CN102258985A

CN102258985A - Material for treating fluorine-containing drinking water, and preparation method thereof

Info

Publication number: CN102258985A
Application number: CN 201110160111
Authority: CN
Inventors: 郭家延
Original assignee: Individual
Current assignee: Individual
Priority date: 2011-06-15
Filing date: 2011-06-15
Publication date: 2011-11-30
Anticipated expiration: 2031-06-15
Also published as: CN102258985B

Abstract

The invention relates to a material for treating fluorine-containing drinking water. Water insoluble polyacrylamide gel is taken as raw materials, triethylene tetramine is taken as an aminating agent for grafting reaction, and a loaded and aminated hydroxymethyl derivative is prepared from metal-loaded, aminated and grafted gel. The loaded and aminated hydroxymethyl derivative material can be used for effectively and efficiently removing fluorine ions in drinking water in an area with high fluorine content, the fluorine content of the treated drinking water is lower than the national standard, and the material has the advantages of low cost, convenience in operation, high adsorption capacity, good fluorine removal effect, and the like, is easy to prepare and is suitable for large-scale production and can be stored for a long time; and the stability and repeatability can meet the fluorine removal work for actual drinking water.

Description

A kind ofly be used to handle material that contains fluorine drinking water and preparation method thereof

Technical field

The invention belongs to the material for water treatment technical field, relate to a kind of material that contains fluorine drinking water and preparation method thereof that is used to handle.

Background technology

Fluorine is a kind of trace element of needed by human, extensively is present in the natural water.Under normal conditions, the fluorine that human body is taken in from the external world is too much, can bad influence be arranged to health.The regulation of China's drinking water sanitary standard: the content of fluorine should not surpass 1.0mg/l in the drinking water, can cause multiple diseases such as fluorine dental plaque, fluorosis of bone, hepatitis and take in the high drinking-water of fluorine content for a long time, also can cause cancer, woman's acyesis, brain damage, Alzheimer syndrome and thyroid disorders, therefore fluoride in the fluorine-containing district of the height drinking water is effectively handled and had crucial meaning undoubtedly, and be subject to people's attention day by day.

Common defluorination method mainly can be divided into the precipitation method and absorption method two classes both at home and abroad at present, and wherein the precipitation method are applied to the processing of industrial fluoride waste more, and absorption method is used for containing the processing of fluorine drinking water more.Also have certain methods in addition, as freezing, ion-exchange-resin process, activated carbon method, electrodialysis etc., because reason such as cost height, fluoride removing rate be low, still seldom apply this area.

One, the precipitation method

The precipitation method are meant by adding chemicals and form the fluoride precipitation, or fluoride are attracted in the formed sediment and co-precipitation, the method for fluoride during separating solids sediment and then remove anhydrates then.In known precipitation method scheme, flocculent precipitation is a kind of not only economy of generally using both at home and abroad at present but also simple effectual method for treating water, but flocculant is water-soluble after utilizing this method defluorination, is difficult for removing.In addition, the high-concentration fluorine-contained waste water of industrial in the past processing all adopts calcium salt precipitation method usually, promptly throws in a certain amount of lime in water, and lime and fluorine ion generate CaF ₂Thereby precipitation reaches removal effect, though this technology is simple to operate, cost is lower, the body refuse sedimentation is slow.

Two, absorption method

Absorption method is to instigate fluorinated water to pass through adsorption column, utilizes adsorbent and fluorine ion to carry out chemical reaction, thereby removes the method for fluorine ion.Absorption method generally is with the fluorine ion absorber packed column of packing into, adopts dynamic suction type to carry out, and it is easy and simple to handle, is applicable to that the less drinking water of the water yield cooked advanced treating, and defluorination effect is better, but absorption method needs the particular processing agent, and prices are rather stiff.In the prior art,, fluorine ion absorber can be divided into and contain the aluminium adsorbent, contain the magnesium adsorbent according to the kind of the sorbent used material of this method, natural polymer adsorbent, rare-earth adsorbent and other class adsorbents.Its method commonly used comprises:

A, activated alumina absorption method

The activated alumina absorption method is general, the most effective most widely used in the world defluorination method, and the defluorination point of China more than 60% adopts this method.It has the adsorption capacity height, stable, be easy to advantages such as regeneration, but the equipment investment height, and the aluminium in the material may be lost in the water in the defluorination process, thereby health is caused adverse effect.

B, activated magnesia absorption method

Activated magnesia has bigger specific area, and its adsorption capacity is better than activated alumina, but this method can cause the total hardness of water outlet and pH to raise, and the regeneration complexity of activated magnesia, so also respective limits this method promote the use of on a large scale.

C, rare-earth oxide absorption method

The rare-earth oxide defluorinating agent is subjected to industry gradually and payes attention to because its adsorbance is big, pollution is little, and its adsorption capacity will be far longer than each aforementioned method.But, be difficult to be directly used in water treatment procedure, and cost an arm and a leg, so its scope of application still is very limited because its hydrous oxide generally all is Powdered.

Summary of the invention

The objective of the invention is to the problem that prior art exists is solved, provide a kind of and go that fluorine is effective, cost is low, be easy to the material that processing that large tracts of land promotes the use of contains fluorine drinking water, also provide simultaneously and be used to obtain this preparation methods.

For achieving the above object and research and development this to be used to handle the material that contains fluorine drinking water be a kind of with polyacrylamide (CH ₂CHCONH ₂) gel is the hydroxymethyl derivative after raw material obtains the load amination, its preparation method is:

One, aminating reaction: polyacrylamide gel and the distilled water weight proportion by 1: 100 times is positioned in the heating container, regulates pH to 8～9.5, under 40 ℃, added thermal agitation 10～15 minutes with NaOH; In container, be added dropwise to formaldehyde (HCHO) earlier, make phthalein amido part methylolation, slowly be added dropwise to triethylene tetramine (C again ₆H ₁₈N ₄); The molal quantity of pressing the polyacrylamide amine monomers calculates, the input material ratio of polyacrylamide gel, formaldehyde, triethylene tetramine is 1: 2.2～2.6: 2.3～2.8, reaction time is 2～2.5 hours, obtain the hydroxymethyl derivative gel after the amination, gel is taken out the back clean, dry with distilled water, gel being crushed to particle diameter is that 3～6mm pellet is standby again;

Two, metal load-reaction: configuration 1mg/ml aluminium standard reserving solution, hydroxymethyl derivative gel pellet after the amination is put into container, add this aluminum solutions, additional proportion is that every 1g gel pellet adds and converts aluminium standard reserving solution 10～20ml, transferring pH with hydrochloric acid is 2.5～3, keep solution in acidity, kept temperature 2～3 hours after solution is heated to 40 ℃～60 ℃, obtain the hydroxymethyl derivative after the load amination.

Deficiency at the prior art existence, technical solution of the present invention is to combine with absorption method in the fluorine-containing drinking water treatment by the flocculence during industrial fluorinated water is handled, start with from the improvement of flocculant, though with traditional soluble in water but polyacrylamide flocculant that be difficult for separating from water replaces to water-fast polyacrylamide gel, with triethylene tetramine is the aminating agent of graft reaction, by the gel after the grafting of metal loaded amine, at last with the fluorine ion in the form removal drinking water of metal and fluorine ion chelatropic reaction.

Compared with prior art, hydroxymethyl derivative material after the load amination of the present invention can be used for removing efficiently, apace the fluorine ion in the high fluorine-containing district large volume drinking water, fluorine content in the water that wherethrough was managed is lower than national standard, but this material has, and preparation is simple, with low cost, easy to operate, adsorption capacity is high, defluorination effect good, be suitable for advantages such as production in enormous quantities and long preservation, and stability and repeatability all can satisfy the defluorination of actual drinking water and deal with the work.

The specific embodiment

Below in conjunction with embodiment content of the present invention is described further, but actual fabrication product of the present invention and preparation technology's flow process are not limited in following embodiment.

By technical solution of the present invention, this is used to handle the preparation process that the material that contains fluorine drinking water is and is divided into the lower part: make polyacrylamide gel in the certain pH value (8～9.5) and the reaction of formaldehyde, the formation hydroxymethyl derivative; Add triethylene tetramine, with the hydroxymethyl derivative amination; Add metal ion, the hydroxymethyl derivative after the load amination.The step of an one concrete manufacture craft is as described below.

1, aminating reaction

Take by weighing the 1.0g polyacrylamide gel and place three-necked bottle, add 100ml distilled water, regulate pH to alkalescence (pH=8～9.5, optimum response pH is 9), under 40 ℃, added thermal agitation 10 minutes with NaOH; Dropwise add formaldehyde by dropping funel, and then slowly drip triethylene tetramine.Three's best material ratio is gel (molal quantity of pressing the polyacrylamide amine monomers calculates): formaldehyde: triethylene tetramine=1: 2.5: 2.6.

Polyacrylamide and formolite reaction make phthalein amido part methylolation, and process is as follows:

Hydroxymethyl derivative reacts with triethylene tetramine again, and process is as follows:

In following formula: n=500～800, m=2～3.The whole aminating reaction time is 2.5 hours.

Behind the aminating reaction gel is taken out from three-necked bottle, clean with distilled water, it is standby to dry, be crushed to the particle diameter 4mm left and right sides.

2, metal load

Configuration 1mg/ml aluminium standard reserving solution takes by weighing gel after the 1g amination in beaker, adds this aluminum solutions of 20ml, transfer pH=2.7 with hydrochloric acid, maintain acidity, kept temperature 2 hours after solution is heated to 40 ℃～60 ℃, obtain the hydroxymethyl derivative after the load amination.

Metal load-reaction process is as follows:

By remaining Al in the S-spectrophotometry solution ³⁺Content, concrete grammar is: determine the aluminum ions absorbance A in 640nm place with 721 ultraviolet specrophotometers, according to the aluminum ions concentration C of residue in the solution behind the aluminum ions calibration curve y=1.65x+0.02 calculating year aluminium ₁, draw and carry the aluminium rate, reflect the degree of metal load with this.It is big more to carry the aluminium rate, and defluorination effect is good more.The computing formula of carrying the aluminium rate is:

Wherein, C ₀Be aluminum ions initial concentration 1mg/ml.

Once carried out the fluorine-containing water sample Processing Test of laboratory simulation with regard to the result of use of this material in the development process of the present invention and to the multiple spot Processing Test and the investigation in the fluorine-containing pool of height.

The test result of use that this material is handled the fluorine-containing water sample of laboratory simulation sees Table 1, and consumption is that every liter of (l) water sample uses this material 0.3～0.5g.

Table 1: change of water quality (mg/l) before and after the treatment of laboratory simulation fluorinated water water sample

The Weinan Prefecture, Shaanxi Province belongs to high fluorine-containing water quality district, get this area's fluorinated volume severe overweight, representative three place's water samples, handle with this material, water sample 1 average fluorine-containing 10mg/l wherein, water sample 2 average fluorine-containing 6mg/l, water sample 3 average fluorine-containing 4mg/l, consumption are that every liter of (l) water sample uses this material 0.3～0.5g.Disposition sees Table 2:

Table 2: handle fluorinated water water sample front and back, Weinan change of water quality (mg/l)

Above-mentionedly experiment showed, that the defluorination effect of this material is obvious, use every index of back water quality all to reach national sanitary standard of drinking water.Compare with other defluorinating agents, this material absorption property is good, and low price, and economic benefit is obvious.In addition, the manufacture craft of this material is simple, cost is low, can easily this material be taken out from water behind the defluorination, has overcome the drawback that traditional material easily runs off, and can not cause secondary pollution.

Claims

1. one kind is used to handle the material that contains fluorine drinking water, it is characterized in that it be a kind of be hydroxymethyl derivative after raw material obtains the load amination with the polyacrylamide gel, its preparation method is:

1.1 aminating reaction: polyacrylamide gel and the distilled water weight proportion by 1: 100 times is positioned in the heating container, regulates pH to 8～9.5, under 40 ℃, added thermal agitation 10～15 minutes with NaOH; In container, be added dropwise to formaldehyde earlier, make phthalein amido part methylolation, slowly be added dropwise to triethylene tetramine again; The molal quantity of pressing the polyacrylamide amine monomers calculates, the input material ratio of polyacrylamide gel, formaldehyde, triethylene tetramine is 1: 2.2～2.6: 2.3～2.8, reaction time is 2～2.5 hours, obtain the hydroxymethyl derivative gel after the amination, gel is taken out the back clean, dry with distilled water, gel being crushed to particle diameter is that 3～6mm pellet is standby again;

1.2 metal load-reaction: configuration 1mg/ml aluminium standard reserving solution, hydroxymethyl derivative gel pellet after the amination is put into container, add this aluminum solutions, additional proportion is that every 1g gel pellet adds and converts aluminium standard reserving solution 10～20ml, transferring pH with hydrochloric acid is 2.5～3, keep solution in acidity, kept temperature 2～3 hours after solution is heated to 40 ℃～60 ℃, obtain the hydroxymethyl derivative after the load amination.