CN103301836A - Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof - Google Patents

Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof Download PDF

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CN103301836A
CN103301836A CN2013102704921A CN201310270492A CN103301836A CN 103301836 A CN103301836 A CN 103301836A CN 2013102704921 A CN2013102704921 A CN 2013102704921A CN 201310270492 A CN201310270492 A CN 201310270492A CN 103301836 A CN103301836 A CN 103301836A
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catalyst
ceo
palladium
cerium
chloromethane
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王野
孙振玲
邓卫平
吴雪娇
张庆红
何洁丽
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Xiamen University
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Abstract

The invention provides a cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and a preparation method thereof, and relates to the cerium-based catalyst. The catalyst is Pd/CeO2 catalyst which is produced from cerium dioxide modified by palladium oxide, or Mn-Pd/CeO2 catalyst which is produced from cerium dioxide modified by palladium oxide and manganese together. The Pd/CeO2 catalyst is produced through the steps of: preparing CeO2 at first, adding a palladium salt solution to water and then adding the CeO2, evaporating to dryness in a water bath, and finally, performing drying and baking. The Mn-Pd/CeO2 catalyst is produced through the steps of: preparing CeO2 at first, mixing a manganese salt solution with a palladium salt solution in water and then adding the CeO2, evaporating to dryness in a water bath, and finally, performing drying and baking. The preparation method is simple and suitable for generating chloromethane by catalytically converting methane through the oxidization reaction of methane chloride. Besides, the catalyst is capable of obviously improving the selectivity of CH3Cl and the conversion rate of methane. The catalyst is also stable in catalytic performance for the oxidization reaction of methane chloride.

Description

Catalyst based and the preparation method of the cerium of catalytic methane oxychloride reaction chloromethane processed
Technical field
The present invention relates to a kind of cerium catalyst based, especially relate to the catalyst based and preparation method of the cerium of a kind of catalytic methane oxychloride reaction chloromethane processed.
Background technology
The energy system of the world today mainly is based upon on oil, coal, these three kinds of fossil resource bases of natural gas.As the natural gas of one of three macrofossil resources, reserves are abundant, and calorific value is higher, and is a kind of clean energy resource.The China's natural gas stock number accounts for 10% of world's total resources, and the reserves of coal bed gas, shale gas are also very abundant in addition.And the main component of these gas resources is methane (CH 4), its content is 60%～99%.In addition, methane also is one of main greenhouse gases, and its greenhouse effects that cause are CO 225 times.Therefore, the exploitation methane conversion is that the effective way of the chemicals (such as aromatic hydrocarbons, alkene, oxygenatedchemicals alcohol aldehyde etc.) of high added value has great reality and strategic importance for reasonable utilization and the environmental protection aspect of fossil resource.
Methane is minimum and the most stable alkane molecule, and it is that four c h bonds of 439kJ/mol form by bond energy, activate the reaction condition that stable methane molecule usually requires harshness, such as high temperature etc.And under the reaction condition of harshness, the extremely difficult stable existence of the chemicals molecule more active than methane is difficult to highly selective and generates.Take oxygen as oxidant one step of methane directly being changed into chemicals is that ideal methane utilizes approach, but because target product yield is low, is difficult to realize course of industrialization.The yield that generates oxygenatedchemicals formaldehyde methyl alcohol such as directly oxidizing methane is no more than 5%, and the yield that methane oxidation coupling generates the C2 hydrocarbon generally is lower than 30% etc.
Compare with the direct conversion of methane, the multistep indirect reformer of methane refers to be the fluid chemical raw material with methane conversion optionally.Comparatively ripe indirect reformer process is through synthesis gas (CO+H at present 2Gaseous mixture, can make by methane vapor reforming or partial oxidation reaction of methane) be the liquid chemical fuels such as methyl alcohol, benzene, alkene with methane conversion.Because preparing the process of synthesis gas from methane is a strong endothermic reaction (～800 ℃), so this process exists, and energy consumption is large, the high in cost of production shortcoming.
Be chloromethane with methane conversion, chloromethane being converted into chemicals is another methane indirect reformer approach again.Compare with the preparation of synthesis gas, generate the reaction condition gentle (～500 ℃) of chloromethane.The applicant discloses a class in Chinese patent CN102344339A to be applicable to the cerium of methane oxychloride reaction catalyst based.The CeO of this patent report 2Through FeO xThe cerium based bi-component composite oxides Ce that modification makes 0.9Fe 0.1O 2-xHave better methane oxychloride reactivity worth, when reaction temperature was 480 ℃, the yield of chloromethanes was about 17%.
The more existing reports of the catalyst based application in catalytic reaction of multiple cerium that palladium oxide and manganese oxide are modified.The people such as Luo Mengfei have prepared CeO 2, PdO/CeO 2, Ce 1-xPd xO 2-δAnd PdO/Ce 1-xPd xO 2-δCatalyst (M.F.Luo, et al., J.Phys.Chem.C, 115 (2011), 19789) is used for the CO oxidation reaction, finds PdO/Ce 1-xPd xO 2-δCatalyst has preferably CO catalytic performance.The people such as Meng Ming study the interpolation of Pd to MnO x-CeO 2Find Pd/MnO during the affecting of Catalyst for CO oxidation reaction performance x-CeO 2Catalyst has the MnO of being better than x-CeO 2The catalytic performance of catalyst, and explain that the existence of Pd has mainly promoted gas phase O 2Activation, thereby so that absorption CO more easily generate CO 2(M.Meng, et al., J.Phys.Chem.C, 114 (2010), 468).The people such as Yang find and Pd/CeO 2Catalyst and Pd/MnO xCatalyst is compared, Pd/MnCeO xCatalyst series shows better catalytic performance and anti-deactivation (Y.H.Yang, et al., J.Catal., 283 (2011), 34) in the reaction of benzyl alcohol oxidation producing benzaldehyde.At 0.5wt%Pd/MnCeO x(Mn/Ce=7/3) on the catalyst, 160 ℃ of lower reaction 1h, the conversion ratio of phenmethylol is 18.4%, benzaldehyde selectively reach 98.6%.
Summary of the invention
The object of the present invention is to provide the catalyst based and preparation method of the cerium of a kind of catalytic methane oxychloride reaction chloromethane processed.
Described cerium is catalyst based, efficiently and stably catalytic conversion reaction thing CH 4, HCl and O 2Carry out oxychloride reaction generation and comprise CH 3Cl and CH 2Cl 2In interior product; It is as follows to be that described catalyst is mainly used methane oxychloride reaction:
Figure BDA00003441586600021
The cerium of described catalytic methane oxychloride reaction chloromethane processed is catalyst based to be that ceria is modified the Pd/CeO that makes through palladium oxide 2Catalyst, or ceria is through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide 2Catalyst.
Described ceria is modified the Pd/CeO that makes through palladium oxide 2Catalyst consisting of by mass percentage: the load capacity of palladium accounts for Pd/CeO 20.5%～2.0% of catalyst gross mass is in Pd.
Described ceria is through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide 2Catalyst consisting of by mass percentage: the load capacity of palladium accounts for Mn-Pd/CeO 20.5%～2.0% of catalyst gross mass is in Pd; The load capacity of manganese oxide accounts for Mn-Pd/CeO 25%～20% of catalyst gross mass is with MnO 2Meter.
The presoma of described palladium oxide can but to be not limited only to be a kind of in the palladium salt such as palladium bichloride, palladium nitrate, palladium, palladium acetylacetonate, the presoma of manganese oxide can but to be not limited only to be a kind of in the manganese salt such as manganese chloride, manganese nitrate, manganese sulfate.
Described ceria is modified the Pd/CeO that makes through palladium oxide 2The preparation method of catalyst may further comprise the steps:
1) CeO 2Preparation: with the metering cerous nitrate be dissolved in the water of 3～6 times of cerous nitrate quality, it is excessive to add again, concentration is the sodium hydroxide solution of 6～9M, then change over to and carry out hydrothermal treatment consists in the autoclave, cooling, suction filtration, washing, until filtrate is neutral (pH=7～8), final drying namely gets CeO after the roasting 2
2) Pd/CeO 2The preparation of catalyst: the palladium salting liquid of metering is added to the water, adds again the CeO that the step 1) of metering makes 2, after the stirring, evaporate to dryness in the water-bath, drying namely gets ceria and modifies the Pd/CeO that makes through palladium oxide after the roasting 2Catalyst.
In step 1), the condition of described hydrothermal treatment consists can be 100～180 ℃ of hydrothermal treatment consists 24h; The condition of described drying can be 100 ℃ of drying 3～5h; The condition of described roasting can be 500～600 ℃ of roasting 6h.
In step 2) in, the time of described stirring can be 12h; The temperature of evaporate to dryness can be 80 ℃ in the described water-bath; The condition of described drying can be 100 ℃ of drying 3～5h; The condition of described roasting can be 500～600 ℃ of roasting 6h.
Described ceria is through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide 2The preparation method of catalyst may further comprise the steps:
1) CeO 2Preparation: the cerous nitrate of metering is dissolved in 3～6 times the water of cerous nitrate quality, it is excessive to add again, concentration is the sodium hydroxide solution of 6～9M, then change over to and carry out hydrothermal treatment consists in the autoclave, cooling, suction filtration, washing, until filtrate is neutral (pH=7～8), final drying namely gets CeO after the roasting 2
2) Mn-Pd/CeO 2The preparation of catalyst: in water, add again the CeO that the step 1) of metering makes by the metering manganese salt solution of ratio and palladium salt solution mix 2, after the stirring, evaporate to dryness in the water-bath, drying namely gets ceria through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide after the roasting 2Catalyst.
In step 1), the condition of described hydrothermal treatment consists can be 100～180 ℃ of hydrothermal treatment consists 24h; The condition of described drying can be 100 ℃ of drying 3～5h; The condition of described roasting can be 500～600 ℃ of roasting 6h.
In step 2) in, the time of described stirring can be 12h; The temperature of evaporate to dryness can be 80 ℃ in the described water-bath; The condition of described drying can be 100 ℃ of drying 3～5h; The condition of described roasting can be 500～600 ℃ of roasting 6h.
The present invention's cerium that to be a class modify through palladium oxide and manganese oxide is catalyst based to be the reaction of chloromethane for transforming methane by the reaction of methane oxychloride.Reactant CH in reaction 4, HCl and O 2, under certain reaction temperature, in fixed bed reactors, contact the generation catalytic reaction with catalyst, generate target product chloromethane (CH 3Cl and CH 2Cl 2) and the accessory substance hydrocarbon.The reaction temperature of methane oxychloride reaction is generally 400～600 ℃, and reaction temperature is 450～550 ℃ preferably, and best reaction temperature is 450～500 ℃.
Compared with the prior art, the present invention has following outstanding advantages:
(1) such method for preparing catalyst is simple, can be applicable to methane oxychloride catalytic reaction and transform methane generation chloromethanes.
(2) for the reaction of methane oxychloride chloromethane processed, with respect to CeO 2Catalyst, ceria are modified the Pd/CeO that makes through palladium oxide 2Catalyst can significantly improve CH 3Cl is selective.
(3) for the reaction of methane oxychloride chloromethane processed, with respect to CeO 2Catalyst, ceria is through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide 2Catalyst is keeping high CH 3The selective while of Cl, significantly improved the conversion ratio of methane.Mn-Pd/CeO 2The highest CH on the catalyst 3The Cl yield is 24.15%, is significantly higher than CeO 2The highest CH on the catalyst 3Cl yield 14.85%.
(4) Pd/CeO 2Catalyst and Mn-Pd/CeO 2The catalytic performance of catalyst aims methane oxychloride reaction is stable.
The specific embodiment
Embodiment 1
The preparation of catalyst:
(1) CeO 2Preparation:
3.47g Ce (NO 3) 36H 2O is dissolved in the 20mL deionized water, stirs the lower 9M of adding NaOH solution 140mL, then changes 100 ℃ of hydro-thermal 24h in the autoclave over to, cooling, and suction filtration, washing, cyclic washing suction filtration 3 times, at last at 100 ℃ of dry 5h, 550 ℃ of roasting 6h make CeO 2
(2) 0.5wt%Pd/CeO 2The preparation of catalyst:
1.70mL0.006g/mL (in Pd) palladium chloride solution is mixed in the 20mL deionized water, stirs the above-mentioned CeO that makes of the lower 2.0g of adding 2, after continuing to stir 12h, evaporate to dryness in 80 ℃ of water-baths, 100 ℃ of dry 5h, 550 ℃ of roasting 6h make 0.5wt%Pd/CeO 2Catalyst.
Catalyst test:
Reaction is carried out in atmospheric fixed bed flow reactor, and reactor is that internal diameter is the quartz glass tube of 10mm, and catalyst amount is 0.500g, and reaction temperature is 480 ℃, CH 4Flow 16.0mL/min, HCl flow 8.0mL/min, O 2Flow 4.0mL/min.Tail gas is analyzed in gas-chromatography, with N 2Do interior mark.The activity rating of embodiment 1 the results are shown in table 1.
Embodiment 2
The preparation of catalyst:
Operating process is undertaken by embodiment 1, and the consumption of palladium chloride solution changes 3.30mL into.The gained catalyst is 1.0wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, the activity rating of embodiment 2 the results are shown in table 1.
Embodiment 3
The preparation of catalyst:
Operating process is undertaken by embodiment 1, and the consumption of palladium chloride solution changes 5.00mL into.The gained catalyst is 1.5wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, the activity rating of embodiment 3 the results are shown in table 1.
Embodiment 4
The preparation of catalyst:
Operating process is undertaken by embodiment 1, and the presoma of palladium oxide changes palladium into, and consumption is 0.062g, is dissolved in the 5.0mL acetone.The gained catalyst is 1.5wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, the activity rating of embodiment 4 the results are shown in table 1.
Embodiment 5
The preparation of catalyst:
Operating process is undertaken by embodiment 1, and the presoma of palladium oxide changes palladium acetylacetonate into, and consumption is 0.086g, is dissolved in the 5.0mL acetone.The gained catalyst is 1.5wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, the activity rating of embodiment 5 the results are shown in table 1.
The activity rating result of table 1 embodiment 1～5
Figure BDA00003441586600051
Embodiment 6
The preparation of catalyst:
(1) CeO 2Preparation:
3.47g Ce (NO 3) 36H 2O is dissolved in the 20mL deionized water, stirs the lower 9M of adding NaOH solution 140mL, then changes 100 ℃ of hydro-thermal 24h in the autoclave over to, cooling, and suction filtration, washing, cyclic washing suction filtration 3 times, at last at 100 ℃ of dry 5h, 550 ℃ of roasting 6h make CeO 2
(2) 5.0wt%Mn-1.0wt%Pd/CeO 2The preparation of catalyst:
0.416g50% manganese nitrate solution and 3.3mL0.006g/mL (in Pd) palladium chloride solution are mixed in the 20mL deionized water, stir the above-mentioned CeO that makes of the lower 2.0g of adding 2, after continuing to stir 12h, evaporate to dryness in 80 ℃ of water-baths, 100 ℃ of dry 5h, 550 ℃ of roasting 6h make 5.0wt%Mn-1wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, reaction temperature is 450 ℃, and the activity rating of embodiment 6 the results are shown in table 2.
The activity rating result of table 2 embodiment 6～11
Figure BDA00003441586600061
Embodiment 7
The preparation of catalyst:
Operating process is undertaken by embodiment 6, and the consumption of manganese nitrate solution changes 0.618g into.The gained catalyst is 7.5wt%Mn-1.0wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, reaction temperature is 450 ℃, and the activity rating of embodiment 7 the results are shown in table 2.
Embodiment 8
The preparation of catalyst:
Operating process is undertaken by embodiment 6, and the consumption of manganese nitrate solution changes 0.823g into.The gained catalyst is 10wt%Mn-1.0wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, reaction temperature is 450 ℃, and the activity rating of embodiment 8 the results are shown in table 2.
Embodiment 9
The preparation of catalyst:
Operating process is undertaken by embodiment 6, and the presoma of manganese oxide changes manganese chloride into, and consumption is 0.455g.The gained catalyst is 10wt%Mn-1.0wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, reaction temperature is 450 ℃, and the activity rating of embodiment 9 the results are shown in table 2.
Embodiment 10
The preparation of catalyst:
Operating process is undertaken by embodiment 6, and the presoma of palladium oxide changes palladium into, and consumption is 0.041g, is dissolved in the 5.0mL acetone.The gained catalyst is 10wt%Mn-1.0wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, reaction temperature is 450 ℃, and the activity rating of embodiment 10 the results are shown in table 2.
Embodiment 11
The preparation of catalyst:
Operating process is undertaken by embodiment 6, and the consumption of manganese nitrate solution changes 1.647g into.The gained catalyst is 20wt%Mn-1.0wt%Pd/CeO 2Catalyst.
Catalyst test:
According to test condition among the embodiment 1, reaction temperature is 450 ℃, and the activity rating of embodiment 11 the results are shown in table 2.
Comparative Examples 1
The preparation of catalyst:
3.47g Ce (NO 3) 36H 2O is dissolved in the 20mL deionized water, stirs the lower 9M of adding NaOH solution 140mL, then changes 100 ℃ of hydro-thermal 24h in the autoclave over to, cooling, and suction filtration, washing, cyclic washing suction filtration 3 times, at last at 100 ℃ of dry 5h, 550 ℃ of roasting 6h make CeO 2
The activity rating result of table 3 Comparative Examples 1
Figure BDA00003441586600071
Catalyst test:
According to test condition among the embodiment 1, the activity rating of Comparative Examples 1 the results are shown in table 3.

Claims (10)

1. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based, it is characterized in that, for ceria is modified the Pd/CeO that makes through palladium oxide 2Catalyst, or ceria is through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide 2Catalyst.
2. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 1, it is characterized in that, described ceria is modified the Pd/CeO that makes through palladium oxide 2Catalyst consisting of by mass percentage: the load capacity of palladium accounts for Pd/CeO 20.5%～2.0% of catalyst gross mass is in Pd;
Described ceria is through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide 2Catalyst consisting of by mass percentage: the load capacity of palladium accounts for Mn-Pd/CeO 20.5%～2.0% of catalyst gross mass is in Pd; The load capacity of manganese oxide accounts for Mn-Pd/CeO 25%～20% of catalyst gross mass is with MnO 2Meter.
3. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 1 or 2, it is characterized in that, the presoma of described palladium oxide can but to be not limited only to be a kind of in palladium bichloride, palladium nitrate, palladium, the palladium acetylacetonate, the presoma of manganese oxide can but to be not limited only to be a kind of in manganese chloride, manganese nitrate, the manganese sulfate.
4. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 1, it is characterized in that, described ceria is modified the Pd/CeO that makes through palladium oxide 2The preparation method of catalyst may further comprise the steps:
1) CeO 2Preparation: with the metering cerous nitrate be dissolved in the water of 3～6 times of cerous nitrate quality, it is excessive to add again, concentration is the sodium hydroxide solution of 6～9M, then changes over to carry out hydrothermal treatment consists in the autoclave, cooling, suction filtration, washing, until filtrate is neutral, final drying namely gets CeO after the roasting 2
2) Pd/CeO 2The preparation of catalyst: the palladium salting liquid of metering is added to the water, adds again the CeO that the step 1) of metering makes 2, after the stirring, evaporate to dryness in the water-bath, drying namely gets ceria and modifies the Pd/CeO that makes through palladium oxide after the roasting 2Catalyst.
5. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 4, it is characterized in that, in step 1), the condition of described hydrothermal treatment consists is 100～180 ℃ of hydrothermal treatment consists 24h; The condition of described drying can be 100 ℃ of drying 3～5h; The condition of described roasting can be 500～600 ℃ of roasting 6h.
6. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 4, it is characterized in that, in step 2) in, the time of described stirring is 12h; The temperature of evaporate to dryness can be 80 ℃ in the described water-bath; The condition of described drying can be 100 ℃ of drying 3～5h; The condition of described roasting can be 500～600 ℃ of roasting 6h.
7. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 1, it is characterized in that, described ceria is through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide 2The preparation method of catalyst may further comprise the steps:
1) CeO 2Preparation: the cerous nitrate of metering is dissolved in 3～6 times the water of cerous nitrate quality, it is excessive to add again, and concentration is the sodium hydroxide solution of 6～9M, then changes over to carry out hydrothermal treatment consists in the autoclave, cooling, suction filtration, washing, until filtrate is neutral, final drying namely gets CeO after the roasting 2
2) Mn-Pd/CeO 2The preparation of catalyst: in water, add again the CeO that the step 1) of metering makes by the metering manganese salt solution of ratio and palladium salt solution mix 2, after the stirring, evaporate to dryness in the water-bath, drying namely gets ceria through palladium oxide and the common Mn-Pd/CeO that makes that modifies of manganese oxide after the roasting 2Catalyst.
8. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 7, it is characterized in that, in step 1), the condition of described hydrothermal treatment consists can be 100～180 ℃ of hydrothermal treatment consists 24h.
9. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 7, it is characterized in that, in step 2) in, the time of described stirring is 12h; The temperature of evaporate to dryness can be 80 ℃ in the described water-bath.
10. the cerium of catalytic methane oxychloride reaction chloromethane processed is catalyst based as claimed in claim 7, it is characterized in that, in step 1) and 2) in, the condition of described drying is 100 ℃ of drying 3～5h; The condition of described roasting can be 500～600 ℃ of roasting 6h.
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CN113976115A (en) * 2021-11-19 2022-01-28 江苏科技大学 Layered core-shell structure catalyst, preparation method and application of catalyst in low-temperature catalytic oxidation of toluene
CN113976115B (en) * 2021-11-19 2023-09-19 江苏科技大学 Layered core-shell structured catalyst, preparation method and application of catalyst in low-temperature catalytic oxidation of toluene
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Application publication date: 20130918