CN105288927A - Dehalogenation and degradation method for halogenated aromatic compound - Google Patents
Dehalogenation and degradation method for halogenated aromatic compound Download PDFInfo
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- CN105288927A CN105288927A CN201510787449.1A CN201510787449A CN105288927A CN 105288927 A CN105288927 A CN 105288927A CN 201510787449 A CN201510787449 A CN 201510787449A CN 105288927 A CN105288927 A CN 105288927A
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Abstract
The invention relates to a dehalogenation and degradation method for a halogenated aromatic compound. The method includes the steps that the halogenated aromatic compound is used as raw materials, alcohol is used as a hydrogen source, and water is used as a solvent; under the action of a supported catalyst, a reaction is performed for 5-50 h at the temperature being 30-260 DEG C under the pressure ranging from 1 MPa to 10 MPa, and the halogenated aromatic compound is subjected to water-phase hydrogen production in-situ dehalogenation and degradation, wherein a benzene ring of the halogenated aromatic compound at least contains one F or Cl or Br or I substituent group, the supported catalyst is formed by active components and a carrier, the active components are composed of mixtures of transitional metal and other metal, the transitional metal is one of Rh, Pd, Pt and Ni, the other metal includes one of Se, Ca, Ba, La and Ce, and the carrier is one of active carbon, kieselguhr, zeolite, gamma-Al2O3, AlF3 and MgO. Active hydrogen is prepared to directly participate in the reaction through in-situ catalysis instead of directly using H2 as a reducing agent. Thus, the dehalogenation and degradation method has the beneficial effects of being high in reaction activity, selectivity and security, environment-friendly and the like, and having the good application prospect.
Description
Technical field
The present invention relates to a kind of dehalogenation biodegrading process of halogenated aromatic compound, be specifically related to the dehalogenation biodegrading process of the high halogenated aromatic compound of high, the selective height of a kind of reactivity, security.
Background technology
The all toxic and difficult degradation of nearly all chlorinated aromatic hydrocarbons and derivative thereof, is listed in U.S. EPA Environment Priority control polluted articles.Many halogenated aromatic compounds stable chemical nature, easily accumulates in vivo, has " carcinogenic, teratogenesis shape, mutagenesis " effect, once enter environment, is difficult to be degraded, can propagates, bring great threat to the mankind at food chain.The production capacity of China's aromatic halides series of products accounts for the over half of global aggregated capacity, and it is produced and holds the balance on the impact of China's medicine, agricultural chemicals, dyestuff, rubber chemicals, engineering plastics industry with application.Therefore, how both to have ensured that aromatic halides industry met national demand and produces good economic benefit, not most important to environmental effects again.The degradation treatment of halogenated aromatic compound becomes research focus in recent years.
The degradation process method of traditional aromatic halides mainly comprises: the methods such as burning, biodegradation and photochemical catalytic oxidation.Wherein, biological degradation method needs to carry out coprocessing in conjunction with other process means usually, and can only with the waste water of slower speed degraded containing low concentration.Burning method and oxidizing process easily produce phosgene with bioxin etc. and cause secondary pollution.But phenyl polychloride is all changed into CO by these methods
2, H
2o, HX, do not realize resource reutilization.
Chinese patent ZL200810143200.7 provides a kind of method of hydrodehalogenation of halogenated alkyl phenol coumpound, and using noble metal as catalyst, water is catalyst, at 50-100 DEG C, carry out dehalogenation hydrogenation reaction.
Chinese patent ZL201110328658.1 provides the hydrodehalogenation method of a kind of organochlorine for pollutant, and reaction system is organic-water two phase solvent system, and catalyst made by transition metal, hydrogenation-dechlorination under normal temperature, normal pressure.
Said method all removes the halogen atom on aromatic ring by catalytic hydrogenation, can reach and reduce compound polluted object, and treated pollutant, can realize resource and again utilize, but uses H
2there is the shortcomings such as selective, security is not good enough in the Catalytic Hydrogenation Techniques for reducing agent, and needs independently hydrogen manufacturing, storage hydrogen or defeated hydrogen storage equipment, and technological process is long, and equipment investment is large.
Summary of the invention
For overcoming the above-mentioned deficiency of existing dehalogenation degradation technique, the present invention aims to provide a kind of dehalogenation degraded new method of halogenated aromatic compound.Alcohol aqueous phase reforming hydrogen production reaction is coupled with the hydrodehalogenation degradation reaction of halogenated aromatic compound by the method, and achieving a kind of is that the halogenated aromatic compound original position hydrogenation selectivity dehalogenation of hydrogen source is degraded into new method that is rudimentary or Halogen aromatic with alcohol.The method does not directly use H
2for reducing agent, but produce reactive hydrogen by situ catalytic and participate in reaction directly, there is higher dehalogenation selective, but also substantially increase the security of production operation.
For achieving the above object, this invention takes following technical scheme:
A dehalogenation biodegrading process for halogenated aromatic compound, employing halogenated aromatic compound is raw material, and alcohol is as hydrogen source, water as solvent, under loaded catalyst effect, in 30-260 DEG C, under pressure 1-10Mpa, reaction 5-50h, aqueous phase hydrogen manufacturing original position dehalogenation degraded halogenated aromatic compound; At least containing F, Cl, Br or I substituting group on the phenyl ring of described halogenated aromatic compound.By by the organic matter liquid-phase hydrogenatin of the alcohols aqueous phase reforming hydrogen production reaction of heat absorption and heat release reaction coupling, achieve the liquid-phase hydrogenation reaction technology that does not directly use hydrogen.
As preferably, described loaded catalyst is made up of active component and carrier, described active component is made up of the mixture of transition metal and other metals, described transition metal is the one in Rh, Pd, Pt and Ni, other metals described are the one in Se, Ca, Ba, La and Ce, and described carrier is active carbon, diatomite, zeolite, γ-Al
2o
3, AlF
3with the one in MgO.Halogenated aromatic compound can produce hydrogen halide in dehalogenation process, easily causes normal load type catalyst poisoning, thus causes catalyst failure, reduces catalytic efficiency.Adopt transition metal and other metal step impregnations to obtain compound supported catalyst, be conducive to the selective and resistance to poison improving catalyst, reduce catalyst cost.
More preferably, the quality of described transition metal is the 1-10% of carrier quality, and the quality of other metals described is the 0-10% of carrier quality, and the mass ratio of described transition metal and other metals is 1:0-3.
As preferably, described loaded catalyst needs activation process before using, described activation process concrete steps be by loaded catalyst at 100-200 DEG C, be placed in H
21-8h is activated in atmosphere.First catalyst is activated in a hydrogen atmosphere the activity and catalytic capability that are conducive to improving catalyst before using.
As preferably, described alcohol is one or more in methyl alcohol, ethanol, isopropyl alcohol and glycerine.
As preferably, described reaction temperature is 50-220 DEG C, pressure 2-5Mpa, reaction time 6-30h.
As preferably, the preparation of described loaded catalyst adopts step impregnation method, and concrete operation method is:
(1) by transition metal inorganic salts incipient impregnation on carrier, after steeped overnight, in 100-150 DEG C of dry 3-6h, then in 300-800 DEG C of roasting 5-10h, obtain transition metal-carrier;
(2) inorganic salt solution of other metals is impregnated on step (1) gained transition metal-carrier, flood after 2-4 hour, regulate solution PH to 8-10 with NaOH, extremely neutral with distilled water wash solution after continuing to stir steeped overnight, again in 100-150 DEG C of dry 3-6h, more namely obtain described loaded catalyst in 300-800 DEG C of roasting 5-10h.
As preferably, the molar ratio of described alcohol and halogenated aromatic compound is 2-5:1, the quality of described water be the 80-150 of halogenated aromatic compound quality doubly, the quality of described loaded catalyst be the 0.3-1 of halogenated aromatic compound quality doubly.
Beneficial effect of the present invention is:
1, adopt alcohols to make hydrogen source, substitute traditional hydrogen catalytic method of reducing, there is high, the selective height of security, advantage that reactivity is high.
2, adopt water as solvent, do not adopt organic solvent in system, decrease three-waste pollution, there is eco-friendly advantage.
3, adopt the catalyst of transition metal and other metal mixed loads, be conducive to the selective and resistance to poison improving catalyst, reduce catalyst cost.
Detailed description of the invention
Explain the present invention further below in conjunction with embodiment, but embodiment does not limit in any form to the present invention.
Embodiment 1
(1) catalyst 1%(wt) Pd/La-Al
2o
3preparation
By 1.59gLa (NO
3)
36H
2o(purity is 98%) incipient impregnation is to 50gAl
2o
3on, after steeped overnight at 100 DEG C dry 5h, at 300 DEG C roasting 5h obtain La-Al
2o
3.By 0.85gPdCl
2(purity is 98%) is impregnated into La-Al after adopting suitable quantity of water to dissolve
2o
3on, regulate solution ph to 9 with NaOH after dipping 2h, after continuing to stir steeped overnight, use distilled water wash solution to neutral.Dry 5h at 110 DEG C again, at 300 DEG C, roasting 5h obtains Pd/La-Al
2o
3catalyst.
(2) Pd/La-Al
2o
3the dechlorination of catalysis 2,4,6-trichloroaniline
The 1%(wt that step (1) obtains is added in 300ml reactor) Pd/La-Al
2o
3catalyst 1g, utilizes H
2180 DEG C are warming up to after air 3 times in displacement still, and at H
22h is maintained under atmosphere.In still, a certain amount of 32g (1mol) methyl alcohol, 70g water and 1g (0.005mol) 2,4,6-trichloroaniline is added after gas is put in catalyst reduction.Open and stir, after question response temperature rises to 180 DEG C, in adjustment still, pressure is to 2.5MPa, and starts to stir (mixing speed is 800r/min), isothermal reaction 16h, reactant liquor after filtration, be separated obtain degradation product, by analysis: 2,4,6-trichloroaniline conversion ratio 100%, selective 86.2% of 2,4-dichloroaniline, selective 12.5% of o-chloraniline.
Embodiment 2
(1) preparation of catalyst P d/Ba-MgO
By 2.86gBa (NO
3)
2incipient impregnation on 50gMgO, after steeped overnight at 120 DEG C dry 3h, at 500 DEG C roasting 8h obtain Ba-MgO.Again by 7.50gPdCl
2be impregnated into after dissolving on Ba-MgO, after dipping 3h, regulate solution ph to 9 with NaOH, after continuing to stir steeped overnight, use distilled water wash solution to neutral.Dry 3h at 120 DEG C again, at 500 DEG C, roasting 8h obtains Pd/La-MgO catalyst.
(2) Pd/Ba-MgO catalysis 1,3,5-tribromo-benzene debrominate
In 300ml reactor, add the Pd/Ba-MgO catalyst 1g prepared, be warming up to 100 DEG C, and at H
21h is maintained under atmosphere.In still, 70g (2.18mol) methyl alcohol, 80g water and 1g (0.003mol) 1,3,5-tribromo-benzene is added after gas is put in catalyst reduction.After question response temperature rises to 50 DEG C, in adjustment still, pressure is to 2MPa, and starts to stir (800r/min) reaction, isothermal reaction 6h, reactant liquor after filtration, be separated obtain degradation product, by analysis, 1,3,5-tribromo-benzene conversion ratio 100%, selective 91.3% of 1,3-dibromobenzene, selective 3.1% of phenyl-monobromide.
Embodiment 3
Adopt embodiment 1(1), (2) identical method of operating, unlike embodiment 1(2) in reaction temperature be 190 DEG C, reaction time is 22h, reaction pressure is 1MPa, by analysis: 2, and 4,6-trichloroaniline conversion ratio 100%, selective 76.5% of 2,4-dichloroaniline, selective 13.2% of o-chloraniline.
Embodiment 4
(1) catalyst 10%(wt) preparation of Pd/La-C
By 15.9gLa (NO
3) 6H
2o(purity is 98%) incipient impregnation on 50gC, after steeped overnight at 150 DEG C dry 6h, at 800 DEG C roasting 10h obtain La-C.Again by 8.5gPdCl
2(purity is 98%) is impregnated on La-C after dissolving, and regulates solution ph to 10 after flooding 4h with NaOH, extremely neutral with distilled water wash solution after continuing to stir steeped overnight.Dry 6h at 150 DEG C again, at 800 DEG C, roasting 10h obtains Pd/La-C catalyst.
(2) Pd/La-C catalysis 1,3,5-trifluoro-benzene defluorinate
The 10%(wt prepared is added in 300ml reactor) Pd/La-C catalyst 0.5g, be warming up to 200 DEG C, and at H
28h is maintained under atmosphere.In still, a certain amount of 153.6g (4.8mol) methyl alcohol and 50g water and 1g (0.008mol) 1,3,5-trifluoro-benzene is added after gas is put in catalyst reduction.After question response temperature rises to 260 DEG C, in adjustment still, pressure is to 10MPa, and starts to stir (800r/min) reaction, isothermal reaction 50h, reactant liquor after filtration, be separated obtain degradation product, by analysis, 1,3,5-trifluoro-benzene conversion ratio 100%, selective 73.1% of 1,3-difluorobenzene, selective 7.8% of phenyl-monofluoride.
Embodiment 5
Adopt and embodiment 1(1), (2) identical method of operating, unlike embodiment 1(2) in solvent be isopropyl alcohol, reaction temperature is 200 DEG C, and the reaction time is 30h, and reaction pressure is 5MPa, by analysis: 2,4,6-trichloroaniline conversion ratio 100%, 2, selective 83.6% of 4-dichloroaniline, selective 7.8% of o-chloraniline.
Embodiment 6
(1) catalyst 2%(wt) the diatomaceous preparation of Pd –
By 1.67gPdCl
2after dissolving, incipient impregnation is on 50g diatomite, after steeped overnight at 150 DEG C dry 6h, at 500 DEG C, roasting 8h obtains Pd-diatomite.
(2) Pd-diatomite catalysis 2,4,6-tribromaniline debrominate
The 2%(wt prepared is added in 300ml reactor) Pd-diatomite catalyst 0.3g, be warming up to 150 DEG C, and at H
26h is maintained under atmosphere.In still, 69g (1.5mol) ethanol, 150g water and 1g (0.003mol) 2,4,6-tribromaniline is added after gas is put in catalyst reduction.After question response temperature rises to 30 DEG C, in adjustment still, pressure is to 1MPa, and starts to stir (800r/min) reaction, isothermal reaction 5h, reactant liquor after filtration, be separated obtain degradation product, by analysis, 1,3,5-tribromo-benzene conversion ratio 100%, selective 6.5% of selective 79.3%, 2, the 4-dibromo aniline of monobromo aniline.
Embodiment 7
(1) catalyst 3%(wt) Pd/Ce-Al
2o
3preparation
By 4.65gCe (NO
3)
36H
2o incipient impregnation is to 50gAl
2o
3on, after steeped overnight at 150 DEG C dry 5h, at 800 DEG C roasting 10h obtain Ce-Al
2o
3.Again by 2.50gPdCl
2ce-Al is impregnated into after dissolving
2o
3on, regulate solution ph to 10 with NaOH after dipping 6h, after continuing to stir steeped overnight, use distilled water wash solution to neutral.Dry 6h at 150 DEG C again, at 400 DEG C, roasting 10h obtains Pd/Ce-Al
2o
3catalyst.
(2) Pd/Ce-Al
2o
3the dechlorination of catalysis 2,4,6-trichloroaniline
The 3%(wt prepared is added in 300ml reactor) Pd/Ce-Al
2o
3catalyst 1g, utilizes H
2180 DEG C are warming up to after air 3 times in displacement still, and at H
25h is maintained under atmosphere.In still, 160g (5mol) methyl alcohol, 100g water and 1g (0.005mol) 2,4,6-trichloroaniline is added after gas is put in catalyst reduction.Open and stir, after question response temperature rises to 180 DEG C, in adjustment still, pressure is to 4MPa, and starts to stir (mixing speed is 800r/min), isothermal reaction 20h, reactant liquor after filtration, be separated obtain degradation product, by analysis: 2,4,6-trichloroaniline conversion ratio 100%, selective 76.4% of 2,4-dichloroaniline, selective 10.5% of o-chloraniline.
Embodiment 8
Catalyst 3%(wt is added in the miniature stainless steel reactor of fixed bed (internal diameter 8mm)) Pd/Ca-Al
2o
3(use H in advance
2(30ml/min) at 300 DEG C, reducing 3h) consumption is 1g, n (H
2o)/n (CH
3oH)=8,2,4,6-trichloroaniline concentration is 0.02mol/L, and reaction temperature is 210 DEG C, and reaction pressure is 3.5MPa, and the space-time speed of mixing material is 1.2h
-1. product, through being separated, obtains degradation product, by analysis, and selective 87.1% of 2,4,6-trichloroaniline conversion ratio 100%, 2,4-dichloroaniline, selective 6.3% of o-chloraniline.
Below only enumerate the preferred embodiments of the invention, protection scope of the present invention is not restricted to this, and any change that those skilled in the art do within the scope of the claims in the present invention all falls in scope.
Claims (8)
1. the dehalogenation biodegrading process of a halogenated aromatic compound, it is characterized in that: employing halogenated aromatic compound is raw material, alcohol is as hydrogen source, water is as solvent, under loaded catalyst effect, in 30-260 DEG C, under pressure 1-10Mpa, reaction 5-50h, aqueous phase hydrogen manufacturing original position dehalogenation degraded halogenated aromatic compound; At least containing F, Cl, Br or I substituting group on the phenyl ring of described halogenated aromatic compound.
2. the dehalogenation biodegrading process of halogenated aromatic compound as claimed in claim 1, it is characterized in that: described loaded catalyst is made up of active component and carrier, described active component is made up of the mixture of transition metal and other metals, described transition metal is the one in Rh, Pd, Pt and Ni, other metals described are the one in Se, Ca, Ba, La and Ce, and described carrier is active carbon, diatomite, zeolite, γ-Al
2o
3, AlF
3with the one in MgO.
3. the dehalogenation biodegrading process of halogenated aromatic compound as claimed in claim 2, it is characterized in that: the quality of described transition metal is the 1-10% of carrier quality, the quality of other metals described is the 0-10% of carrier quality, and the mass ratio of described transition metal and other metals is 1:0-3.
4. the dehalogenation biodegrading process of the halogenated aromatic compound as described in claim 1-3 any one, is characterized in that: described loaded catalyst needs activation process before using, described activation process concrete steps be by loaded catalyst at 100-200 DEG C, be placed in H
21-8h is activated in atmosphere.
5. the dehalogenation biodegrading process of halogenated aromatic compound as claimed in claim 1, is characterized in that: described alcohol is one or more in methyl alcohol, ethanol, isopropyl alcohol and glycerine.
6. the dehalogenation biodegrading process of halogenated aromatic compound as claimed in claim 1, is characterized in that: described reaction temperature is 50-200 DEG C, pressure 2-5Mpa, reaction time 6-30h.
7. the dehalogenation biodegrading process of halogenated aromatic compound as claimed in claim 2 or claim 3, is characterized in that: the preparation of described loaded catalyst adopts step impregnation method, and concrete operation method is:
(1) by transition metal inorganic salts incipient impregnation on carrier, after steeped overnight, in 100-150 DEG C of dry 3-6h, then in 300-800 DEG C of roasting 5-10h, obtain transition metal-carrier;
(2) inorganic salt solution of other metals is impregnated on step (1) gained transition metal-carrier, flood after 2-4 hour, regulate solution PH to 8-10 with NaOH, extremely neutral with distilled water wash solution after continuing to stir steeped overnight, again in 100-150 DEG C of dry 3-6h, more namely obtain described loaded catalyst in 300-800 DEG C of roasting 5-10h.
8. the dehalogenation biodegrading process of halogenated aromatic compound as claimed in claim 1, it is characterized in that: the molar ratio of described alcohol and halogenated aromatic compound is 200-1000:1, the quality of described water is 50-150 times of halogenated aromatic compound quality, and the quality of described loaded catalyst is 0.3-1 times of halogenated aromatic compound quality.
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| CN113908861A (en) * | 2021-11-01 | 2022-01-11 | 扬州大学 | Preparation method of carbon-based selenium material and application of carbon-based selenium material in dimethyl carbonate dehalogenation |
| CN113908861B (en) * | 2021-11-01 | 2024-04-09 | 扬州大学 | Preparation method of carbon-based selenium material and application of carbon-based selenium material in dehalogenation of dimethyl carbonate |
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