CN1064226A

CN1064226A - Deleading ion sieve

Info

Publication number: CN1064226A
Application number: CN 92102475
Authority: CN
Inventors: 王榕树
Original assignee: Tianjin University
Current assignee: Tianjin University
Priority date: 1992-04-10
Filing date: 1992-04-10
Publication date: 1992-09-09
Anticipated expiration: 2007-04-10
Also published as: CN1022983C

Abstract

A kind of the high-effect of Drinking Water purification, manufacture method of reproducible deleading ion sieve and the application of this ion sieve of being used for.

Deleading ion sieve is to carry on the attached titaniferous compound at silica gel, introduces an amount of lead ion, makes it maintenance through heat treatment, again with the lead ion wash-out, promptly has been covered with the specific sieve aperture that adapts with lead ion in this compound inside.During application, water body to be clean does not need any processing, can directly feed the adsorption column that this ion sieve is housed, thereby reaches the purpose of taking off plumbous purification.

Description

Deleading ion sieve

The invention belongs to method of chemical treatment and purify Drinking Water, to remove the lead contamination in the water body.

Plumbous pollution and murder by poisoning took place very early.At ancient rome era, lead is used for making water pipe, diet vessel etc. in a large number.Rich Roman selects the plumbous cooker of making for use, because plumbous system cooker can dissolve in lead acetate (being the sugar of lead) and food is sweetened.These vessel make ruling group of ancient Roman become the victim of lead poisoning just, have impelled the collapse decline of this ancient kingdom.Modern times, ceramic splendid attire acidic liquid with leaded glaze also all took place in states such as Yugoslavia, English, the U.S., impel plumbous stripping, and cause several lead poisoning incidents.

The approach that lead enters human body mainly is by containing lead dust gas, is subjected to the lead contamination water body through respiratory tract and alimentary canal and absorbed.Lead all can cause certain infringement to human central nervous system, medulla hematopoietic system, kidney and male gonad.Wherein, serious is plumbous to neural injury, from causing the peripheral neuritis beginning, motion and sensory disturbance occur.And then plumbous with blood inflow brain tissue, infringement cerebellum and brain cortex cell, the interference metabolic activity develops into diffuse brain damage.On July 15th, 1991, U.S.'s Newsweek (NEWSWEEK) has been published one piece of long report of Waldman (S.Waldmqn), points out that " age is most possibly suffered from lead poisoning 6 months children to 6 one full year of life, intellectual developmental disorder and abnormal behavior occur." micro-lead can also see through placenta materna, invades in the fetus body and brain tissue.The lead of this article is that " public health official scream: lead is children's No.1 environmental threat.”

Environment water is directly connected to the public's physical and mental health, thereby all very improvement of concern for the environment water quality of a lot of country, especially to Drinking Water water quality, not only standard improves, detect the control project and also be on the increase, nature, the investment intensity of processing is also in corresponding increase.In May, 1991, U.S.'s " chemistry and engineering magazine " (C﹠amp; EN) reported the new limit value of the new Pb in Drinking Water content of formulating of Environmental Protection Agency (EPA), this regulations of rules, lead concentration permissible value in the drinking water will be from the value of the limiting the quantity of (1ppb=10 of the 50ppb in past ^-9), be reduced to mean value 5ppb.These rules also require the plumbous whereabouts in the hundreds of millions cover dwelling houses of the whole nation of the public water supply station monitoring of various places.Environmental Protection Agency estimates " to carry out these rules and will cost 800,000,000 dollars every year, but confirm very easily extra-cost of its income." in view of this,, make strict more control to the potential lead contamination bigger now with harm reality, be very necessary.

At present, adopt ion sieve method efficiently, the directly work of deleading at home and abroad still is not reported from Drinking Water.The present invention is a purpose to take off plumbous and to increase water quality.Content is: a kind of application that is used for deleading ion sieve and manufacture method and this ion sieve of Drinking Water purification.This deleading ion sieve can be removed the lead ion in the water body efficiently, quickly and easily, and feed water can directly feed the exchange adsorption column without any need for preliminary treatment.Its water outlet can reach predetermined water standard satisfactorily.

The manufacture method of this deleading ion sieve is;

One, the preliminary treatment of carrier silica gel

Get commercially available primary colors silochrom (about 500 meters of specific surface ²/ gram, the aperture is about the 8-14 nanometer), wash secondary through the deionized water hot dipping, to remove the solid impurity of silica gel surface attachment, embathe once with ethanol again, to remove the organic matter on silica gel surface.Silica gel after washing places thermostatic drying chamber, 120 ℃ of drying and dehydratings, then, press substantially desired particle size range (as 20～50 orders) grind broken, after standard screen get final product after sieving the silica-gel carrier of a series of different-grain diameters.

Two, the preparation of matrix

Get titanium sulfate acyl (T _iOSO ₄H ₂O), be made into the solution that concentration is 0.6 mol (mol/L), put into the silica-gel carrier of treated mistake, the accent pH value is 1-2, boiled 6 hours, and ageing 18 hours, then β-the metatitanic acid of reaction formation is able to firm deposition in the hole of silica gel and on the surface.Filter and fully washing, to remove unreacted or not to be attached to material on the silica gel.Then, dried by the fire burning 4 hours down, promptly obtain silica gel-titaniferous compound complex matrix at 480～500 ℃.

Three, Qian introducing

Above-mentioned matrix is immersed in the lead acetate solution of 0.08 mol (mol/L),, reaches capacity to treat its adsorpting lead ion through 24 hours.Filter out, then the silica gel-titaniferous compound of maintenance (lead) compound not.

Four, heat treatment is the thermodynamics recrystallization stage

Silica gel-titaniferous compound (lead) compound that has adsorbed lead ion is inserted in the roasting apparatus, and temperature is 510 ± 10 ℃, and roasting is about 6 hours in air stream.At this moment, the lead of introducing is able to the fixed position by thermodynamic recrystallization in matrix.This is plumbous type ion sieve sieve nest.

Five, pickling becomes sieve

Hydrochloric acid with 0.2 mol (mol/L) elutes lead ion from above-mentioned sieve nest, has so just caused the ad-hoc location that is consistent with lead ion in above-mentioned sieve nest inside, thereby, can from water body, realize special efficacy selectivity exchange absorption to lead ion.

(i.e. absorption reaches saturated) ion sieve with having lacked can repeatedly use by this pickling regeneration.This is high-effect, reproducible deleading ion sieve.

The application process of this deleading ion sieve

This deleading ion sieve effectively contacts with water body to be clean, can remove the lead ion in the water body.

The way of contact can be carried out continuously, also may be carried out batchwise.Continuous Contact be the water body that will be subject to processing continuously by the ion sieve sieve nest layer in the bed (or post), can reach and take off plumbous purpose.Intermittent Contact needs to carry out in having the reactor of agitating device.Nature, the economy of Continuous Contact can be much better.

In distributed small-scale is handled, as mountain area barracks, house owed by a citizen water, or some interim contaminated sub-district water, can make general pillar equipment, interior this deleading ion sieve of filling is connected in relevant network of rivers end as filtering layer, enters the user.

In the collecting water supply system engineering, can consider that at former technology end set up a series of fixedly exchange adsorbent beds (as adopting 3), filler is this deleading ion sieve in the bed.Adopt the mode of continuous flow upstream contact to handle, make water body to be clean successively by the deleading ion sieve in each adsorbent bed.After using many days, when the ion sieve in the 1st that at first contacts with water body almost by sieve attached lead ion institute when saturated, deleading ion sieve in the 2nd sieves attached lead ion quantity and lacks, and the rest may be inferred, is sieved till the attached lead ion until last detects.After the 1st deleading ion sieve is saturated by lead ion institute, can withdraw from (with the hydrochloric acid leaching regeneration of 0.2 mol (mol/L), stand-by), at this moment, water body to be clean should be introduced the 2nd, and augment fresh (or regeneration) deleading ion sieve at the flow process end, so that carry out the last processing that contacts with water body.Adsorbent bed can be recycled.In a word, use this deleading ion sieve, bed formula contact technique routinely can reach satisfied clean-up effect.

Embodiment:

Example 1, certain Drinking Water, before and after this deleading ion sieve purified treatment, testing result such as table 1.

Table 1

Test item	Plumbous	Mercury	Cadmium	Chromium (sexavalence)	Total iron	Manganese
							Before the purified treatment (mg/litre)	0.098	0.001	0.009	0.045	0.12	0.05
Take off the plumbous back (mg/litre) that purifies	0.003	0.0008	0.006	0.042	0.03	0.04

Test item	Fluoride	Cyanide	Arsenide	Sulfate	Volatile Phenols
						Before the purified treatment (mg/litre)	0.98	0.01	0.02	208	0.001
Take off the plumbous back (mg/litre) that purifies	0.88	0.01	0.02	196	0.001

Example 2, certain water body, it is plumbous and add the dosing test of radioactivity radium to have made enriching, and before and after this deleading ion sieve purified treatment, testing result is listed in table 2.

Table 2

Test item	Plumbous (enriching)	Mercury	Cadmium	Chromium (sexavalence)	Total iron	Manganese
							Before the purified treatment (mg/litre)	3.50	0.001	0.009	0.045	0.12	0.05
Take off the plumbous back (mg/litre) that purifies	0.004	0.0008	0.006	0.042	0.04	0.04

Test item	Fluoride	Cyanide	Arsenide	Sulfate	Volatile Phenols	Radium-226 (joining people's test)
							Before the purified treatment (mg/litre)	0.98	0.01	0.02	208	0.001	5.0 Becquerel/liter
Take off the plumbous back (mg/litre) that purifies	0.86	0.01	0.02	190	0.001	0.01 Becquerel/liter

Experimental results show that:

1. this deleading ion sieve has remarkable function to the lead of removing in the water body, and effluent quality can be better than GB GB 5749-85(drinking water sanitary standard greatly), also can meet lead that the U.S. newly the works out new standard of limiting the quantity of, lead content can be removed below 5ppb.

2. plumbous 35 times of evidences of water distribution enriching, this deleading ion sieve can be applied to certain special water that needs strict restriction lead content.

3. water distribution adds the evidence of radium, and this deleading ion sieve has good effect for the radionuclide radium-226 of removing in the water body.

4. this deleading ion sieve has both certain effect to falling iron, to the optimization of other plurality of detection project, effect is arranged also.

Claims

1, a kind of be used for that Drinking Water purifies high-effect, reproducible deleading ion sieve is characterized in that by the titaniferous compound complex matrix that is attached on the silica gel, introduces through lead, the heat treatment maintenance becomes sieve series to get deleading ion sieve with pickling.

2, according to the said silica gel of claim 1, it is characterized in that the primary colors silochrom is washed secondary through the deionized water hot dipping, embathe once with ethanol again, place 120 ℃ of thermostatic drying chambers to dewater, to make granularity be 20～50 purpose silica-gel carriers through grinding fragmentation,

3,, it is characterized in that with concentration being the titanium sulfate acyl (TiOSO of 0.6 mol (mol/L) according to the said titaniferous compound complex matrix that is attached on the silica gel of claim 1 ₄H ₂O) solution is put into the silica-gel carrier that makes, and transferring pH value is 1～2, boils 6 hours, and ageing 18 hours is washed after filtration and fully, and baking was burnt 4 hours under 480～500 ℃, made silica gel titaniferous compound complex matrix,

4, introduce through lead according to claim 1 is said, it is characterized in that silica gel titaniferous compound complex matrix is immersed in the lead acetate solution that concentration is 0.08 mol (mol/L),, filter, make the not silica gel-titaniferous compound of maintenance (lead) compound through 24 hours,

5, according to the said heat treatment maintenance of claim 1, it is characterized in that it is 510 ± 10 ℃ roasting apparatus that silica gel-titaniferous compound (lead) compound is placed temperature, roasting made the plumbous type ion sieve sieve nest of maintenance about 6 hours,

6, said pickling becomes sieve according to claim 1, it is characterized in that the hydrochloric acid wash-out that the plumbous type ion sieve sieve nest concentration with maintenance is 0.2 mol (mol/L) removes lead ion, make deleading ion sieve, use deleading ion sieve absorption and take off lead and reach when saturated, adopt pickling regeneration.