CN103848708B - 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
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- CN103848708B CN103848708B CN201410109001.XA CN201410109001A CN103848708B CN 103848708 B CN103848708 B CN 103848708B CN 201410109001 A CN201410109001 A CN 201410109001A CN 103848708 B CN103848708 B CN 103848708B
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- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 title claims abstract description 134
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000006298 dechlorination reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 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 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 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 11
- 230000002829 reductive effect Effects 0.000 claims abstract description 7
- 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
- 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 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000003610 charcoal Substances 0.000 claims description 18
- 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
- 230000000694 effects Effects 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 7
- 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
- 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
- 239000002105 nanoparticle Substances 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 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
- 238000007789 sealing Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 47
- 230000009466 transformation Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- -1 aromatic hydrocarbons organic compound Chemical class 0.000 description 6
- 150000004945 aromatic hydrocarbons 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000007385 chemical modification Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 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
- 230000008569 process Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 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
- 238000012360 testing method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001721 carbon Chemical class 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
- 238000005516 engineering process Methods 0.000 description 1
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- 239000000706 filtrate Substances 0.000 description 1
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- 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
- 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
- 238000012545 processing 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
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- 230000001131 transforming effect Effects 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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 technical field of fine, 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 by volatilization or as agricultural chemicals degraded product and in entered environment.Poisonous and the difficult degradation of chlorobenzene, is listed in U.S. EPA Environment Priority control polluted articles.Its stable chemical nature, easily accumulates in vivo, and 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, the toxicity of chlorinated aromatic hydrocarbons mainly due to the introducing of chlorine element, if so 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 find 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 solvent.Its purposes is very extensive, is the very important solvent of chemical field, reagent and raw materials.At present, mainly benzene catalytic hydrogenation is obtained in the preparation of hexanaphthene, or is obtained by crude petroleum fractions.The cyclohexane purity that crude petroleum fractions preparation obtains is not high, and as obtained highly purified hexanaphthene, refining operation is very complicated, and preparation cost is higher.Although benzene catalytic hydrogenation can obtain the higher cyclohexane of purity, the cost of purified petroleum benzin is higher.
Chlorobenzene hydrodechlorination can obtain hexanaphthene, but the technique of existing chlorobenzene hydrodechlorination, there is complex process, condition is harsh, yield is low, can not 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 to be catalyzer, adopt amorphous cobalt and water to react original position and produce hydrogen as reductive agent, chloride arene organic compound conversions is become corresponding arene organic compound.This defective workmanship is: amorphous cobalt is expensive, and this poor catalyst stability, 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: in the presence of base, in low-carbon alcohol solvent, the dechlorination reaction of nickelous catalyzer at room temperature catalysis chlorinated aromatic hydrocarbons.The defect of the method is: need to add alkali, and reaction conditions is complicated, and nickelous catalyzer can not recycle, and catalytic activity is low.
Summary of the invention
One of technical problem that the present invention solves is: propose a kind of method that chlorobenzene catalysis dechlorination prepares hexanaphthene, both the chlorion in chlorobenzene can have been removed, reduce its pollution to environment, discarded chlorobenzene can be used again 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: propose 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 prepares 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 with catalyst activity charcoal loaded with nano platinum in methanol solvate, and seals; Pass into H
2carry out hydrogenation reduction repeatedly, obtained 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, nanometer platinum colloid solution is prepared:
Be reactant with Platinic chloride, take ethylene glycol as solvent and reductive agent, sodium hydroxide is catalyzer, and stirring and refluxing prepares the Pt nano particle colloidal solution of particle diameter at 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, is dissolved in ethylene glycol respectively according to the ratio of 1:50g/mL by Platinic chloride, and be dissolved in equally in ethylene glycol by NaOH according to the ratio of 1:50g/mL, it is identical in quality that Platinic chloride and NaOH add.By above-mentioned two kinds of mixed solution mixing, and be heated to 160 DEG C, constantly stir in Hybrid Heating process, obtain the Pt colloidal solution of brownish black after stirring and refluxing 3h, 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, pre-treatment is carried out to absorbent charcoal carrier: according to the ratio of 1:10g/mL, gac (AC) is dispersed in the HNO that concentration is 65-68%
3in, to stir under temperature 50 C and after back flow reaction 5h, suction filtration, repeatedly with deionized water wash to neutral, under temperature 60 C, after vacuum-drying 10h, obtain the gac of modification.
4, activated carbon supported nm Pt catalyst is prepared:
By 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, filter after stirring 24h, dry obtained activated carbon supported nm Pt catalyst, for subsequent use.
Beneficial effect of the present invention is: reduce chlorobenzene to the pollution of environment, the hexanaphthene that obtained purity is higher, with activated carbon supported nano-noble metal for catalyzer, can rapid hydrogenation chlorobenzene at normal temperatures and pressures, be converted into product hexanaphthene, reduce cost, catalytic activity is high, transformation efficiency is high, and speed of reaction is fast, good to the selectivity of hexanaphthene.
Accompanying drawing explanation
Fig. 1 is that the transmission electron microscope of Pt/ ethylene glycol characterizes (i.e. TEM) photo;
Fig. 2 is the grain size distribution 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
The present invention is illustrated below in conjunction with embodiment.
Embodiment 1:
1, activated carbon supported nm Pt catalyst is prepared:
(1) nanometer platinum colloid solution is prepared:
Under nitrogen protection condition, respectively 1.0g Platinic chloride is dissolved in 50mL ethylene glycol, 1.0gNaOH is dissolved in 50mL ethylene glycol equally.By above-mentioned two kinds of mixed solution mixing, and be heated to 160 DEG C, constantly stir in Hybrid Heating process, obtain the Pt colloidal solution of brownish black after stirring and refluxing 3h, be designated as Pt/ ethylene glycol.By colloidal solution constant volume, for subsequent use.
During heating, the color of reaction soln, by after deepening gradually from initial glassy yellow, shoals instantaneously, then becomes brownish black instantaneously, after reaction 3h, successfully obtain brownish black platinum colloid.Obtained Pt colloidal solution at room temperature can preserve the several months for a long time, occurs, also nano platinum particle can be impelled to separate out by adjust ph, and can again be dissolved in other solvents there are no precipitation.
Above-mentioned obtained Pt/ ethylene glycol transmission electron microscope is characterized, according to electromicroscopic photograph, randomly draws about 300 particles and carry out particle diameter statistics, calculate the median size of Pt colloidal particle and the standard deviation of size distribution.The transmission electron microscope of Pt/ ethylene glycol characterizes (i.e. 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 uniform, does not see the agglomeration of obvious metal colloid particles.As shown in Figure 2, the median size of obtained 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) pre-treatment is carried out to the absorbent charcoal carrier that step (2) is selected: 5g gac (AC) is dispersed in the HNO that 50mL concentration is 65-68%
3in, to stir under temperature 50 C and after back flow reaction 5h, suction filtration, repeatedly with deionized water wash to neutral, under temperature 60 C, after vacuum-drying 10h, obtain the gac AC of modification
-HNO3.
(4) activated carbon supported nm Pt catalyst is prepared:
Gac step (3) 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, filter after stirring 24h, dry obtained activated carbon supported nm Pt catalyst and (be designated as
), for subsequent use.
After load, catalyzer is through washing, and filter, 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%, demonstrates the complete load of nano platinum particle.As can be seen from Figure 3, nano platinum particle well load on absorbent charcoal carrier, there is no obvious agglomeration.
2, chlorobenzene catalysis dechlorination prepares 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 with catalyst activity charcoal loaded with nano platinum in methanol solvate, and seals; Pass into H
2carry out hydrogenation reduction repeatedly, obtained hexanaphthene, the reaction times is 6 ~ 8h.The transformation efficiency of chlorobenzene reaches 100.00%, reaches 80.25%-95.52% to the selectivity of hexanaphthene,
By stratographic analysis, Pt/AC only has benzene and hexanaphthene to the product that the hydrodechlorination of chlorobenzene reacts.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.
Use chromatographic chlorobenzene, the content of benzene and hexanaphthene.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; Pressure 0.04MPa before post; Hydrogen pressure 0.08MPa; Air pressure 0.08MPa; Sampler temperature 170 DEG C; Hydrogen flame ionization detector temperature 170 DEG C; Column temperature 50 DEG C.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, thus calculate 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%, reaches 80.25% to the selectivity of hexanaphthene; When 8h is carried out in reaction, reach 95.52% to the selectivity of hexanaphthene, 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 when reacting and starting, meanwhile, benzene is also transforming to hexanaphthene, and that is, benzene is the intermediate product that chlorobenzene is converted into hexanaphthene.Also can find out from Fig. 4, along with the change of time, the activity of catalysis chlorobenzene is declining gradually.Because after reaction 1h, the transformation efficiency of chlorobenzene reaches 86.87%, chlorobenzene density loss; Can produce chlorion in catalysis dechlorination process, chlorion adsorbs at catalyst surface and occupies active sites simultaneously, and chlorobenzene, benzene competition active hydrogen, hinders the carrying out of reaction.In reaction process, the impact how eliminating hydrogenchloride improves transformation efficiency important in inhibiting.Use Pd/Al
2o
3during catalysis chlorobenzene dechlorination, product is benzene and a small amount of hexanaphthene mainly; Because HCl is in the absorption in active centre, the activity of catalyzer fails in time.When using Pd/SBA-1 catalysis chlorobenzene, need to add NaOH in reaction system, the HCl that neutralization reaction produces, reaction just can be made to 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 relative polystream.If can obtain good effect when processing chlorobenzene, Pt/AC catalyzer equally can other organic pollutant of catalysis.
Embodiment 2:
Divided by outside lower difference, other are with embodiment 1.
1, activated carbon supported nm Pt catalyst is prepared:
(3) pre-treatment is carried out to the absorbent charcoal carrier that step (2) is selected: 5g gac (AC) is dispersed in the H that 50mL concentration is 65-68%
2o
2in, to stir under temperature 50 C and after back flow reaction 5h, suction filtration, repeatedly with deionized water wash to neutral, under temperature 60 C, after vacuum-drying 10h, obtain the gac of modification.
Finally obtained activated carbon supported nm Pt catalyst, is designated as Pt/AC-
h2O2.
Embodiment 3:
Divided by outside lower difference, other are with embodiment 1.
1, activated carbon supported nm Pt catalyst is prepared:
(3) no longer pre-treatment is carried out to the absorbent charcoal carrier that step (2) is selected.Finally obtained activated carbon supported nm Pt catalyst, is designated as Pt/AC.
Use the activated carbon supported nm Pt catalyst that embodiment 1-3 is obtained respectively, under equal conditions catalysis dechlorination reaction is carried out to chlorobenzene.Testing data is as shown in table 1.
In neutral conditions, the Activity Results of 298K, 6h catalytic hydrogenation chlorobenzene reaction is as shown in table 1 for catalyzer.In chemical modification activated carbon supported catalyst chlorobenzene hydrogenation, the selectivity of hexanaphthene is all improve.At Pt/AC-
hNO3on, chlorobenzene transformation ratio is 100.00%, and the selectivity of hexanaphthene is 91.46%.For Pt/AC-
h2O2catalyzer, chlorobenzene transformation ratio slightly declines, but the selectivity of hexanaphthene brings up to 83.97%.
Table 1 chemical modification is on the impact of catalyst chlorobenzene performance
The pore structure of catalyzer and size have important impact to the absorption of reactant in liquid phase reaction and the desorption of product.In the mesopore that most metals active site is distributed in catalyzer and macropore, be 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 being less than 0.39nm can not participate in the hydrogenation of chlorobenzene.AC is through HNO
3after process, 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 adds a large amount of oxy radicals, and the increase of carboxyl enhances 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.
The surface texture parameters of Binding experiment result and absorbent charcoal carrier, surface chemical property: use HNO
3activated carbon supported nm Pt catalyst obtained after pre-treatment, its activity is higher, higher to the catalysis dechlorination transformation efficiency of chlorobenzene, better to the selectivity of hexanaphthene.
Embodiment 4:
Divided by outside lower difference, other are with embodiment 1.
1, activated carbon supported nm Pt catalyst is prepared:
(2) select sugar charcoal chemical grade gac as absorbent charcoal carrier, be designated as AC-1.
Embodiment 3:
Divided by outside lower difference, other are with embodiment 1.
1, activated carbon supported nm Pt catalyst is prepared:
(2) select lignifying classes and grades in school gac as absorbent charcoal carrier, be designated as AC-2.
Use the activated carbon supported nm Pt catalyst that embodiment 1,4,5 is obtained respectively, under equal conditions catalysis dechlorination reaction is carried out to chlorobenzene.Testing data is as shown in table 2.
In neutral conditions, the Activity Results of 298K, 6h catalytic hydrogenation chlorobenzene reaction is as shown in table 2 for catalyzer.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 ratio 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 table 2 different activities high-area carbon is on the impact of catalysis chlorobenzene performance
Associative list 2 can be found out, uses the activated carbon supported Platinum Nanoparticles of wooden pharmaceutical grade, higher to the transformation efficiency of chlorobenzene catalysis dechlorination, and speed of reaction is faster, better to the selectivity of hexanaphthene.
Claims (3)
1. a chlorobenzene catalysis dechlorination prepares 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 with catalyst activity charcoal loaded with nano platinum in methanol solvate, and seals; Pass into H
2carry out hydrogenation reduction repeatedly, obtained 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) nanometer platinum colloid solution is prepared:
Be reactant with Platinic chloride, take ethylene glycol as solvent and reductive agent, sodium hydroxide is catalyzer, and stirring and refluxing prepares the Pt nano particle colloidal solution of particle diameter at below 5nm;
The chemical equation of above-mentioned reaction is:
(2) select wooden pharmaceutical grade gac as absorbent charcoal carrier;
(3) pre-treatment is carried out to absorbent charcoal carrier: according to the ratio of 1:10g/mL, gac is dispersed in the HNO that concentration is 65-68%
3in, to stir under temperature 50 C and after back flow reaction 5h, suction filtration, repeatedly with deionized water wash to neutral, under temperature 60 C, after vacuum-drying 10h, obtain the gac of modification;
(4) activated carbon supported nm Pt catalyst is prepared:
By 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, filter after stirring 24h, dry obtained activated carbon supported nm Pt catalyst.
2. a preparation method for activated carbon supported nm Pt catalyst, its preparation process is as follows:
(1) nanometer platinum colloid solution is prepared:
Be reactant with Platinic chloride, take ethylene glycol as solvent and reductive agent, sodium hydroxide is catalyzer, and stirring and refluxing prepares the Pt nano particle colloidal solution of particle diameter at below 5nm;
The chemical equation of above-mentioned reaction is:
(2) select wooden pharmaceutical grade gac as absorbent charcoal carrier;
(3) pre-treatment is carried out to absorbent charcoal carrier: according to the ratio of 1:10g/mL, gac is dispersed in the HNO that concentration is 65-68%
3in, to stir under temperature 50 C and after back flow reaction 5h, suction filtration, repeatedly with deionized water wash to neutral, under temperature 60 C, after vacuum-drying 10h, obtain the gac of modification;
(4) activated carbon supported nm Pt catalyst is prepared:
By 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, filter after stirring 24h, dry obtained activated carbon supported nm Pt catalyst.
3. the preparation method of activated carbon supported nm Pt catalyst according to claim 2, is characterized in that, described step (1) prepares nanometer platinum colloid solution, and concrete steps are:
Under nitrogen protection condition, be dissolved in ethylene glycol respectively according to the ratio of 1:50g/mL by Platinic chloride, be dissolved in equally in ethylene glycol by NaOH according to the ratio of 1:50g/mL, it is identical in quality that Platinic chloride and NaOH add; By above-mentioned two kinds of mixed solution mixing, and be heated to 160 DEG C, constantly stir in Hybrid Heating process, after stirring and refluxing 3h, obtain the Pt colloidal solution of brownish black, by colloidal solution constant volume, for subsequent use.
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| 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 |
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| 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 |
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