CN1053017A - Catalyst of carbon monoxide oxidation (palladium-nickel/tin ash) and preparation method thereof - Google Patents
Catalyst of carbon monoxide oxidation (palladium-nickel/tin ash) and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 21
- 229910052759 nickel Inorganic materials 0.000 title abstract description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 32
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000003197 catalytic effect Effects 0.000 claims abstract description 21
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract 3
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 24
- 239000013078 crystal Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000010970 precious metal Substances 0.000 abstract description 2
- 239000000969 carrier Substances 0.000 abstract 1
- 239000000470 constituent Substances 0.000 abstract 1
- 230000002950 deficient Effects 0.000 abstract 1
- 239000003595 mist Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000004913 activation Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
Description
本发明涉及一种催化氧化一氧化碳的催化剂及其制备方法，具体地是一种以二氧化锡为载体所附载的钯-镍（Pd-Ni）的二元金属催化剂。The invention relates to a catalyst for catalyzing the oxidation of carbon monoxide and a preparation method thereof, in particular to a palladium-nickel (Pd-Ni) binary metal catalyst with tin dioxide as a carrier.
通过文献检索，目前催化氧化一氧化碳的催化剂有三种类型：贵金属型、钙钛矿型氧化物及贱金属氧化物型。贵金属型催化剂制备价格高，催化剂价格也高，且只在少数载体上具有催化性能高，活性温度较低的特性。后两类催化剂虽价格便宜，但催化活性温度更高，在常温或较低温度下几乎没有催化作用。According to literature search, there are currently three types of catalysts that catalyze the oxidation of carbon monoxide: noble metal type, perovskite type oxide and base metal oxide type. Precious metal-type catalysts are expensive to prepare, and the price of the catalyst is also high, and they only have the characteristics of high catalytic performance and low activation temperature on a small number of supports. Although the latter two types of catalysts are cheap, they have higher catalytic activity temperature and almost no catalytic effect at normal temperature or lower temperature.
US4490482公开了一种催化氧化一氧化碳的Pd/SnO2催化剂。活性载体SnO2的制备方法是先将SnCl4溶于水中，加NH3·H2O调PH值，再加HCl加热，再加入SnCl2·H2O晶体，加热，加氨水调PH值，加碱加热，再加H2O2得SnO2沉淀，过滤、漂洗、干燥，其步骤多，试剂耗量大。催化剂中的活性金属成分只有钯，其价格昂贵。US4490482 discloses a Pd/ SnO2 catalyst that catalyzes the oxidation of carbon monoxide. The preparation method of the active carrier SnO 2 is to dissolve SnCl 4 in water first, add NH 3 ·H 2 O to adjust the pH value, add HCl to heat, then add SnCl 2 ·H 2 O crystals, heat, add ammonia water to adjust the pH value, Add alkali to heat, add H 2 O 2 to obtain SnO 2 precipitation, filter, rinse, and dry, which involves many steps and consumes a lot of reagents. The only active metal component in the catalyst is palladium, which is expensive.
本发明的目的是研制一种以二氧化锡为载体，附载钯、镍二元体系的催化剂，即Pd-Ni/SnO2催化剂及其制备方法，以及二氧化锡（SnO2）载体的制备方法。本催化剂在常温至100℃间具有良好的催化氧化一氧化碳的性能，且价格较纯钯便宜，载体制备过程简单，耗试剂少。The purpose of the present invention is to develop a catalyst with tin dioxide as a carrier and a binary system of palladium and nickel, that is, Pd-Ni/SnO 2 catalyst and its preparation method, and a preparation method of tin dioxide (SnO 2 ) carrier . The catalyst has good performance in catalytic oxidation of carbon monoxide between normal temperature and 100 DEG C, and the price is cheaper than pure palladium, the preparation process of the carrier is simple, and the consumption of reagent is less.
本发明的目的是以下述方式实现的，Pd-Ni/SnO2催化剂的活性组分（重量%）为：The object of the present invention is achieved in the following way, Pd-Ni/SnO The active component (weight %) of catalyst is:
Pd 0.5-3Pd 0.5-3
Ni 1-10Ni 1-10
Sn 87-98Sn 87-98
催化条件：常温或常温以上，常压Catalytic conditions: normal temperature or above, normal pressure
催化效率：50-98%Catalytic efficiency: 50-98%
形状：颗粒状、块状、海绵状Shape: granular, lumpy, sponge
颜色：催化剂 灰色或黑色，载体 白色Color: catalyst gray or black, carrier white
本催化剂的制备方法是，将0.1-0.8gPdCl2溶于5-10ml蒸馏水中，加入0.4-1.0gNi（NO3）2晶体，搅匀，用HCl调PH＝2-5.5，加入5gSnO2活性载体，并加10ml还原剂肼，乙醛等，加热至沸，待还原充分，SnO2表面变黑后过滤，在170℃-200℃下干燥。The preparation method of this catalyst is as follows: dissolve 0.1-0.8g PdCl 2 in 5-10ml distilled water, add 0.4-1.0g Ni(NO 3 ) 2 crystal, stir well, adjust the pH to 2-5.5 with HCl, add 5g SnO 2 active carrier , and add 10ml of reducing agent hydrazine, acetaldehyde, etc., heat to boiling, after the reduction is complete, the surface of SnO2 turns black, filter, and dry at 170°C-200°C.
活性SnO2载体的制备方法是，将42-55gSnCl4溶于60ml36%HCl中，再加入40ml水和43-57gSnCl2晶体，待溶解均匀后，加入28%NH3·H2O调至PH＝7，待形成乳白色凝胶后煮沸，再加入30%的过氧化氢溶液约30-35g，充分搅拌氧化，此时凝胶由白→红→灰→土黄色，且伴随有气体放出，抽滤，用蒸馏水洗净后在102℃下干燥6小时，冷后放入干燥器中待用。The preparation method of the active SnO 2 carrier is to dissolve 42-55g of SnCl 4 in 60ml of 36% HCl, then add 40ml of water and 43-57g of SnCl 2 crystals. 7. After the milky white gel is formed, boil it, then add about 30-35g of 30% hydrogen peroxide solution, stir and oxidize fully. At this time, the gel changes from white → red → gray → khaki, accompanied by gas release, and then filter with suction , washed with distilled water, dried at 102°C for 6 hours, cooled and put into a desiccator for use.
催化剂性能测试及实验结果见附图及附表。Catalyst performance test and experimental results are shown in the accompanying drawings and attached tables.
图1 Pd/SnO2，Pd-Ni/SnO2催化剂催化效率与温度的关系Fig.1 Relationship between catalytic efficiency and temperature of Pd/SnO 2 and Pd-Ni/SnO 2 catalysts
图2 Pd-Ni/SnO2催化剂在不同温度下的反应速率常数Fig.2 Reaction rate constants of Pd-Ni/ SnO2 catalyst at different temperatures
图3 Pd/SnO2催化剂在不同温度下的反应速率常数Fig.3 Reaction rate constants of Pd/ SnO2 catalysts at different temperatures
在正常工作的色谱仪上进行催化剂性能指标测试，空速为1100h-1下，在CO和O2浓度比为1∶1的气氛中（其中N2约含88%），测得Pd/SnO2和Pd-Ni/SnO2催化剂催化效率与温度的关系如图1。图中曲线1为Pd/SnO2催化效率与温度的关系，曲线2、3、4分别为Pd、Ni原子比为4∶1，1∶1，1∶2的Pd-Ni/SnO2催化剂的催化效率与温度的关系。Catalyst performance index test was carried out on a normal working chromatograph, at a space velocity of 1100h -1 , in an atmosphere with a concentration ratio of CO and O2 of 1:1 (in which N2 contains about 88%), the measured Pd/SnO 2 and Pd-Ni/SnO 2 catalyst catalytic efficiency and temperature relationship is shown in Figure 1. Curve 1 in the figure is the relationship between Pd/ SnO2 catalytic efficiency and temperature, and curves 2, 3 and 4 are the Pd-Ni/ SnO2 catalysts with Pd and Ni atomic ratios of 4:1, 1:1, and 1:2, respectively. The relationship between catalytic efficiency and temperature.
从图1可见，当Pd、Ni原子比为4∶1时，在相同条件下，Pd-Ni/SnO2的催化效率与Pd/SnO2的催化效率基本相同。当提高催化剂中活性成分镍的含量后，本催化剂也有好的催化效率。It can be seen from Figure 1 that when the atomic ratio of Pd and Ni is 4:1, the catalytic efficiency of Pd-Ni/SnO 2 is basically the same as that of Pd/SnO 2 under the same conditions. When the content of the active component nickel in the catalyst is increased, the catalyst also has good catalytic efficiency.
以Pd/SnO2，Pd-Ni/SnO2（Pd∶Ni＝4∶1）为催化剂催化氧化CO，CO+1/2O2→CO2时，对于在管状反应器中进行反应的速率通式可表示为：When using Pd/SnO 2 , Pd-Ni/SnO 2 (Pd:Ni=4:1) as the catalyst to catalyze the oxidation of CO, when CO+1/2O 2 →CO 2 , the general formula for the reaction rate in the tubular reactor Can be expressed as:
R＝Fco (dxco)/(dv) （1）R＝Fco(dxco)/(dv) (1)
反应的动力学方程可表达为：The kinetic equation of the reaction can be expressed as:
R＝KCcoαCoβ 2（2）R＝KCco α Co β 2 (2)
由（1）、（2）可得From (1), (2) can get
Fco (dxco)/(dv) ＝RCαcoCoβ 2（3）Fco (dxco)/(dv) = RC α coCo β 2 (3)
由实验结果并计算得到α＝-1，β＝1，According to the experimental results and calculation, α=-1, β=1,
即该反应在催化剂作用下的动力学方程为：That is, the kinetic equation of the reaction under the action of the catalyst is:
R=K ([Q2])/([CO]) (4)R=K ([Q 2 ])/([CO]) (4)
根据实验数据，应用（4）式推算出Pd/SnO2，Pd-Ni/SnO2催化剂催化氧化CO在不同温度时的速率常数，其结果见表1、表2。According to the experimental data, the rate constants of CO catalytic oxidation by Pd/SnO 2 and Pd-Ni/SnO 2 catalysts at different temperatures were calculated by using formula (4). The results are shown in Table 1 and Table 2.
以 (VR)/(Fco) 为横坐标，以2ln（1- (Xco)/2 ）+2Xco为纵坐标作图，画出四条直线，直线的斜率即为该温度下的反应速率常数。Pd-Ni/SnO2测定的结果见图2，图中直线1、2、3、4分别为333.2k，323.2k，313.2k，303.2k温度下的反应速率常数。Take (VR)/(Fco) as the abscissa and 2ln(1- (Xco)/2 )+2Xco as the ordinate to plot, draw four straight lines, and the slope of the straight line is the reaction rate constant at the temperature. The results of Pd-Ni/SnO 2 measurement are shown in Fig. 2, and the straight lines 1, 2, 3, and 4 in the figure are the reaction rate constants at temperatures of 333.2k, 323.2k, 313.2k, and 303.2k, respectively.
从图2、图3可见，Pd-Ni/SnO2（Pd∶Ni＝4∶1）催化剂与Pd/SnO2催化剂相比较，在相同温度下前者速率常数与后者基本上相近（不相差一个数量级）。It can be seen from Figure 2 and Figure 3 that, compared with Pd-Ni/SnO 2 (Pd:Ni=4:1) catalyst and Pd/SnO 2 catalyst, the rate constant of the former is basically similar to that of the latter at the same temperature (no difference of one Magnitude).
从图1-图3还可见，根据不同的催化氧化一氧化碳的具体反应，可选择不同钯、镍配比的Pd-Ni/SnO2催化剂以适应不同的需要。对于高精度反应，活性成分Pd的含量高，对于低精度的可提高活性成分镍的含量，从而降低生产成本。It can also be seen from Fig. 1-Fig. 3 that according to the specific reactions of different catalytic oxidation of carbon monoxide, Pd-Ni/ SnO2 catalysts with different palladium and nickel ratios can be selected to meet different needs. For high-precision reactions, the content of active component Pd is high, and for low-precision reactions, the content of active component nickel can be increased, thereby reducing production costs.
本发明的Pd-Ni/SnO2催化剂的活化能经计算为68.1KJ/mol。The activation energy of the Pd-Ni/ SnO2 catalyst of the present invention is calculated to be 68.1KJ/mol.
本发明的载体制备方法比US4，490，482的SnO2载体制备方法步骤少，NH3·H2O用量减少。本发明的催化剂活性金属成分贵金属钯而外，加入了镍，降低了催化剂的成本，且催化效率与Pd/SnO2催化剂基本相近。本催化剂克服了一般催化剂在低温下催化氧化CO性能不高的缺陷，对CO浓度较高的混合气体当然也能适用。Compared with the SnO 2 carrier preparation method of US 4,490,482, the carrier preparation method of the present invention has fewer steps, and the amount of NH 3 ·H 2 O is reduced. In addition to the precious metal palladium, the catalyst active metal component of the present invention adds nickel, which reduces the cost of the catalyst, and the catalytic efficiency is basically similar to that of the Pd/ SnO2 catalyst. The catalyst overcomes the defect that general catalysts have low performance in catalytic oxidation of CO at low temperature, and is certainly applicable to mixed gases with high CO concentration.
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| CN89109718A CN1022988C (en) | 1989-12-30 | 1989-12-30 | Carbon monoxide oxidation catalyst (Pd-Ni/SnO2) and prepn. thereof |
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| CN89109718A CN1022988C (en) | 1989-12-30 | 1989-12-30 | Carbon monoxide oxidation catalyst (Pd-Ni/SnO2) and prepn. thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088401C (en) * | 1998-08-03 | 2002-07-31 | 中国科学院山西煤炭化学研究所 | CO catalyst for low-temp oxidization |
| CN102583265A (en) * | 2012-02-09 | 2012-07-18 | 西北工业大学 | Method for preparing coralline tin oxide nanoparticles |
| CN103752326A (en) * | 2013-11-25 | 2014-04-30 | 邵建军 | Preparation and catalysis application of Au/Co3O4 / CeO2 catalyst |
| CN104014353A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Palladium chloride-cupric chloride catalyst applied to normal-temperature catalytic oxidation of carbon monoxide and preparation |
| CN105473221A (en) * | 2013-08-23 | 2016-04-06 | 巴斯夫公司 | Catalysts for oxidation of carbon monoxide and/or volatile organic compounds |
| CN107126962A (en) * | 2017-05-17 | 2017-09-05 | 厦门大学 | A kind of ammonia nitrogen waste water catalysts for treating and its preparation method and application |
| CN109314011A (en) * | 2016-04-06 | 2019-02-05 | Abb瑞士股份有限公司 | Equipment for generating, transmitting, distributing and/or using electrical energy, especially electrical switching devices |
-
1989
- 1989-12-30 CN CN89109718A patent/CN1022988C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1088401C (en) * | 1998-08-03 | 2002-07-31 | 中国科学院山西煤炭化学研究所 | CO catalyst for low-temp oxidization |
| CN102583265A (en) * | 2012-02-09 | 2012-07-18 | 西北工业大学 | Method for preparing coralline tin oxide nanoparticles |
| CN105473221A (en) * | 2013-08-23 | 2016-04-06 | 巴斯夫公司 | Catalysts for oxidation of carbon monoxide and/or volatile organic compounds |
| CN103752326A (en) * | 2013-11-25 | 2014-04-30 | 邵建军 | Preparation and catalysis application of Au/Co3O4 / CeO2 catalyst |
| CN104014353A (en) * | 2014-05-28 | 2014-09-03 | 上海纳米技术及应用国家工程研究中心有限公司 | Palladium chloride-cupric chloride catalyst applied to normal-temperature catalytic oxidation of carbon monoxide and preparation |
| CN104014353B (en) * | 2014-05-28 | 2016-07-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Palladous chloride. copper chloride catalyst and preparation for carbon monoxide room-temperature catalytic oxidation |
| CN109314011A (en) * | 2016-04-06 | 2019-02-05 | Abb瑞士股份有限公司 | Equipment for generating, transmitting, distributing and/or using electrical energy, especially electrical switching devices |
| CN109314011B (en) * | 2016-04-06 | 2020-09-25 | Abb电网瑞士股份公司 | Equipment for generating, transmitting, distributing and/or using electrical energy, especially electrical switching devices |
| CN107126962A (en) * | 2017-05-17 | 2017-09-05 | 厦门大学 | A kind of ammonia nitrogen waste water catalysts for treating and its preparation method and application |
| CN107126962B (en) * | 2017-05-17 | 2019-10-25 | 厦门大学 | Catalyst for ammonia nitrogen wastewater treatment and its preparation method and application |
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| Publication number | Publication date |
|---|---|
| CN1022988C (en) | 1993-12-08 |
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