CN103183395B - Decolorizing trapping agent - Google Patents

Decolorizing trapping agent Download PDF

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Publication number
CN103183395B
CN103183395B CN201310084901.9A CN201310084901A CN103183395B CN 103183395 B CN103183395 B CN 103183395B CN 201310084901 A CN201310084901 A CN 201310084901A CN 103183395 B CN103183395 B CN 103183395B
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parts
aluminium
content
iron
reaction
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CN103183395A (en
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庞红信
芮小平
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PANG JINTONG
TANG YINGKUANG
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PANG JINTONG
TANG YINGKUANG
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Abstract

The invention provides a decolorizing trapping agent which comprises basic aluminum chloride, anionic polyacrylamide, sodium chlorate, powdered activated carbon or high-activity diatomite according to the weight ratio. The decolorizing trapping agent has the effects of decolorizing wastewater and removing harmful substances such as COD (chemical oxygen demand), cyanide and the like, and can replace a coagulating agent-polyferric sulfate or polyaluminium chloride generally used in the process of treating phenol and cyanogen wastewater in domestic coking industry; and the outlet water after the wastewater is treated with the decolorizing trapping agent meets the wastewater recycling or emission standards, and the indexes such as the colority, the COD, the cyanide and the like of the outlet water can reach the relevant national standards of industrial wastewater recycling or emission.

Description

A kind of decolouring trapping agent
Technical field
The present invention relates to coal coking industry wastewater containing phenol and cyanide processing technology field, be especially exclusively used in a kind of decolouring trapping agent that coal coking industry wastewater containing phenol and cyanide is processed.
Technical background
The important component part of coal tar Hua Shi China chemical industry, China's coke annual production accounts for the more than 70% of the whole world, in the many provinces and cities of China especially in Shanxi, the large province of coal such as Inner Mongol and Shaanxi, the coke-oven plant of scale from hundreds of thousands of ton/year to millions of tons/year is seen everywhere.In the process of coke production, process for refining due to coking and gas purification and coking by-products, give off and contain in a large number phenol, cyanogen, the coking wastewater containing phenol and cyanide of the hazardous and noxious substances such as oil and ammonia nitrogen, wherein process can not (integrated wastewater discharge standard GB8978-1996) up to standard for the coking wastewater containing phenol and cyanide of many coke-oven plants, although this coking wastewater containing phenol and cyanide is that to take the remained ammonia producing in ammonia still process process be main source, but be wherein also mixed with a large amount of crude benzol Separation of Waters, gas condensed water and separating methanol water and sanitary sewage etc., the contained pollutent of coking wastewater containing phenol and cyanide comprises phenols, Ppolynuclear aromatic heterogeneous ring compound and nitrogen, sulphur, cyanogen compound etc., a kind of typical pollutent and the high trade effluent of hardly degraded organic substance content, due to aldehydes matter content in coking wastewater containing phenol and cyanide high (800-1200mg/L), biochemical system is had to obvious restraining effect, containing difficult degradation type organics such as quinoline, indoles, arsenic pyridine, carbazole, biphenyl, terphenyls, waste water ammonia nitrogen concentration is high, and variation water quality is large, prussiate in waste water has very strong toxicity, chroma in waste water is high, is the features such as dark color of soy sauce and difficult removal, so the processing of coking wastewater containing phenol and cyanide, is also a great problem of domestic and international field of waste water treatment all the time.
Trace it to its cause: Yi Shi China does not have the special disposal technique for coking industry wastewater containing phenol and cyanide, the treatment process of coking industry wastewater containing phenol and cyanide is all that traditional water technology has been carried out to adaptability reform and combination at present, apply to the processing of coking chemical waste water, although also obtained certain effect; The 2nd, the biochemical processing being widely adopted in coking waste water treatment process, to having relatively high expectations of practitioner's technical quality and treatment facility; The 3rd, the domestic special medicament that does not carry out advanced treatment for this waste water back segment, generally taking at present to add traditional coagulating agent Polyferric Sulfate (or poly-aluminium) is processed, cause that water outlet color after advanced treatment is poor, COD content is generally higher at the total cyanogen content of water outlet of 220-300mg/L left and right and part coke-oven plant, can not qualified discharge or reuse water recycling.
The main technique route that domestic coking industry wastewater containing phenol and cyanide is processed is: oil removing → air supporting → equalizing tank → biochemical system A2/0 (anaerobism → anoxic → aerobic) or A2/02 (anaerobism → anoxic → aerobic → aerobic) → second pond → coagulative precipitation tank → catalytic oxidation → effluent reuse.
This operational path can be divided into three phases: leading portion pre-treatment → stage casing biological treatment → back segment coagulating treatment, this technique has been strengthened leading portion pre-treatment, be provided with grease removal tank and flotation cell, and be provided with 24 hours equalizing tanks and accident pool, prevent the impact of change of water quality on biochemical system, back segment completes the water outlet after biochemical denitrification phenol removal has been carried out to coagulating treatment, and generally aeration time is 24 hours, processes waste water and returned sluge and enters aeration tank simultaneously.In the back segment coagulating treatment stage of above-mentioned technique, generally adopt and add traditional coagulating agent Polyferric Sulfate or poly-aluminium at present, although the water outlet after this art breading meets wastewater discharge standard, the colourity of water outlet (best also more than 200 times) and COD content (300mg/L left and right) still can not be up to standard, ammonia nitrogen also total cyanogen contents higher, even many enterprises exist exceed standard more.
Summary of the invention
The object of the invention is a kind of a kind of decolouring trapping agent that there is good decolouring, removes the objectionable impuritiess such as COD and prussiate using in the special back segment advanced treatment process for coking industry wastewater containing phenol and cyanide.
In order to achieve the above object, main component of the present invention comprises: aluminium chlorohydroxide iron, anionic polyacrylamide, sodium chlorate, powdered carbon (or high reactivity diatomite) form according to mass ratio.
In order to achieve the above object, the invention provides following technical scheme: a kind of decolouring trapping agent, by following composition, according to weight ratio, formed 60 parts-70 parts of aluminium chlorohydroxide iron, 0.08 part-0.1 part of powdery anionic polyacrylamide, 30 parts-35 parts of sodium chlorate, 35 parts of-40 parts of compositions of wood powder shaped activated carbon.
In technique scheme, described wood powder shaped activated carbon iodine sorption value >=950mg/g, methylene blue number >=10mL.
In technique scheme, described wood powder shaped activated carbon granularity is 180 object particles.
Preferred technical scheme, 70 parts of aluminium chlorohydroxide iron, 0.08 part of anionic polyacrylamide, 35 parts of sodium chlorate, 35 parts of wood powder shaped activated carbons.
The invention provides the alternate embodiments of technique scheme, use high reactivity diatomite to replace wood powder shaped activated carbon, concrete technical scheme is: a kind of decolouring trapping agent, by following composition, according to weight ratio, formed 60 parts-70 parts of aluminium chlorohydroxide iron, 0.08 part-0.1 part of powdery anionic polyacrylamide, 30 parts-35 parts of sodium chlorate, 30 parts of-40 parts of compositions of high reactivity diatomite.
Preferred technical scheme, 70 parts of aluminium chlorohydroxide iron, 0.1 part of powdery anionic polyacrylamide, 35 parts of sodium chlorate, 40 parts of compositions of high reactivity diatomite.
In technique scheme, described high reactivity diatomite granularity is 325 object particles.
In technique scheme, described high reactivity diatomite iodine sorption value >=950mg/g, methylene blue number >=10mL.
The decolouring trapping agent that the present invention makes has waste water decoloring, removes the effect of COD and prussiate etc., the coagulating agent Polyferric Sulfate or the poly-aluminium that in can subrogate country, in coking industry wastewater containing phenol and cyanide back segment advanced treatment process, generally adopt, through using the present invention to decolour, water outlet that trapping agent carries out after wastewater treatment meets waste water reclamation utilization or emission standard, and the indexs such as the colourity of water outlet, COD and prussiate can reach trade effluent recycle or outer row's relevant national standard.
Embodiment
Below in conjunction with the present invention, technical scheme of the present invention is clearly and completely described, obviously, described embodiment is only the present invention's part embodiment, rather than whole embodiment.Embodiment based in the present invention, those of ordinary skills, not making the every other embodiment obtaining under creative work prerequisite, belong to the scope of protection of the invention.
A decolouring trapping agent, consists of by weight following composition, 60 parts-70 parts of aluminium chlorohydroxide iron, 0.08 part-0.1 part of powdery anionic polyacrylamide, 30 parts-35 parts of sodium chlorate, 35 parts of-40 parts of compositions of wood powder shaped activated carbon.Wherein, wood powder shaped activated carbon can substitute by use office active diatom soil.
Described wood powder shaped activated carbon or high reactivity diatomite iodine sorption value >=950mg/g, methylene blue number >=10mL.
Described aluminium chlorohydroxide iron can be used the highly purified finished product of buying on market, otherwise can make effect not reach desirable effect.
For improving effect of the present invention, the invention provides the manufacture craft of aluminium chlorohydroxide iron:
The iron raw material of doing of aluminium chlorohydroxide is used degree Beaume 19,110 parts of the by-product hydrochloric acids of density 1.15g/L; Al 2o 3content is 20 parts of 28% bauxitic clays; Al 2o 3content is 140 parts of 60% aluminium scrap ashes; 10 parts of iron oxide reds; Al 2o 3content is that 53%, CaO content is that 10 parts of 13% calcium aluminates are prepared aluminium chlorohydroxide iron solid.
Step 1,110 parts of the by-product hydrochloric acids of degree Beaume 19 are placed in to enamel reaction still, note controlling total amount and can not be greater than maximum still capacity, add a certain amount of tap water dilute hydrochloric acid to till degree Beaume 12.Then 20 parts of the activated bauxites of alumina content 28% are evenly dropped in hydrochloric acid, in reactor, pass into high pressure steam simultaneously, pressure remains on 8MPa and opens mechanical stirring and makes bauxitic clay fully contact and react with hydrochloric acid, and temperature of reaction system keeps 110 ℃ to continue 2 hours;
Step 2, in batches by Al 2o 3content is that 140 parts of 60% aluminium scrap ashes are gently thrown in the liquor alumini chloridi making above in reactor, do not stop to stir, rotating speed is less than 60r/min, and keeps temperature of reaction system 110-140 ℃ simultaneously, because this reaction is that thermopositive reaction please notes control blanking rhythm, in order to avoid spilling, hydrothermal solution hurts sb.'s feelings;
Step 3,10 parts of operations with reference to step 2 of iron oxide red are dropped into reactors participate in polyreactions;
Step 4, reaction so far, can obtain aluminium chlorohydroxide ferrous solution, but solution basicity is too low, can not meet requiredly, also need Al 2o 3content is 53%, CaO content is that 10 parts of operations with reference to step 2 of 13% calcium aluminate drop into and in reactors, adjust the basicity that improves solution, this complex reaction is complete, just can make high and the easy dry and good aluminium chlorohydroxide ferrous solution of flocculating property of alumina content, so far, obtain qualified aluminium chlorohydroxide ferrous solution, at least need to expend 4-5h;
Step 5, to continuing again logical steam-stirring 1h in above aluminium iron polychloride solution system, be the process that reaction system completes slaking, the concentration of the mixing solutions making is high, need to add tap water to be diluted to degree Beaume 22-23; Then, shift mixing solutions to cooling in settling tank, standing 7 days or adopt plate filter by sediment filtering, get supernatant liquor pending;
Step 6, the supernatant liquor after step 5 is standing with the rotating drum dryer of logical 280 ℃ of constant temp. steams are dried processing, obtain solid alkali formula aluminium chloride ferrum product.
Then, use 70 parts of aluminium chlorohydroxide iron, molecular weight 1,200 ten thousand, high degree of hydrolysis, containing 0.08 part of the powdery anionic polyacrylamide of granularity 120 order >=90%, 30 parts of the sodium chlorate of butt 99%, 40 parts of the wood powder shaped activated carbons of 180 order granularities (iodine sorption value >=950mg/g, methylene blue number >=10mL), four kinds of pressed powders mix and obtain special agent of the present invention by machinery equipment---decolouring trapping agent.
The invention provides the alternate embodiments of technique scheme, use high reactivity diatomite to replace wood powder shaped activated carbon, concrete technical scheme is: a kind of decolouring trapping agent, by following composition, according to weight ratio, formed, 70 parts of aluminium chlorohydroxide iron, molecular weight 1,200 ten thousand, high degree of hydrolysis, containing 0.1 part of the powdery anionic polyacrylamide of granularity 120 order >=90%, 35 parts of the sodium chlorate of butt 99%, granularity 325 object high reactivity diatomite (iodine sorption value >=950mg/g, methylene blue number >=10mL) 40 parts, four kinds of pressed powders mix and obtain special agent of the present invention with equipment---decolouring trapping agent.
The principle of disposing of sewage of active diatom soil is: diatomite is to take extinct plants and animal diatom as main biogenic sediment ore deposit, and its main component is SIO 2, inside is noncrystal porous structure.Through 1400 ℃ of high-temperature activations, process and adopt permanent magnet to implement the active diatom soil that magnetic strengthens, because internal void is flourishing, specific surface area is large, the positively charged ion in water and organism etc. being had to stronger charge neutrality and absorption property.
Active diatom soil adds in sewage, under stirring action, a large amount of positive charge group during the negative charge on bergmeal particle surface is easy to and in sewage, causes the ζ-potential of colloid in system or micelle particle to reduce rapidly de-steady, thereby makes the contaminant particle in water that sedimentation occur fast.Meanwhile, diatomite has large specific surface area, makes it have stronger absorption property, and particulate in water is adsorbed onto to its surface, instantaneous sinking and water body generation centrifugation.
High reactivity diatomite can be prepared voluntarily, the diatomite material that buying is come is after fragmentation, pulverize (granularity 325 orders) are processed, dropping into end is provided with in the rotary kiln of permanent magnet, the huge thermal bake-out producing with raw coal combustion, temperature of reaction is controlled at 1370 ℃-1480 ℃, continue roasting 48 hours above after cooling, by the examination criteria detection of active diatomite of wood powder shaped activated carbon: the alternative wood powder shaped activated carbon of active diatom soil of iodine sorption value >=950mg/g and methylene blue number >=10mL/g.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; can expect easily changing or replacing, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion by the described protection domain with claim.

Claims (1)

1. a decolouring trapping agent, consists of 60 parts-70 parts of aluminium chlorohydroxide iron, 0.08 part-0.1 part of powdery anionic polyacrylamide, 30 parts-35 parts of sodium chlorate, 35 parts of-40 parts of compositions of wood powder shaped activated carbon according to weight ratio following composition; Described wood powder shaped activated carbon is 180 order particles; Described wood powder shaped activated carbon iodine sorption value >=950mg/g, methylene blue number >=10mL;
It is characterized in that, described aluminium chlorohydroxide iron is prepared by following technique:
The iron raw material of doing of aluminium chlorohydroxide is used degree Beaume 19,110 parts of the by-product hydrochloric acids of density 1.15g/L; Al 2o 3content is 20 parts of 28% bauxitic clays; Al 2o 3content is 140 parts of 60% aluminium scrap ashes; 10 parts of iron oxide reds; Al 2o 3content is that 53%, CaO content is that 10 parts of 13% calcium aluminates are prepared aluminium chlorohydroxide iron solid;
Step 1) 110 parts of the by-product hydrochloric acids of degree Beaume 19 are placed in to enamel reaction still, note controlling total amount and can not be greater than maximum still capacity, add a certain amount of tap water dilute hydrochloric acid to degree Beaume 12, then 20 parts of the activated bauxites of alumina content 28% are evenly dropped in hydrochloric acid, in reactor, pass into high pressure steam simultaneously, pressure remains on 8MPa and opens mechanical stirring and makes bauxitic clay fully contact and react with hydrochloric acid, and temperature of reaction system keeps 110 ℃ to continue 2 hours;
Step 2) in batches by Al 2o 3content is that 140 parts of 60% aluminium scrap ashes are gently thrown in the liquor alumini chloridi making above in reactor, do not stop to stir, rotating speed is less than 60r/min, and keeps temperature of reaction system 110-140 ℃ simultaneously, because this reaction is that thermopositive reaction please notes control blanking rhythm, in order to avoid spilling, hydrothermal solution hurts sb.'s feelings;
Step 3) by 10 parts of iron oxide reds with reference to step 2) operation drop into reactor and participate in polyreaction;
Step 4) reaction so far, can obtain aluminium chlorohydroxide ferrous solution, but solution basicity is too low, can not meet requiredly, also needs Al 2o 3content is 53%, CaO content is that 10 parts of 13% calcium aluminates are with reference to step 2) operation drop into and in reactor, adjust the basicity that improves solution, this complex reaction is complete, just can make high and the easy dry and good aluminium chlorohydroxide ferrous solution of flocculating property of alumina content, so far, obtain qualified aluminium chlorohydroxide ferrous solution, at least need to expend 4-5h;
Step 5) in above aluminium iron polychloride solution system, continuing logical steam-stirring 1h, is the process that reaction system completes slaking again, and the concentration of the mixing solutions making is high, need to add tap water to be diluted to degree Beaume 22-23; Then, shift mixing solutions to cooling in settling tank, standing 7 days or adopt plate filter by sediment filtering, get supernatant liquor pending;
Step 6) with the rotating drum dryer of logical 280 ℃ of constant temp. steams step 5) supernatant liquor after standing is dried processing, obtains solid alkali formula aluminium chloride ferrum product.
CN201310084901.9A 2013-03-18 2013-03-18 Decolorizing trapping agent Expired - Fee Related CN103183395B (en)

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109052595A (en) * 2018-08-20 2018-12-21 上海优帛环境技术有限公司 A kind of compound coagulant quickly handled for quenching waste water and its application method
CN109384276B (en) * 2018-10-22 2022-05-31 鞍山市鑫诚水处理有限公司 Wastewater treatment agent for efficiently decoloring, decyanating and degrading COD (chemical oxygen demand)
WO2020231802A1 (en) * 2019-05-10 2020-11-19 Sabre Intellectual Property Holdings Llc Compositions and methods using chlorate to break polyacrylamide
CN112239245A (en) * 2019-07-18 2021-01-19 山东万和环保节能技术有限公司 Decolorizing agent for removing COD and cyanide
CN110759393A (en) * 2019-10-30 2020-02-07 陕西驭腾实业有限公司 Cyanogen removing agent and preparation method and application thereof
CN114455617B (en) * 2022-02-24 2023-07-21 肇庆南都再生铝业有限公司 Method for producing calcium aluminate by using aluminum ash

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051157A (en) * 1989-10-21 1991-05-08 西安公路学院 A kind of composite macromolecule coagulant and compound method

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1051157A (en) * 1989-10-21 1991-05-08 西安公路学院 A kind of composite macromolecule coagulant and compound method

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