CN1238270C - Technological method of producing highly toxic heavy metal waste water treatment agent - Google Patents
Technological method of producing highly toxic heavy metal waste water treatment agent Download PDFInfo
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- CN1238270C CN1238270C CN 03126367 CN03126367A CN1238270C CN 1238270 C CN1238270 C CN 1238270C CN 03126367 CN03126367 CN 03126367 CN 03126367 A CN03126367 A CN 03126367A CN 1238270 C CN1238270 C CN 1238270C
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Abstract
The present invention provides a technical method for producing a heavy metal waste water treatment agent with high poison content, which belongs to the treating technology of metal ions. The treatment agent which is produced by the present invention has stronger selectivity and adsorption capacity to heavy metal ions, particularly hydrargyrum ions, cadmium ions and plumbum irons to adsorb and remove heavy metal ions in liquid to achieve the goal of water quality treatment, and moreover, the heavy metal ions are recovered according to requirements. The technical method of the present invention mainly comprises the steps: equivalent acid is added, the weight of which is 1.5 times more than that of the original silica gel to heat and out heating and pickle the original silica gel; wet air from a reaction still of sodium bromide/potassium bromide saturated liquid enters water vapor saturated air with silica gel to make the surface of the silica gel form a water molecular single layer; the hydrated silica gel, hexane and silane coupling agent carry out silanizing reactions to obtain the silanized silica gel; the silanized silica gel and an ethylenimine polymer carry out graft reactions and react with vinyl thioether to obtain the heavy metal waste water treatment agent with high poison content.
Description
Affiliated technical field
The invention belongs to the metal ion treatment technology, what relate generally to is a kind of processing method of producing high malicious heavy metal containing wastewater treatment agent.
Background technology
The main effect of treatment agent provided by the present invention relates to the processing to heavy metal wastewater thereby, and the heavy metal that is about in the waste water is removed as other heavy metal absorption that exists in lead, cadmium, mercury, chromium, copper and the waste water, makes waste water reach the heavy metal concentration and the total amount of permission.Also can be used for the elementary recovery of counterweight underground metal mining, the processing of municipal wastewater, trade effluent etc. relates to the social concern of environmental pollution and human body health.At present more to the treatment technology scheme of waste water, as: chemicals purifying treatment, ion exchange resin adsorption treatment etc., but the above measure effect that absorption is also removed to the heavy metal in the water is not satisfactory.
Summary of the invention
Purpose of the present invention promptly is to propose a kind of processing method of producing high malicious heavy metal containing wastewater treatment agent, its treatment agent of producing especially has stronger selectivity and adsorptive power to mercury ion, cadmium ion, lead ion to heavy metal ion, thereby with the heavy metal ion adsorbed removal in the liquid, reach the purpose of water conditioning, and make heavy metal ion obtain reclaiming as required.
The present invention realizes that processing method that above-mentioned purpose is taked comprises several steps in the following order:
Former silica gel is added in the reactor of corrosion resistant band stirring, add the normal acid of silica gel weight more than 1.5 times from elevated dosing vessel then, carry out heated and boiled and slowly stirring, in order to avoid damage silica gel; Stirring and pickling under bubble point temperature, the greasy dirt of flush away silica gel and the metal ion of surface attachment; To the logical cooling water temperature of chuck of reactor, make and emit silica gel when temperature of charge drops to normal temperature in the still then; The silica gel of emitting is in the filtration washing device, and the elimination acid solution is washed silica gel with deionized water then, stops washing when washing water show neutrality, carries out separating of silica gel and water, then silica gel is dried; When silica gel reaches constant weight, take out, enter next procedure.
Putting in the water vapor saturex through pickling and the silica gel that is dried to constant weight, start the damp atmosphere that air compressor bromizates sodium or Potassium Bromide saturated solution reactor and enter in the water vapor saturex, make the silica gel surface generate the water molecules individual layer; Between 2.0-5.0%, hydration is finished to the water ratio that records hydrated silica gel.
Hydrated silica gel is put into the reactor that another corrosion resistant band stirs, hexane elevated dosing vessel and silane coupling agent elevated dosing vessel through this reactor top, in reactor, put the hexane of quite former silica gel weight more than two times, the silane coupling agent more than 0.5 times into respectively, slowly mix then; Silica gel carries out the Silanization reaction under the normal temperature in reactor, the reaction times should guarantee more than 10 hours; Carry out separating of silica gel and raffinate after reaction is finished, again silanized silica gel is washed; Washed silanized silica gel is dried, get final product when the rate of body weight gain that records silanized silica gel is between 15-22%, this is a silanized silica gel.
Silanized silica gel is added in the reactor of a corrosion resistant band stirring, to reactor, add ethyleneimine polymkeric substance and deionized water from elevated dosing vessel respectively then, slowly mix; When temperature of reaction drops to below 40 ℃, add quite former silica gel weight 0.5-1.5 methyl alcohol doubly again, adding the back, to feed in reacting kettle jacketing that hot water heats and keep the reacting kettle jacketing water temperature be slowly to stir below 69 ℃, silica gel after recording grafting be former silica gel weight more than 1.5 times the time, grafting is finished.Graft reaction will wash after grafting silica gel and the solution separating after finishing.Wherein, the add-on of ethyleneimine polymkeric substance requires to be equal in weight with former silica gel at least, and it is more than the twice of former silica gel weight that the deionized water add-on requires.Dry and record water ratio, obtain a kind of low concentration heavy metal water treatment agent material in 10% discharging when following.
The low concentration heavy metal water treatment agent of above-mentioned acquisition and vinyl thioether reactant generate the high malicious heavy metal containing wastewater treatment agent of the present invention; The vinyl thioether is put into the reactor that a corrosion-resistant band stirs, add deionized water to reactor, and slowly stir the weight of the add-on of vinyl thioether 〉=above-mentioned low concentration heavy metal water treatment agent by elevated dosing vessel; Do not smash silica gel when preventing to stir, the add-on of deionized water is controlled at more than 2 times of above-mentioned low concentration heavy metal water treatment agent weight, and then adds the low concentration heavy metal water treatment agent that above-mentioned steps obtained, and treatment agent is all soaked; At this moment, starting hot water pump is sent to the hot water in the hot water tank in the chuck of reactor, solution temperature is remained between 45 ℃-70 ℃, reaction is carried out more than 20 hours, after reaction finishes, with material and solution separating, and then wash with deionized water, at last material is dried, stop oven dry and discharging when following 10%, obtain the high malicious heavy metal containing wastewater treatment agent material that the present invention produces to material water ratio.
The high malicious heavy metal containing wastewater treatment agent that processing method of the present invention obtained, it has very strong selectivity and adsorptive power to the heavy metal ion in liquid, formed inner complex is fixed on the silica gel active surface, but it can other light metal ion of chelating, as sodium, potassium, calcium, zinc etc., and there is the absorption that also can not influence heavy metal ion in these ionic.The treatment agent that the present invention obtained only needs the simple operation condition just can be used for handling heavy metal ion, as mercury, chromium, cadmium, lead, copper etc., and can recycle for 3000 times, and its adsorptive power just descends 10%.Since its unique selectivity and adsorptive power, and desorption process is very simple, the poisonous and harmful heavy metallic ion obtains recycling through concentrating, and treated water quality is effectively improved.Particularly processing, foodstuffs industry water and the tap water trace heavy metal ionic of nuclear industry waste water are removed so this treatment agent can be widely used in trade effluent, the fields such as elementary recovery of heavy metal ore deposit exploitation, to environmental improvement and human health, realize that the resources sustainable development strategy is very useful.
The specific functional groups of high malicious heavy metal containing wastewater treatment agent can make inner complex selectively in conjunction with high malicious heavy metal ion, especially adsorbs mercury ion, cadmium ion, lead ion.
Embodiment
The following examples can make those skilled in the art more fully understand processing method of the present invention, but do not limit the present invention in any way:
The processing method of producing high malicious heavy metal containing wastewater treatment agent is:
500 kilograms of former silica gel are added in the reactor of corrosion-resistant band stirring, add 1500 liters an equivalent hydrochloric acid then from elevated dosing vessel, also can be nitric acid; The beginning heated and boiled.Stirring velocity is controlled at below 60 rev/mins, in order to avoid damage silica gel.Stirring and pickling is 6 hours under bubble point temperature, then to the logical cooling water temperature of chuck of reactor, makes and emits silica gel when temperature of charge drops to normal temperature in the still.The silica gel of emitting is in the filtration washing device, and the elimination acid solution is washed silica gel with deionized water again, stops washing when washing water show neutrality, carries out separating of silica gel and water, then silica gel is dried.When silica gel reaches constant weight, take out, enter next procedure.
Putting in the water vapor saturex through pickling and the silica gel that is dried to constant weight, start the damp atmosphere that air compressor bromizates sodium (also Potassium Bromide) saturated solution reactor and enter in the water vapor saturex, make the silica gel surface generate the water molecules individual layer.At 4.5% o'clock, hydration was finished to the water ratio that records hydrated silica gel, then can guarantee carrying out smoothly of three-step reaction.
Hydrated silica gel is put into the reactor that another corrosion resistant band stirs,, in reactor, put 1500 liters normal hexane and 300 kilograms chloropropyl trichloro-silane into respectively, slowly mix then through the elevated dosing vessel of this reactor top.Hexane can also be to mix hexane, heptan hexane etc., and silane coupling agent can also be r-chloropropyl trimethoxyl silane, chloropropyl triethoxysilane; Also can be γ-An Bingjisanyiyangjiguiwan, to be KH-550, the external trade mark be (A-1100) etc. to its product grade.Beginning had a large amount of HCL gas to disengage in three hours, and the HCL gas that disengages generates hydrochloric acid as byproduct after the absorption tower water absorbs.Silica gel carries out the Silanization reaction under the normal temperature in reactor, the reaction times was at 16 hours.After finishing, reaction carries out separating of silica gel and solution, and first to silica gel again with washing with deionized water behind the hexane.Dry putting moisture eliminator into through the silica gel of deionized water wash, take out at 17% o'clock to the rate of body weight gain that records silica gel, this is a silanized silica gel.In addition, should put into the distillation recovery tower to washing exhausted hexane and distill recovery, recycling.
Silanized silica gel is added in the reactor of a corrosion resistant band stirring, to reactor, add 450 liters of polymines (PEI) and 1300 liters of deionized waters from elevated dosing vessel respectively then, slowly mix.The ethyleneimine polymkeric substance can also be a polyvinylamine, polymine-ODI, polymine-PO.The methyl alcohol that adds 600 liters after the cooling again adds that the back feeds in reacting kettle jacketing that hot water heats and slowly stirred 72 hours at 65 ℃ keeping the reacting kettle jacketing water temperature, the silica gel after recording grafting be former silica gel weight more than 1.5 times the time grafting finish.Graft reaction with grafting silica gel and solution separating, behind deionized water rinsing, is used half normal sulfuric acid scrubbing 1 time, 3 times, 1 normal ammonia scrubbing of deionized water wash 1 time, deionized water wash 3 times, methanol wash 2 times after finishing again.The grafting silica gel that methanol wash is crossed carries out wind at last, and it is for behind the sand sample, dries again.To recording water ratio, obtain a kind of low concentration heavy metal water treatment agent in 9% discharging when following.
Low concentration heavy metal water treatment agent that above-mentioned steps obtained and vinyl thioether reactant generate the high malicious heavy metal containing wastewater treatment agent material of the present invention: 800 kilograms of vinyl thioethers are put into the reactor that a corrosion-resistant band stirs, add 1400 liters of deionized waters by elevated dosing vessel to this reactor, and slowly stir.And then add the low concentration heavy metal water treatment agent material that above-mentioned steps obtained, the low concentration heavy metal water treatment agent material of adding is all soaked.At this moment, starting hot water pump is sent to the hot water in the hot water tank in the chuck of reactor, make solution temperature remain on 60 ℃, reaction was carried out at 28 hours, after reaction finishes, with material and solution separating, and then wash with deionized water, at last material is dried, stopped oven dry and discharging at 8% o'clock, obtain the high malicious heavy metal containing wastewater treatment agent that the present invention produces to material water ratio.
The high malicious heavy metal containing wastewater treatment agent that the present invention produces, its specific functional groups can make inner complex selectively in conjunction with high malicious heavy metal ion, especially adsorbs mercury ion, cadmium ion, lead ion.
Claims (1)
1, a kind of processing method of producing high malicious heavy metal containing wastewater treatment agent, feature of the present invention is: its processing method comprises several steps in the following order:
1), former silica gel is added in the reactor that corrosion resistant band stirs, adds the normal acid of silica gel weight more than 1.5 times from elevated dosing vessel then, carry out heated and boiled and slowly stir, in order to avoid damage silica gel; Stirring and pickling under bubble point temperature, the greasy dirt of flush away silica gel and the metal ion of surface attachment; To the logical cooling water temperature of chuck of reactor, make and emit silica gel when temperature of charge drops to normal temperature in the still then; The silica gel of emitting is in the filtration washing device, and the elimination acid solution is washed silica gel with deionized water then, stops washing when washing water show neutrality, carries out separating of silica gel and water, then silica gel is dried; When silica gel reaches constant weight, take out, enter next procedure;
Putting in the water vapor saturex through pickling and the silica gel that is dried to constant weight, start the damp atmosphere that air compressor bromizates sodium or Potassium Bromide saturated solution reactor and enter in the water vapor saturex, make the silica gel surface generate the water molecules individual layer; Between 2.0-5.0%, hydration is finished to the water ratio that records hydrated silica gel;
Hydrated silica gel is put into the reactor that another corrosion resistant band stirs, hexane elevated dosing vessel and silane coupling agent elevated dosing vessel through this reactor top, in reactor, put the hexane of quite former silica gel weight more than two times, the silane coupling agent more than 0.5 times into respectively, slowly mix then; Silica gel carries out the Silanization reaction under the normal temperature in reactor, the reaction times should guarantee more than 10 hours; Carry out separating of silica gel and raffinate after reaction is finished, again silanized silica gel is washed; Washed silanized silica gel is dried, get final product when the rate of body weight gain that records silanized silica gel is between 15-22%, this is a silanized silica gel;
Silanized silica gel is added in the reactor of a corrosion resistant band stirring, to reactor, add ethyleneimine polymkeric substance and deionized water from elevated dosing vessel respectively then, slowly mix; When temperature of reaction drops to below 40 ℃, add quite former silica gel weight 0.5-1.5 methyl alcohol doubly again, adding the back, to feed in reacting kettle jacketing that hot water heats and keep the reacting kettle jacketing water temperature be slowly to stir below 69 ℃, silica gel after recording grafting be former silica gel weight more than 1.5 times the time, grafting is finished; Graft reaction will wash after grafting silica gel and the solution separating after finishing; Wherein, the add-on of ethyleneimine polymkeric substance requires to be equal in weight with former silica gel at least, and it is more than the twice of former silica gel weight that the deionized water add-on requires; Dry and record water ratio, obtain a kind of low concentration heavy metal water treatment agent material in 10% discharging when following;
2), the low concentration heavy metal water treatment agent of above-mentioned acquisition and vinyl thioether reactant generate the high malicious heavy metal containing wastewater treatment agent of the present invention; Its processing method is as follows:
The vinyl thioether is put into the reactor that a corrosion-resistant band stirs, add deionized water to reactor, and slowly stir the weight of the add-on of vinyl thioether 〉=above-mentioned low concentration heavy metal water treatment agent by elevated dosing vessel; Do not smash silica gel when preventing to stir, the add-on of deionized water is controlled at more than 2 times of above-mentioned low concentration heavy metal water treatment agent weight, and then adds the low concentration heavy metal water treatment agent that above-mentioned steps obtained, and treatment agent is all soaked; At this moment, starting hot water pump is sent to the hot water in the hot water tank in the chuck of reactor, solution temperature is remained between 45 ℃-70 ℃, reaction is carried out more than 20 hours, after reaction finishes, with material and solution separating, and then wash with deionized water, at last material is dried, stop oven dry and discharging when following 10%, obtain the high malicious heavy metal containing wastewater treatment agent material that the present invention produces to material water ratio.
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| CN 03126367 CN1238270C (en) | 2003-09-21 | 2003-09-21 | Technological method of producing highly toxic heavy metal waste water treatment agent |
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| CN 03126367 CN1238270C (en) | 2003-09-21 | 2003-09-21 | Technological method of producing highly toxic heavy metal waste water treatment agent |
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| CN1238270C true CN1238270C (en) | 2006-01-25 |
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| CN102814166A (en) * | 2011-06-08 | 2012-12-12 | 工信华鑫科技有限公司 | Preparation method of copper ion special-purposed adsorption material |
| CN102671644B (en) * | 2012-05-28 | 2014-12-31 | 陕西厚亿节能环保新材料科技有限公司 | Silica gel loaded polymeric amine and 8-hydroxyquinoline dual-function base compound adsorption material and preparation method |
| CN109161703A (en) * | 2018-09-17 | 2019-01-08 | 石家庄凯念科技有限公司 | A kind of method of ion type rareearth mine mother liquor concentrations |
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Granted publication date: 20060125 Termination date: 20170921 |