CN102784644A

CN102784644A - Heterogeneous catalysis ozonization load type catalyst and preparation method thereof

Info

Publication number: CN102784644A
Application number: CN201210312162XA
Authority: CN
Inventors: 张振慧; 刘微; 胡丽
Original assignee: Individual
Current assignee: Individual
Priority date: 2012-08-29
Filing date: 2012-08-29
Publication date: 2012-11-21

Abstract

The invention discloses a heterogeneous catalysis ozonization load type catalyst and a preparation method of the catalyst. The preparation method comprises the steps of mixing basic cupric carbonate and an ammonia bicarbonate solution or ammonia water according to certain ratio, completely dissolving basic cupric carbonate in the ammonia bicarbonate solution or the ammonia water to form a blue complex solution, soaking a carrier in the blue complex solution, and taking out the carrier to be aired, and keeping temperature and drying the carrier at 200-250 DEG C to allow copper oxide to be separated out and agglomerated on a hole surface of the carrier to form a catalysis layer, thereby preparing the heterogeneous catalysis ozonization load type catalyst. During the preparation process, as the basic cupric carbonate is a non-strong oxidant, no hidden trouble exists, no harmful gas is generated, and no environment pollution is caused. According to the preparation method disclosed by the invention, the simplicity is realized, a baking process is saved, the preparation period is shortened, and the power consumption and the cost are reduced; and the generated catalyst has high catalysis activity, can run off easily, does not introduce secondary pollution, and can be regenerated and recycled.

Description

A kind of multi-phase catalytic ozonation loaded catalyst and preparation method thereof

Technical field

The present invention relates to water technology, particularly handle persistent organic pollutants, be specifically related to the improvement of a kind of multi-phase catalytic ozonation loaded catalyst and preparation method thereof.

Background technology

Traditional O3 catalytic oxidation method is catalyst to be configured to certain density solution be added in the waste water; Catalyst exists in the waste water with ionic species, feeds ozone then and carries out the homogeneous catalysis oxidation, though can improve treatment effect; But this kind catalyst exists and is difficult to reclaim; Cause secondary pollution, medicament expense with high, the utilization rate of ozone is low, and it is bad to locate the dose-effect fruit.Therefore to a great extent limit the application in wastewater treatment.So, how to utilize O3 catalytic oxidation to carry out heterogeneous catalysis, improve ozone utilization rate, strengthen the ozone oxidation ability, problems such as reduction processing cost cause the attention of domestic and international institution of higher learning and scientific research institutions.Multi-phase catalytic ozonation has been carried out a large amount of research, confirmed that the heterogeneous catalysis ozonation technology is a high stability in the removal water, content is low, harm is big, the effective technology of persistent organic pollutants.But up to the present, still there are some problems in its achievement in research: the one, lack actual production property experimental data, and its research mainly is to be the bench teat test of body with distilled water; The 2nd, the multi-phase catalytic ozonation principle also is in the supposition stage, still can not know its reaction mechanism fully; The 3rd, because contamination class is more, chemical composition varies, and catalyst is had different selections.(modern chemical industry; The 27th 3 phases of volume of March in 2007; The water treatment multi-phase catalytic ozonation state of the art); Chinese patent ZL200910186028.8 discloses heterogeneous catalysis ozone oxidation supported catalyst and preparation method, and it is to be carrier with the honeycomb haydite, is the supported catalyst of active constituent with the oxide of copper.Its preparation method divided for five steps: 1, select carrier, and selecting the honeycomb haydite of particle diameter 5-8mm is carrier; 2, the copper nitrate solution of configuration 18-20%; 3, dipping: carrier was immersed copper nitrate solution more than 4 hours; 4, drying: will flood the carrier of accomplishing and from copper nitrate solution, take out, and at room temperature dry the back and in 100-120 ℃ drying oven, dry more than 12 hours; 5, again at 400-600 ℃ roasting kiln roasting more than 4 hours.This preparation method one is that the manufacture craft time is long, becomes loaded catalyst to need more than 20 hours approximately even the longer time from configuration solution to roasting, and production efficiency is low; The 2nd, copper nitrate solution is a kind of strong oxidizer; Be to make it change into the cupric oxide agglomeration on the pore surface of honeycomb haydite in the production process of catalyst; Not only transform the cost height; While is total to heat, friction and bump with powdered carbon, sulphur and other incendivity property material in the drying and roasting process, can cause and burn and explode, and has serious potential safety hazard; The 3rd, also can produce the poisonous hyponitric acid gas of smell with irritating during roasting, serious environment pollution, energy consumption is high again.

Summary of the invention

To existing problem in the above-mentioned prior art, the present invention provides a kind of energy consumption little, and cost is low, and production process does not have the multi-phase catalytic ozonation loaded catalyst of potential safety hazard and non-environmental-pollution.

The technical scheme that the technical problem that the present invention will solve is taked is: said multi-phase catalytic ozonation loaded catalyst adopts following method to be prepared from: in proportion basic copper carbonate is mixed with ammonium bicarbonate solution or ammoniacal liquor earlier; Basic copper carbonate is dissolved in fully forms blue complex solution in ammonium bicarbonate solution or the ammoniacal liquor; Again with carrier impregnation in blue complex solution; The dipping back is taken out and is dried; Heat preservation and dryness under 200-250 ℃ of temperature makes cupric oxide separate out agglomeration and on the hole surface of carrier, forms Catalytic Layer, thereby processes the multi-phase catalytic ozonation loaded catalyst again.

Said carrier is processed with inorganic porous non-metallic particle, and said inorganic porous non-metallic particle is honeycomb haydite, bauxite, diatomite or active carbon etc.

Multi-phase catalytic ozonation supported catalyst preparation method concrete steps according to the invention are following:

1, select particle diameter to process carrier less than the inorganic porous non-metallic particle of 50mm,

2, the preparation weight percent concentration is ammonium bicarbonate solution or the ammoniacal liquor of 12-14% earlier; Press part by weight 2～3 ︰ 97～98 of basic copper carbonate and ammonium bicarbonate solution or ammoniacal liquor again; Under agitation basic copper carbonate is joined in ammonium bicarbonate solution or the ammoniacal liquor; Basic copper carbonate is dissolved in fully forms blue complex solution in ammonium bicarbonate solution or the ammoniacal liquor

3, carrier is immersed in the blue complex solution, dip time is no less than 4 hours again,

4, carrier is taken out in the dipping back; Carrier is at room temperature dried moisture; Again carrier is placed on after drying that heat preservation and dryness made cupric oxide separate out agglomeration and on the hole surface of carrier, forms Catalytic Layer more than 4 hours under 200-250 ℃ the temperature, promptly can be made into the multi-phase catalytic ozonation loaded catalyst.

Though the present invention the same with prior art final all be to make to form one deck copper oxide catalyzation layer on the hole surface of carrier; But innovation point of the present invention is: be dissolved in ammonium bicarbonate solution or the ammoniacal liquor through basic copper carbonate and form blue complex solution, again with carrier impregnation in blue complex solution, the dipping back is taken out and is dried and drying under 200-250 ℃ of low temperature; Just can on the hole surface of carrier, form the copper oxide catalyzation layer; Through adopting non-strong oxidizer-basic copper carbonate to change into the cupric oxide agglomeration on the hole surface of carrier, do not need roasting at high temperature, both shortened preparation technology's cycle; Saved the required energy of high-temperature roasting again; Eliminated potential safety hazard, also can not produce toxic gas with irritating, the environmental protection again of whole process of preparation safety.It with prior art in the supported catalyst preparation method compare and have following advantage:

1, in the preparation process,, pernicious gas can be do not produced yet, environmental pollution can be do not caused because basic copper carbonate is non-strong oxidizer, thereby does not exist potential safety hazard,

2, the preparation method is simple, has saved roasting technique, has shortened manufacturing cycle, has reduced energy consumption and cost,

3, catalytic activity is high, is difficult for running off, and does not introduce secondary pollution, renewable repeated use.

The specific embodiment

Embodiment 1

The preparation carrier: the selection average grain diameter is the carrier 1000kg that the honeycomb haydite of 40-45mm is processed, and washes down out its surface dirt and impurity with wind,

Maceration extract preparation: get the 60kg ammonium hydrogencarbonate and be dissolved in the 440kg water; Be mixed with weight percent concentration and be 12% ammonium bicarbonate soln; Basic copper carbonate is water insoluble; But being dissolved in ammonium bicarbonate solution, is the ratio of 2 ︰ 98 in basic copper carbonate and ammonium bicarbonate solution weight ratio, and getting the 10kg basic copper carbonate, under agitation to join the 490kg weight percent concentration slowly be in 12% the ammonium bicarbonate solution it to be dissolved fully; Make basic copper carbonate and ammonium bicarbonate solution form 500kg blue complex solution

3, the carrier of 1000kg honeycomb haydite being processed immerses in the 500kg blue complex solution, and dip time is 5 hours,

4, drying: from blue complex solution, take out above-mentioned carrier; After room temperature is dried moisture; Put into baking oven again; Heat preservation and dryness is 6 hours under 200 ℃ temperature, makes cupric oxide separate out agglomeration and on the hole surface of the carrier that above-mentioned honeycomb haydite is processed, forms Catalytic Layer, promptly processes the multi-phase catalytic ozonation loaded catalyst.

Embodiment 2

1, preparation carrier: the selection average grain diameter is the carrier 1000kg that the bauxite ore particles of 20-30mm is processed, and washes down out its surface dirt and impurity with wind,

Maceration extract preparation: get the 70kg ammonium hydrogencarbonate and be dissolved in the 430kg water; Be mixed with weight percent concentration and be 14% ammonium bicarbonate soln; Basic copper carbonate is water insoluble; But being dissolved in ammonium bicarbonate solution, is the ratio of 2 ︰ 97 in basic copper carbonate and ammonium bicarbonate solution part by weight, and getting the 10kg basic copper carbonate, under agitation to join the 485kg weight percent concentration slowly be dissolving fully in 14% the ammonium bicarbonate solution; Make basic copper carbonate and ammonium bicarbonate solution form 495kg blue complex solution

3, the carrier of the 1000kg bauxite ore particles being processed immerses in the 495kg blue complex solution, and dip time is 6 hours,

4, drying: from blue complex solution, take out above-mentioned carrier; After room temperature is dried moisture; Put into baking oven again; Heat preservation and dryness is 4.5 hours under 240 ℃ temperature, makes cupric oxide separate out agglomeration and on the hole surface of the carrier that above-mentioned bauxite ore particles is processed, forms Catalytic Layer, promptly processes the multi-phase catalytic ozonation loaded catalyst.

In addition; The aqueous ammonia to replace embodiment 1 of available identical weight percent concentration and the ammonium bicarbonate solution among the embodiment 2; Available active carbon or diatomite particle replace honeycomb haydite or the bauxite ore particles among the embodiment 2 among the embodiment 1 to prepare carrier, and the preparation method of its loaded catalyst is identical with preparation method among embodiment 1 and the embodiment 2.

Claims

1. the preparation method of a multi-phase catalytic ozonation loaded catalyst; It is characterized in that: in proportion basic copper carbonate is mixed with ammonium bicarbonate solution or ammoniacal liquor earlier; Basic copper carbonate is dissolved in fully forms blue complex solution in ammonium bicarbonate solution or the ammoniacal liquor; Again with carrier impregnation in blue complex solution, dipping back is taken out and is dried, again heat preservation and dryness under 200-250 ℃ of temperature; Make cupric oxide separate out agglomeration and on the hole surface of carrier, form Catalytic Layer, thereby process the multi-phase catalytic ozonation loaded catalyst.