CN108014848A - One kind prepares ozone catalytic agent method using spent FCC catalyst - Google Patents

One kind prepares ozone catalytic agent method using spent FCC catalyst Download PDF

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CN108014848A
CN108014848A CN201610935439.2A CN201610935439A CN108014848A CN 108014848 A CN108014848 A CN 108014848A CN 201610935439 A CN201610935439 A CN 201610935439A CN 108014848 A CN108014848 A CN 108014848A
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catalyst
spent fcc
fcc catalyst
ozone
temperature
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魏令勇
李昕阳
邱松
杨芳芳
万国晖
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/90—Regeneration or reactivation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/638—Pore volume more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/084—Decomposition of carbon-containing compounds into carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]

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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Catalysts (AREA)

Abstract

The present invention relates to one kind ozone catalytic agent method is prepared using spent FCC catalyst.The present invention be by spent FCC catalyst be in air atmosphere 2~4h in 600~800 DEG C, time under the conditions of carry out natural cooling after abundant calcination；Will be for charcoal agent, calcination spent FCC catalyst after cooling, binding agent and adjuvant using weight ratio meter as 100:(10‑20):(20‑35):(1 5) are dry after mixing, carbonize, activate, post processing, obtain ozone catalyst.Ozone catalyst prepared by this method has the advantages that catalyst is easily isolated, high mechanical strength, catalytic performance are good, long catalytic life, and the preparation also have technique is simple, energy consumption is low and is easy to the advantages such as industrial applications, there is preferable economy and application value.

Description

One kind prepares ozone catalytic agent method using spent FCC catalyst
Technical field
It is specifically a kind of to prepare ozone using spent FCC catalyst the present invention relates to field of solid waste treating technology Catalyst method.The ozone catalyst espespecially ozone heterogeneous catalysis agent.
Background technology
With world's crude oil constantly heaviness and in poor quality, catalytic cracking technology (FCC, Fluid Catalytic Cracking) become domestic and international Petrochemical Enterprises and greatly develop one of light materialization of heavy oil process.
The materials such as heteroatomic compound, the resin and asphalts such as metal pollutant, sulfur-bearing nitrogen in crude oil, are catalyzed FCC Agent often results in heavy metal pollution inactivation, carbon distribution inactivation and hydrothermal deactivation so that catalyst reaction is selectively deteriorated, can not be extensive Reach due activity and reaction selectivity again, therefore generate spent FCC catalyst.Since spent FCC catalyst contains largely Heavy metal, belongs to the category of danger wastes, and outer committee's processing cost is very high.
Spent FCC catalyst has porous molecular sieve carrier structure, there is very big specific surface area, containing substantial amounts of lanthanum and The rare earth elements such as cerium, and the transition metal such as Ni-V-Fe and aluminium, therefore, spent FCC catalyst still has certain catalytic capability, It can be used among other catalyst system and catalyzings.
The method of ozone heterogeneous catalysis oxidation sewage treatment is since its energy consumption is low, degradation efficiency is high and does not cause secondary pollution The advantages that as removing, water stability is high, effective methods of persistent organic pollutants.Ozone heterogeneous catalysis oxidation technology Involved in catalyst type mainly include metal oxide catalyst (such as MnO of non-loading type2、Al2O3And TiO2Deng) and it is more Porous materials (such as activated carbon, zeolite and ceramic honey comb) and load type metal or metal oxide supporting catalyst (such as copper, manganese, The metals such as titanium, iron, platinum, ruthenium, lanthanum and cerium and its oxide).At present, loaded catalyst is in ozone heterogeneous catalysis oxidation technology The catalyst of most study, the catalytic active center of metallic element or its oxide as ozone loaded catalyst.
Spent FCC catalyst has the correlation properties of load type metal or metal oxide supporting catalyst, and existing document is given Go out and spent FCC catalyst is directly used as ozone heterogeneous catalysis agent, but there is catalytic effect is high, spent FCC catalyst particle diameter It is too small to be difficult to be separated from water the problems such as being easy to run off with metal active centres.
The content of the invention
For defect existing in the prior art, prepared it is an object of the invention to provide one kind using spent FCC catalyst Ozone catalytic agent method, overcome in the prior art spent FCC catalyst be directly used as ozone heterogeneous catalysis agent, existing catalytic activity It is not high, spent FCC catalyst particle diameter is too small is difficult to be separated from water the problems such as being easy to run off with metal active centres.
To achieve the above objectives, the present invention adopts the technical scheme that：
One kind prepares ozone catalytic agent method using spent FCC catalyst, includes the following steps：
The first step：Spent FCC catalyst is carried out to natural cooling after abundant calcination in air atmosphere；
Second step：By the spent FCC catalyst after cooling of calcination in the first step, mixed with for charcoal agent, binding agent and adjuvant It is dry after uniformly, obtain siccative；The shape of the siccative can be bar shaped；
3rd step：Siccative described in second step is carbonized；
4th step：Siccative after being carbonized in 3rd step is activated；
5th step：Siccative after 4th step is activated is post-processed, and obtains ozone catalyst.
Using spent FCC catalyst prepare ozone catalytic agent method above-mentioned, in the first step, the temperature of calcination for 600~ 800 DEG C, the time is 2~4h.
In the above-mentioned preparation ozone catalytic agent method using spent FCC catalyst, in second step, after charcoal agent, calcination cooling Spent FCC catalyst, binding agent, adjuvant is using weight ratio meter as 100:(10-20):(20-35):(1-5) is mixed.
In above-mentioned utilization spent FCC catalyst prepares ozone catalytic agent method, the confession charcoal agent is that granularity is 150~250 The mixture of purpose anthracite or bituminous coal or both, when for both mixtures when, anthracitic ratio is 65-75% (weights Amount), the ratio of bituminous coal is 25-35% (weight)；
And/or the binding agent is high temperature coal-tar, i.e., the coal tar that coal produces more than 1000 DEG C；
It is preferably neopelex and/or the adjuvant is surfactant.
In the above-mentioned preparation ozone catalytic agent method using spent FCC catalyst, in second step, drying temperature is 90~105 DEG C, drying time 4-6h.
In the above-mentioned preparation ozone catalytic agent method using spent FCC catalyst, in the 3rd step, the treatment conditions of the charing For：
Carbonization heating rate is 10-15 DEG C/min,
It is 600-800 DEG C to carbonize final temperature temperature,
Charing constant temperature time is 0.2-0.4h,
Carbonization Atmospheres are N2And CO2One or both of mixture.
In the above-mentioned preparation ozone catalytic agent method using spent FCC catalyst, in the 4th step, the treatment conditions of the activation For：
It is 800-950 DEG C to activate final temperature temperature,
Soak time is 5-15h,
Activator is vapor, CO2With one or more of mixtures in air.
In the above-mentioned preparation ozone catalytic agent method using spent FCC catalyst, in the 5th step, the post processing includes as follows Step：Siccative after activation process is subjected to pickling, rinsing and drying, obtains ozone catalyst.
In the above-mentioned preparation ozone catalytic agent method using spent FCC catalyst, the acid is 0.01mol/L sulfuric acid；It is described Dry temperature is 105 DEG C, time 2h.
The ozone catalyst and its aoxidized in ozone heterogeneous catalysis that any of the above-described the method for present invention protection is prepared Application in treated sewage.
Beneficial effects of the present invention are as follows：
Catalyst of the present invention using spent FCC catalyst preparation ozone catalytic agent method preparation is easy with catalyst In separation, the advantages that high mechanical strength, catalytic performance be good, long catalytic life, and the preparation process is simple, energy consumption is low and is easy to work The advantages such as industryization application, have preferable economy and application value.
Embodiment
It is of the present invention to prepare ozone catalytic agent method using spent FCC catalyst, prepare coal base using spent FCC catalyst Support type ozone catalyst, includes the following steps：
The first step：Spent FCC catalyst is carried out to natural cooling after abundant calcination in air atmosphere, can specifically be cooled to room Temperature；
Second step：By the spent FCC catalyst after cooling of calcination in the first step, mixed with for charcoal agent, binding agent, adjuvant Even, press strip and drying form siccative bar；
3rd step：Siccative bar described in second step is carbonized；
4th step：Siccative article after being carbonized in 3rd step is activated；
5th step：Siccative article after being activated in 4th step is post-processed, obtains ozone catalyst.
On the basis of such scheme, the temperature of calcination is 600~800 DEG C in the first step, and the time is 2~4h.
On the basis of such scheme, for charcoal agent, calcination spent FCC catalyst after cooling, binding agent, auxiliary in second step Agent is using weight ratio meter as 100:(10-20):(20-35):(1-5) is mixed；
It is described for the mixture that charcoal agent is anthracite that granularity is 150~250 mesh or bituminous coal or both, when for both mixed During compound, anthracitic ratio is 65-75% (weight), and the ratio of bituminous coal is 25-35% (weight)；
The binding agent is high temperature coal-tar, i.e., the coal tar that coal produces more than 1000 DEG C；
The adjuvant is surfactant, is preferably neopelex.
On the basis of such scheme, bar mill press strip is used in second step, is rolled into the material strip of a diameter of 4mm,
Then the material strip to be dried, drying condition is 90~105 DEG C, drying time 4-6h of drying temperature,
Dried material strip is finally cut into the siccative bar of 20mm long.
On the basis of such scheme, pass through mechanical mixture in second step so that in final ozone catalyst product Distribution as the spent FCC catalyst of catalytic active center has homogenieity, can make up ozone catalyst because mechanical friction is made Into outer surface activated centre be lost in and caused by catalyst failure, it is ensured that the catalytic effect and more that the ozone catalyst is stablized Long service life.
On the basis of such scheme, the treatment conditions carbonized described in the 3rd step are：
Carbonization heating rate is 10-15 DEG C/min,
It is 600-800 DEG C to carbonize final temperature temperature,
Charing constant temperature time is 0.2-0.4h,
Carbonization Atmospheres are N2And CO2One or both of mixture.
On the basis of such scheme, the treatment conditions activated described in the 4th step are：
It is 800-950 DEG C to activate final temperature temperature,
Soak time is 5-15h,
Activator is vapor, CO2With one or more of mixtures in air.
On the basis of such scheme, post processing described in the 5th step is used to remove the impurity in the material strip after activation process, Concretely comprise the following steps：
Material strip after activation process is subjected to pickling, rinsing and dry finally obtained ozone catalyst；
Wherein：The material strip after activation process described in 0.01mol/L sulfuric acid scrubbings is used first, and then clear water rinses 2-3 times, connects Dehydration, finally the dry 2h at 105 DEG C.
On the basis of such scheme, using the ozone catalyst of above method preparation, catalytic active center is urged in ozone Distribution in agent has homogenieity, i.e. the catalytic active center is evenly distributed on the various pieces of ozone catalyst rather than only exists Its surface.
Compared with prior art, the catalyst prepared using the method for the invention, since spent FCC catalyst is in the present invention Ozone catalyst in, the distribution in metal oxide oxidation catalyst activated centre has homogenieity, can make up external ozone catalyst The loss at superficial catalytic activation center and cause its service life it is longer, catalytic effect is more stable.
The ozone catalyst prepared using the above method can be used for ozone heterogeneous catalysis oxidation sewage treatment.
It is specific embodiment below.
Embodiment 1, catalyst preparation
(1) after spent FCC catalyst being carried out abundant calcination in air atmosphere, cooled to room temperature；The temperature of calcination For 650 DEG C, the time of calcination is 2h.
(2) by spent FCC catalyst of the spent FCC catalyst after calcination for charcoal agent, in step (1) after calcination, binding agent and Adjuvant is using weight ratio meter as 100:20:30:5 are uniformly mixed, press strip and drying form siccative bar；
Wherein, the mixing that charcoal agent is anthracite and bituminous coal that granularity is 200 mesh is supplied described in the spent FCC catalyst after calcination Thing, anthracitic ratio are 70% (weight), and the ratio of bituminous coal is 30% (weight)；
The binding agent is high temperature coal-tar, i.e., the coal tar that coal produces more than 1000 DEG C；
The adjuvant is surfactant sodium dodecyl base benzene sulfonic acid sodium salt.
Above-mentioned mixed uniformly material is rolled into the material strip of a diameter of 4mm using bar mill, then dries the material strip, Drying condition is 90 DEG C, drying time 4h of drying temperature, and siccative bar is finally cut into the small bar of 20mm long.
(3) the siccative bar described in step (2) is subjected to following charing process：Carbonization heating rate is 10 DEG C/min, charcoal It is 700 DEG C to change final temperature temperature, and charing constant temperature time is 0.3h, Carbonization Atmospheres N2。
(4) the siccative bar after being carbonized described in step (3) is subjected to following activation process：Activation temperature is 900 DEG C, activation Time is 10h, and activator is vapor.
(5) the siccative bar in step (4) after activation process is post-processed, including：Pickling, rinsing and drying, Finally obtained ozone catalyst, is denoted as 1# ozone catalysts.
The post-processing step includes：Material strip described in 0.01mol/L sulfuric acid scrubbings is used first, then clear water rinses 3 times, Then it is dehydrated, finally the dry 2h at 105 DEG C.
Embodiment 2, catalyst preparation
(1) after spent FCC catalyst being carried out abundant calcination in air atmosphere, cooled to room temperature；The temperature of calcination For 600 DEG C, the time of calcination is 4h.
(2) by spent FCC catalyst of the spent FCC catalyst after calcination for charcoal agent, in step (1) after calcination, binding agent, auxiliary Auxiliary agent is using weight ratio meter as 100:10:20:1 is uniformly mixed, press strip and drying form siccative bar；
For the mixture that charcoal agent is anthracite that granularity is 150 mesh and both bituminous coal described in spent FCC catalyst after calcination, Anthracitic ratio is 75% (weight), and the ratio of bituminous coal is 25% (weight)；
The binding agent is high temperature coal-tar, i.e., the coal tar that coal produces more than 1000 DEG C；
The adjuvant is surfactant sodium dodecyl base benzene sulfonic acid sodium salt.
Above-mentioned mixed uniformly material is rolled into the material strip of a diameter of 4mm using bar mill, then dries the material strip, Drying condition is 100 DEG C, drying time 6h of drying temperature, and siccative bar is finally cut into the small bar of 20mm long.
(3) dried siccative bar described in step (2) is subjected to following charing process：Carbonization heating rate for 15 DEG C/ Min, charing final temperature temperature is 800 DEG C, and charing constant temperature time is 0.2h, Carbonization Atmospheres CO2。
(4) material strip after being carbonized described in step (3) is subjected to following activation process：Activation temperature is 850 DEG C, during activation Between be 15h, activator is vapor and CO2。
(5) the siccative bar in step (4) after activation process is post-processed, including：Pickling, rinsing and drying, Finally obtained ozone catalyst, is denoted as 2# ozone catalysts.
Post-processing step of the present invention includes：Material strip described in 0.01mol/L sulfuric acid scrubbings is used first, and then clear water floats Wash 2 times, be then dehydrated, finally the dry 2h at 105 DEG C.
Embodiment 3, catalyst preparation
(1) after spent FCC catalyst being carried out abundant calcination in air atmosphere, cooled to room temperature；The temperature of calcination 800 DEG C, the time of calcination is 3h.
(2) by spent FCC catalyst of the spent FCC catalyst after calcination for charcoal agent, in step (1) after calcination, binding agent, auxiliary Auxiliary agent is using weight ratio meter as 100:15:35:2 are uniformly mixed, press strip and drying form siccative bar；
For the mixture that charcoal agent is anthracite that granularity is 250 mesh and bituminous coal described in spent FCC catalyst after calcination, smokelessly The ratio of coal is 65% (weight), and the ratio of bituminous coal is 35% (weight)；
The binding agent is high temperature coal-tar, i.e., the coal tar that coal produces more than 1000 DEG C；
The adjuvant is surfactant sodium dodecyl base benzene sulfonic acid sodium salt.
Above-mentioned mixed uniformly material is rolled into the material strip of a diameter of 4mm using bar mill, then dries the material strip, Drying condition is 105 DEG C, drying time 5h of drying temperature, and siccative bar is finally cut into the small bar of 20mm long.
(3) dried siccative bar described in step (2) is being subjected to following charing process：Carbonization heating rate is 12 DEG C/min, charing final temperature temperature is 600 DEG C, and charing constant temperature time is 0.4h.Carbonization Atmospheres are N2And CO2。
(4) material strip after being carbonized described in step (3) is subjected to following activation process：Activation temperature is 950 DEG C, during activation Between be 5h, activator is vapor and air.
(5) the siccative bar in step (4) after activation process is post-processed, including：Pickling, rinsing and drying, Finally obtained ozone catalyst, is denoted as 3# ozone catalysts.
The post-processing step includes：Material strip described in 0.01mol/L sulfuric acid scrubbings is used first, then clear water rinses 2 times, Then it is dehydrated, finally the dry 2h at 105 DEG C.
Embodiment 4, catalyst preparation
(1) after spent FCC catalyst being carried out abundant calcination in air atmosphere, cooled to room temperature；The temperature of calcination For 700 DEG C, the time of calcination is 4h.
(2) by spent FCC catalyst of the spent FCC catalyst after calcination for charcoal agent, in step (1) after calcination, binding agent, auxiliary Auxiliary agent is using weight ratio meter as 100:20:25:3 uniformly mix, press strip and drying form siccative bar；
For the mixture that charcoal agent is anthracite that granularity is 200 mesh and bituminous coal described in spent FCC catalyst after calcination, smokelessly The ratio of coal is 70% (weight), and the ratio of bituminous coal is 30% (weight)；
The binding agent is high temperature coal-tar, i.e., the coal tar that coal produces more than 1000 DEG C；
The adjuvant is surfactant sodium dodecyl base benzene sulfonic acid sodium salt.
Above-mentioned mixed uniformly material is rolled into the material strip of a diameter of 4mm using bar mill, then dries the material strip, Drying condition is 100 DEG C, drying time 5h of drying temperature, and siccative bar is finally cut into the small bar of 20mm long.
(3) the siccative bar described in step (2) is being subjected to following charing process：Carbonization heating rate is 14 DEG C/min, It is 700 DEG C to carbonize final temperature temperature, and charing constant temperature time is 0.3h, Carbonization Atmospheres N2。
(4) the siccative bar after being carbonized described in step (3) is subjected to following activation process：Activation temperature is 800 DEG C, activation Time is 10h, and activator is vapor, CO2And air.
(5) the siccative bar in step (4) after activation process is post-processed, including：Pickling, rinsing and drying, Finally obtained ozone catalyst, is denoted as 4# ozone catalysts.
The post-processing step includes：Material strip described in 0.01mol/L sulfuric acid scrubbings is used first, then clear water rinses 2 times, Then it is dehydrated, finally the dry 2h at 105 DEG C.
Comparative example 1, catalyst preparation
(1) will be for charcoal agent, binding agent and adjuvant using weight ratio meter as 100:25:3 are uniformly mixed, press strip and drying are formed Siccative bar；
It is described for the mixture that charcoal agent is anthracite that granularity is 200 mesh and bituminous coal, anthracitic ratio is 70% (weight Amount), the ratio of bituminous coal is 30% (weight)；
The binding agent is high temperature coal-tar, i.e., the coal tar that coal produces more than 1000 DEG C；
The adjuvant is surfactant sodium dodecyl base benzene sulfonic acid sodium salt.
Above-mentioned mixed uniformly material is rolled into the material strip of a diameter of 4mm using bar mill, then dries the material strip, Drying condition is 90 DEG C, drying time 5h of drying temperature, and siccative bar is finally cut into the small bar of 20mm long.
(2) the siccative bar described in step (1) is being subjected to following charing process：Carbonization heating rate is 14 DEG C/min, It is 700 DEG C to carbonize final temperature temperature, and charing constant temperature time is 0.3h, Carbonization Atmospheres N2。
(3) the siccative bar after being carbonized described in step (2) is subjected to following activation process：Activation temperature is 800 DEG C, activation Time is 10h, and activator is vapor, CO2And air.
(4) the siccative bar in step (3) after activation process is post-processed, including：Pickling, rinsing and drying, Finally obtained ozone catalyst, is denoted as 1# comparative catalysts.
The post-processing step includes：Material strip described in 0.01mol/L sulfuric acid scrubbings is used first, and then clear water rinses 2 times, connects Dehydration, finally the dry 2h at 105 DEG C.
Embodiment 5, catalyst performance contrast
Catalyst made from embodiment 1-4 and comparative example 1 is respectively used to sewage under identical following experiment condition Ozone heterogeneous catalysis oxidation processing technique among：
The property of sewage：PH value is 7.32, CODCrFor 132.7mg/L；
Experiment condition：Processing water sample is 1L；Processing time is 30min；Treatment temperature is room temperature；Catalyst charge is 20g/L；Ozone dosage 0.05g/min；
As a result：As shown in table 1.
1 catalyst performance of table contrasts
The content not being described in detail in this specification belongs to the prior art known to professional and technical personnel in the field.

Claims (10)

1. one kind prepares ozone catalytic agent method using spent FCC catalyst, it is characterised in that includes the following steps：
The first step：Spent FCC catalyst is carried out to natural cooling after abundant calcination in air atmosphere；
Second step：By the spent FCC catalyst after cooling of calcination in the first step, it is uniformly mixed with for charcoal agent, binding agent and adjuvant After dry, obtain siccative；
3rd step：Siccative described in second step is carbonized；
4th step：Siccative after being carbonized in 3rd step is activated；
5th step：Siccative after 4th step is activated is post-processed, and obtains ozone catalyst.
2. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 1, it is characterised in that：
In the first step, the temperature of calcination is 600~800 DEG C, and the time is 2~4h.
3. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 1, it is characterised in that：
In second step, for charcoal agent, calcination spent FCC catalyst after cooling, binding agent, adjuvant using weight ratio meter as 100:(10- 20):(20-35):(1-5) is mixed.
4. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 3, it is characterised in that：It is described to supply charcoal Agent is the mixture of the anthracite that granularity is 150~250 mesh or bituminous coal or both, when for both mixtures when, it is anthracitic Ratio is 65-75%, and the ratio of bituminous coal is 25-35%；
And/or the binding agent is high temperature coal-tar；
And/or the adjuvant is surfactant.
5. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 1, it is characterised in that：In second step, Drying temperature is 90~105 DEG C, drying time 4-6h.
6. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 1, it is characterised in that：In 3rd step, The treatment conditions of the charing are：
Carbonization heating rate is 10-15 DEG C/min,
It is 600-800 DEG C to carbonize final temperature temperature,
Charing constant temperature time is 0.2-0.4h,
Carbonization Atmospheres are N2And CO2One or both of mixture.
7. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 1, it is characterised in that：In 4th step, The treatment conditions of the activation are：
It is 800-950 DEG C to activate final temperature temperature,
Soak time is 5-15h,
Activator is vapor, CO2With one or more of mixtures in air.
8. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 1, it is characterised in that：In 5th step, The post processing includes the following steps：Siccative after activation process is subjected to pickling, rinsing and drying, obtains ozone catalyst.
9. ozone catalytic agent method is prepared using spent FCC catalyst as claimed in claim 8, it is characterised in that：The acid is 0.01mol/L sulfuric acid；The temperature of the drying is 105 DEG C, time 2h.
10. any the method is prepared in claim 1-9 ozone catalyst and its at ozone heterogeneous catalysis oxidation Manage the application in sewage.
CN201610935439.2A 2016-11-01 2016-11-01 One kind prepares ozone catalytic agent method using spent FCC catalyst Pending CN108014848A (en)

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Application publication date: 20180511