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 PDFInfo
- Publication number
- 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
- Authority
- CN
- China
- Prior art keywords
- ceo
- catalyst
- palladium
- cerium
- chloromethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 121
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 23
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 title abstract description 9
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 89
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 34
- 229910003445 palladium oxide Inorganic materials 0.000 claims abstract description 27
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 150000002940 palladium Chemical class 0.000 claims abstract description 5
- 150000002696 manganese Chemical class 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 22
- LEMJKBQFTSWJDG-UHFFFAOYSA-N O(Cl)Cl.C Chemical compound O(Cl)Cl.C LEMJKBQFTSWJDG-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 18
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000010335 hydrothermal treatment Methods 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 56
- MCZQGJXPPZHLTG-UHFFFAOYSA-N C.[Cl] Chemical compound C.[Cl] MCZQGJXPPZHLTG-UHFFFAOYSA-N 0.000 abstract 2
- 229910000420 cerium oxide Inorganic materials 0.000 abstract 2
- 239000000460 chlorine Substances 0.000 abstract 2
- 229940050176 methyl chloride Drugs 0.000 abstract 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- -1 alcohol aldehyde Chemical class 0.000 description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
催化甲烷氯氧化反应制氯代甲烷的铈基催化剂及制备方法，涉及铈基催化剂。催化剂为二氧化铈经氧化钯修饰制得的Pd/CeO2催化剂，或二氧化铈经氧化钯和氧化锰共同修饰制得的Mn-Pd/CeO2催化剂。Pd/CeO2催化剂：先制备CeO2，把钯盐溶液加入水中，再加入CeO2，水浴中蒸干，干燥焙烧后即得Pd/CeO2催化剂。Mn-Pd/CeO2催化剂：先制备CeO2，把锰盐溶液和钯盐溶液混合于水中，再加入CeO2，水浴中蒸干，干燥焙烧后即得Mn-Pd/CeO2催化剂。制备方法简单，能够适用于甲烷氯氧化反应催化转化甲烷生成氯甲烷。可显著提高CH3Cl选择性和甲烷的转化率。针对甲烷氯氧化反应的催化性能稳定。The invention discloses a cerium-based catalyst for preparing methyl chloride by catalyzing the chlorine oxidation reaction of methane and a preparation method thereof, relating to the cerium-based catalyst. The catalyst is a Pd/CeO 2 catalyst prepared by modifying cerium oxide with palladium oxide, or a Mn-Pd/CeO 2 catalyst prepared by modifying cerium oxide with palladium oxide and manganese oxide. Pd/CeO 2 catalyst: first prepare CeO 2 , add palladium salt solution into water, then add CeO 2 , evaporate to dryness in water bath, dry and roast to obtain Pd/CeO 2 catalyst. Mn-Pd/CeO 2 catalyst: first prepare CeO 2 , mix manganese salt solution and palladium salt solution in water, then add CeO 2 , evaporate to dryness in water bath, dry and roast to obtain Mn-Pd/CeO 2 catalyst. The preparation method is simple, and can be applied to methane chlorine oxidation reaction to catalyze the conversion of methane into methyl chloride. The selectivity of CH 3 Cl and the conversion rate of methane can be significantly improved. The catalytic performance for methane chlorine oxidation reaction is stable.
Description
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:
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
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
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
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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102704921A CN103301836A (en) | 2013-07-01 | 2013-07-01 | Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013102704921A CN103301836A (en) | 2013-07-01 | 2013-07-01 | Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103301836A true CN103301836A (en) | 2013-09-18 |
Family
ID=49127811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013102704921A Pending CN103301836A (en) | 2013-07-01 | 2013-07-01 | Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103301836A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190108077A (en) * | 2018-03-13 | 2019-09-23 | 주식회사 엘지화학 | Method for partial oxidation of carbonate hydrogen |
| KR20200009844A (en) * | 2018-07-20 | 2020-01-30 | 주식회사 엘지화학 | Catalyst for partial oxidation of hydrocarbon and method for preparation method for carbon monooxide |
| KR102151067B1 (en) * | 2019-09-30 | 2020-09-02 | 한국과학기술원 | Catalyst for oxidative coupling of methane containing palladium supported on cerium palladium solid solution and oxidative coupling method using the same |
| CN113274999A (en) * | 2020-02-20 | 2021-08-20 | 中国科学院大连化学物理研究所 | Pd/CeO2Catalyst and synthesis and application thereof |
| 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 |
| CN116447886A (en) * | 2023-04-24 | 2023-07-18 | 北京皓天百能环保工程有限公司 | A method for catalytic combustion and utilization of combustible CO in sintering flue gas |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318875A (en) * | 2008-06-25 | 2008-12-10 | 厦门易工化学科技有限公司 | Process for producing chloromethane |
-
2013
- 2013-07-01 CN CN2013102704921A patent/CN103301836A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101318875A (en) * | 2008-06-25 | 2008-12-10 | 厦门易工化学科技有限公司 | Process for producing chloromethane |
Non-Patent Citations (2)
| Title |
|---|
| HAO-XINMAI等: "Shape-Selective Synthesis and Oxygen Storage Behavior of Ceria Nanopolyhedra,Nanorods, and Nanocubes", 《J.PHYS.CHEM.B》 * |
| 孙振玲等: "氧化钯及氧化锰对甲烷氯氧化制氯甲烷二氧化铈纳米棒催化剂的修饰作用", 《第16届全国催化学术会议论文集》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190108077A (en) * | 2018-03-13 | 2019-09-23 | 주식회사 엘지화학 | Method for partial oxidation of carbonate hydrogen |
| KR102243161B1 (en) * | 2018-03-13 | 2021-04-22 | 주식회사 엘지화학 | Method for partial oxidation of carbonate hydrogen |
| US11986803B2 (en) | 2018-03-13 | 2024-05-21 | Lg Chem, Ltd. | Partial oxidation process of hydrocarbons |
| KR20200009844A (en) * | 2018-07-20 | 2020-01-30 | 주식회사 엘지화학 | Catalyst for partial oxidation of hydrocarbon and method for preparation method for carbon monooxide |
| KR102542195B1 (en) * | 2018-07-20 | 2023-06-09 | 주식회사 엘지화학 | Catalyst for partial oxidation of hydrocarbon and method for preparation method for carbon monooxide |
| KR102151067B1 (en) * | 2019-09-30 | 2020-09-02 | 한국과학기술원 | Catalyst for oxidative coupling of methane containing palladium supported on cerium palladium solid solution and oxidative coupling method using the same |
| CN113274999A (en) * | 2020-02-20 | 2021-08-20 | 中国科学院大连化学物理研究所 | Pd/CeO2Catalyst and synthesis and application thereof |
| 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 structure catalyst, preparation method, application in low-temperature catalytic oxidation of toluene |
| CN116447886A (en) * | 2023-04-24 | 2023-07-18 | 北京皓天百能环保工程有限公司 | A method for catalytic combustion and utilization of combustible CO in sintering flue gas |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102344339B (en) | Application of cerium-based catalyst in methane oxyhalogenation methods used for preparing halogenated methane | |
| CN102441383B (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN103301836A (en) | Cerium-based catalyst for producing chloromethane by catalyzing oxidization reaction of methane chloride and preparation method thereof | |
| WO2018120576A1 (en) | Catalyst for preparing hydrocarbons from carbon dioxide by one-step hydrogenation and method for preparing same | |
| CN101015803B (en) | A kind of catalyst and its preparation method and the purposes in carbon tetrachloride hydrogenation dechlorination | |
| Wu et al. | Highly efficient hydrogenation of carbon dioxide to methyl formate over supported gold catalysts | |
| CN103230810A (en) | Fischer-Tropsch synthetic catalyst for preparing low-carbon olefin by utilizing synthetic gas, modified molecular sieve carrier and preparation method | |
| CN105289710B (en) | A kind of CO2Catalyst of Hydrogenation isoparaffin and its preparation method and application | |
| CN104549325B (en) | Catalyst for preparing low-carbon olefin from synthesis gas by one-step method, preparation method and application of catalyst | |
| CN102218320A (en) | Catalyst for hydrogenation, preparation method and application thereof | |
| CN103933978B (en) | A kind of carrier nanometer catalyst for catalysis transform of carbon dioxide and its preparation method and application | |
| CN108404918A (en) | Tumer ester through hydrogenation produces the copper zinc SiO 2 catalyst and preparation method thereof of ethyl alcohol | |
| CN101940958A (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN102600852B (en) | Catalyst for preparing dimethyl ether as well as preparation method and application thereof | |
| CN103145545B (en) | A kind of method preparing hydroxymalonic acid for glycerol catalysis oxidation | |
| CN102908957B (en) | Method for Fischer-Tropsch synthesis | |
| CN103613483A (en) | Application of layered loading catalyst in preparation of lower alcohol by using synthesis gas | |
| CN104549352B (en) | The catalyst and its application method of synthesis gas production low-carbon alkene | |
| CN101543775B (en) | A VOx/CeO2/TiO2 composite oxide and its preparation and application | |
| CN108855158B (en) | Preparation method and application of cobalt-ruthenium bimetallic heterogeneous catalyst | |
| CN103769102B (en) | A kind of cobalt-base catalyst and its preparation method and application | |
| CN103769227B (en) | A kind of modified silica gel carrier and its preparation method and application | |
| CN112892542B (en) | Barium-aluminum spinel composite oxide cobalt-based catalyst for autothermal reforming of acetic acid to produce hydrogen | |
| CN104725187B (en) | Technology for directly preparing ethyl alcohol and co-generating methane from synthesis gas | |
| CN104148105B (en) | By porous catalyst of direct synthesis of dimethyl ether from synthesis gas and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130918 |