CN1548226A - Catalyst for hydrodehalogenation of arene halide and its prepn and application - Google Patents
Catalyst for hydrodehalogenation of arene halide and its prepn and application Download PDFInfo
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Abstract
The present invention relates to supported noble catalyst, and is especially one kind of catalyst for hydrodehalogenation of arene halide and its preparation and application. The catalyst consists of carrier and active component, the carrier is one or several selected from Al2O3, SiO2, active carbon and TiO2, and the active component is mainly Ni in the supported amount of 0.1-30 wt%. The active component exists in the catalyst as metal, metal oxide or other form. The present invention has high catalytic activity, mild reaction condition and simple reaction system, and provides one economic, practical and environment friendly organic aromatic halide pollutant degrading method.
Description
Technical Field
The invention relates to a supported non-noble metal catalyst, in particular to a catalyst for hydrodehalogenation of halogenated aromatic hydrocarbon, and preparation and application thereof.
Background
In recent years, it has become possible to provide,there is increasing interest in the integrated remediation of volatile halogenated aromatic contaminants, including Polychlorinated Biphenyls (Polychlorinated Biphenyls). The traditional method for eliminating halogenated aromatic pollutants is incineration, which often requires combustion temperatures higher than 1000 ℃ and large amounts of organic fuel, and is costly to invest and maintain, and more seriously, combustion under oxidizing conditions results in the higher toxic pollutant Dioxin (Dioxin)s) (including polychlorinated dibenzodioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs)). The catalytic combustion process can treat halogenated aromatic pollutants directly without adding fuel, but it is only suitable for treating pollutants with low content (<1%) and difficult recycling under gas phase conditions, see chinese patent application nos. 00110236.2 and 00122988.5.
Dioxin can be avoided by chemical reductionsThe activity of the reducing agent is very high, such as U.S. patents (publication numbers US4950833 and US6414212), european patents (publication number EP476053) and the like, which use sodium as the reducing agent; U.S. Pat. No. 4,430,870 for LiAlH4Is a reducing agent; U.S. Pat. No. 4,430,667 uses sodium naphthalene to dehalogenate aromatic halohydrocarbons; U.S. patent publication No. US 4910353; chinese patent application No. 95110017.3, dehalogenates aryl halohydrocarbons using sodium hydride as a reducing agent; these strong extremely active reducing agents have high dehalogenation efficiency, but they are extremely sensitive to airand water, are easily deactivated, and are potentially hazardous during storage and use.
The heterogeneous catalytic hydrogenation degradation of halogenated organic pollutants is a high-efficiency, energy-saving, economic and safe treatment method, and is more suitable for large-scale industrial treatment of organic wastes containing halogenated aromatic hydrocarbons. It is generally considered that the noble metal-based catalyst in which noble metals such as Pd, Pt, Rh and the like are supported on various carriers can achieve dehalogenation of halogenated aromatic hydrocarbons under mild conditions (Dini, P., Bart, J.C., Giordano, N.J.Chem.Soc., PerkinII, 1975, 1479; Laura P., Michele R., Appl.Catal.B: 1999, 23, 135; Carlos, A., Marques, M.S., Pietro T.J., Chem.Perkin., Trans., 1993, 1, 529; Yuji, U.S., Satoshi K., Tatsuo M.Appl.Catal.B: 2000, 27, 97; for example, Chinese patent application No. 93111071.8) can achieve complete conversion of chlorobenzene at 65 ℃ over 4 hours with a palladium complex supported on a polymeric carrier as a catalyst; U.S. Pat. No. 5,149,170 discloses Ru as the main component of the catalyst; the U.S. Pat. No. 5,515 (publication No. 5,5783515) uses Ir as the main component of the catalyst and can show higher activity under different conditions; also US patents (publication nos. US4749817 and US4618686) and so on. However, halogens or hydrogen halides generated during dehalogenation poison them and deactivate them quickly, and a large amount of expensive noble metals are used to prepare the catalyst.
Examples of catalysts that may be used include Ni, Mo, Co, Ni-Mo, Co-Mo, Fe (Hagh, B.F.; Allen, D.T. AICHE J.1990, 36(5), 773; Suzdoif, A.R.; Moroxv, S.V.; Anshits, N.N.; Tsiganova, S.I.; Anshits, A.G.Cat. Le1994, 29, 49; Gioia, E.; Famiglietl, V.; Murena, F.J.Hazard. Mater.1993, 33, 63; Hagh, B.F.; Allem, D.T.Chem.Eng.Sci.1990, 45 (8)), 2695; Moanrldo, R.ahan, S.E., Larser, D.En.W.1997, U.31, C.409; noble metals, which are most likely to be used in place of the same type of noble catalysts, and may be used in place of the inexpensive catalysts, not only noble metals, but are available, and are available; although they exhibit some stability, they generally require higher temperatures and higher pressures to exhibit some activity; as another example, U.S. Pat. No. 6,6271168 uses a Fe-P-S-Na complex catalyst to treat halogenated aromatics at 300 ℃.
Disclosure of Invention
The invention aims to provide a catalyst for hydrodehalogenation of halogenated aromatic hydrocarbon, which has high catalytic activity and mild reaction conditions, and preparation and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the catalyst consists of a carrier and an active component, wherein the carrier is selected from Al2O3、SiO2Activated carbon, activated carbon,TiO2One or more of the active components, mainly Ni, and the loading amount of the active components is 0.1-30 wt%.
The active component is in the state of metal, metal oxide or other forms (such as aluminate, silicate, etc.) in the catalyst; the loading amount of the active component Ni is preferably 5-15%; the carrier is preferably activated carbon; the catalyst can contain a valence-variable transition metal element M as An auxiliary agent, wherein the M is selected from one or more of Co, Cu, V, Fe, Zn, An, Ag, Ce and Ln, and the molar ratio of the M to the main active component Ni is 1: 10-20; m is preferably one or more of Cu, Ag, Ce and Co;
the loading of active component nickel on the activated carbon is as follows: in general, the active components of the supported metal catalysts are present in a highly dispersed state on the carrier, and the smaller the metal crystal grains, the higher the specific surface area of the metal, and the higher the catalytic activity. For a particular carrier, there exists a critical value of grain size in relation to the loading of active ingredient, known as mono-layer dispersion, which can be determined by X-ray diffraction; when the carrying capacity exceeds the single-layer dispersion amount, the crystal grains grow gradually, the specific surface area is reduced, and the activity is reduced; therefore, when the loading amount exceeds 30 wt%, the crystal grains become very large, the activity is reduced to be close to that of bulk phase nickel, and the utilization rate of metal is not high; whereas at too low a loading, less than 0.1% (theoretically, the catalytic activity can be exhibited as long as nickel crystallites are present on the support), although the metal particles can be kept small, in practice the amount of active component available per unit mass of catalyst is small and the utilization of the support is not high, and therefore is not practical.
The preparation method of the catalyst comprises the following steps: loading nitrate of an active component on a carrier by adopting an isometric loading method, and directly activating and using a catalyst precursor loaded with the nitrate of the active component after vacuum dehydration at 100-140 ℃; or activating for use after vacuum roasting at 200-500 ℃;
the loading can be carried out by a normal pressure method or a vacuum method in one step or in steps; the vacuum method is preferably used for one-step impregnation loading; the catalyst precursor loaded with the nitrate as the active component is preferably directly activated for use after vacuum dehydration at 110-130 ℃; or preferably activated after vacuum roasting at 250-350 ℃.
The application conditions of the catalyst are as follows: in the presence of activated supported catalyst, at 40-100 ℃, using lower aliphatic alcohol as solvent and stoichiometric strong base as proton absorbent, at 1-15 x 105And (3) reacting under the pressure of hydrogen Pa.
The reaction temperature is preferably 60 to 70 ℃, and the strong base is preferably NaOH or Ca (OH)2As for the reaction medium, lower aliphatic alcohol, theoretically, as long as it can provide protons on hydroxyl groups, and has a low viscosity, it can be used as the reaction medium of the present invention to facilitate the sufficient dissolution and contact of various reactants, and methanol and isopropanol, for example, can be used as the reaction medium, and ethanol is preferred in view of toxicity, price, and the like.
The catalyst of the invention is used for catalytic hydrogenation degradation of organic halogenated aromatic hydrocarbon pollutants, and the reaction formula can be expressed as follows:
The invention has the following advantages:
1. low cost and good practicability. The organic halogenated aromatic compound is a substance with great harm and strong chemical stability, has strong toxicity, difficult degradability and strong biological enrichment, widely exists in waste gas, waste and wastewater, particularly polychlorinated biphenyl is widely applied to various countries in the world as an insulating medium of a power capacitor, and the halogenated aromatic compound usually exists in high concentration in the dielectric fluids; compared with the prior art for treating the organic halogenated aromatic compound, the invention provides a simple technical route for treating the waste liquid containing the high-concentration or low-concentration halogenated aromatic compound, namely the waste liquid is directly or dissolved in a proper organic solvent to carry out catalytic hydrogenation dehalogenation, reactants can be easily separated after the reaction, and the solvent and the dehalogenation product can be recycled; the catalyst is non-noble metal, and has the characteristics of low price, high catalytic activity, mild reaction conditions and the like.
2. Wide application range and environment protection. The reaction system and the technical route of the invention are simple, convenient and practical, the by-product is nontoxic and harmless, and the invention is particularly suitable for catalytic hydrogenation degradation of organic halogenated aromatic hydrocarbon pollutants, and can be widely used for catalytic hydrogenation dehalogenation of a large amount of waste liquid containing high-concentration halogenated aromatic hydrocarbon in chemical industry and electric power industry.
Detailed Description
The present invention is described in further detail below by way of examples.
Example 1
Preparation of the catalyst
Dissolving metal salt in water to prepare impregnation liquid with required concentration, adding carriers such as activated alumina, silica gel, activated carbon and the like pretreated by dilute nitric acid, impregnating for 24 hours under reduced pressure, drying at constant temperature of 80 ℃, dehydrating for 3 hours at 120 ℃ under reduced pressure, and naturally cooling. The single-component or double-component supported metal catalysts with different loading amounts and different components are respectively prepared. Before reaction, a certain amount of catalyst is taken to be arranged in a quartz tube, reduction activation is carried out in pure hydrogen or mixed gas of nitrogen and hydrogen for 4 ℃/min, the temperature is raised to 450 ℃, reduction is carried out for 2 hours at constant temperature, the temperature is naturally cooled to room temperature, and the reaction liquid is added for reduction dehalogenation under the protection of nitrogen.
Example 2
Influence of carrier on chlorobenzene catalytic hydrogenation dechlorination performance of Ni-based catalyst
The performance evaluation of the catalytic hydrogenation degradation of the organic halogenated aromatic hydrocarbon pollutants is carried out in a 300ml high-pressure reaction kettle, the dosage of the catalyst is about 0.2-4.0g, wherein the content of Ni as a main active component is about 0.04g, the organic halogenated aromatic pollutants can be directly dehalogenated or dissolved in a suitable solvent (100 ml of an ethanol solution containing 51370ppm of chlorobenzene), about 2.0g of NaOH is used for absorbing hydrogen halide generated in the reaction, and the pressure of hydrogen is 10.1X 105Pa, and reacting at 70 ℃ for 60 minutes in a constant volume way. Study of different vectorsThe chlorobenzene catalytic hydrogenation performance of the bulk Ni-based catalyst under the same conditions is shown in table 1.
TABLE 1 Chlorobenzene catalytic hydrodechlorination performance of Ni-based catalysts with different supports
Catalyst and process for preparing samea | Temperature/. degree.C | Conversion rate/% | Selectivity (benzene) % | Other products /% |
γ-Al2O3 b | 70 | 8.6 | 4.1 | 95.9 |
Activated carbonb | 70 | 6.7 | 4.6 | 95.4 |
Ni/C | 70 | 100.0 | 91.8 | 8.2 |
Ni/γ -Al2O3 | 70 | 13.3 | 31.4 | 68.6 |
Ni/SiO2 | 70 | 15.6 | 28.7 | 71.3 |
aThe content of the nickel component is 10 wt%;bblank experiment
Example 3
Chlorobenzene catalytic hydrogenation dechlorination performance of Ni/C catalysts with different loads
Chlorobenzene catalytic hydrodechlorination experiments were performed on Ni/C catalysts of different loadings under the same reaction conditions as in example 2, and the results of comparison are shown in table 2.
TABLE 2 Chlorobenzene catalytic hydrodechlorination performance of Ni/C catalysts of different loadings
Catalyst and process for preparing same | Nickel content /wt.% | Conversion rate/% | Selectivity (benzene) % | Other products /% |
Ni/C | 1 | 100.0 | 80.5 | 19.5 |
5 | 100.0 | 89.3 | 10.7 | |
10 | 100.0 | 91.8 | 8.2 | |
15 | 94.3 | 91.6 | 8.4 | |
20 | 56.2 | 91.6 | 8.4 |
Example 4
Influence of metal auxiliary agent on catalytic hydrogenation and dechlorination performance of chlorobenzene of loaded metalcatalyst
The effect of the metal promoter on the chlorobenzene-catalyzed hydrodechlorination performance of the supported metal catalyst was examined under the same reaction conditions as in example 2, and the results are shown in table 3.
TABLE 3 influence of Metal auxiliary on Chlorobenzene catalytic hydrodechlorination Performance of Supported Metal catalystsa
Catalyst and process for preparing same | Ni∶Metalb | Conversion rate% | Selectivity (benzene) % | Other products /% |
Ni-Cu/C | 20∶1 | 97.9 | 85.6 | 14.4 |
Ni-Zn/C | 10∶1 | 76.8 | 84.4 | 15.6 |
Ni-Fe/C | 10∶1 | 60.0 | 84.5 | 15.5 |
Ni-Co/C | 10∶1 | 90.2 | 82.6 | 17.4 |
Ni-Ag/C | 10∶1 | 100.0 | 87.7 | 12.3 |
Ni-La/C | 10∶1 | 85.5 | 89.4 | 10.6 |
Ni-Ce/C | 10∶1 | 100.0 | 90.7 | 9.3 |
Ni-Co-Ag/C | 10∶0.5∶0.5 | 99.8 | 85.4 | 14.6 |
Ni-Co-Ce/C | 10∶0.5∶0.5 | 100.0 | 85.5 | 14.5 |
Ni-Ag-Ce/C | 10∶0.5∶0.5 | 44.1 | 82.1 | 17.9 |
The content of the nickel component is 10 percent;at is 90 minutes;bmass ratio of substances
Example 5
Influence of reaction conditions on catalytic hydrogenation experimentof chlorobenzene on Ni/C catalyst
A catalytic hydrogenation of chlorobenzene was carried out on a 10% Ni/C catalyst under different reaction conditions than in example 2, and the results are shown in Table 4.
TABLE 4 Effect of different reaction conditions on catalytic hydrogenation of chlorobenzene on Ni/C catalysts
Catalyst and process for preparing same | Temperature of /℃ | pressure/Pa | Conversion rate /% | Selectivity (benzene) /% | Other products /% |
10%Ni/C | 50 | 10.1×105 | 92.2 | 89.5 | 10.5 |
60 | 10.1×105 | 100.0 | 85.4 | 14.6 | |
70 | 10.1×105 | 100.0 | 91.8 | 8.2 | |
80 | 10.1×105 | 88.4 | 91.0 | 9.0 | |
70 | 5.0×105 | 49.1 | 86.9 | 13.1 | |
15%Ni/C | 70 | 10.1×105 | 94.3 | 91.6 | 8.4 |
70a | 10.1×105 | 94.7 | 96.8 | 3.2 |
aDissolving NaOH in solvent in advance
Example 6
The effect of the heat treatment temperature on the catalytic hydrogenation performance of the supported Ni-based catalyst was examined under the same reaction conditions as in example 2, and the reaction time was 60 minutes, and the results are shown in table 5.
TABLE 5 influence of Heat treatment temperature on the catalytic hydrogenation Performance of the Supported Ni-based catalyst
Catalyst and process for preparing same | Temperature/. degree.C | Conversion rate/% | Selectivity (benzene) /% | Other products /% |
10%Ni/C | 100ab | 86.7 | 86.6 | 13.4 |
120a | 100.0 | 91.8 | 8.2 | |
140a | 99.4 | 92.9 | 7.1 | |
200 | 98.9 | 88.6 | 11.4 | |
300c | 100.0 | 94.3 | 5.7 | |
400 | 87.1 | 89.3 | 10.7 | |
500 | 88.9 | 91.3 | 8.7 |
aTemperature of dehydrationb90 minutesc40 minutes
Example 7
Influence of different preparation modes on catalytic hydrogenation performance of supported Ni-based catalyst
The effect of different preparation methods on the catalytic hydrogenation performance of the supported Ni-based catalyst was examined under the same reaction conditions as in example 2, and the results are shown in Table 6.
TABLE 6 influence of different preparation methods on the catalytic hydrogenation performance of the supported nickel-based catalysta
Reduced/atmospheric pressure | Number of impregnations | Conversion rate/% | Selectivity (benzene)/%) | Other products/%) |
Reduced pressure | 1 | 86.7 | 86.6 | 13.4 |
2 | 86.8 | 82.4 | 17.6 | |
Atmospheric pressure | 1 | 85.7 | 78.0 | 22.0 |
2 | 45.5 | 84.7 | 15.3 |
The content of nickel component is 10%;adehydrating in vacuum at 100 deg.C.
Example 8
Catalytic hydrodechlorination performance of polychlorinated benzene on 10% Ni/C catalyst
A catalytic hydrodehalogenation experiment of polychlorinated benzenes was carried out with 10% Ni/C catalyst under the same reaction conditions as in example 2, and the results of comparison are shown in Table 7.
TABLE 7 catalytic hydrodechlorination of polychlorinated benzenes over 10% Ni/C catalyst
# | Conversion (%) | Product distribution (%) | |||||
X(C- Cl) | CBs | Bz | CB | o-D CB | m-D CB | -DCB | |
CB | 100.0 | 100.0 | 91.8 | -- | -- | -- | -- |
o-DCB | 95.2 | 96.4 | 96.9 | 2.4 | -- | -- | -- |
m-DCB | 90.8 | 94.4 | 82.0 | 4.1 | -- | -- | -- |
p-DCB | 66.2 | 79.5 | 91.0 | 9.4 | -- | -- | -- |
mixture of DCBa,b | 80.5 | 94.5 | 91.8 | 2.6 | -- | -- | -- |
1,2,3-TCB | 49.7 | 68.2 | 41.1 | 10.7 | 35.3 | -- | -- |
1,2,4-TCB | 80.5 | 93.8 | 72.5 | 5.8 | 7.8 | 4.3 | 4.3 |
X (C-Cl): the removal rate of chlorine atoms; CBs: chlorobenzene; bz: benzene; CB: chlorobenzene; o-DCB: o-dichlorobenzene; m-DCB: m-dichlorobenzene; p-DCB: p-dichlorobenzene; TCB: trichlorobenzene;adichlorobenzene mixture (substance quantity ratio 1: 1);bthe conversion of o-, m-, p-dichlorobenzene was 98.1%, 95.4% and 90.2%, respectively.
The catalytic hydrodechlorination efficiency of polychlorinated benzene is reduced along with the increase of the substitution number of chlorine atoms, but is higher than the results reported in the literature.
Example 9
Catalytic hydrogenation dehalogenation performance of halogenated benzene on 10% Ni/C catalyst
Under the same reaction conditions as in example 2, Ni: C-X was 56: 1, and a catalytic hydrodehalogenation experiment of halogenated benzene was performed using a 10% Ni/C catalyst, and the comparison results are shown in table 8.
TABLE 8 catalytic hydrodehalogenation of halobenzenes over 10% Ni/C catalyst
Reactants | Temperature/%) | Conversion rate/% | Selectivity (benzene)/%) | Other products/%) |
Chlorobenzene | 70 | 100.0 | 91.8 | 8.2 |
Bromobenzene | 70 | 100.0* | 92.3 | 7.7 |
Iodobenzene | 70 | 34.5* | 83.4 | 16.6 |
Time: 50min
Example 10
Comparison of Nickel-based catalyst activity with commercial catalyst
Comparative experiments werecarried out under the same reaction conditions as in example 2 and the results are shown in Table 9.
TABLE 9 comparison of Nickel-based catalyst to commercial catalyst Activity
Catalyst and process for preparing same | Time/min | Conversion rate/% | Selectivity (benzene)/%) | Other products/%) |
Raney-Ni | 60 | 19.8 | 86.0 | 14.0 |
5%Pd/Ca | 30 | 98.9 | 93.1 | 6.9 |
5%Ni/C | 40 | 100.0 | 89.3 | 10.7 |
aPd∶C-Cl=250∶1
Claims (8)
1. A catalyst for hydrogenation and dehalogenation of halogenated aromatic hydrocarbon comprises a carrier and active components, and is characterized in that: the carrier is selected from Al2O3、SiO2Activated carbon, TiO2One or more of the active components, mainly Ni, and the loading amount of the active components is 0.1-30 wt%.
2. A catalyst for hydrodehalogenation of halogenated aromatic hydrocarbons according to claim 1 wherein: the loading amount of the active component Ni is 5-15%.
3. Catalyst for the hydrodehalogenation of halogenated aromatic hydrocarbons according to claim 1 or 2, characterized in that: the catalyst contains a valence-variable transition metal element M as an auxiliary agent, wherein the M is one or more selected from Co, Cu, V, Fe, Zn, Ag, Ce and Ln, and the molar ratio of the M to the main active component Ni is 1: 10-20.
4. Catalyst for the hydrodehalogenation of halogenated aromatic hydrocarbons according to claim 1 or 2, characterized in that: m is selected from one or more of Cu, Ag, Ce and Co.
5. A process for the preparation of a catalyst for the hydrodehalogenation of halogenated aromatic hydrocarbons according to claim 1, wherein: loading nitrate of an active component on a carrier by adopting an isometric loading method, and directly activating and using a catalyst precursor loaded with the nitrate of the active component after vacuum dehydration at 100-140 ℃; or activating for use after vacuum roasting at 200-500 ℃.
6. A process for the preparation of a catalyst for the hydrodehalogenation of halogenated aromatic hydrocarbons according to claim 5, wherein: the load is one-step impregnation load by a vacuum method, and the catalyst precursor loaded with the nitrate serving as the active component is directly activated for use after vacuum dehydration at 110-130 ℃; or activating and using after vacuum roasting at 250-350 ℃.
7. Use of a catalyst for hydrodehalogenation of halogenated aromatic hydrocarbons according to claim 1, wherein: in the presence of activated supported catalyst, at 40-100 ℃, using lower aliphatic alcohol as solvent and stoichiometric strong base as proton absorbent, at 1-15 x 105And (3) reacting under the pressure of hydrogen Pa.
8. Use of a catalyst for hydrodehalogenation of halogenated aromatic hydrocarbons according to claim 1, wherein: the reaction temperature is 60-70 ℃, the solvent is ethanol, and the strong base is NaOH or Ca (OH)2。
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CN1132685C (en) * | 2001-10-30 | 2003-12-31 | 中国石油化工股份有限公司 | Catalyzer for hydrogenization of nano nickel and its preparation method |
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