The preparation method of the compound little electrolysis filtrate of a kind of carbon back of porous
Technical field
The present invention relates to a kind of preparation method of the compound little electrolysis filtrate of carbon back of the porous for sewage disposal, belong to the technical field of material of little electrolysis filtrate.
Background technology
Traditional little electrolysis filtrate just began to use in the seventies in 20th century; it mainly is that iron filings particle and coke granule are mixed the back use; utilize the bigger material of these two kinds of potential differences of iron and carbon to form galvanic cell reaction in acid waste water, the electric current that utilizes little electrolysis of galvanic cell to produce comes organism or the heavy metal ion in the redox water.Traditional Fe-C Micro Electrolysis Method has that cost is low, the advantage of wide adaptability, but also exist harden easily, problem such as passivation, influence lasting reaction effect.If the way with recoil regularly prevents from hardening and passivation, because the specific gravity difference of iron filings and coke granule is too big, the speed that the recoil back falls has larger difference, several times after the recoil, the layering gradually of iron filings and coke granule, thus had influence on the effect of little electrolysis.In addition, because micro-electrolysis reaction has only iron filings consuming, coke granule is not loss substantially, and after the time grown, iron-carbon ratio can change, and the effect of little electrolysis also can change, and can't reach the effect of steady operation.Therefore, the popularization of traditional Fe-C Micro Electrolysis Method is hindered.
In order to solve the problem that the conventional iron carbon micro-electrolysis exists, also the someone has considered various ways, by the retrieval to the prior art document, Granted publication is number for mentioning in the Chinese invention patent of CN1048005C " Fe-C flocculation bed device ", the loose material particle that adds as porous plastics grain and so in traditional iron-carbon micro-electrolysis filtrate suppresses to harden, but still can not solve the problem that reaction back iron-carbon ratio progressively changes.Publication number is that the Chinese invention patent " preparation method who is used for the porous catalytic filler of interior electrolysis process " of CN1569656A is mentioned, the bulk idiosome that to adopt ultra high molecular polyethylene be the honeycomb hole of 50mm with the bonding diameter that is pressed into many vertical interlaceds in length and breadth of iron powder, carbon dust and little amount of catalyst, the heat treating method by about 220 ℃ is cured again.Thisly can avoid the problem that hardens to a certain extent with the bonding bulk that is pressed into honeycomb hole of polyethylene, but the preparation cost height, volume takies greatly, and can't solve the stepping problem of iron-carbon ratio.
Summary of the invention
The objective of the invention is: at the deficiency of above-mentioned existence, the preparation method of the compound little electrolysis filtrate of a kind of porous carbon back is provided, do not add other packing material that does not participate in micro-electrolysis reaction or matrix materials, directly one or more metal powders and carbonaceous mesophase phase powder are fully mixed the back compacting sintering and form.
For achieving the above object, the technical solution used in the present invention is:
The preparation method of the compound little electrolysis filtrate of a kind of carbon back of porous, one or more metal-powders that with mass ratio are 1-9:1 at normal temperatures mix fully with carbonaceous mesophase phase powder, compression moulding then, under the condition of anoxybiotic to its heating, the control temperature is 500-900 ℃, insulation 40-80min naturally cools to room temperature then and gets final product.
The above-mentioned metal-powder of mentioning is iron powder, and the particle size range of described iron powder is 10-60 orders.
Be the mixture of iron powder and copper powder, iron powder and manganese powder or iron powder and copper powder, manganese powder perhaps, wherein iron powder accounts for 50%-90% of mixture quality.
Above-mentioned its particle size range of carbonaceous mesophase phase powder of mentioning is 10-60 orders.
The compound little electrolysis filtrate of the carbon back of the porous that the present invention is prepared has tangible characteristics, not only the positive and negative pole material of little electrolysis is compounded in the good integral particle of same intensity, can tolerate regular recoil repeatedly and the layering separation problem of metal and carbon does not take place, avoid hardening; This particle also has vesicular structure simultaneously.This porous is not the macropore of the cellular macroscopic view in the aforesaid CN1569656A patent of invention of picture, but similar gac is nanometer level microporous, specific surface area reaches more than 30 meters squared per gram, thereby has an ability of certain adsorption and enrichment pollutent, the Pollutant levels of granule interior are raise, be conducive to the raising of micro-electrolysis reaction effect.Because metal powder and carbon dust that the compound little electrolysis filtrate of this carbon back uses are all thinner, size is less than 60 orders, and be not use other bonding composition compacting sintering to form after mixing, carrying out along with micro-electrolysis reaction, after the corrosion that metal powder takes place and the consumption, adjacent with it carbon dust will come off, and because carbon dust is very thin very light, can be in the process of recoil and normal operation, nature is discharged with these current, guaranteed that the metal of the compound little electrolysis filtering material particle of carbon back and the mass ratio of carbon keep stable, thereby reaction effect is also more stable.Because carbon dust can be discharged smoothly naturally, does not have the variation of component proportions, can not occur again hardening and passivation, therefore just need not to carry out the replacing of filtrate, only need regular replenishment to get final product, reduced the operation difficulty.
Advantage of the present invention is: mix fully with carbonaceous mesophase phase powder with one or more metal-powders, then behind compression moulding and the process high temperature sintering, obtain the compound little electrolysis filtrate of carbon back of porous, the complex body that the compound little electrolysis filtering material particle of carbon back that utilizes this method preparation is metal and carbon, itself can form more micropore, specific surface area reaches more than 30 meters squared per gram, can carry out micro-electrolysis reaction in adsorption and enrichment, improves reaction efficiency; Have the above ultimate compression strength of 5MPa simultaneously, tolerate powerful back flushing, solved the passivation of traditional little electrolysis filtrate and the problem that hardens.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.Wherein cited embodiment is just in order to illustrate the present invention, and do not lie in restriction protection scope of the present invention.
The preparation method of the compound little electrolysis filtrate of the carbon back of a kind of porous of the present invention is: one or more metal-powders that with mass ratio are 1-9:1 at normal temperatures mix fully with carbonaceous mesophase phase powder, compression moulding then, under the condition of anoxybiotic to its heating, the control temperature is 500-900 ℃, insulation 40-80min naturally cools to room temperature then and gets final product.
Embodiment 1
After 60 purpose iron powders and 60 purpose carbonaceous mesophase phase powder are the mixed of 1:1 with the quality, be pressed into the 12mm diameter, the disk shape particle of thickness 3mm is heated to 500 ℃ of insulations then and naturally cools to room temperature after 1 hour.
Embodiment 2
Be the mixed of 9:1 with 60 purpose carbonaceous mesophase phase powder with the quality with 60 purpose iron powders, be pressed into the 12mm diameter, the disk shape particle of thickness 3mm naturally cools to room temperature after being heated to 900 ℃ of insulation 40min then.
Embodiment 3
After 60 purpose iron powders and 60 purpose copper powders are fully mixed in each ratio of 50% of quality, with mixed metal powder and the mixed of carbonaceous mesophase phase powder with mass ratio 2:1, be pressed into the 12mm diameter, the disk shape particle of thickness 3mm is heated to 800 ℃ of insulations then and naturally cools to room temperature behind the 80min.
Embodiment 4
With 60 purpose iron powders and 60 purpose manganese powders after the mixed with mass ratio 10:1, and then with mixed metal powder and the mixed of carbonaceous mesophase phase powder with mass ratio 4:1, be pressed into the 12mm diameter, the disk shape particle of thickness 3mm is heated to 700 ℃ of insulations then and naturally cools to room temperature behind the 50min.
Embodiment 5
After 60 purpose iron powders and 60 purpose copper powders and the mixed of 60 purpose manganese powders with mass ratio 20:1:1, then with mixed metal powder and the mixed of carbonaceous mesophase phase powder with mass ratio 5:1, be pressed into the 12mm diameter, the disk shape particle of thickness 3mm is heated to 600 ℃ of insulations then and naturally cools to room temperature after 1 hour.