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 PDFInfo
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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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- 239000003054 catalyst Substances 0.000 title claims abstract description 119
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 50
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 38
- 238000001354 calcination Methods 0.000 claims abstract description 38
- 239000003610 charcoal Substances 0.000 claims abstract description 21
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- 239000002671 adjuvant Substances 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000012805 post-processing Methods 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims description 36
- 238000001994 activation Methods 0.000 claims description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000002802 bituminous coal Substances 0.000 claims description 16
- 238000003763 carbonization Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000011280 coal tar Substances 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 13
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 10
- 239000012190 activator Substances 0.000 claims description 8
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 8
- 239000003830 anthracite Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000010865 sewage Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 16
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 29
- 239000003245 coal Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000005201 scrubbing Methods 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004231 fluid catalytic cracking Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
-
- B01J35/617—
-
- B01J35/638—
-
- 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]
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
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.
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