CN1623652A - Active carbon activating treatment for zeolite and its preparation application and regeneration - Google Patents

Abstract

A process for activating and regenerating zeolite includes such steps as choosing the grayish-green clinoptilolite particles, calcining in the oxygen filled non-metal furnace, air-floating in the low-concentration acid solution, high-temp steaming by alkali solution, washing, immersing in the solution aluminium salt and alum, cyclic boiling for regenerating, high-temp steam washing, immersing in the solution of stabilizer for raising pH value, fast drying and sealing in plastic bags.

Description

Zeolite activity carbon activation processing and preparation thereof are used and regeneration

Technical field

The water quality that the present invention relates to drinking water is transformed the field.

Background technology

At first found zeolite as far back as 1756 by Sweden mines expert, this century, the fifties was found since the extensive appositional pattern zeolite deposit, along with the further investigation to zeolite purposes aspect becomes a kind of extremely promising raw mineral materials in the industrial or agricultural with it, China is that professor Li Guirong develops activating zeolite together and handles in the water fluorine-containing since the additive just finding the zeolite ore deposit in 1972 and just identified by national department or buearu level science and technology in 1986 and be only limited to feed and cement up to we and Lanzhou Railway College's environmental sanitation in 1992, iron, metals such as manganese, be applied to the partly defluorination at station of northwest by first Huashan environmental protection equipment factory of Engineering Bureau of the Ministry of Railways, and at 93 years monographs of railway standard design, issue CN11-2987/U delivers zeolite deferrization and demanganization technology, front cover LH-II type fluoride-removing equipment photo.In August, 2000 to December in Beijing activating zeolite technology (technology and imperfection also required further improvement at that time) do missionary work to should Sun Hao people such as the Sun Hao of Pekinese rings ring obtain, through we do missionary work to patented technology till the end of the year 2000, remain best defluorination way, overcome the shortcoming of other five kinds of defluorinations, the way of this Zeolite modifying is perfect not enough but we slowly do not report patent to be, there is certain shortcoming, as calcine anoxic and calcine, zeolite ironization etc., must carry out the acid solution soaking and washing handles for this reason, ferromagneticization that has, can not thoroughly remove, it is that big iron pan also is difficult to leave ferromagneticization that aqueous slkali boils common device, infusion method is adopted in the regeneration of aluminium salt alum, regeneration can not be thorough, therefore defluorination effect is still not really high, about 500 milligrams of the highest per kilogram modification modified zeolite defluorinations, this scope of soaking solution 1%-10% of soda acid is too big simultaneously, 1% concentration can not work at all, 10% concentration surpasses 8% pair of equipment again and causes heavy corrosion, the corrosion back produces directly influence to the zeolite that soaks, and is therefore unrealistic.

Summary of the invention

We further study again and have invented zeolite activity carbon at above-mentioned shortcoming, through nine road activating process, 1, selected: through national collection investigation and have only alkalescence through evidence tiltedly the performance of the green zeolite of burnt hair is best, and to select the filtrate of 0.5-2.5mm material for use be best; 2, thermalization is that oxygenation does not have the metal calcining, and its characteristics change the structure of zeolite oxygen, and it is extremely uneven to reach the negative and positive electric charge, increases adsorption capacity; 3, acidifying is only removed the magnetized problem of metal in the zeolite with the acid solution of 3-5% concentration, and is 0.35MPa with 100-200 ℃ of steam vapour pressure, and decatize certain hour in jar promptly strengthens the reflection of structure, again foreign material in the zeolite pores is rinsed out, and cleans more thorough; 4, alkalization is steamed certain hour with 100-200 ℃ of high-temperature steam equally with 5%-7% concentration aqueous slkali, and is more completely than boiling; 5, biochemical with the floating degree of 5-7% concentration alum solution vaporization regeneration cycle, regeneration effect is very good, strengthens about 2 times than general immersion regeneration; 6, the vaporization zeolite activity carbon that activating and regenerating is good is vaporized specially and is reached the activity function of active zeolite activated carbon higher degree; 7, stability is handled mainly and to be made into reagent with soda acid and to soak with 5% concentration again and reach pH value and be stabilized in and prolong life cycle between the 6.5-8.5; 8, the dried machine flash baking of making an uproar is adopted in mummification, preserve certain moisture; 9, preserve moisture and handle and adopt polybag to install to keep uniform temperature and air to separate, the moisture and of must exempting to run off by air pollution.

Zeolite activity carbon behind overactivation reaches the nearly 500m of the absorption every gram of porosity ²Contact area, it is extremely uneven that the diameter of hole reaches tens micron zwitterion positive and negative charges, the active zeolite activated carbon is done water treatment filter material and is exceeded tens times than the adsorption capacity of best activated carbon for this reason, also has the stronger diadochy that activated carbon does not have simultaneously, can replace above-mentioned all water treatment absorption, the advantage that displacement reaction is handled has also overcome their all shortcomings simultaneously.

Particularly relatively there is outstanding character to have more 4 progressive different poling processing techniques with modified zeolite.

1. iron-free oxygenation calcining is more abundant than modified zeolite calcining reflection, because oxygen can be combustion-supporting, the zeolite Main Ingredients and Appearance is SiAiO ₂Connect shape crystal structure O more ₂The variation that occupies cation extremely unstable oxygen in absolute position for common edge is big especially to the zeolite structured influence of changing its course, the oxygenation calcining is to play great role to be fabricated into no any Metal Contact zeolite from calciner to changing zeolite character for this reason, be magnetized into descending road acidification technology to reduce the heavy burdens greatly exempting from the zeolite metal, save the acid solution labor and material saving.

2, vaporization steaming technology accounts for most of technology, and in handling the activating process process, the raising treatment temperature is accelerated processing and reflected as acidifying, alkalization, biochemistry or the like, and effect is handled than modified zeolite will improve 2 times.

3, zeolite is all vaporized and not only acceleration reflection of unsteady processing after the regenerative process neutralisation treatment, and it is thorough towards removing to the undesired impurities of handling in the zeolite pores of back, make the zeolite after the activation completely prolong life cycle, strengthen treatment effect, defluorination can reach per kilogram active zeolite 1000mg-1500mg, and deironing can reach 3000mg/kg and improve 1-2 doubly than modified zeolite.

4, strengthen the stable together stabilizing agent of handling preparation and can guarantee that the IP value is operated in the time of 6.5-8.5, effluent quality prolongs processing time and cycle near handling marginal value for this reason when the IP value drops to 6.5.

Though the height that the activating technology of active zeolite activated carbon requires, technological operation require accurately, permanent repeated regeneration effect, the long cost of life cycle is low, handles wide advantage such as effective.

The present invention adopts active zeolite to process the material of water, the activating process difference, the harmful substance of handling in the water also is different, it can be removed heavy metal such as fluorine in the water, iron, manganese, network, mercury, femaleization thing, hardness, turbidity, colourity and be harmful to human material, the harmful substance that also can remove down in the water reaches sewage disposals such as discharge standard, develops three kinds of different water treatment facilities at present.

1, small home is used water treatment facilities;

2, the medium-sized water treatment facilities of using;

3, residential quarter water processing mode.

The activation processing of zeolite activity carbon is also stronger for the strictest equipment and technology with defluorinating process.

Description of drawings

Fig. 1 is a process chart of the present invention;

Fig. 2 is process portion system equipment figure of the present invention.

1 water valve from the beginning among the figure, 2 aqueous slkali ponds, 3 aqueous slkali pumps suction valve, 4 aqueous slkali pump field penstocks, 5 aqueous slkali pumps, the three string stones of handling well together on 6 are carried alkalization jar control valve, the 7 aqueous slkalis control valve that floats, 8 alkali treatment jar safety valves, 9 alkali jar control valves, 10 clean backwater valve, 11 Pressure gauges, 12 circulation valves, 13 water circulating pumps, 14 circulating pump blooming water valves, 15 back-water valve (BWV)s, 16 circulating pump suction valves, 17 alkali jar zeolites are asked regenerating tank conveying control valve, 18 alkalization clear water reserviors, 19 water valves from the beginning, 20 alkalization jars, 21 steam boilers, 22 safety valves, 23 steam oven control valves, 24 steam gauges, 25 send the vapour control valve to alkalization jar, 26 to the Biochemical pot induction valve, 27 water valves from the beginning, 28 regeneration liquid pools, 29 suction valves, 30 biochemical regenerative pumps, 31 blooming water valves, 32 blooming water valves, 33 discharging valves, 34 circulating pump blooming water valves, 35 suction valves, 36 regeneration cycle pumps, 37 water valves from the beginning, 38 Pressure gauges, 39 safety valves, 40 regenerated liquid control valves, 41 circulating pump control valves, 42 regenerating tank control valves, 43 carry the zeolite valve, 44 downward road technologies are carried the zeolite valve, 45 Biochemical pots, 46 regeneration clear water reserviors, 47 aqueous slkali reflux valves, 48 regeneration alum solution recovery valves.

The specific embodiment

Realization program with alkalization and the whole nine road technologies of biochemical twice implementation of processes procedure declaration.Alkalization and biochemical twice process implementing program.At first opening the good zeolite transfer valve 6 of upper track PROCESS FOR TREATMENT, zeolite is filled alkalization jar, is that water pressurizes and finishes.Open aqueous slkali pump 5, suction valve 3, blooming water valve 4, aqueous slkali is got in the jar, valve-off 9,6,17,12,4, open steam transfer valve 25, in the alkalization jar, send 0.35m vapour pressure, temperature was carried out decatize certain hour for 200 ℃, stop steam bleeding, aqueous slkali reflux valve 47 is opened, aqueous slkali is put back in the pond, close aqueous slkali reflux valve 47, the aqueous slkali pump valve 4 that pumps up water, back-water valve (BWV) 15, open and clean backwater valve 10, circulation valve 12, circulating pump blooming water valve 14, alkali jar control valve 9, clean backwater valve 10, start flushing water pump and carry out wash cycles, then open steam valve 25 again, add the vapour flushing.18 water in the pond are put into withdrawal pond (not drawing), open water valve 19 from the beginning, change clear water into, carry out wash cycles again till the IP value drops near running water IP value, this road technology is finished substantially.At this moment with each valve closing, open and carry zeolite control valve 17,43, open a water valve 12, circulating valve 10, put back to valve 33, water pump blooming water valve 32, starting pump fetches water with high pressure in the alkalization jar, zeolite in the alkali jar all is transported in the regenerating tank 45, water flows in the pond from reflux valve 33, conveying finishes, open steam valve 42,40, start regenerative pump 30 behind each valve, carried out 10 hours, stop the static regeneration 24 hours of floating, then open steam valve 26 and in jar, fill 200 ℃, 0.35mpa the steam of vapour pressure 2 hours, carried out circular regeneration 10 hours with regenerative pump again, clean with clarified water pump 36 at last and get final product in 10-20 minute, regeneration technology is finished the zeolite of according to same manner regeneration being got well the again gasifying pot that veers away and is vaporized, open the material taking hole of jar after the cleaning and emit mummification, pack water conservation branch is transported to the effect that the user installs to performance active zeolite activated carbon in the equipment.

Claims (1)

1. the activation processing of a zeolite activity carbon and preparation thereof are used and regeneration, it is characterized in that the method that prepare zeolite activity carbon comprises:＜1〉selection has Si, Ai, O ₂For the oblique fermentation of Main Ingredients and Appearance is expected green zeolite, and selected be 0.5～2.5mm particle;＜2〉no metal oxygenation calcining, because of handling the different calcining heat differences of object, deironing, manganese, hardness 200-400 ℃, 400-800 ℃ of mercury, periodicalization thing, inferior raw silk Barbiturates, 800-110 ℃ in heavy metal fluorine etc.;＜3〉acid solution carries out acidification, contacts to preventing the small amounts of iron existence because must bear in the calcining with metal species, handles 3～5% with the concentration of province's amount acid;＜4〉basification adopts high-temperature steam to carry out boiling and the unsteady cleaning of vapour;＜5〉regeneration is soaked with 5～7% concentration alum solutions, and high-temperature steam (100～200 ℃) vapour floats and circular regeneration;＜6〉vaporization runs through whole activation process, temperature 100-200 ℃;＜7〉the stable processing, what main employing was prepared stablizes 6 doses, improves the HP value, keeps about 8.0;＜8〉mummification, can not do naturally, must adopt dryer flash baking cannot not reach wetly, do not do and preserve certain moisture content and get final product;＜9〉preserve and to adorn polybag immediately after moisture content is handled and seal, isolated with air, must exempt to pollute and change.

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