment method |
| CN105036434A (en) * | 2015-08-26 | 2015-11-11 | 广东省工程技术研究所 | Method for treating landfill leachate nanofiltration concentrated solution through iron-carbon micro-electrolysis synergistic with microwave |
| CN107324613A (en) * | 2017-08-29 | 2017-11-07 | 博瑞德环境集团股份有限公司 | A kind of high concentration methionine production wastewater treatment device and method |
| CN112093972A (en) * | 2019-06-18 | 2020-12-18 | 上海睿易环境科技有限公司 | Biological industrial wastewater treatment system and method |
| CN110436709A (en) * | 2019-08-14 | 2019-11-12 | 浙江巨能环境工程有限公司 | A kind of high concentration waste water of cis-anhydride processing unit and processing method |
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| JPH09323091A (en) * | 1996-06-04 | 1997-12-16 | Hymo Corp | Aerobic treating device |
| CN100471798C (en) * | 2004-05-01 | 2009-03-25 | 姜峰 | Highly effective waste water treatment technique |
| JP4492268B2 (en) * | 2004-09-16 | 2010-06-30 | 栗田工業株式会社 | Biological treatment equipment |
| CN101113063A (en) * | 2006-07-28 | 2008-01-30 | 中国海洋石油总公司 | High-chlorine high-heat heavy crude sewage water treating method |
| CN100522850C (en) * | 2007-09-14 | 2009-08-05 | 中国成达工程公司 | Method for treating waste water of 1,4-butanediol production |
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