CN108014828A - A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge - Google Patents
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge Download PDFInfo
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- CN108014828A CN108014828A CN201711491571.XA CN201711491571A CN108014828A CN 108014828 A CN108014828 A CN 108014828A CN 201711491571 A CN201711491571 A CN 201711491571A CN 108014828 A CN108014828 A CN 108014828A
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- nitrogen oxides
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge; boehmite, corner Zinc oxide particles, vanadium oxide particles are uniformly mixed; add water mashing; wherein slurry solid content is 42 50 weight %, is 3 according to the weight ratio of hydrochloric acid and boehmite:1 adds hydrochloric acid acidifying, after being acidified 30 50min, adds chlorination iron particle, silica dioxide granule and titanium dioxide granule, the wherein weight ratio of iron chloride and titanium dioxide is 23:1:1, then spraying and drying, obtain microsphere particle, and microsphere particle is roasted 30 40min in 400 500 DEG C, then impregnates microballoon with copper chloride solution saturation, is 130 150 DEG C of drying, that is, obtain the composition of the suppression nitrogen oxides in effluent discharge.
Description
Technical field
The invention belongs to catalyst technical field, discloses a kind of carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge
Preparation method.
Background technology
Nitrogen oxides mostlys come from vehicle exhaust, power plant and oil-refining chemical factory.The particularly catalytic cracking of oil-refining chemical factory
The NOx of device discharge accounts for 10% of NOx emission total amount in air, although more other pollution sources much less, because it discharges phase
To concentrating, location environment can be caused seriously to pollute.In fluid catalytic cracking process, the catalyst of green coke inactivation is through vapour
Enter regenerator after carrying and carry out coke burning regeneration, the nitrogenous compound in coke can produce NOx in burning process.
US6596249 discloses a kind of base metal one containing copper-aluminium-cerium-aluminium composite oxide and alumina support and aoxidizes
Carbon burning catalyst and preparation method thereof, the catalyst contain the cerium-aluminium composite oxide and copper aluminium loaded successively on alumina
Composite oxides, and the load weight ratio Ce-Al-O/ aluminium oxide of the two is 0.02-0.10, and Cu-Al-O/ aluminium oxide is
0.05-0.15, the Copper-Aluminum compound oxide are dispersed in its surface with the cerium aluminum composite oxide of high dispersive with cluster state
On the alumina support of thing nano microcrystalline covering.The catalyst, which is used for catalytic cracking process, can reduce NOx emission.
CN1480246 discloses a kind of sulphur transfer combustion-supporting triple effect auxiliary agent of denitrogenation, including adsorbent and oxidation catalyst, oxidation
Catalyst is dispersed in adsorbent, and oxidation catalyst includes vanadic anhydride and the compound containing cerium, and adsorbent is class point
Spar composite oxides.
US6881390 is disclosed for reducing the NOx produced during the FCC that partially or incompletely burns and reduction-state gas phase
The composition of nitrogen substance, said composition include：(i) acidic metal oxide substantially free of zeolite；(ii) alkali metal, alkali
Earth metal and their mixture；(iii) oxygen storage components；(iv) noble metal component.The existing reduction NOx emission containing transition metal
Auxiliary agent, for FCC processes, the performance for reducing NOx emission has much room for improvement.
The content of the invention
In order to solve the above technical problems, the technical problem to be solved in the present invention is a kind of suppression is provided in prior art basis
The preparation method of the carbon monoxide-olefin polymeric of discharged nitrous oxides in tobacco curing gas.
The present invention adopts the following technical scheme that to complete above-mentioned purpose：
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, and wherein slurry solid content is 42-50 weight %, according to
The weight ratio of hydrochloric acid and boehmite is 3:1 adds hydrochloric acid acidifying, after being acidified 30-50min, adds chlorination iron particle, dioxy
The weight ratio of silicon carbide particle and titanium dioxide granule, wherein iron chloride, silica and titanium dioxide is 2-3:1:1, then spray
Mist and drying, obtain microsphere particle, microsphere particle are roasted 30-40min in 400-500 DEG C, then with copper chloride solution saturation
Microballoon is impregnated, is 130-150 DEG C of drying, that is, obtains the composition for suppressing nitrogen oxides in effluent discharge.
It is preferred that without roasting after described 130-150 DEG C drying.
It is preferred that the microsphere particle roasting is carried out in Muffle furnace.
It is preferred that preferably slurry solid content is 45 weight %.
It is preferred that it is 3 preferably according to the weight ratio of hydrochloric acid and boehmite:1 adds hydrochloric acid acidifying, is acidified 40min.
It is preferred that microsphere particle is roasted into 35min in 500 DEG C.
It is preferred that in 140-150 DEG C of drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
It is preferred that in 145-150 DEG C of drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
It is preferred that in 150 DEG C of drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
Embodiment
The present invention is further described in detail with reference to specific embodiment.
Embodiment 1
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, wherein slurry solid content is 42 weight %, according to salt
The weight ratio of acid and boehmite is 3:1 adds hydrochloric acid acidifying, after being acidified 30min, adds chlorination iron particle, silica
Grain and titanium dioxide granule, the wherein weight ratio of iron chloride, silica and titanium dioxide are 2:1:1, then spraying and drying,
Microsphere particle is obtained, microsphere particle is roasted into 40min in 400-500 DEG C, then microballoon is impregnated with copper chloride solution saturation, is
150 DEG C of drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
Embodiment 2
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, wherein slurry solid content is 45 weight %, according to salt
The weight ratio of acid and boehmite is 3:1 adds hydrochloric acid acidifying, after being acidified 40min, adds chlorination iron particle, silica
Grain and titanium dioxide granule, the wherein weight ratio of iron chloride, silica and titanium dioxide are 3:1:1, then spraying and drying,
Microsphere particle is obtained, microsphere particle is roasted into 35min in 450 DEG C, then microballoon is impregnated with copper chloride solution saturation, is 130
DEG C drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
Embodiment 3
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, wherein slurry solid content is 50 weight %, according to salt
The weight ratio of acid and boehmite is 3:1 adds hydrochloric acid acidifying, after being acidified 40min, adds chlorination iron particle, silica
Grain and titanium dioxide granule, the wherein weight ratio of iron chloride, silica and titanium dioxide are 2.5:1:1, then spraying is with doing
It is dry, microsphere particle is obtained, microsphere particle is roasted into 30min in 440 DEG C, then microballoon is impregnated with copper chloride solution saturation, is
135 DEG C of drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
Embodiment 4
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, wherein slurry solid content is 48 weight %, according to salt
The weight ratio of acid and boehmite is 3:1 adds hydrochloric acid acidifying, after being acidified 38min, adds chlorination iron particle, silica
Grain and titanium dioxide granule, the wherein weight ratio of iron chloride, silica and titanium dioxide are 2.7:1:1, then spraying is with doing
It is dry, microsphere particle is obtained, microsphere particle is roasted into 35min in 441 DEG C, then microballoon is impregnated with copper chloride solution saturation, is
136 DEG C of drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
Embodiment 5
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, wherein slurry solid content is 46 weight %, according to salt
The weight ratio of acid and boehmite is 3:1 adds hydrochloric acid acidifying, after being acidified 38min, adds chlorination iron particle, silica
Grain and titanium dioxide granule, the wherein weight ratio of iron chloride, silica and titanium dioxide are 3:1:1, then spraying and drying,
Microsphere particle is obtained, microsphere particle is roasted into 32min in 405 DEG C, then microballoon is impregnated with copper chloride solution saturation, is 146
DEG C drying, that is, obtain the composition for suppressing nitrogen oxides in effluent discharge.
Comparative example 1
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, wherein slurry solid content is 46 weight %, according to salt
The weight ratio of acid and boehmite is 3:1 adds hydrochloric acid acidifying, after being acidified 38min, adds chlorination iron particle, silica
Grain and titanium dioxide granule, the wherein weight ratio of iron chloride, silica and titanium dioxide are 2.1:1:1, then spraying is with doing
It is dry, microsphere particle is obtained, microsphere particle is roasted into 32min in 405 DEG C, then microballoon is impregnated with copper chloride solution saturation, is
146 DEG C of drying, then roast 20min at 400 DEG C again, that is, obtain the combination for suppressing nitrogen oxides in effluent discharge
Thing.
Comparative example 2
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, boehmite plus water are beaten
Slurry, wherein slurry solid content is 50 weight %, is 3 according to the weight ratio of hydrochloric acid and boehmite:1 adds hydrochloric acid acidifying, acid
After changing 40min, chlorination iron particle, silica dioxide granule and titanium dioxide granule, wherein iron chloride, silica and dioxy are added
The weight ratio for changing titanium is 2.5:1:1, then spraying and drying, obtain microsphere particle, and microsphere particle is roasted 30min in 440 DEG C,
Then with copper chloride solution saturation dipping microballoon, it is 135 DEG C of drying, that is, obtains the suppression nitrogen oxides in effluent discharge
Composition.
Comparative example 3
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, corner
Zinc oxide particles add water to be beaten, and wherein slurry solid content is 50 weight %, are 3 according to the weight ratio of hydrochloric acid and boehmite:1
Hydrochloric acid acidifying is added, after being acidified 40min, adds chlorination iron particle, silica dioxide granule and titanium dioxide granule, wherein chlorination
The weight ratio of iron, silica and titanium dioxide is 2.5:1:1, then spraying and drying, obtain microsphere particle, by microsphere particle
30min is roasted in 440 DEG C, then impregnates microballoon with copper chloride solution saturation, is 135 DEG C of drying, that is, obtains the suppression
The composition of nitrogen oxides in effluent discharge.
Comparative example 4
A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, by boehmite, five oxygen
Change two vanadium particles to be uniformly mixed, add water mashing, wherein slurry solid content is 50 weight %, according to hydrochloric acid and boehmite
Weight ratio is 3:1 adds hydrochloric acid acidifying, after being acidified 40min, adds chlorination iron particle, silica dioxide granule and titanium dioxide
Grain, the wherein weight ratio of iron chloride, silica and titanium dioxide are 2.5:1:1, then spraying and drying, obtain microballoon
Grain, roasts 30min in 440 DEG C by microsphere particle, then impregnates microballoon with copper chloride solution saturation, be 135 DEG C of drying, to obtain the final product
To the composition for suppressing nitrogen oxides in effluent discharge.
The technique effect of the present invention is as follows,
1 1-3 of the embodiment of the present invention of table and comparative example comparison result
2 4-5 of the embodiment of the present invention of table and comparative example comparison result
The composition of above-mentioned simulated flue gas is：C, H, S, the percentage by weight of N element are respectively 80%, 10%, 2%, 8%.
Inhibiting rate be by add the carbon monoxide-olefin polymeric of embodiment or comparative example and blank test carry out contrast be computed obtained by knot
Fruit.
Embodiment above is only the preferred embodiment of this creation, all in this wound not to limit this creation
Any modification, equivalent substitution, improvement and etc. done within the spirit and principle of work, should be included in this creation protection domain it
It is interior.
Claims (9)
1. a kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge, it is characterised in that thin water will be intended
Aluminium stone, corner Zinc oxide particles, vanadium oxide particles are uniformly mixed, and add water mashing, and wherein slurry solid content is 42-50 weights
% is measured, is 3 according to the weight ratio of hydrochloric acid and boehmite:1 adds hydrochloric acid acidifying, after being acidified 30-50min, adds iron chloride
The weight ratio of particle, silica dioxide granule and titanium dioxide granule, wherein iron chloride and titanium dioxide is 2-3:1:1, then spray
Mist and drying, obtain microsphere particle, microsphere particle are roasted 30-40min in 400-500 DEG C, then with copper chloride solution saturation
Microballoon is impregnated, is 130-150 DEG C of drying, that is, obtains the composition for suppressing nitrogen oxides in effluent discharge.
2. the method as described in claim 1, it is characterised in that without roasting after described 130-150 DEG C drying.
3. the method as described in claim 1, it is characterised in that the microsphere particle roasting is carried out in Muffle furnace.
4. the method as described in claim 1, it is characterised in that preferred slurry solid content is 45 weight %.
5. the method as described in claim 1, it is characterised in that preferably according to the weight ratio of hydrochloric acid and boehmite be 3:1
Hydrochloric acid acidifying is added, is acidified 40min.
6. the method as described in claim 1, it is characterised in that microsphere particle is roasted into 35min in 500 DEG C.
7. the method as described in claim 1, it is characterised in that in 140-150 DEG C of drying, that is, obtain in the suppression flue gas
The composition of discharged nitrous oxides.
8. the method for claim 7, it is characterised in that in 145-150 DEG C of drying, that is, obtain in the suppression flue gas
The composition of discharged nitrous oxides.
9. method as claimed in claim 8, it is characterised in that in 150 DEG C of drying, that is, obtain nitrogen oxygen in the suppression flue gas
The composition of compound discharge.
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| CN201711491571.XA CN108014828A (en) | 2017-12-30 | 2017-12-30 | A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge |
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| CN201711491571.XA CN108014828A (en) | 2017-12-30 | 2017-12-30 | A kind of preparation method for the carbon monoxide-olefin polymeric for suppressing nitrogen oxides in effluent discharge |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188427A (en) * | 1995-04-21 | 1998-07-22 | 计划地球工业公司 | Enhanced adsorbent and room temperature catalyst particle and method of making and using therefor |
| CN101311248A (en) * | 2007-05-24 | 2008-11-26 | 中国石油化工股份有限公司 | Composition for reducing discharge of NOx in FCC stack gas |
| CN102366722A (en) * | 2011-11-21 | 2012-03-07 | 国电科学技术研究院 | Denitrition catalyst with mercury removal effect and its preparation method |
-
2017
- 2017-12-30 CN CN201711491571.XA patent/CN108014828A/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1188427A (en) * | 1995-04-21 | 1998-07-22 | 计划地球工业公司 | Enhanced adsorbent and room temperature catalyst particle and method of making and using therefor |
| CN101311248A (en) * | 2007-05-24 | 2008-11-26 | 中国石油化工股份有限公司 | Composition for reducing discharge of NOx in FCC stack gas |
| CN102366722A (en) * | 2011-11-21 | 2012-03-07 | 国电科学技术研究院 | Denitrition catalyst with mercury removal effect and its preparation method |
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