CN103848708A - Method for preparing cyclohexane through catalytic dechlorination on chlorobenzene and preparation method of catalyst used in method - Google Patents
Method for preparing cyclohexane through catalytic dechlorination on chlorobenzene and preparation method of catalyst used in method Download PDFInfo
- Publication number
- CN103848708A CN103848708A CN201410109001.XA CN201410109001A CN103848708A CN 103848708 A CN103848708 A CN 103848708A CN 201410109001 A CN201410109001 A CN 201410109001A CN 103848708 A CN103848708 A CN 103848708A
- Authority
- CN
- China
- Prior art keywords
- chlorobenzene
- catalyst
- gac
- activated carbon
- ethylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 title claims abstract description 136
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 100
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 230000002829 reductive effect Effects 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 230000035484 reaction time Effects 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 81
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 22
- 239000003610 charcoal Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 17
- 239000002250 absorbent Substances 0.000 claims description 14
- 230000002745 absorbent Effects 0.000 claims description 14
- 239000000084 colloidal system Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000002203 pretreatment Methods 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000012453 solvate Substances 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 48
- 230000009466 transformation Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- -1 aromatic hydrocarbons organic compound Chemical class 0.000 description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 241000370738 Chlorion Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 230000001988 toxicity Effects 0.000 description 3
- 231100000419 toxicity Toxicity 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical group 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a chlorobenzene catalytic dechlorination method and a preparation method of a catalyst used in the chlorobenzene catalytic dechlorination method. The chlorobenzene catalytic dechlorination method comprises that chlorobenzene and catalyst activated carbon loaded nano platinum are mixed in a methanol solvent in mole ratio of chlorobenzene to Pt ion of 1:0.05, and sealing; introducing H2, and carrying out hydrogenation reduction reaction repeatedly, so that cyclohexane is prepared, wherein the reaction time is 6-8 hours. By adopting the chlorobenzene catalytic dechlorination method, pollution of chlorobenzene to the environment can be reduced, high-purity cyclohexane is prepared, activated carbon loaded nano precious metal is taken as a catalyst, chlorobenzene can be rapidly hydrogenized and converted into cyclohexane product at normal temperature and normal pressure, cost is reduced, catalytic activity is high, the conversion rate is high, the reaction rate is high, and the selectivity on cyclohexane is good.
Description
Technical field
The invention belongs to fine chemical technology field, specifically, relate to a kind of method of chlorobenzene catalysis dechlorination and the preparation method of catalyzer thereof.
Background technology
Chlorobenzene is a kind of important industrial chemicals and pesticide intermediate, can be by volatilization or as the degraded product of agricultural chemicals and in entered environment.Poisonous and the difficult degradation of chlorobenzene, is listed in U.S. EPA Environment Priority control pollutent.Its stable chemical nature, easily accumulation in vivo, natural, ecological and human health in serious threat.Therefore, the control of the chlorinated aromatic hydrocarbons such as chlorobenzene has become the focus that people pay close attention to, and the toxicity of chlorinated aromatic hydrocarbons is mainly the introducing due to chlorine element, so if chlorine wherein can be taken off with the form of ion, just can effectively reduce its toxicity.The research of chlorinated aromatic hydrocarbons catalysis dechlorination not only can be found effective solution route for removing industrial hypertoxic rubbish polychlorinated biphenyl, and can be effectively used to organic synthesis.
Hexanaphthene is the liquid of colourless irritant smell.Water insoluble, be dissolved in most organic solvents.Its purposes is very extensive, is the very important solvent of chemical field, reagent and raw materials.At present, the preparation of hexanaphthene is mainly that benzene catalytic hydrogenation makes, or is made by crude petroleum fractions.The cyclohexane purity that crude petroleum fractions makes is not high, and as obtained highly purified hexanaphthene, refining operation is very complicated, and preparation cost is higher.Although benzene catalytic hydrogenation can make the cyclohexane that purity is higher, the cost of purified petroleum benzin is higher.
Chlorobenzene hydrodechlorination can make hexanaphthene, but the technique of existing chlorobenzene hydrodechlorination, exists that complex process, condition harshness, yield are low, dechlorination be converted into the problems such as hexanaphthene completely.
Patent application CN102173492A discloses a kind of method of chlorinated aromatic hydrocarbons organic compound catalysis dechlorination, it adopts amorphous cobalt carried noble metal is catalyzer, adopt amorphous cobalt to react original position with water and produce hydrogen as reductive agent, chloride arene organic compound is transformed into corresponding arene organic compound.This defective workmanship is: amorphous cobalt is expensive, and this poor catalyst stability, and catalytic activity is low.
Patent application CN101475428A discloses a kind of a kind of room temperture nickel catalysis dechlorination method of chlorinated aromatic hydrocarbons, and the method is: under the existence of alkali, in low-carbon alcohol solvent, nickelous catalyzer is the dechlorination reaction of catalysis chlorinated aromatic hydrocarbons at room temperature.The defect of the method is: need to add alkali, and reaction conditions complexity, nickelous catalyzer can not recycle, and catalytic activity is low.
Summary of the invention
One of technical problem that the present invention solves is: proposed a kind of method that chlorobenzene catalysis dechlorination is prepared hexanaphthene, both can remove the chlorion in chlorobenzene, reduce its pollution to environment, can use again discarded chlorobenzene to replace purified petroleum benzin to prepare hexanaphthene, reduce the production cost of hexanaphthene.
Two of the technical problem that the present invention solves is: proposed a kind of activated carbon supported nano-noble metal and preparation method thereof, this catalyzer can recycle, and catalytic activity is good, and its preparation method is simple.
Technical scheme of the present invention is: a kind of chlorobenzene catalysis dechlorination is prepared the method for hexanaphthene, be 0.1～0.5Mpa at pressure, temperature is under 25～50 DEG C of conditions, according to mol ratio chlorobenzene: Pt ion=1:0.05, chlorobenzene is mixed in methanol solvate with catalyst activity charcoal loaded with nano platinum, and sealing; Pass into H
2carry out hydrogenation reduction repeatedly, make hexanaphthene, the reaction times is 6～8h;
The reaction formula of above-mentioned reaction is:
The preparation method of described activated carbon supported nm Pt catalyst is:
1, prepare nanometer platinum colloid solution:
Taking Platinic chloride as reactant, taking ethylene glycol as solvent with reductive agent, sodium hydroxide is catalyzer, and stirring and refluxing is prepared the nanometer Pt colloidal solution of particle diameter below 5nm;
The chemical equation of above-mentioned reaction is:
The molecular formula of described Platinic chloride: H
2ptCl
66H
2o.
Concrete preparation process is: under nitrogen protection condition, according to the ratio of 1:50g/mL, Platinic chloride is dissolved in ethylene glycol respectively, according to the ratio of 1:50g/mL, NaOH is dissolved in ethylene glycol equally, it is identical in quality that Platinic chloride and NaOH add.Above-mentioned two kinds of mixed solution are mixed, and be heated to 160 DEG C, in Hybrid Heating process, constantly stir, after stirring and refluxing 3h, obtain the Pt colloidal solution of brownish black, be designated as Pt/ ethylene glycol.By colloidal solution constant volume, for subsequent use.
In above-mentioned reaction, ethylene glycol is simultaneously as reductive agent.
2, select wooden pharmaceutical grade gac as absorbent charcoal carrier.
3, absorbent charcoal carrier is carried out to pre-treatment: according to the ratio of 1:10g/mL, gac (AC) is dispersed in to the HNO that concentration is 65-68%
3in, under temperature 50 C, after stirring back flow reaction 5h, suction filtration repeatedly by extremely neutrality of deionized water wash, obtains the gac of modification under temperature 60 C after vacuum-drying 10h.
4, prepare activated carbon supported nm Pt catalyst:
Press charge capacity 1.0% by gac and Pt/ ethylene glycol colloidal solution mix and blend, stirring velocity is 350r/min, then slowly drip and the isopyknic distilled water of Pt/ ethylene glycol colloidal solution, destroy the stability of colloid, promote that nano Pt particles loads on gac, after stirring 24h, filter, dry and make activated carbon supported nm Pt catalyst, for subsequent use.
Beneficial effect of the present invention is: reduce the pollution of chlorobenzene to environment, make the hexanaphthene that purity is higher, taking activated carbon supported nano-noble metal as catalyzer, rapid hydrogenation chlorobenzene at normal temperatures and pressures, is converted into product hexanaphthene, has reduced cost, catalytic activity is high, transformation efficiency is high, and speed of reaction is fast, good to the selectivity of hexanaphthene.
Brief description of the drawings
Fig. 1 is that the transmission electron microscope of Pt/ ethylene glycol characterizes (being TEM) photo;
Fig. 2 is the size distribution figure of Pt/ ethylene glycol;
Fig. 3 is the TEM photo of activated carbon supported nm Pt catalyst;
Fig. 4 is the carrying out along with reaction, chlorobenzene, the composition history curve of hexanaphthene and benzene.
Embodiment
Illustrate the present invention below in conjunction with embodiment.
Embodiment 1:
1, prepare activated carbon supported nm Pt catalyst:
(1) prepare nanometer platinum colloid solution:
Under nitrogen protection condition, respectively 1.0g Platinic chloride is dissolved in 50mL ethylene glycol, 1.0gNaOH is dissolved in 50mL ethylene glycol equally.Above-mentioned two kinds of mixed solution are mixed, and be heated to 160 DEG C, in Hybrid Heating process, constantly stir, after stirring and refluxing 3h, obtain the Pt colloidal solution of brownish black, be designated as Pt/ ethylene glycol.By colloidal solution constant volume, for subsequent use.
When heating, the color of reaction soln is by from initial glassy yellow is deepened gradually, and moment shoals, then moment become brownish black, successfully obtained brownish black platinum colloid in reaction after 3h.Prepared Pt colloidal solution can at room temperature be preserved the several months for a long time, occurs there are no precipitation, also can impel nano platinum particle to separate out by adjusting pH value, and can again be dissolved in other solvents.
The above-mentioned Pt/ ethylene glycol transmission electron microscope making is characterized, according to electromicroscopic photograph, randomly draw approximately 300 particles and carry out particle diameter statistics, calculate the standard deviation of median size and the size distribution of Pt colloidal particle.The transmission electron microscope of Pt/ ethylene glycol characterizes (being TEM) photo and asks for an interview Fig. 1, and the size distribution of Pt/ ethylene glycol please as shown in Figure 2.
As can be seen from Figure 1, the dispersion of Pt/ ethylene glycol colloid is uniformly, does not see the agglomeration of obvious metal colloid particles.As shown in Figure 2, the median size of prepared Pt/ ethylene glycol colloid is 2.3nm, and the size of particles of colloid is between 1.0～4.0nm, and the standard deviation of particle diameter is 0.4nm.
(2) select wooden pharmaceutical grade gac as absorbent charcoal carrier, be designated as AC.
(3) the selected absorbent charcoal carrier of step (2) is carried out to pre-treatment: 5g gac (AC) is dispersed in to the HNO that 50mL concentration is 65-68%
3in, under temperature 50 C, after stirring back flow reaction 5h, suction filtration repeatedly by extremely neutrality of deionized water wash, obtains the gac AC of modification under temperature 60 C after vacuum-drying 10h
-HNO3.
(4) prepare activated carbon supported nm Pt catalyst:
Gac step (3) being obtained by charge capacity 1.0% and Pt/ ethylene glycol colloidal solution mix and blend, stirring velocity is 350r/min, then slowly drip and the isopyknic distilled water of Pt/ ethylene glycol colloidal solution, destroy the stability of colloid, promote that nano Pt particles loads on gac, after stirring 24h, filter, oven dry makes activated carbon supported nm Pt catalyst and (is designated as
), for subsequent use.
After load, catalyzer, through washing, filters, and filtrate does not all have color, illustrates that nano platinum particle is fully adsorbed on activated carbon surface, and ICP measuring and calculation charge capacity is 1.00%, has verified the complete load of nano platinum particle.As can be seen from Figure 3, nano platinum particle loads on absorbent charcoal carrier well, there is no obvious agglomeration.
2, chlorobenzene catalysis dechlorination is prepared hexanaphthene:
At 25 DEG C, under hydrogen pressure 0.1MPa, carry out the reaction of chlorobenzene catalysis dechlorination.According to mol ratio chlorobenzene: Pt ion=1:0.05, chlorobenzene is mixed in methanol solvate with catalyst activity charcoal loaded with nano platinum, and sealing; Pass into H
2carry out hydrogenation reduction repeatedly, make hexanaphthene, the reaction times is 6～8h.The transformation efficiency of chlorobenzene reaches 100.00%, and the selectivity of hexanaphthene is reached to 80.25%-95.52%,
By stratographic analysis, the product of the hydrogenation dechlorination reaction of Pt/AC to chlorobenzene only has benzene and hexanaphthene.In the initial period of reaction, product is made up of jointly benzene and hexanaphthene, and after reaction 6-8h, the further hydrogenation of benzene is hexanaphthene.
Analyze chlorobenzene, the content of benzene and hexanaphthene with gas chromatograph.Chromatographic column AC-10 capillary column, 30m × 0.53mm × 1.0mm, stationary liquid is 14% nitrile propyl phenyl 86% polydimethylsiloxane.Sample introduction 0.2 μ L; Before post, press 0.04MPa; Hydrogen pressure 0.08MPa; Air pressure 0.08MPa; 170 DEG C of sampler temperature; 170 DEG C of hydrogen flame ionization detector temperature; 50 DEG C of column temperatures.Use marker method to detect the content of each material in analytical reaction system, octane is chromatogram internal standard substance.By measured data, reacted each product is analyzed, thereby calculated reactive behavior and selectivity.Obtain shown in Fig. 4 according to the method: along with the carrying out of reaction, chlorobenzene, the composition history curve of hexanaphthene and benzene.
As seen in Figure 4: the reaction of Pt/AC catalytic hydrogenation chlorobenzene can be carried out under normal temperature (25～50 DEG C), normal pressure (0.1～0.5MPa) condition.When 6h is carried out in reaction, the transformation efficiency of chlorobenzene reaches 100.00%, and the selectivity of hexanaphthene is reached to 80.25%; When 8h is carried out in reaction, the selectivity of hexanaphthene is reached to 95.52%, known, phenyl originally can change into hexanaphthene completely.
As can be seen from Figure 4: the concentration of carrying out reactant chlorobenzene with reaction reduces gradually, the concentration of hexanaphthene increases gradually simultaneously, and the concentration of benzene increases sharply in the time that reaction starts, meanwhile, benzene also to hexanaphthene transform, that is to say, benzene is the intermediate product that chlorobenzene is converted into hexanaphthene.From Fig. 4, also can find out, along with the variation of time, the activity of catalysis chlorobenzene is declining gradually.Because after reaction 1h, the transformation efficiency of chlorobenzene has reached 86.87%, chlorobenzene density loss; Simultaneously in catalysis dechlorination process, can produce chlorion, chlorion adsorb and occupies active sites at catalyst surface, and chlorobenzene, benzene competition active hydrogen, has hindered the carrying out reacting.In reaction process, impact how to eliminate hydrogenchloride improves transformation efficiency important in inhibiting.Use Pd/Al
2o
3when catalysis chlorobenzene dechlorination, product is mainly benzene and a small amount of hexanaphthene; Because HCl is in the absorption in active centre, the activity of catalyzer fails in time.While using Pd/SBA-1 catalysis chlorobenzene, need in reaction system, add NaOH, the HCl that neutralization reaction produces, just can make reaction proceed.Pt/AC catalyzer can make benzene change into hexanaphthene completely substantially.And chlorobenzene only has a chlorine substituent, be a kind of material of lasting toxicity, the more difficult dechlorination of polystream relatively.If can obtain good effect in the time processing chlorobenzene, Pt/AC catalyzer equally can other organic pollutant of catalysis.
Embodiment 2:
Outside lower difference, other are with embodiment 1.
1, prepare activated carbon supported nm Pt catalyst:
(3) the selected absorbent charcoal carrier of step (2) is carried out to pre-treatment: 5g gac (AC) is dispersed in to the H that 50mL concentration is 65-68%
2o
2in, under temperature 50 C, after stirring back flow reaction 5h, suction filtration repeatedly by extremely neutrality of deionized water wash, obtains the gac of modification under temperature 60 C after vacuum-drying 10h.
The activated carbon supported nm Pt catalyst finally making, is designated as Pt/AC-
h2O2.
Embodiment 3:
Outside lower difference, other are with embodiment 1.
1, prepare activated carbon supported nm Pt catalyst:
(3) the selected absorbent charcoal carrier of step (2) is no longer carried out to pre-treatment.The activated carbon supported nm Pt catalyst finally making, is designated as Pt/AC.
The activated carbon supported nm Pt catalyst that uses respectively embodiment 1-3 to make, under equal conditions carries out catalysis dechlorination reaction to chlorobenzene.Testing data is as shown in table 1.
Catalyzer is under neutrallty condition, and the active result of 298K, the reaction of 6h catalytic hydrogenation chlorobenzene is as shown in table 1.In the activated carbon supported catalyst chlorobenzene of chemical modification hydrogenation, the selectivity of hexanaphthene is all improved.At Pt/AC-
hNO3upper, chlorobenzene transformation efficiency is 100.00%, and the selectivity of hexanaphthene is 91.46%.For Pt/AC-
h2O2catalyzer, chlorobenzene transformation efficiency slightly declines, but the selectivity of hexanaphthene brings up to 83.97%.
The impact of table 1 chemical modification on catalyst chlorobenzene performance
The absorption on reactant in liquid phase reaction of the pore structure of catalyzer and size and the desorption of product have important impact.Most metals active site is distributed in the mesopore and macropore of catalyzer, is beneficial to diffusion and the absorption of organic molecule; But also have a small amount of active site to be distributed in micropore, be unfavorable for diffusion and the absorption of organic molecule.Chlorobenzene molecule is 0.39nm, and therefore, the micropore that is less than 0.39nm can not participate in the hydrogenation of chlorobenzene.AC is through HNO
3after processing, pore volume increases, and micropore reduces, Pt/AC
-HNO3in the hydrogenation of catalysis chlorobenzene is anti-, be beneficial to the diffusion of chlorobenzene and product, speed of reaction improves, and the selectivity of hexanaphthene improves; But Pt/AC
-H2O2mesopore and macropore increase, speed of reaction is relatively low.
Carboxyl is electron donor(ED), and phenyl ring is electron acceptor(EA), and after chemical modification, carried by active carbon surface has increased a large amount of oxy radicals, and the increase of carboxyl has strengthened the adsorptive power of catalyzer to phenyl ring, is beneficial to and generates benzene continuation hydrogenation generation hexanaphthene.Therefore,, in two kinds of catalyst chlorobenzene hydrogenations, the selectivity of hexanaphthene is all improved.
Surface tissue parameter, surface chemical property in conjunction with experimental result and absorbent charcoal carrier: use HNO
3the activated carbon supported nm Pt catalyst making after pre-treatment, its activity is higher, higher to the catalysis dechlorination transformation efficiency of chlorobenzene, better to the selectivity of hexanaphthene.
Embodiment 4:
Outside lower difference, other are with embodiment 1.
1, prepare activated carbon supported nm Pt catalyst:
(2) select sugar charcoal chemical grade gac as absorbent charcoal carrier, be designated as AC-1.
Embodiment 3:
Outside lower difference, other are with embodiment 1.
1, prepare activated carbon supported nm Pt catalyst:
(2) select lignifying classes and grades in school gac as absorbent charcoal carrier, be designated as AC-2.
The activated carbon supported nm Pt catalyst that uses respectively embodiment 1,4,5 to make, under equal conditions carries out catalysis dechlorination reaction to chlorobenzene.Testing data is as shown in table 2.
Catalyzer is under neutrallty condition, and the active result of 298K, the reaction of 6h catalytic hydrogenation chlorobenzene is as shown in table 2.On Pt/AC-2 catalyzer, the transformation efficiency of chlorobenzene is 11.75%, and the selectivity of hexanaphthene is 78.03%; And on Pt/AC-1, chlorobenzene transformation efficiency is increased to 97.89%, the selectivity of hexanaphthene drops to 63.28%.For Pt/AC catalyzer, chlorobenzene transforms completely, and the selectivity of hexanaphthene brings up to 80.25%.
Activated carbon supported nm Pt catalyst prepared by the table 2 different activities charcoal carrier impact on catalysis chlorobenzene performance
Claims (4)
1. a chlorobenzene catalysis dechlorination is prepared the method for hexanaphthene, be 0.1～0.5MPa at pressure, temperature is under 25～50 DEG C of conditions, according to mol ratio chlorobenzene: Pt ion=1:0.05, chlorobenzene is mixed in methanol solvate with catalyst activity charcoal loaded with nano platinum, and sealing; Pass into H
2carry out hydrogenation reduction repeatedly, make hexanaphthene, the reaction times is 6～8h;
The reaction formula of above-mentioned reaction is:
2. chlorobenzene catalysis dechlorination according to claim 1 is prepared the method for hexanaphthene, it is characterized in that, the preparation method of described activated carbon supported nm Pt catalyst is:
(1) prepare nanometer platinum colloid solution:
Taking Platinic chloride as reactant, taking ethylene glycol as solvent with reductive agent, sodium hydroxide is catalyzer, and stirring and refluxing is prepared the nanometer Pt colloidal solution of particle diameter below 5nm;
The chemical equation of above-mentioned reaction is:
(2) select wooden pharmaceutical grade gac as absorbent charcoal carrier;
(3) absorbent charcoal carrier is carried out to pre-treatment: according to the ratio of 1:10g/mL, gac is dispersed in to the HNO that concentration is 65-68%
3in, under temperature 50 C, after stirring back flow reaction 5h, suction filtration repeatedly by extremely neutrality of deionized water wash, obtains the gac of modification under temperature 60 C after vacuum-drying 10h;
(4) prepare activated carbon supported nm Pt catalyst:
Press charge capacity 1.0% by gac and Pt/ ethylene glycol colloidal solution mix and blend, stirring velocity is 350r/min, then slowly drip and the isopyknic distilled water of Pt/ ethylene glycol colloidal solution, destroy the stability of colloid, promote that nano Pt particles loads on gac, after stirring 24h, filter, dry and make activated carbon supported nm Pt catalyst.
3. a preparation method for activated carbon supported nm Pt catalyst, its preparation process is as follows:
(1) prepare nanometer platinum colloid solution:
Taking Platinic chloride as reactant, taking ethylene glycol as solvent with reductive agent, sodium hydroxide is catalyzer, and stirring and refluxing is prepared the nanometer Pt colloidal solution of particle diameter below 5nm;
The chemical equation of above-mentioned reaction is:
(2) select wooden pharmaceutical grade gac as absorbent charcoal carrier;
(3) absorbent charcoal carrier is carried out to pre-treatment: according to the ratio of 1:10g/mL, gac is dispersed in to the HNO that concentration is 65-68%
3in, under temperature 50 C, after stirring back flow reaction 5h, suction filtration repeatedly by extremely neutrality of deionized water wash, obtains the gac of modification under temperature 60 C after vacuum-drying 10h;
(4) prepare activated carbon supported nm Pt catalyst:
Press charge capacity 1.0% by gac and Pt/ ethylene glycol colloidal solution mix and blend, stirring velocity is 350r/min, then slowly drip and the isopyknic distilled water of Pt/ ethylene glycol colloidal solution, destroy the stability of colloid, promote that nano Pt particles loads on gac, after stirring 24h, filter, dry and make activated carbon supported nm Pt catalyst.
4. the preparation method of activated carbon supported nm Pt catalyst according to claim 3, is characterized in that, described step (1) is prepared nanometer platinum colloid solution, and concrete steps are:
Under nitrogen protection condition, according to the ratio of 1:50g/mL, Platinic chloride is dissolved in ethylene glycol respectively, according to the ratio of 1:50g/mL, NaOH is dissolved in ethylene glycol equally, it is identical in quality that Platinic chloride and NaOH add.Above-mentioned two kinds of mixed solution are mixed, and be heated to 160 DEG C, in Hybrid Heating process, constantly stir, after stirring and refluxing 3h, obtain the Pt colloidal solution of brownish black, by colloidal solution constant volume, for subsequent use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410109001.XA CN103848708B (en) | 2014-03-21 | 2014-03-21 | Method for preparing cyclohexane through catalytic dechlorination on chlorobenzene and preparation method of catalyst used in method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410109001.XA CN103848708B (en) | 2014-03-21 | 2014-03-21 | Method for preparing cyclohexane through catalytic dechlorination on chlorobenzene and preparation method of catalyst used in method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103848708A true CN103848708A (en) | 2014-06-11 |
| CN103848708B CN103848708B (en) | 2015-06-03 |
Family
ID=50856878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410109001.XA Active CN103848708B (en) | 2014-03-21 | 2014-03-21 | Method for preparing cyclohexane through catalytic dechlorination on chlorobenzene and preparation method of catalyst used in method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103848708B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801298A (en) * | 2014-10-15 | 2015-07-29 | 青岛科技大学 | Method for preparing platinum-carbon catalyst |
| CN107602318A (en) * | 2017-09-08 | 2018-01-19 | 郑州大学 | A kind of method of halogenated aryl hydrocarbon liquid-phase reduction dehalogenation under temperate condition |
| CN111495358B (en) * | 2020-04-23 | 2021-08-17 | 中国科学院地球环境研究所 | Formaldehyde remover with normal-temperature catalytic activity and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502797A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Platinum-based selective hydrogenation catalyst as well as preparation method and use thereof |
| CN101602645A (en) * | 2009-07-21 | 2009-12-16 | 青岛科技大学 | A kind of catalytic hydrogenation halogenated aryl hydrocarbon prepares the method for aromatic hydrocarbon and/or naphthenic hydrocarbon |
-
2014
- 2014-03-21 CN CN201410109001.XA patent/CN103848708B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101502797A (en) * | 2008-12-30 | 2009-08-12 | 西安凯立化工有限公司 | Platinum-based selective hydrogenation catalyst as well as preparation method and use thereof |
| CN101602645A (en) * | 2009-07-21 | 2009-12-16 | 青岛科技大学 | A kind of catalytic hydrogenation halogenated aryl hydrocarbon prepares the method for aromatic hydrocarbon and/or naphthenic hydrocarbon |
Non-Patent Citations (3)
| Title |
|---|
| LAURA PRATI ET AL.: "Reductive catalytic dehalogenation of light chlorocarbons", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| MANHONG LIU ET AL.: "Selective hydrogenation of o-chloronitrobenzene using supported platinum nanoparticles without solvent", 《APPLIED CATALYSIS A: GENERAL》 * |
| 韩文忠等: "Pt 纳米粒子的制备", 《青岛科技大学学报(自然科学版)》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801298A (en) * | 2014-10-15 | 2015-07-29 | 青岛科技大学 | Method for preparing platinum-carbon catalyst |
| CN107602318A (en) * | 2017-09-08 | 2018-01-19 | 郑州大学 | A kind of method of halogenated aryl hydrocarbon liquid-phase reduction dehalogenation under temperate condition |
| CN107602318B (en) * | 2017-09-08 | 2020-06-05 | 郑州大学 | Method for liquid-phase reduction dehalogenation of halogenated aromatic hydrocarbon under mild condition |
| CN111495358B (en) * | 2020-04-23 | 2021-08-17 | 中国科学院地球环境研究所 | Formaldehyde remover with normal-temperature catalytic activity and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103848708B (en) | 2015-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Gonçalves et al. | Relationship of the physicochemical properties of novel ZnO/biochar composites to their efficiencies in the degradation of sulfamethoxazole and methyl orange | |
| Cheng et al. | One-step fabrication of graphene oxide enhanced magnetic composite gel for highly efficient dye adsorption and catalysis | |
| Bootharaju et al. | Uptake of toxic metal ions from water by naked and monolayer protected silver nanoparticles: an X-ray photoelectron spectroscopic investigation | |
| Su et al. | Imidazolium-based porous organic polymers: anion exchange-driven capture and luminescent probe of Cr2O72– | |
| Liu et al. | Metal-organic framework-templated synthesis of magnetic nanoporous carbon as an efficient absorbent for enrichment of phenylurea herbicides | |
| Laszlo et al. | Heterogeneity of polymer-based active carbons in adsorption of aqueous solutions of phenol and 2, 3, 4-trichlorophenol | |
| Huang et al. | Electrospun graphene oxide/MIL-101 (Fe)/poly (acrylonitrile-co-maleic acid) nanofiber: A high-efficient and reusable integrated photocatalytic adsorbents for removal of dye pollutant from water samples | |
| Jiang et al. | Enhancing the catalytic activity and stability of noble metal nanoparticles by the strong interaction of magnetic biochar support | |
| Lavorato et al. | Pd/TiO2 doped faujasite photocatalysts for acetophenone transfer hydrogenation in a photocatalytic membrane reactor | |
| Zhang et al. | Crystal engineering of TiO2 enhanced photothermal catalytic degradation of DEHP on Pt catalysts | |
| Siara et al. | ZnAl2O4 supported on lychee-biochar applied to ibuprofen photodegradation | |
| Vandarkuzhali et al. | Arachis hypogaea derived activated carbon/Pt catalyst: reduction of organic dyes | |
| Hao et al. | Preparation of nickel-doped nanoporous carbon microspheres from metal-organic framework as a recyclable magnetic adsorbent for phthalate esters | |
| Li et al. | Influence of adsorption sites of biochar on its adsorption performance for sulfamethoxazole | |
| Bikshapathi et al. | Modification of activated carbon fiber by metal dispersion and surface functionalization for the removal of 2-chloroethanol | |
| Wang et al. | A novel hydroxyl-riched covalent organic framework as an advanced adsorbent for the adsorption of anionic azo dyes | |
| CN103848708B (en) | Method for preparing cyclohexane through catalytic dechlorination on chlorobenzene and preparation method of catalyst used in method | |
| Wu et al. | Spherical covalent organic framework supported Cu/Ag bimetallic nanoparticles with highly catalytic activity for reduction of 4-nitrophenol | |
| Zhao et al. | Transformation from 3D boron organic polymers to 1D nanorod arrays: loading highly dispersed nanometal for green catalysis | |
| Manavalan et al. | Binder-free modification of a glassy carbon electrode by using porous carbon for voltammetric determination of nitro isomers | |
| Xu et al. | Mechanism and impact of synthesis conditions on the one-step green synthesis of hybrid RGO@ Fe/Pd nanoparticles | |
| Xu et al. | Rh-Pd-alloy catalyzed electrochemical hydrodefluorination of 4-fluorophenol in aqueous solutions | |
| Lee et al. | Thermocatalytic oxidation of a three-component mixture of volatile organic compounds by a titanium dioxide-supported platinum catalyst | |
| Wang et al. | Porous graphene oxide functionalized by covalent organic framework for the application in adsorption and electrochemical: The effect of CF bonds to structure | |
| Hou et al. | Effective adsorption and catalytic reduction of nitrophenols by amino-rich Cu (I)–I coordination polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |