CN108404973A - A kind of bimetallic catalyst and the preparation method and application thereof of ZSM-5 loads - Google Patents
A kind of bimetallic catalyst and the preparation method and application thereof of ZSM-5 loads Download PDFInfo
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- CN108404973A CN108404973A CN201810147078.4A CN201810147078A CN108404973A CN 108404973 A CN108404973 A CN 108404973A CN 201810147078 A CN201810147078 A CN 201810147078A CN 108404973 A CN108404973 A CN 108404973A
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- molecular sieve
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 46
- 239000010941 cobalt Substances 0.000 claims abstract description 46
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 26
- 238000006298 dechlorination reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 62
- 239000002808 molecular sieve Substances 0.000 claims description 36
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 36
- 239000002253 acid Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000460 chlorine Substances 0.000 claims description 19
- 229910052801 chlorine Inorganic materials 0.000 claims description 19
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 18
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 13
- 239000006228 supernatant Substances 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 2
- 150000004818 1,2-dichlorobenzenes Chemical class 0.000 claims description 2
- 150000004822 1,4-dichlorobenzenes Chemical class 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000003863 metallic catalyst Substances 0.000 claims 2
- 238000002242 deionisation method Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000012545 processing Methods 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 238000012360 testing method Methods 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 42
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Polymers C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 230000009466 transformation Effects 0.000 description 13
- 239000002245 particle Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- -1 aromatic hydrocarbon organic compound Chemical class 0.000 description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003570 air Substances 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
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B01J35/33—
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
Abstract
The invention discloses a kind of bimetallic catalyst of ZSM 5 loads, bimetallic is palladium cobalt, and the mass content of palladium is 0.1~10wt%, and the mass content of cobalt is 5~15wt%, and specific surface area is 250~350m2/g.The invention also discloses a kind of bimetallic catalysts loaded using ZSM 5 to the method for chloro organic cpd catalysis dechlorination, includes the following steps：The bimetallic catalyst that ZSM 5 is loaded is added into chloro organic cpd solution, is stirred to react under condition of different pH completely, tests and analyzes the content of chloro organic cpd in reaction solution.The bimetallic catalyst that the ZSM 5 of the present invention is loaded has higher catalytic activity, and preparation method is simple, catalytic activity is high, long lifespan, the processing of chloro organic cpd suitable for waste water, the application prospect with Industrial Wastewater Treatment.
Description
Technical field
The present invention relates to bimetallic catalysts of a kind of ZSM-5 loads and preparation method thereof more particularly to one kind can be used for
The bimetallic catalyst of the ZSM-5 loads of chlorination aromatic hydrocarbon organic compound catalytic hydrogenation and dechlorination.
Background technology
Chlorinated aromatic hydrocarbons compound is mainly used for the fields such as medicine, pesticide, organic synthesis, and chlorinated aromatic hydrocarbons compound has high poison
Property, refractory organics and high persistence, are present in soil, air and water body, have threatened natural environment for the survival of mankind.Cause
This, it is most important for the contamination control of such compound.
Chlorinated aromatic hydrocarbons processing method in common waste water has biodegradation, burning, catalytic hydrogenation and dechlorination, absorption method etc.,
In, biological degradation method is only applicable to the processing of low concentration chloro organic cpd；For burning, product often releases after burning
Than the by-product of parent pollutant toxicity bigger；Absorption method due to its it is relatively easy it is easy to operate, inexpensive and easy scale is wide
General application；Catalytic hydrogenation and dechlorination method is the preferable green catalysis process of Atom economy.
Extraction and nanometer iron metal technology relies on its simple, efficient, cheap advantage, and carrying out pollution amelioration with it especially contains chlorine
The removal of organic compound is increasingly becoming an active research field.Although the reproducibility of Zero-valent Iron is stronger, can remove more
Kind pollutant, but the activity of Zero-valent Iron processing chlorinated aromatic hydrocarbons compound is not high, reaction needs long time；Iron in reaction
Outer layer can form passivation layer, hinder contact of the Zero-valent Iron with pollutant and inactivate.Zero-valent Iron and other transition metal or noble metal
Combined system has higher activity, such as Ni/Fe, Ag/Fe, Pt/Fe, Cu/Fe, Pd/Fe nanoscale bimetallic system are catalyzed
Agent.To be prepared for PdCoB non-by precipitating reduction method by Liu et al. people (Catalysis Communications, 48 (2014) 33-37)
Crystalline-state catalyst, the hydrogenation-dechlorination for chlorobenzene compound react, and discovery is higher than in the catalytic activity of the 298K catalyst
The catalyst such as Pd/Fe.Bimetallic catalyst there are the shortcomings that：Surface, which is easy to be corroded, during the reaction leads to active component
Fall off, surface by hydroxide cover etc., make catalyst activity reduction.
Xu et al. (Journal of Hazardous Materials, 225 (2012) 36-45) is easy group for Zero-valent Iron
The shortcomings of gathering, being passivated multi-walled carbon nanotube is introduced to stabilize supported palladium iron double metal nano particle, it is found that Zero-valent Iron is uniformly steady
The fixed surface for being distributed in multi-walled carbon nanotube, high activity and cycle are shown in the catalytic hydrogenation and dechlorination of 2,4- chlorophenesic acids
Apply mechanically stability.
It is prepared by Anil K.Saroha et al. (Chemical Engineering Journal, 271 (2015) 195-203)
Charcoal stabilizes the ferronickel bimetallic catalyst of load, and nickel adulterates the corrosion and passivation that can prevent Zero-valent Iron, containing five
In the waste water of chlorophenol, the bimetallic high hydrogenation-dechlorination ability of the good adsorption capacity of charcoal, ferronickel makes such catalyst have
Very high pentachlorophenol removal ability.
Invention content
The purpose of the present invention is to provide the chlorination aromatic hydrocarbon organic compounds that can be used for of a kind of activity height, long lifespan to be catalyzed
The bimetallic catalyst of the ZSM-5 loads of hydrogenation-dechlorination.
It is a further object to provide a kind of preparation methods of the bimetallic catalyst of the ZSM-5 loads.
It is also another object of the present invention to provide a kind of bimetallic catalyst using ZSM-5 loads is organic to chloro
The method of compound for catalysis dechlorination.
To achieve the goals above, the technical solution adopted by the present invention is as follows：
One aspect of the present invention provides a kind of bimetallic catalyst of ZSM-5 loads, and bimetallic is palladium cobalt, the matter of palladium
Amount content is 0.1~10wt%, and the mass content of cobalt is 5~15wt%, and specific surface area is 250~350m2/g。
The mass content of the bimetallic catalyst of the ZSM-5 loads, palladium is 0.1~1wt%, and the mass content of cobalt is 8
~10%.
In the bimetallic catalyst of the ZSM-5 loads, Pd：Co：Ranging from the 1 of the mass ratio of B：(1~50)：(1~
10)。
Another aspect of the present invention provides a kind of preparation method of the bimetallic catalyst of the ZSM-5 loads, packet
Include following steps：
The first：It will be stood after the precursor solution of cobalt and ZSM-5 molecular sieve ultrasonic mixing, drying obtains the ZSM- containing cobalt
5 molecular sieves；Chlorine palladium acid solution is added into the ZSM-5 molecular sieve containing cobalt to be stirred, sodium borohydride solution stirring, reaction is added dropwise
Supernatant is poured out after completely, is washed with deionized until being precipitated to pH=7, drying obtains the bimetallic of the ZSM-5 loads
Catalyst；
Or, second：It will be stood after the precursor solution of cobalt and ZSM-5 molecular sieve ultrasonic mixing, drying is obtained containing cobalt
ZSM-5 molecular sieve；Sodium borohydride solution stirring is added dropwise into the ZSM-5 molecular sieve containing cobalt, supernatant is poured out after the reaction was complete, uses
Until deionized water washing is precipitated to pH=7, chlorine palladium acid solution is added and is stirred, pours out supernatant after the reaction was complete, spends
Until ion water washing is precipitated to pH=7, drying obtains the bimetallic catalyst of the ZSM-5 loads；
Or, the third：It will be stood after the precursor solution of cobalt and ZSM-5 molecular sieve ultrasonic mixing, drying is obtained containing cobalt
ZSM-5 molecular sieve；Alkaline agent solution is added dropwise into the ZSM-5 molecular sieve containing cobalt, chlorine palladium acid solution is then added and is stirred,
Sodium borohydride solution stirring is added dropwise again, pours out supernatant after the reaction was complete, is washed with deionized until being precipitated to pH=7, dries
The dry bimetallic catalyst for obtaining the ZSM-5 loads.
The presoma of the cobalt is at least one of cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate, cobalt carbonate etc..
The alkaline reagent is at least one of sodium hydroxide, potassium carbonate.
The mass percentage that the presoma of the cobalt accounts for ZSM-5 molecular sieve is 0.5~1.5%, preferably 1%.
The mass percentage that the chlorine palladium acid accounts for the ZSM-5 molecular sieve containing cobalt is 0.25~1.5%, preferably 1%.
The mass ratio of the sodium borohydride and the ZSM-5 molecular sieve containing cobalt is (3~4)：1, preferably 3.3：1.
The mass percentage that the alkaline reagent accounts for the ZSM-5 molecular sieve containing cobalt is 1~5%, preferably 2%.
The time of the standing is at least 6h.
The temperature of the drying is at least 50 DEG C, and the time is at least 6h.
The time that sodium borohydride is added dropwise is 60~120min, and drop rate is 1~2mL/min.
Another aspect of the invention provides a kind of bimetallic catalyst loaded using ZSM-5 to chloro organic compound
The method of object catalysis dechlorination, includes the following steps：
The bimetallic catalyst of ZSM-5 loads is added into chloro organic cpd solution, is stirred under condition of different pH
The reaction was complete, tests and analyzes the content of chloro organic cpd in reaction solution.
The chloro organic cpd is at least one in chlorobenzene, 1,2- dichloro-benzenes, 1,4- dichloro-benzenes, 1,2,4- trichloro-benzenes
Kind.
The chloro organic cpd solution refers to that chloro organic cpd is soluble in water, a concentration of 10~400mg/L.
The mass percentage that the chloro organic cpd accounts for the bimetallic catalyst of ZSM-5 loads is 2~15%, excellent
It is selected as 4%.
The temperature being stirred to react is 20~40 DEG C.
It is acid or alkalinity that the condition of different pH, which is directed to that sour, alkali is added in reaction solution to adjust pH value, or holding pH is
7。
The acid is at least one of hydrochloric acid, nitric acid, sulfuric acid.
The alkali is at least one of sodium hydroxide, potassium carbonate.
Due to the adoption of the above technical scheme, the present invention has the following advantages and beneficial effect：
The bimetallic catalyst of the ZSM-5 loads of the present invention has higher catalytic activity, can be compared with being urged under low palladium content
Change the catalytic hydrogenation and dechlorination that chloro organic cpd includes chlorobenzene and polystream, method for preparing catalyst is simple, catalytic activity is high,
Long lifespan, the processing of chloro organic cpd suitable for waste water, the application prospect with Industrial Wastewater Treatment.
The bimetallic catalyst of ZSM-5 loads prepared by the present invention has original position production hydrogen, flash hydrogcnation dechlorination that chloro is fragrant
Hydrocarbon is converted into the catalytic activity of no chlorine arene compound, using catalyst magnetism easily by itself and reaction liquid after reaction
Separation.
Description of the drawings
Fig. 1 is the schematic diagram that different pH influence the water phase hydrogenation-dechlorination reactivity of chlorobenzene.
Specific implementation mode
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
ZSM-5 molecular sieve used in the embodiment of the present invention is purchased from Catalyst Factory, Nankai Univ, silica alumina ratio 25.
CoSO used in the embodiment of the present invention4·7H2O be purchased from the smooth Science and Technology Co., Ltd. of upper Haitai, purity >=
99.0%.
Embodiment 1
10g ZSM-5 molecular sieves are placed in the CoSO of a concentration of 20g/L of 5mL4·7H2In O solution, placed after ultrasonic 10min
12h.It is then placed in 100 DEG C of oven drying 6h.ZSM-5 molecular sieve containing cobalt after taking 0.2g to dry, is placed in containing 10mL distilled water
In 50mL round-bottomed flasks, the 5g/L chlorine palladium acid solutions of 0.4mL are added, stir 5min.Then constant speed dropwise addition 22mL is a concentration of dropwise
30g/L sodium borohydride solutions are restored, and the time that sodium borohydride is added dropwise is 60~120min, and drop rate is 1~2mL/
Min, and keep strong stirring 1h；Supernatant liquor is finally poured out, solid particle is washed with deionized up to pH=7, then will consolidate
Body particle is positioned in 60 DEG C of vacuum drying chamber dry 6h, obtains catalyst PdCoB/ZSM-5-CR, palladium catalyst load capacity
For 1wt%, the mass content of cobalt is 10wt%, Pd in catalyst PdCoB/ZSM-5-CR：Co：The mass ratio of B is 1：10：5, than
Surface area is 300m2/g。
The configuration method of chlorine palladium acid solution is as follows：By 44.5mg PdCl2The HCl for being dissolved in a concentration of 20mmol/L of 25mL is molten
In liquid, heating water bath makes it completely dissolved, and obtains chlorine palladium acid solution.
Embodiment 2
10g ZSM-5 molecular sieves are placed in the CoSO of a concentration of 20g/L of 5mL4·7H2In O solution, placed after ultrasonic 10min
12h.It is then placed in 100 DEG C of oven drying 6h.ZSM-5 molecular sieve containing cobalt after taking 0.2g to dry, is placed in containing 10mL distilled water
50mL round-bottomed flasks in.Then constant speed is added dropwise a concentration of 30g/L sodium borohydride solutions of 22mL and is restored dropwise, and boron hydrogen is added dropwise
The time for changing sodium is 60~120min, and drop rate is 1~2mL/min, keeps strong stirring 1h.Supernatant liquor is finally poured out,
Solid particle is washed with deionized to pH=7.The 5g/L chlorine palladium acid solutions of 0.4mL are added, it is clear to pour out upper layer after stirring 30min
Liquid rinses solid particle to pH=7 with deionized water, then solid particle is positioned in 60 DEG C of vacuum drying chamber dry 6h,
Catalyst PdCoB/ZSM-5-RR is obtained, palladium catalyst load capacity is 1wt%, and the mass content of cobalt is 10wt%, catalyst
Pd in PdCoB/ZSM-5-CR：Co：The weight ratio of B is 1：10：5, specific surface area 300m2/g。
Embodiment 3
10g ZSM-5 molecular sieves are placed in the CoSO of a concentration of 20g/L of 5mL4·7H2In O solution, placed after ultrasonic 10min
12h.It is then placed in 100 DEG C of oven drying 6h.ZSM-5 molecular sieve containing cobalt after taking 0.2g to dry, is placed in containing 10mL distilled water
50mL round-bottomed flasks in.Then the NaOH solution of a concentration of 20g/L of 0.2mL is added dropwise, and the 5g/L chlorine palladium acid that 0.4mL is added is molten
Liquid stirs 5min, then constant speed is added dropwise a concentration of 30g/L sodium borohydride solutions of 22mL and is restored dropwise, and sodium borohydride is added dropwise
Time is 60~120min, and drop rate is 1~2mL/min, keeps strong stirring 1h, finally pour out supernatant liquor and spend from
Sub- water rinses solid particle to pH=7, then solid particle is positioned in 60 DEG C of vacuum drying chamber dry 6h, obtains catalyst
PdCoB/ZSM-5-PR, palladium catalyst load capacity are 1wt%, and the mass content of cobalt is 10wt%, catalyst PdCoB/ZSM-5-
Pd in CR：Co：The weight ratio of B is 1：10：5, specific surface area 300m2/g。
Embodiment 4
Using the bimetallic catalyst of ZSM-5 loads to the method for chloro organic cpd catalysis dechlorination, including following step
Suddenly：The water phase hydrogenation-dechlorination that the present embodiment carries out chlorobenzene using catalyst prepared by Examples 1 to 3 is tested, and takes 80mL a concentration of
100mg/L chlorobenzene aqueous solutions are added in 50mL round-bottomed flasks, and the bimetallic catalyst that 200mg ZSM-5 loads are added (is implemented
Catalyst prepared by example 1~3)；50mL round-bottomed flask reactors are full of by solution at normal temperatures and pressures, hardly stay other spaces
And seal, it is reacted under strong stirring.Chromatography reaction solution after reaction, the results showed that chlorobenzene is turned by catalytic hydrogenation
It is melted into benzene, is generated without other products.Chlorobenzene transformation ratio data are listed in table 1, within 30~60min times, embodiment 1 and implementation
Catalyst prepared by example 2 shows higher catalytic activity, and chlorobenzene transformation ratio reaches 100%.Catalyst prepared by embodiment 3
Chlorobenzene transformation ratio is 69% in 60min.
Water phase hydrogenation-dechlorination performance of the catalyst of the different preparation methods of table 1 for chlorobenzene
Embodiment 5
10g ZSM-5 molecular sieves are placed in the CoSO of a concentration of 20g/L of 5mL4·7H2In O solution, placed after ultrasonic 10min
12h.It is then placed in 100 DEG C of oven drying 6h.ZSM-5 molecular sieve containing cobalt after taking 0.2g to dry, is placed in containing 10mL distilled water
50mL round-bottomed flasks in.Then the NaOH solution of a concentration of 20g/L of 0.2mL is added dropwise, and the 5g/L chlorine palladium acid that 0.2mL is added is molten
Liquid stirs 5min.Then constant speed is added dropwise a concentration of 30g/L sodium borohydride solutions of 22mL and is restored dropwise, and sodium borohydride is added dropwise
Time be 60~120min, drop rate is 1~2mL/min, keeps strong stirring 1h, finally pours out supernatant liquor and spend
Ionized water rinses solid particle to pH=7, then solid particle is positioned in 60 DEG C of vacuum drying chamber dry 6h, is catalyzed
Agent PdCoB/ZSM-5-PR, palladium catalyst load capacity are 0.5wt%, and the mass content of cobalt is 10wt%, catalyst PdCoB/
Pd in ZSM-5-CR：Co：The weight ratio of B is 1：20：5, specific surface area 310m2/g。
Embodiment 6
10g ZSM-5 molecular sieves are placed in the CoSO of a concentration of 20g/L of 5mL4·7H2In O solution, placed after ultrasonic 10min
12h.It is then placed in 100 DEG C of oven drying 6h.ZSM-5 molecular sieve containing cobalt after taking 0.2g to dry, is placed in containing 10mL distilled water
50mL round-bottomed flasks in.Then the NaOH solution of a concentration of 20g/L of 0.2mL is added dropwise, and the 5mg/L chlorine palladium acid of 0.1mL is added
Solution stirs 5min.Then constant speed is added dropwise the sodium borohydride solution of a concentration of 30g/L of 22mL and is restored dropwise, and boron hydrogen is added dropwise
The time for changing sodium is 60~120min, and drop rate is 1~2mL/min, keeps strong stirring 1h, finally pours out supernatant liquor simultaneously
Solid particle is rinsed to pH=7 with deionized water, then solid particle is positioned in 60 DEG C of vacuum drying chamber dry 6h, is obtained
Catalyst PdCoB/ZSM-5-PR, palladium catalyst load capacity are 0.25wt%, and the mass content of cobalt is 10wt%, catalyst
Pd in PdCoB/ZSM-5-CR：Co：The weight ratio of B is 1：40：5, specific surface area 315m2/g。
Embodiment 7
According to the method for embodiment 4, catalyst prepared by testing example 5, embodiment 6 is to water phase chlorobenzene hydrogenation-dechlorination
Activity, after reaction chromatography reaction solution, the results showed that chlorobenzene, at benzene, is given birth to by catalytic hydroconversion without other products
At.Chlorobenzene transformation ratio data are listed in table 2, and the catalyst prepared with embodiment 3 is compared, when the content of Pd is down to 0.5%,
Within the 60min times, chlorobenzene transformation ratio is close to 100%；Pd contents are further decreased to 0.25%, and chlorobenzene transformation ratio is still up to
84%, show that the bimetallic catalyst of ZSM-5 loads has very high activity to chlorobenzene hydrogenation-dechlorination.
Influence of the Pd contents to water phase chlorobenzene hydrogenation-dechlorination catalytic performance in 2 catalyst of table
Embodiment 8
With embodiment 4 catalyst prepared by 200mg embodiments 3 is added, by the pH value dust technology of reaction solution in reaction condition
Solution is adjusted to 3, and chlorobenzene transformation ratio reaches 60% in 40min, as shown in Figure 1.
Embodiment 9
With embodiment 4 catalyst prepared by 200mg embodiments 3 is added, by the dilute hydrogen-oxygen of the pH value of reaction solution in reaction condition
Change sodium solution and be adjusted to 10, chlorobenzene transformation ratio reaches 100% in 20min, as shown in Figure 1.
Embodiment 10
With embodiment 4 catalyst prepared by 200mg embodiments 3 is added, by the dilute hydrogen-oxygen of the pH value of reaction solution in reaction condition
Change sodium solution and be adjusted to 12, chlorobenzene transformation ratio reaches 100% in 30min, as shown in Figure 1.
Embodiment 4, embodiment 8, embodiment 9, as shown in FIG. 1, FIG. 1 is not for the curve graph of the chlorobenzene transformation ratio of embodiment 10
The schematic diagram that the water phase hydrogenation-dechlorination reactivity of chlorobenzene is influenced with pH.It can be seen from the figure that the chlorobenzene conversion of embodiment 4
The curve graph (▲ curve represented) of rate, chlorobenzene is completely converted into benzene in 30min；The curve of the chlorobenzene transformation ratio of embodiment 8
Figure (■ represent curve), in acid condition, chlorobenzene is not completely converted into benzene in 40min, still residue 35% or so
Chlorobenzene is unconverted；The curve graph (curve that ▼ is represented) of the chlorobenzene transformation ratio of embodiment 9, under alkaline condition, the chlorine in 20min
Benzene is completely converted into benzene；The curve graph (● the curve of representative) of the chlorobenzene transformation ratio of embodiment 10, under alkaline condition,
Chlorobenzene is completely converted into benzene in 30min.It can be seen that within the identical reaction time, react under alkaline or neutral conditions, chlorine
Complete for organic compound conversions, dechlorination effect is best, in acid condition, chloro organic cpd Partial Conversion, dechlorination effect
Fruit is preferable.
The basic principles, main features and advantages of the present invention have been shown and described above.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, various changes and improvements may be made to the invention without departing from the spirit and scope of the present invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent defines.
Claims (10)
1. a kind of bimetallic catalyst of ZSM-5 loads, it is characterised in that：Bimetallic is palladium cobalt, the mass content of palladium is 0.1~
The mass content of 10wt%, cobalt are 5~15wt%, and specific surface area is 250~350m2/g。
2. the bimetallic catalyst of ZSM-5 loads according to claim 1, it is characterised in that：Pair of the ZSM-5 loads
The mass content of metallic catalyst, palladium is 0.1~1wt%, and the mass content of cobalt is 8~10%.
3. the bimetallic catalyst of ZSM-5 loads according to claim 1, it is characterised in that：Pair of the ZSM-5 loads
In metallic catalyst, Pd：Co：Ranging from the 1 of the mass ratio of B：(1~50)：(1~10).
4. a kind of preparation method of the bimetallic catalyst of claims 1 to 3 any one of them ZSM-5 loads, feature exist
In：Include the following steps：
The first：It will be stood after the precursor solution of cobalt and ZSM-5 molecular sieve ultrasonic mixing, drying obtains the ZSM-5 containing cobalt points
Son sieve；Chlorine palladium acid solution is added into the ZSM-5 molecular sieve containing cobalt to be stirred, sodium borohydride solution stirring is added dropwise, has reacted
Supernatant is poured out after complete, is washed with deionized until being precipitated to pH=7, the bimetallic that drying obtains the ZSM-5 loads is urged
Agent；
Or, second：It will be stood after the precursor solution of cobalt and ZSM-5 molecular sieve ultrasonic mixing, drying obtains the ZSM-5 containing cobalt
Molecular sieve；Into the ZSM-5 molecular sieve containing cobalt be added dropwise sodium borohydride solution stirring, pour out supernatant after the reaction was complete, spend from
Until sub- water washing is precipitated to pH=7, chlorine palladium acid solution is added and is stirred, pours out supernatant after the reaction was complete, uses deionization
Until water washing is precipitated to pH=7, drying obtains the bimetallic catalyst of the ZSM-5 loads；
Or, the third：It will be stood after the precursor solution of cobalt and ZSM-5 molecular sieve ultrasonic mixing, drying obtains the ZSM-5 containing cobalt
Molecular sieve；Alkaline agent solution is added dropwise into the ZSM-5 molecular sieve containing cobalt, chlorine palladium acid solution is then added and is stirred, then drips
Add sodium borohydride solution to stir, supernatant is poured out after the reaction was complete, be washed with deionized until being precipitated to pH=7, drying obtains
Obtain the bimetallic catalyst of the ZSM-5 loads.
5. the preparation method of the bimetallic catalyst of ZSM-5 loads according to claim 4, it is characterised in that：The cobalt
Presoma be cobaltous sulfate, cobalt nitrate, cobalt chloride, cobalt acetate, at least one of cobalt carbonate；
The alkaline reagent is at least one of sodium hydroxide, potassium carbonate；
The mass percentage that the presoma of the cobalt accounts for ZSM-5 molecular sieve is 0.5~1.5%, preferably 1%.
6. the preparation method of the bimetallic catalyst of ZSM-5 loads according to claim 4, it is characterised in that：The chlorine
The mass percentage that palladium acid accounts for the ZSM-5 molecular sieve containing cobalt is 0.25~1.5%, preferably 1%；
The mass ratio of the sodium borohydride and the ZSM-5 molecular sieve containing cobalt is (3~4)：1, preferably 3.3：1；
The mass percentage that the alkaline reagent accounts for the ZSM-5 molecular sieve containing cobalt is 1~5%, preferably 2%.
7. the preparation method of the bimetallic catalyst of ZSM-5 loads according to claim 4, it is characterised in that：It is described quiet
The time set is at least 6h；
The temperature of the drying is at least 50 DEG C, and the time is at least 6h；
The time that sodium borohydride is added dropwise is 60~120min, and drop rate is 1~2mL/min.
8. a kind of bimetallic catalyst using 3 any one of them ZSM-5 loads of claims 1 to 3 is to chloro organic cpd
The method of catalysis dechlorination, it is characterised in that：Include the following steps：
The bimetallic catalyst of ZSM-5 loads is added into chloro organic cpd solution, is stirred to react under condition of different pH
Completely, the content of chloro organic cpd in reaction solution is tested and analyzed.
9. the bimetallic catalyst according to claim 8 using ZSM-5 loads is to chloro organic cpd catalysis dechlorination
Method, it is characterised in that：The chloro organic cpd is chlorobenzene, 1,2- dichloro-benzenes, 1,4- dichloro-benzenes, 1,2,4- trichloro-benzenes
At least one of；
The chloro organic cpd solution refers to that chloro organic cpd is soluble in water, a concentration of 10~400mg/L；
The mass percentage that the chloro organic cpd accounts for the bimetallic catalyst of ZSM-5 loads is 2~15%, preferably
4%；
The temperature being stirred to react is 20~40 DEG C；
The condition of different pH is directed to be added acid, alkali adjusting pH value in reaction solution as acid or alkalinity, or it is 7 to keep pH.
10. the bimetallic catalyst according to claim 9 using ZSM-5 loads is to chloro organic cpd catalysis dechlorination
Method, it is characterised in that：The acid is at least one of hydrochloric acid, nitric acid, sulfuric acid；
The alkali is at least one of sodium hydroxide, potassium carbonate.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111569894A (en) * | 2020-06-05 | 2020-08-25 | 华东理工大学 | Supported Cu-Fe-based catalyst and preparation method and application thereof |
| CN112844466A (en) * | 2021-02-02 | 2021-05-28 | 华南农业大学 | Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof |
| CN113198475A (en) * | 2021-04-29 | 2021-08-03 | 清创人和生态工程技术有限公司 | Preparation method and application of ferroalloy catalyst |
| CN114790168A (en) * | 2021-05-18 | 2022-07-26 | 上海素馨化工科技有限公司 | Preparation method of 2-amino-4-trifluoromethylpyridine and 2-amino-4-trifluoromethylpyridine |
| CN115121283A (en) * | 2022-07-21 | 2022-09-30 | 安徽国星生物化学有限公司 | Preparation method of loaded dispersion type monatomic catalyst for pyridine base production |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007281A (en) * | 2007-01-26 | 2007-08-01 | 南开大学 | Novel preparation method of amorphous alloy catalyst |
| CN102173492A (en) * | 2011-01-13 | 2011-09-07 | 华东理工大学 | Catalytic dechlorination method for chlorinated aromatic hydrocarbon organic compounds |
-
2018
- 2018-02-12 CN CN201810147078.4A patent/CN108404973A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101007281A (en) * | 2007-01-26 | 2007-08-01 | 南开大学 | Novel preparation method of amorphous alloy catalyst |
| CN102173492A (en) * | 2011-01-13 | 2011-09-07 | 华东理工大学 | Catalytic dechlorination method for chlorinated aromatic hydrocarbon organic compounds |
Non-Patent Citations (1)
| Title |
|---|
| JÁNOS HALÁSZ等: "HYDRODECHLORINATION OF CHLOROPHENOLS OVER Pt- AND Co-CONTAINING ZSM-5 ZEOLITE CATALYSTS", 《REACT.KINET.CATAL.LETT.》 * |
Cited By (8)
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|---|---|---|---|---|
| CN111569894A (en) * | 2020-06-05 | 2020-08-25 | 华东理工大学 | Supported Cu-Fe-based catalyst and preparation method and application thereof |
| CN112844466A (en) * | 2021-02-02 | 2021-05-28 | 华南农业大学 | Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof |
| CN112844466B (en) * | 2021-02-02 | 2022-03-25 | 华南农业大学 | Green biomass charcoal modified molecular sieve supported metal catalyst and preparation method and application thereof |
| CN113198475A (en) * | 2021-04-29 | 2021-08-03 | 清创人和生态工程技术有限公司 | Preparation method and application of ferroalloy catalyst |
| CN113198475B (en) * | 2021-04-29 | 2023-04-25 | 清创人和生态工程技术有限公司 | Preparation method and application of ferroalloy catalyst |
| CN114790168A (en) * | 2021-05-18 | 2022-07-26 | 上海素馨化工科技有限公司 | Preparation method of 2-amino-4-trifluoromethylpyridine and 2-amino-4-trifluoromethylpyridine |
| CN114790168B (en) * | 2021-05-18 | 2024-02-09 | 上海素馨化工科技有限公司 | Preparation method of 2-amino-4-trifluoromethyl pyridine and 2-amino-4-trifluoromethyl pyridine |
| CN115121283A (en) * | 2022-07-21 | 2022-09-30 | 安徽国星生物化学有限公司 | Preparation method of loaded dispersion type monatomic catalyst for pyridine base production |
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Application publication date: 20180817 |