CN114660256B - Method for measuring content of copper in each valence state in copper-zinc catalyst - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 239000010949 copper Substances 0.000 title claims abstract description 131
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 title claims abstract description 88
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 41
- 230000036284 oxygen consumption Effects 0.000 claims abstract description 75
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 73
- 238000012360 testing method Methods 0.000 claims abstract description 72
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 55
- 230000003647 oxidation Effects 0.000 claims abstract description 54
- 230000009467 reduction Effects 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- 239000011701 zinc Substances 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 230000010354 integration Effects 0.000 claims abstract description 32
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 24
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 11
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims description 71
- 239000000126 substance Substances 0.000 claims description 63
- 238000012545 processing Methods 0.000 claims description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 239000011787 zinc oxide Substances 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 10
- 229910000431 copper oxide Inorganic materials 0.000 claims description 10
- 238000012937 correction Methods 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000003556 assay Methods 0.000 abstract 2
- 239000004480 active ingredient Substances 0.000 abstract 1
- 229940108928 copper Drugs 0.000 abstract 1
- 229960004643 cupric oxide Drugs 0.000 abstract 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 39
- 238000010926 purge Methods 0.000 description 24
- 230000001681 protective effect Effects 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001124569 Lycaenidae Species 0.000 description 1
- 241000940835 Pales Species 0.000 description 1
- 206010033546 Pallor Diseases 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000014987 copper Nutrition 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
Description
技术领域Technical field
本发明涉及一种铜锌催化剂中各价态铜含量的测定方法，属于催化剂活性成分含量测定技术领域。The invention relates to a method for measuring the content of copper in various valence states in a copper-zinc catalyst, and belongs to the technical field of measuring the content of active components of the catalyst.
背景技术Background technique
铜基催化剂具有较好的催化性能，在脱氢、加氢和氧化反应中广泛使用。在铜基催化剂中，ZnO的加入可以促进铜的分散和还原，增强催化剂的稳定性能，而Cu-ZnO界面之间的相互作用对催化剂活性也有重要影响。铜锌催化剂在工业上已用于催化合成气制甲醇、低碳醇反应、水煤气变换反应等。近年来铜锌催化剂在以CO2加氢为依托构建起来的C1化学中成为了研究热点，以CO2为原料合成甲醇、二甲醚、甲烷、低碳醇等可以减少CO2的排放，对实现碳中和意义重大。随着铜锌催化剂研究工作的深入，催化剂合成方法更加多样，应用领域也不断拓展，大量研究表明，铜锌催化剂中铜主要以零价金属、+1价和+2价盐类或氧化物形式存在，而对于不同催化反应，对催化剂中活性铜价态存在形式的要求不同，因此铜锌催化剂中不同价态铜的测定尤为重要。Copper-based catalysts have good catalytic performance and are widely used in dehydrogenation, hydrogenation and oxidation reactions. In copper-based catalysts, the addition of ZnO can promote the dispersion and reduction of copper and enhance the stability of the catalyst. The interaction between the Cu-ZnO interface also has an important impact on the catalyst activity. Copper-zinc catalysts have been used in industry to catalyze synthesis gas to methanol, low-carbon alcohol reactions, water-gas shift reactions, etc. In recent years, copper-zinc catalysts have become a research hotspot in C1 chemistry based on CO 2 hydrogenation. Using CO 2 as raw materials to synthesize methanol, dimethyl ether, methane, low-carbon alcohols, etc. can reduce CO 2 emissions, which is Achieving carbon neutrality is huge. With the deepening of research on copper-zinc catalysts, catalyst synthesis methods have become more diverse and application fields have continued to expand. A large number of studies have shown that copper in copper-zinc catalysts is mainly in the form of zero-valent metals, +1-valent and +2-valent salts or oxides exists, and for different catalytic reactions, the requirements for the existence form of the active copper valence state in the catalyst are different, so the determination of different valence states of copper in copper-zinc catalysts is particularly important.
目前对铜锌催化剂中各种价态铜的测定，主要是通过X射线光电子光谱(XPS)和俄歇电子能谱进行表征，其精度和准确度比较可靠，可以通过测得各个元素的结合能谱，与标准能谱进行对比并且分峰处理计算，得到表层各元素或同一元素不同价态的比例。但是XPS受制于电子逃逸深度，测量深度一般只有2纳米左右，所以主要测定的是催化剂表层(或表相)的特征，对催化剂体相的定量分析相形见绌。由于表面集聚效应，催化剂表层元素含量不等同于催化剂中真实的元素含量，也表述为体相元素含量。目前没有便捷的方法定量测定铜锌催化剂中不同价态铜的量。At present, the determination of various valence states of copper in copper-zinc catalysts is mainly characterized by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy. Its precision and accuracy are relatively reliable, and the binding energy of each element can be measured. The spectrum is compared with the standard energy spectrum and calculated through peak splitting to obtain the ratio of each element on the surface or different valence states of the same element. However, XPS is limited by the electron escape depth, and the measurement depth is generally only about 2 nanometers. Therefore, it mainly measures the characteristics of the catalyst surface layer (or surface phase), and the quantitative analysis of the catalyst bulk phase pales in comparison. Due to the surface aggregation effect, the element content on the surface of the catalyst is not equal to the actual element content in the catalyst, which is also expressed as the bulk element content. Currently, there is no convenient method to quantitatively determine the amount of copper in different valence states in copper-zinc catalysts.
发明内容Contents of the invention
本发明针对现有技术中铜锌催化剂中不同价态铜测定的问题，提供一种铜锌催化剂中各价态铜含量的测定方法，即根据不同价态铜氧化或还原性能的差异，结合程序升温还原(H2-TPR)测试和程序升温氧化(O2-TPO)测试法，得到催化剂的H2-TPR曲线和O2-TPO曲线，由于不同价态铜还原或氧化的难易程度不同和差异性，在H2-TPR曲线、O2-TPO曲线上不同价态铜对应的耗氢峰或耗氧峰的出峰位置不同，根据出峰位置并结合耗氢峰或耗氧峰峰面积，分别通过O2-TPO联合H2-TPR测定(TPO-TPR)和H2-TPR联合O2-TPO测定(TPR-TPO)，得到H2-TPR和O2-TPO的曲线，进行峰积分处理后得到对应的耗氢峰峰面积和耗氧峰峰面积，计算出铜锌催化剂中零价铜、氧化亚铜和氧化铜的摩尔比，以及催化剂中的铜锌摩尔比。本发明可便捷测定铜锌催化剂中不同价态铜的量和铜锌比例。Aiming at the problem of measuring copper in different valence states in copper-zinc catalysts in the prior art, the present invention provides a method for measuring the content of copper in various valence states in copper-zinc catalysts, that is, based on the difference in oxidation or reduction performance of copper in different valence states, combined with a program Temperature-increasing reduction (H 2 -TPR) test and programmed temperature-increasing oxidation (O 2 -TPO) test method were used to obtain the H 2 -TPR curve and O 2 -TPO curve of the catalyst. Since copper in different valence states has different eases of reduction or oxidation, and difference. On the H 2 -TPR curve and O 2 -TPO curve, the hydrogen consumption peak or oxygen consumption peak corresponding to different valence coppers has different peak positions. According to the peak position and combined with the hydrogen consumption peak or oxygen consumption peak, area, respectively, through O 2 -TPO combined with H 2 -TPR measurement (TPO-TPR) and H 2 -TPR combined with O 2 -TPO measurement (TPR-TPO) to obtain the curves of H 2 -TPR and O 2 -TPO. After peak integration processing, the corresponding hydrogen consumption peak area and oxygen consumption peak peak area were obtained, and the molar ratio of zero-valent copper, cuprous oxide and copper oxide in the copper-zinc catalyst was calculated, as well as the molar ratio of copper-zinc in the catalyst. The invention can conveniently measure the amount of copper in different valence states and the copper-zinc ratio in the copper-zinc catalyst.
本发明将程序升温还原(H2-TPR)和程序升温氧化(O2-TPO)联合，根据不同价态铜氧化或还原性能的差异性，且耗氢量或耗氧量与耗氢峰峰面积或耗氧峰峰面积呈固定比例的关系，来定量计算催化剂中各价态铜的比例；The invention combines temperature-programmed reduction (H 2 -TPR) and temperature-programmed oxidation (O 2 -TPO). According to the difference in oxidation or reduction performance of copper in different valence states, the hydrogen consumption or oxygen consumption is related to the hydrogen consumption peak. The area or oxygen consumption peak area is in a fixed ratio relationship to quantitatively calculate the proportion of copper in each valence state in the catalyst;
H2-TPR涉及到反应式(1)和(2)，O2-TPO涉及到反应式(3)和(4)：H 2 -TPR involves reaction formulas (1) and (2), and O 2 -TPO involves reaction formulas (3) and (4):
CuO+H2＝Cu+H2O (1)CuO+H 2 =Cu+H 2 O (1)
Cu2O+H2＝2Cu+H2O (2)Cu 2 O+H 2 =2Cu+H 2 O (2)
2Cu+O2＝2CuO (3)2Cu+O 2 =2CuO (3)
2Cu2O+O2＝4CuO (4)2Cu 2 O+O 2 =4CuO (4)
一种铜锌催化剂中各价态铜含量的测定方法，具体步骤如下：A method for measuring the content of copper in various valence states in a copper-zinc catalyst. The specific steps are as follows:
(1)将待测的铜锌催化剂分为A组铜锌催化剂和B组铜锌催化剂；(1) Divide the copper-zinc catalysts to be tested into group A copper-zinc catalysts and group B copper-zinc catalysts;
(2)A组铜锌催化剂进行程序升温氧化O2-TPO测试，得到O2-TPO曲线A；再进行程序升温还原H2-TPR测试，得到H2-TPR曲线A；(2) Group A copper-zinc catalyst was subjected to a temperature-programmed oxidation O 2 -TPO test to obtain an O 2 -TPO curve A; and then a temperature-programmed reduction H 2 -TPR test was performed to obtain an H 2 -TPR curve A;
(3)B组铜锌催化剂进行程序升温还原H2-TPR测试得到H2-TPR曲线B；再进行程序升温氧化O2-TPO测试，得到O2-TPO曲线B；(3) Group B copper-zinc catalyst was subjected to a temperature-programmed reduction H 2 -TPR test to obtain H 2 -TPR curve B; then a temperature-programmed oxidation O 2 -TPO test was performed to obtain O 2 -TPO curve B;
(4)纯CuO进行程序升温还原H2-TPR测试得到H2-TPR曲线C；(4) Pure CuO was subjected to temperature-programmed reduction H 2 -TPR test to obtain H 2 -TPR curve C;
所述程序升温氧化O2-TPO测试和程序升温还原H2-TPR测试中仅处理气的种类和测试的结束温度不同，其它工艺条件均相同(例如起始温度、温度变化速率、处理气流速、气体压力等均保持一致)，以排除动力学参数不一致造成的影响；程序升温氧化O2-TPO测试的处理气为含O2的氧化性气体，程序升温还原H2-TPR测试的处理气为含H2的还原性气体；In the temperature-programmed oxidation O 2 -TPO test and the temperature-programmed reduction H 2 -TPR test, only the type of processing gas and the end temperature of the test are different, and other process conditions are the same (such as starting temperature, temperature change rate, processing gas flow rate , gas pressure, etc. are all consistent) to eliminate the influence of inconsistent kinetic parameters; the processing gas for the programmed temperature-increasing oxidation O 2 -TPO test is an oxidizing gas containing O 2 , and the processing gas for the programmed temperature-increasing reduction H 2 -TPR test It is a reducing gas containing H 2 ;
(5)设定催化剂样品中Cu单质物质的量对应的耗氧峰面积为a1，Cu2O物质的量对应的耗氧峰面积为a2；CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积为a3；(5) Set the oxygen consumption peak area corresponding to the amount of Cu elemental substance in the catalyst sample to a 1 , and the oxygen consumption peak area corresponding to the amount of Cu 2 O substance in the catalyst sample to be a 2 ; CuO is first reduced to Cu in H 2 -TPR 0 oxidizes CuO in O 2 -TPO, and the corresponding oxygen consumption peak area is a 3 ;
对O2-TPO曲线A进行分峰和峰面积积分处理得到Cu单质物质的量对应的耗氧峰面积为a1和Cu2O物质的量对应的耗氧峰面积为a2；The O 2 -TPO curve A is subjected to peak splitting and peak area integration processing to obtain that the oxygen consumption peak area corresponding to the amount of Cu elemental substance is a 1 and the oxygen consumption peak area corresponding to the amount of Cu 2 O substance is a 2 ;
对O2-TPO曲线B进行峰面积积分处理得到总积分面积为a0；由于氧化锌在程序升温还原H2-TPR测试中部分被还原，并且在O2-TPO过程这部分被还原的锌会被氧化，故，a0中包含了该部分锌氧化的耗氧峰，锌氧化温度为200℃左右，O2-TPO曲线B中锌氧化温度(200℃左右)时积分处理得到耗氧峰峰面积a4；Perform peak area integration processing on O 2 -TPO curve B to obtain a total integrated area of a 0 ; because zinc oxide was partially reduced in the temperature programmed reduction H 2 -TPR test, and this part of the zinc was reduced in the O 2 -TPO process It will be oxidized, so a 0 contains the oxygen consumption peak of this part of zinc oxidation. The zinc oxidation temperature is about 200°C. The oxygen consumption peak is obtained by integration at the zinc oxidation temperature (about 200°C) in the O 2 -TPO curve B. Peak area a 4 ;
计算出CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积为a3；再根据耗氧峰面积a1、耗氧峰面积为a2和耗氧峰面积a3计算出零价铜、氧化亚铜和氧化铜的摩尔比；It is calculated that CuO is first reduced to Cu 0 in H 2 -TPR and then oxidized to CuO in O 2 -TPO. The corresponding oxygen consumption peak area is a 3 ; then according to the oxygen consumption peak area a 1 , the oxygen consumption peak area is a 2 and Oxygen consumption peak area a 3 Calculate the molar ratio of zero-valent copper, cuprous oxide and copper oxide;
(6)H2-TPR曲线A进行峰面积积分处理得到所有氢消耗峰拟合的总积分面积b0；对H2-TPR曲线C进行峰面积积分处理得到纯CuO的耗氢峰峰面积为b1；(6) Perform peak area integration processing on H 2 -TPR curve A to obtain the total integrated area b 0 of all hydrogen consumption peak fits; perform peak area integration processing on H 2 -TPR curve C to obtain the hydrogen consumption peak area of pure CuO: b1 ;
铜锌催化剂中，H2-TPR过程中还原温度为600℃以上，有部分氧化锌被还原，需要对耗氢峰进行校正，即需要扣除H2-TPR曲线A中氧化锌还原产生的耗氢峰，计算出校正后催化剂样品中铜对应的耗氢峰b′0；In copper-zinc catalysts, the reduction temperature during the H 2 -TPR process is above 600°C, and some zinc oxide is reduced. The hydrogen consumption peak needs to be corrected, that is, the hydrogen consumption generated by zinc oxide reduction in H 2 -TPR curve A needs to be deducted. Peak, calculate the hydrogen consumption peak b′ 0 corresponding to copper in the catalyst sample after correction;
计算出铜锌催化剂中Cu与Zn的摩尔比。Calculate the molar ratio of Cu to Zn in the copper-zinc catalyst.
所述CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积a3的计算公式为The CuO is first reduced to Cu 0 in H 2 -TPR and then oxidized to CuO in O 2 -TPO. The corresponding calculation formula for the oxygen consumption peak area a 3 is:
a3＝a0-a1-2a2-a4 a 3 =a 0 -a 1 -2a 2 -a 4
零价铜、氧化亚铜和氧化铜的摩尔比为The molar ratio of zerovalent copper, cuprous oxide and copper oxide is
Cu:Cu2O:CuO＝a1:a2:a3 Cu:Cu 2 O:CuO＝a 1 :a 2 :a 3
式中，a1为催化剂样品中Cu单质物质的量对应的耗氧峰面积，a2为Cu2O物质的量对应的耗氧峰面积；a3为CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积；a4为锌氧化温度时的耗氧峰峰面积；a0为O2-TPO曲线B进行峰面积积分处理得到总积分面积。In the formula, a 1 is the oxygen consumption peak area corresponding to the amount of Cu elemental substance in the catalyst sample, a 2 is the oxygen consumption peak area corresponding to the amount of Cu 2 O substance; a 3 is CuO first reduced in H 2 -TPR to Cu 0 oxidizes CuO in O 2 -TPO, corresponding oxygen consumption peak area; a 4 is the oxygen consumption peak area at the zinc oxidation temperature; a 0 is the peak area integration processing of O 2 -TPO curve B to obtain the total integrated area .
进一步的，所述校正后催化剂样品中铜对应的耗氢峰b′0的计算公式为Further, the calculation formula for the hydrogen consumption peak b′ 0 corresponding to copper in the corrected catalyst sample is:
铜锌催化剂中Cu与Zn的摩尔比为The molar ratio of Cu to Zn in the copper-zinc catalyst is
Cu∶Zn＝b′0:(b1-b′0)Cu:Zn=b′ 0 : (b 1 -b′ 0 )
式中，a0为O2-TPO曲线B进行峰面积积分处理得到总积分面积，a4为锌氧化温度时的耗氧峰峰面积，H2-TPR曲线A进行峰面积积分处理得到所有氢消耗峰拟合的总积分面积b0，b′0为校正后催化剂样品中铜对应的耗氢峰，b1为H2-TPR曲线C进行峰面积积分处理得到纯CuO的耗氢峰峰面积。In the formula, a 0 is the peak area integration process of O 2 -TPO curve B to obtain the total integrated area, a 4 is the oxygen consumption peak area at the zinc oxidation temperature, and the peak area integration process of H 2 -TPR curve A is obtained to obtain all hydrogen The total integrated area b 0 of the consumption peak fitting, b′ 0 is the hydrogen consumption peak corresponding to copper in the catalyst sample after correction, b 1 is the H 2 -TPR curve C, and the peak area integration process of the H 2 -TPR curve C is performed to obtain the hydrogen consumption peak area of pure CuO .
所述含O2的氧化性气体为O2/N2、O2/Ar或O2/He；含H2的还原性气体为H2/N2、H2/Ar或H2/He。The oxidizing gas containing O 2 is O 2 /N 2 , O 2 /Ar or O 2 /He; the reducing gas containing H 2 is H 2 /N 2 , H 2 /Ar or H 2 /He.
优选的，步骤(2)的具体方法为Preferably, the specific method of step (2) is
1)将A组铜锌催化剂置于化学吸附仪的样品管中，采用保护气体在温度低于200℃的温区内对A组铜锌催化剂样品进行吹扫；1) Place the Group A copper-zinc catalyst in the sample tube of the chemical adsorption instrument, and use protective gas to purge the Group A copper-zinc catalyst sample in a temperature zone below 200°C;
2)吹扫结束后进行程序升温氧化(O2-TPO)测试：向化学吸附仪的样品管中通入含O2的氧化性气体，以1-10K/min的升温速率对A组铜锌催化剂样品程序升温，化学吸附仪记录信号，得到以温度为横坐标，A组铜锌催化剂样品信号值为纵坐标的O2-TPO曲线A；2) After the purge is completed, perform the temperature programmed oxidation (O 2 -TPO) test: pass the oxidizing gas containing O 2 into the sample tube of the chemical adsorption instrument, and test the copper and zinc of Group A at a heating rate of 1-10K/min. The catalyst sample is programmed to heat up, and the chemical adsorption instrument records the signal to obtain the O 2 -TPO curve A with the temperature as the abscissa and the signal value of the copper-zinc catalyst sample of Group A as the ordinate;
3)结束程序升温氧化(O2-TPO)测试后进行程序升温还原H2-TPR测试：向化学吸附仪的样品管中通入保护气体进行吹扫，降温到50℃以下时，切换处理气为含H2的还原性气体，以1-10K/min的升温速率对样品管中的样品进行程序升温，化学吸附仪记录信号，得到以温度为横坐标，样品信号值为纵坐标的H2-TPR曲线A；3) After completing the programmed temperature oxidation (O 2 -TPO) test, perform the programmed temperature reduction H 2 -TPR test: Pour protective gas into the sample tube of the chemical adsorption instrument for purging. When the temperature drops below 50°C, switch the processing gas. It is a reducing gas containing H 2. The sample in the sample tube is heated at a heating rate of 1-10K/min. The chemical adsorption instrument records the signal and obtains H 2 with the temperature as the abscissa and the sample signal value as the ordinate. -TPR curve A;
优选的，步骤(3)的具体方法为Preferably, the specific method of step (3) is
1)将B组铜锌催化剂置于化学吸附仪的样品管中，采用保护气体在温度低于200℃的温区内对B组铜锌催化剂样品进行吹扫；1) Place the Group B copper-zinc catalyst in the sample tube of the chemical adsorption instrument, and use protective gas to purge the Group B copper-zinc catalyst sample in a temperature zone below 200°C;
2)吹扫结束后进行程序升温还原H2-TPR测试:向化学吸附仪的样品管中通入含H2的还原性气体，以1-10K/min的升温速率对B组铜锌催化剂样品进行程序升温，化学吸附仪记录信号，得到以温度为横坐标，B组铜锌催化剂样品信号值为纵坐标的H2-TPR曲线B；2) After the purge is completed, perform the programmed temperature reduction H 2 -TPR test: pass the reducing gas containing H 2 into the sample tube of the chemical adsorption instrument, and test the copper-zinc catalyst sample of Group B at a heating rate of 1-10K/min. Perform a programmed temperature rise, record the signal with a chemical adsorption instrument, and obtain the H 2 -TPR curve B with the temperature as the abscissa and the signal value of the copper-zinc catalyst sample of Group B as the ordinate;
3)结束程序升温还原H2-TPR测试后进行程序升温氧化(O2-TPO)测试：向化学吸附仪的样品管中通入保护气体进行吹扫，降温到50℃以下时，切换处理气为含O2的氧化性气体，以1-10K/min的升温速率对样品管中的样品程序升温，化学吸附仪记录信号，得到以温度为横坐标，样品信号值为纵坐标的O2-TPO曲线B；3) After completing the programmed temperature reduction H 2 -TPR test, perform the temperature programmed oxidation (O 2 -TPO) test: Pour protective gas into the sample tube of the chemical adsorption instrument for purging. When the temperature drops below 50°C, switch the processing gas. It is an oxidizing gas containing O 2. The sample in the sample tube is heated at a heating rate of 1-10K/min. The chemical adsorption instrument records the signal and obtains O 2 - with the temperature as the abscissa and the sample signal value as the ordinate. TPO curve B;
优选的，步骤(4)的具体方法为Preferably, the specific method of step (4) is
1)将纯CuO置于化学吸附仪的样品管中，采用保护气体在温度低于200℃的温区内对纯CuO催化剂样品进行吹扫；1) Place pure CuO in the sample tube of the chemical adsorption instrument, and use protective gas to purge the pure CuO catalyst sample in a temperature zone below 200°C;
2)吹扫结束后进行程序升温还原H2-TPR测试:向化学吸附仪的样品管中通入含H2的还原性气体，以1-10K/min的升温速率对纯CuO催化剂样品进行程序升温，化学吸附仪记录信号，得到以温度为横坐标，纯CuO催化剂样品信号值为纵坐标的H2-TPR曲线C。2) After purging, perform programmed temperature reduction H 2 -TPR test: Pour reducing gas containing H 2 into the sample tube of the chemical adsorption instrument, and program the pure CuO catalyst sample at a temperature rise rate of 1-10K/min. The temperature is raised, the chemical adsorption instrument records the signal, and the H 2 -TPR curve C is obtained, with the temperature as the abscissa and the signal value of the pure CuO catalyst sample as the ordinate.
所述保护气体为N2、Ar或He。The protective gas is N 2 , Ar or He.
本发明的有益效果是：The beneficial effects of the present invention are:
(1)本发明根据不同价态铜氧化或还原性能的差异，利用程序升温还原/氧化测铜锌催化剂中各价态铜比例，即联用程序升温还原(H2-TPR)测试和程序升温氧化(O2-TPO)测试法，得到催化剂的H2-TPR曲线和O2-TPO曲线，对H2-TPR曲线和O2-TPO曲线进行分峰和峰积分处理得到对应的耗氢峰峰面积和耗氧峰峰面积，便捷计算出铜锌催化剂中零价铜、氧化亚铜和氧化铜的摩尔比，以及催化剂中的铜锌摩尔比；(1) Based on the differences in the oxidation or reduction properties of copper in different valence states, the present invention uses programmed temperature reduction/oxidation to measure the proportion of copper in each valence state in the copper-zinc catalyst, that is, combined temperature programmed reduction (H 2 -TPR) testing and programmed temperature rise Oxidation (O 2 -TPO) test method, obtain the H 2 -TPR curve and O 2 -TPO curve of the catalyst, perform peak splitting and peak integration processing on the H 2 -TPR curve and O 2 -TPO curve to obtain the corresponding hydrogen consumption peak Peak area and oxygen consumption peak area, conveniently calculate the molar ratio of zero-valent copper, cuprous oxide and copper oxide in the copper-zinc catalyst, as well as the molar ratio of copper-zinc in the catalyst;
(2)本发明可便捷精确的测定铜锌催化剂中不同价态铜的量和铜锌比例。(2) The present invention can conveniently and accurately determine the amount of copper in different valence states and the copper-zinc ratio in the copper-zinc catalyst.
附图说明Description of drawings
图1为实施例1的O2-TPO曲线A；Figure 1 is O 2 -TPO curve A of Example 1;
图2为实施例1的H2-TPR曲线A；Figure 2 is H 2 -TPR curve A of Example 1;
图3为实施例1的H2-TPR曲线B；Figure 3 is H 2 -TPR curve B of Example 1;
图4为实施例1的O2-TPO曲线B；Figure 4 is O 2 -TPO curve B of Example 1;
图5为实施例1和2的H2-TPR曲线C；Figure 5 is the H 2 -TPR curve C of Examples 1 and 2;
图6为实施例2的O2-TPO曲线A；Figure 6 is O 2 -TPO curve A of Example 2;
图7为实施例2的H2-TPR曲线A；Figure 7 is H 2 -TPR curve A of Example 2;
图8为实施例2的H2-TPR曲线B；Figure 8 is H 2 -TPR curve B of Example 2;
图9为实施例2的O2-TPO曲线B。Figure 9 is O 2 -TPO curve B of Example 2.
具体实施方式Detailed ways
下面结合具体实施方式对本发明作进一步详细说明，但本发明的保护范围并不限于所述内容。The present invention will be further described in detail below in conjunction with specific embodiments, but the protection scope of the present invention is not limited to the content described.
实施例1：Example 1:
制备多价态铜的铜锌催化剂A：以乙酰丙酮铜和乙酰丙酮锌为前驱体，配成水溶液后放入水热反应釜，水热反应釜中在180℃的温度下反应24h，制备铜锌催化剂，其中Cu:Zn＝5:4(摩尔比)，过滤生成的固体产物，用去离子水洗涤后干燥，得到的铜锌催化剂A；Copper-zinc catalyst A for preparing polyvalent copper: use copper acetylacetonate and zinc acetylacetonate as precursors, prepare an aqueous solution and put it into a hydrothermal reactor. React in the hydrothermal reactor at a temperature of 180°C for 24 hours to prepare copper. Zinc catalyst, wherein Cu:Zn=5:4 (molar ratio), filter the generated solid product, wash with deionized water and dry to obtain copper-zinc catalyst A;
一种铜锌催化剂中各价态铜含量的测定方法，具体步骤如下：A method for measuring the content of copper in various valence states in a copper-zinc catalyst. The specific steps are as follows:
(1)将待测的铜锌催化剂A分为A组铜锌催化剂(30mg)和B组铜锌催化剂(30mg)；(1) Divide the copper-zinc catalyst A to be tested into group A copper-zinc catalyst (30 mg) and group B copper-zinc catalyst (30 mg);
(2)A组铜锌催化剂进行程序升温氧化O2-TPO测试，得到O2-TPO曲线A；再进行程序升温还原H2-TPR测试，得到H2-TPR曲线A；(2) Group A copper-zinc catalyst was subjected to a temperature-programmed oxidation O 2 -TPO test to obtain an O 2 -TPO curve A; and then a temperature-programmed reduction H 2 -TPR test was performed to obtain an H 2 -TPR curve A;
具体方法为The specific method is
1)将30mg A组铜锌催化剂置于化学吸附仪的样品管中，通入保护气体He，以10℃/min升温至50℃，对A组铜锌催化剂样品吹扫60min；1) Place 30 mg of Group A copper-zinc catalyst in the sample tube of the chemical adsorption instrument, pass in the protective gas He, raise the temperature to 50°C at 10°C/min, and purge the Group A copper-zinc catalyst sample for 60 minutes;
2)吹扫结束后进行程序升温氧化(O2-TPO)测试：向化学吸附仪的样品管中通入含O2的氧化性气体(4％O2-96％He)，以10K/min的升温速率对A组铜锌催化剂样品程序升温至800℃，化学吸附仪记录信号，得到以温度为横坐标，A组铜锌催化剂样品信号值为纵坐标的O2-TPO曲线A(见图1)；2) After the purge is completed, perform the temperature programmed oxidation (O 2 -TPO) test: pass the oxidizing gas containing O 2 (4% O 2 -96% He) into the sample tube of the chemical adsorption instrument at 10K/min. Program the temperature of the copper-zinc catalyst sample of Group A to 800°C at a heating rate, record the signal with a chemical adsorption instrument, and obtain the O 2 -TPO curve A with the temperature as the abscissa and the signal value of the copper-zinc catalyst sample of Group A as the ordinate (see figure 1);
3)结束程序升温氧化(O2-TPO)测试后进行程序升温还原H2-TPR测试：向化学吸附仪的样品管中通入保护气体He进行吹扫60min并降温到50℃以下时，切换处理气为含H2的还原性气体(10％H2-90％Ar)，以10K/min的升温速率对样品管中的样品进行程序升温至1000℃，化学吸附仪记录信号，得到以温度为横坐标，样品信号值为纵坐标的H2-TPR曲线A(见图2)；3) After completing the temperature programmed oxidation (O 2 -TPO) test, perform the temperature programmed reduction H 2 -TPR test: pass the protective gas He into the sample tube of the chemical adsorption instrument and purge it for 60 minutes and cool it down to below 50°C, switch The processing gas is a reducing gas containing H 2 (10% H 2 -90% Ar). The sample in the sample tube is programmed to heat up to 1000°C at a heating rate of 10K/min. The chemical adsorption instrument records the signal and obtains the temperature is the abscissa, and the sample signal value is the H 2 -TPR curve A on the ordinate (see Figure 2);
测试过程中气体流速均为20mL/min，除气氛不同外，其他参数设定均保持一致；During the test process, the gas flow rate was 20mL/min. Except for the different atmospheres, other parameter settings remained consistent;
(3)B组铜锌催化剂进行程序升温还原H2-TPR测试得到H2-TPR曲线B；再进行程序升温氧化O2-TPO测试，得到O2-TPO曲线B；(3) Group B copper-zinc catalyst was subjected to a temperature-programmed reduction H 2 -TPR test to obtain H 2 -TPR curve B; then a temperature-programmed oxidation O 2 -TPO test was performed to obtain O 2 -TPO curve B;
具体方法为The specific method is
1)将30mg B组铜锌催化剂置于化学吸附仪的样品管中，通入保护气体He，以10℃/min升温至50℃，对B组铜锌催化剂样品进行吹扫60min；1) Place 30 mg of Group B copper-zinc catalyst in the sample tube of the chemical adsorption instrument, pass in the protective gas He, raise the temperature to 50°C at 10°C/min, and purge the Group B copper-zinc catalyst sample for 60 minutes;
2)吹扫结束后进行程序升温还原H2-TPR测试:向化学吸附仪的样品管中通入含H2的还原性气体(10％H2-90％Ar)，以10K/min的升温速率对B组铜锌催化剂样品进行程序升温至1000℃，化学吸附仪记录信号，得到以温度为横坐标，B组铜锌催化剂样品信号值为纵坐标的H2-TPR曲线B(见图3)；2) After the purge is completed, perform the programmed temperature reduction H 2 -TPR test: Pour the reducing gas containing H 2 (10% H 2 -90% Ar) into the sample tube of the chemical adsorption instrument, and raise the temperature at 10K/min. The copper-zinc catalyst sample of Group B is programmed to heat up to 1000°C at a certain rate, and the chemical adsorption instrument records the signal to obtain the H 2 -TPR curve B with the temperature as the abscissa and the signal value of the copper-zinc catalyst sample of Group B as the ordinate (see Figure 3 );
3)结束程序升温还原H2-TPR测试后进行程序升温氧化(O2-TPO)测试：向化学吸附仪的样品管中通入保护气体He进行吹扫60min并降温到50℃以下时，切换处理气为含O2的氧化性气体(4％O2-96％He)，以10K/min的升温速率对样品管中的样品程序升温至800℃，化学吸附仪记录信号，得到以温度为横坐标，样品信号值为纵坐标的O2-TPO曲线B(见图4)；3) After completing the programmed temperature reduction H 2 -TPR test, perform the temperature programmed oxidation (O 2 -TPO) test: pass the protective gas He into the sample tube of the chemical adsorption instrument and purge it for 60 minutes and cool it down to below 50°C, switch The treatment gas is an oxidizing gas containing O 2 (4% O 2 -96% He). The sample in the sample tube is heated to 800°C at a heating rate of 10K/min. The chemical adsorption instrument records the signal and obtains the temperature as The abscissa, the sample signal value is the O 2 -TPO curve B on the ordinate (see Figure 4);
(4)纯CuO进行程序升温还原H2-TPR测试得到H2-TPR曲线C；(4) Pure CuO was subjected to temperature-programmed reduction H 2 -TPR test to obtain H 2 -TPR curve C;
具体方法为The specific method is
1)将30mg纯CuO置于化学吸附仪的样品管中，通入保护气体He，以10℃/min升温至50℃，对纯CuO催化剂样品进行吹扫60min；1) Place 30 mg of pure CuO into the sample tube of the chemical adsorption instrument, pass in the protective gas He, raise the temperature to 50°C at 10°C/min, and purge the pure CuO catalyst sample for 60 minutes;
2)吹扫结束后进行程序升温还原H2-TPR测试:向化学吸附仪的样品管中通入含H2的还原性气体(10％H2-90％Ar)，以10K/min的升温速率对纯CuO催化剂样品进行程序升温至1000℃，化学吸附仪记录信号，得到以温度为横坐标，纯CuO催化剂样品信号值为纵坐标的H2-TPR曲线C(见图5)；2) After the purge is completed, perform the programmed temperature reduction H 2 -TPR test: Pour the reducing gas containing H 2 (10% H 2 -90% Ar) into the sample tube of the chemical adsorption instrument, and raise the temperature at 10K/min. The pure CuO catalyst sample is programmed to heat up to 1000°C at a certain rate, and the chemical adsorption instrument records the signal to obtain the H 2 -TPR curve C with the temperature as the abscissa and the signal value of the pure CuO catalyst sample as the ordinate (see Figure 5);
所述程序升温氧化O2-TPO测试和程序升温还原H2-TPR测试中仅处理气的种类和测试的结束温度不同，其它工艺条件均相同(例如起始温度、温度变化速率、处理气流速、气体压力等均保持一致)，以排除动力学参数不一致造成的影响；程序升温氧化O2-TPO测试的处理气为含O2的氧化性气体，程序升温还原H2-TPR测试的处理气为含H2的还原性气体；In the temperature-programmed oxidation O 2 -TPO test and the temperature-programmed reduction H 2 -TPR test, only the type of processing gas and the end temperature of the test are different, and other process conditions are the same (such as starting temperature, temperature change rate, processing gas flow rate , gas pressure, etc. are all consistent) to eliminate the influence of inconsistent kinetic parameters; the processing gas for the programmed temperature-increasing oxidation O 2 -TPO test is an oxidizing gas containing O 2 , and the processing gas for the programmed temperature-increasing reduction H 2 -TPR test It is a reducing gas containing H 2 ;
(5)设定催化剂样品中Cu单质物质的量对应的耗氧峰面积为a1，Cu2O物质的量对应的耗氧峰面积为a2；CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积为a3；(5) Set the oxygen consumption peak area corresponding to the amount of Cu elemental substance in the catalyst sample to a 1 , and the oxygen consumption peak area corresponding to the amount of Cu 2 O substance in the catalyst sample to be a 2 ; CuO is first reduced to Cu in H 2 -TPR 0 oxidizes CuO in O 2 -TPO, and the corresponding oxygen consumption peak area is a 3 ;
对O2-TPO曲线A进行分峰和峰面积积分处理得到Cu单质物质的量对应的耗氧峰面积为a1和Cu2O物质的量对应的耗氧峰面积为a2；The O 2 -TPO curve A is subjected to peak splitting and peak area integration processing to obtain that the oxygen consumption peak area corresponding to the amount of Cu elemental substance is a 1 and the oxygen consumption peak area corresponding to the amount of Cu 2 O substance is a 2 ;
对O2-TPO曲线B进行峰面积积分处理得到总积分面积为a0；由于氧化锌在程序升温还原H2-TPR测试中部分被还原，并且在O2-TPO过程这部分被还原的锌会被氧化，故，a0中包含了该部分锌氧化的耗氧峰，锌氧化温度为200℃左右，O2-TPO曲线B中锌氧化温度(200℃左右)时积分处理得到耗氧峰峰面积a4；Perform peak area integration processing on O 2 -TPO curve B to obtain a total integrated area of a 0 ; because zinc oxide was partially reduced in the temperature programmed reduction H 2 -TPR test, and this part of the zinc was reduced in the O 2 -TPO process It will be oxidized, so a 0 contains the oxygen consumption peak of this part of zinc oxidation. The zinc oxidation temperature is about 200°C. The oxygen consumption peak is obtained by integration at the zinc oxidation temperature (about 200°C) in the O 2 -TPO curve B. Peak area a 4 ;
计算出CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积为a3；CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积a3的计算公式为It is calculated that CuO is first reduced to Cu 0 in H 2 -TPR and then oxidized to CuO in O 2 -TPO, and the corresponding oxygen consumption peak area is a 3 ; CuO is first reduced to Cu 0 in H 2 -TPR and then O 2 -TPO For medium oxidation of CuO, the corresponding oxygen consumption peak area a 3 is calculated as:
a3＝a0-a1-2a2-a4 a 3 =a 0 -a 1 -2a 2 -a 4
再根据耗氧峰面积a1、耗氧峰面积为a2和耗氧峰面积a3计算出零价铜、氧化亚铜和氧化铜的摩尔比；Then calculate the molar ratio of zero-valent copper, cuprous oxide and copper oxide based on the oxygen consumption peak area a 1 , the oxygen consumption peak area a 2 and the oxygen consumption peak area a 3 ;
零价铜、氧化亚铜和氧化铜的摩尔比为The molar ratio of zerovalent copper, cuprous oxide and copper oxide is
Cu:Cu2O:CuO＝a1:a2:a3 Cu:Cu 2 O:CuO＝a 1 :a 2 :a 3
式中，a1为催化剂样品中Cu单质物质的量对应的耗氧峰面积，a2为Cu2O物质的量对应的耗氧峰面积；a3为CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积；a4为锌氧化温度时的耗氧峰峰面积；a0为O2-TPO曲线B进行峰面积积分处理得到总积分面积；In the formula, a 1 is the oxygen consumption peak area corresponding to the amount of Cu elemental substance in the catalyst sample, a 2 is the oxygen consumption peak area corresponding to the amount of Cu 2 O substance; a 3 is CuO first reduced in H 2 -TPR to Cu 0 oxidizes CuO in O 2 -TPO, corresponding oxygen consumption peak area; a 4 is the oxygen consumption peak area at the zinc oxidation temperature; a 0 is the peak area integration processing of O 2 -TPO curve B to obtain the total integrated area ;
(6)H2-TPR曲线A进行峰面积积分处理得到所有氢消耗峰拟合的总积分面积b0；对H2-TPR曲线C进行峰面积积分处理得到纯CuO的耗氢峰峰面积为b1；(6) Perform peak area integration processing on H 2 -TPR curve A to obtain the total integrated area b 0 of all hydrogen consumption peak fits; perform peak area integration processing on H 2 -TPR curve C to obtain the hydrogen consumption peak area of pure CuO: b1 ;
铜锌催化剂中，H2-TPR过程中还原温度为600℃以上，有部分氧化锌被还原，需要对耗氢峰进行校正，即需要扣除H2-TPR曲线A中氧化锌还原产生的耗氢峰，计算出校正后催化剂样品中铜对应的耗氢峰b′0；校正后催化剂样品中铜对应的耗氢峰b′0的计算公式为In copper-zinc catalysts, the reduction temperature during the H 2 -TPR process is above 600°C, and some zinc oxide is reduced. The hydrogen consumption peak needs to be corrected, that is, the hydrogen consumption generated by zinc oxide reduction in H 2 -TPR curve A needs to be deducted. Peak, calculate the hydrogen consumption peak b′ 0 corresponding to copper in the catalyst sample after correction; the calculation formula of the hydrogen consumption peak b′ 0 corresponding to copper in the catalyst sample after correction is:
计算出铜锌催化剂中Cu与Zn的摩尔比，铜锌催化剂中Cu与Zn的摩尔比为Calculate the molar ratio of Cu to Zn in the copper-zinc catalyst. The molar ratio of Cu to Zn in the copper-zinc catalyst is
Cu∶Zn＝b′0:(b1-b′0)Cu:Zn=b′ 0 : (b 1 -b′ 0 )
本实施例中a1＝72.57，a2＝297.44，a0＝1129.59，b0＝17755.77，b1＝31877.62，a4＝15.83，计算出In this embodiment, a 1 =72.57, a 2 =297.44, a 0 =1129.59, b 0 =17755.77, b 1 =31877.62, a 4 =15.83, calculated
Cu:Cu2O:CuO＝8.721:35.744:55.536Cu:Cu 2 O:CuO＝8.721:35.744:55.536
Cu:Zn＝0.5492:0.4508Cu:Zn＝0.5492:0.4508
等离子体发射光谱仪(ICP-AES)测定结果为Cu:Zn＝0.5479:0.4521，两者结果基本吻合。The measurement result of plasma optical emission spectrometer (ICP-AES) is Cu:Zn=0.5479:0.4521, and the two results are basically consistent.
实施例2：Example 2:
制备多价态铜的铜锌催化剂B：以乙酰丙酮铜和乙酰丙酮锌为前驱体，配成水溶液后放入水热反应釜，水热反应釜中在180℃的温度下反应24h，制备铜锌催化剂，其中Cu:Zn＝4:5(摩尔比)，过滤生成的固体产物，用去离子水洗涤后干燥，得到的铜锌催化剂B；Preparation of copper-zinc catalyst B for polyvalent copper: Use copper acetylacetonate and zinc acetylacetonate as precursors, prepare an aqueous solution and put it into a hydrothermal reactor. React in the hydrothermal reactor at a temperature of 180°C for 24 hours to prepare copper. Zinc catalyst, wherein Cu:Zn=4:5 (molar ratio), filter the generated solid product, wash with deionized water and dry to obtain copper-zinc catalyst B;
一种铜锌催化剂中各价态铜含量的测定方法，具体步骤如下：A method for measuring the content of copper in various valence states in a copper-zinc catalyst. The specific steps are as follows:
(1)将待测的铜锌催化剂A分为A组铜锌催化剂(50mg)和B组铜锌催化剂(50mg)；(1) Divide the copper-zinc catalyst A to be tested into group A copper-zinc catalyst (50 mg) and group B copper-zinc catalyst (50 mg);
(2)A组铜锌催化剂进行程序升温氧化O2-TPO测试，得到O2-TPO曲线A；再进行程序升温还原H2-TPR测试，得到H2-TPR曲线A；(2) Group A copper-zinc catalyst was subjected to a temperature-programmed oxidation O 2 -TPO test to obtain an O 2 -TPO curve A; and then a temperature-programmed reduction H 2 -TPR test was performed to obtain an H 2 -TPR curve A;
具体方法为The specific method is
1)将50mg A组铜锌催化剂置于化学吸附仪的样品管中，通入保护气体Ar，以10℃/min升温至50℃，对A组铜锌催化剂样品吹扫60min；1) Place 50 mg of Group A copper-zinc catalyst in the sample tube of the chemical adsorption instrument, pass in the protective gas Ar, raise the temperature to 50°C at 10°C/min, and purge the Group A copper-zinc catalyst sample for 60 minutes;
2)吹扫结束后进行程序升温氧化(O2-TPO)测试：向化学吸附仪的样品管中通入含O2的氧化性气体(4％O2-96％Ar)，以10K/min的升温速率对A组铜锌催化剂样品程序升温至800℃，化学吸附仪记录信号，得到以温度为横坐标，A组铜锌催化剂样品信号值为纵坐标的O2-TPO曲线A(见图6)；2) After purging, perform a temperature-programmed oxidation (O 2 -TPO) test: Pour the oxidizing gas containing O 2 (4% O 2 -96% Ar) into the sample tube of the chemical adsorption instrument at 10K/min. Program the temperature of the copper-zinc catalyst sample of Group A to 800°C at a heating rate, record the signal with a chemical adsorption instrument, and obtain the O 2 -TPO curve A with the temperature as the abscissa and the signal value of the copper-zinc catalyst sample of Group A as the ordinate (see figure 6);
3)结束程序升温氧化(O2-TPO)测试后进行程序升温还原H2-TPR测试：向化学吸附仪的样品管中通入保护气体Ar进行吹扫60min并降温到50℃以下时，切换处理气为含H2的还原性气体(10％H2-90％Ar)，以10K/min的升温速率对样品管中的样品进行程序升温至1000℃，化学吸附仪记录信号，得到以温度为横坐标，样品信号值为纵坐标的H2-TPR曲线A(见图7)；3) After completing the temperature programmed oxidation (O 2 -TPO) test, perform the temperature programmed reduction H 2 -TPR test: pass protective gas Ar into the sample tube of the chemical adsorption instrument and purge it for 60 minutes and cool it down to below 50°C, switch The processing gas is a reducing gas containing H 2 (10% H 2 -90% Ar). The sample in the sample tube is programmed to heat up to 1000°C at a heating rate of 10K/min. The chemical adsorption instrument records the signal and obtains the temperature is the abscissa, and the sample signal value is the H 2 -TPR curve A on the ordinate (see Figure 7);
测试过程中气体流速均为20mL/min，除气氛不同外，其他参数设定均保持一致；During the test process, the gas flow rate was 20mL/min. Except for the different atmospheres, other parameter settings remained consistent;
(3)B组铜锌催化剂进行程序升温还原H2-TPR测试得到H2-TPR曲线B；再进行程序升温氧化O2-TPO测试，得到O2-TPO曲线B；(3) Group B copper-zinc catalyst was subjected to a temperature-programmed reduction H 2 -TPR test to obtain H 2 -TPR curve B; then a temperature-programmed oxidation O 2 -TPO test was performed to obtain O 2 -TPO curve B;
具体方法为The specific method is
1)将50mg B组铜锌催化剂置于化学吸附仪的样品管中，通入保护气体Ar，以10℃/min升温至50℃，对B组铜锌催化剂样品进行吹扫60min；1) Place 50 mg of Group B copper-zinc catalyst in the sample tube of the chemical adsorption instrument, pass in the protective gas Ar, raise the temperature to 50°C at 10°C/min, and purge the Group B copper-zinc catalyst sample for 60 minutes;
2)吹扫结束后进行程序升温还原H2-TPR测试:向化学吸附仪的样品管中通入含H2的还原性气体(10％H2-90％Ar)，以10K/min的升温速率对B组铜锌催化剂样品进行程序升温至1000℃，化学吸附仪记录信号，得到以温度为横坐标，B组铜锌催化剂样品信号值为纵坐标的H2-TPR曲线B(见图8)；2) After the purge is completed, perform the programmed temperature reduction H 2 -TPR test: Pour the reducing gas containing H 2 (10% H 2 -90% Ar) into the sample tube of the chemical adsorption instrument, and raise the temperature at 10K/min. The copper-zinc catalyst sample of Group B is programmed to heat up to 1000°C at a certain rate, and the chemical adsorption instrument records the signal to obtain the H 2 -TPR curve B with the temperature as the abscissa and the signal value of the copper-zinc catalyst sample of Group B as the ordinate (see Figure 8 );
3)结束程序升温还原H2-TPR测试后进行程序升温氧化(O2-TPO)测试：向化学吸附仪的样品管中通入保护气体Ar进行吹扫60min并降温到50℃以下时，切换处理气为含O2的氧化性气体(4％O2-96％Ar)，以10K/min的升温速率对样品管中的样品程序升温至800℃，化学吸附仪记录信号，得到以温度为横坐标，样品信号值为纵坐标的O2-TPO曲线B(见图9)；3) After completing the programmed temperature reduction H 2 -TPR test, perform the temperature programmed oxidation (O 2 -TPO) test: pass protective gas Ar into the sample tube of the chemical adsorption instrument and purge it for 60 minutes and cool it down to below 50°C, switch The processing gas is an oxidizing gas containing O 2 (4% O 2 -96% Ar). The sample in the sample tube is heated to 800°C at a heating rate of 10K/min. The chemical adsorption instrument records the signal and obtains the temperature as The abscissa, the sample signal value is the O 2 -TPO curve B on the ordinate (see Figure 9);
(4)纯CuO进行程序升温还原H2-TPR测试得到H2-TPR曲线C；(4) Pure CuO was subjected to temperature-programmed reduction H 2 -TPR test to obtain H 2 -TPR curve C;
具体方法为The specific method is
1)将50mg纯CuO置于化学吸附仪的样品管中，通入保护气体Ar，以10℃/min升温至50℃，对纯CuO催化剂样品进行吹扫60min；1) Place 50 mg of pure CuO into the sample tube of the chemical adsorption instrument, pass in the protective gas Ar, raise the temperature to 50°C at 10°C/min, and purge the pure CuO catalyst sample for 60 minutes;
2)吹扫结束后进行程序升温还原H2-TPR测试:向化学吸附仪的样品管中通入含H2的还原性气体(10％H2-90％Ar)，以10K/min的升温速率对纯CuO催化剂样品进行程序升温至1000℃，化学吸附仪记录信号，得到以温度为横坐标，纯CuO催化剂样品信号值为纵坐标的H2-TPR曲线C(见图5)；2) After the purge is completed, perform the programmed temperature reduction H 2 -TPR test: Pour the reducing gas containing H 2 (10% H 2 -90% Ar) into the sample tube of the chemical adsorption instrument, and raise the temperature at 10K/min. The pure CuO catalyst sample is programmed to heat up to 1000°C at a certain rate, and the chemical adsorption instrument records the signal to obtain the H 2 -TPR curve C with the temperature as the abscissa and the signal value of the pure CuO catalyst sample as the ordinate (see Figure 5);
所述程序升温氧化O2-TPO测试和程序升温还原H2-TPR测试中仅处理气的种类和测试的结束温度不同，其它工艺条件均相同(例如起始温度、温度变化速率、处理气流速、气体压力等均保持一致)，以排除动力学参数不一致造成的影响；程序升温氧化O2-TPO测试的处理气为含O2的氧化性气体，程序升温还原H2-TPR测试的处理气为含H2的还原性气体；In the temperature-programmed oxidation O 2 -TPO test and the temperature-programmed reduction H 2 -TPR test, only the type of processing gas and the end temperature of the test are different, and other process conditions are the same (such as starting temperature, temperature change rate, processing gas flow rate , gas pressure, etc. are all consistent) to eliminate the influence of inconsistent kinetic parameters; the processing gas for the programmed temperature-increasing oxidation O 2 -TPO test is an oxidizing gas containing O 2 , and the processing gas for the programmed temperature-increasing reduction H 2 -TPR test It is a reducing gas containing H 2 ;
(5)设定催化剂样品中Cu单质物质的量对应的耗氧峰面积为a1，Cu2O物质的量对应的耗氧峰面积为a2；CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积为a3；(5) Set the oxygen consumption peak area corresponding to the amount of Cu elemental substance in the catalyst sample to a 1 , and the oxygen consumption peak area corresponding to the amount of Cu 2 O substance in the catalyst sample to be a 2 ; CuO is first reduced to Cu in H 2 -TPR 0 oxidizes CuO in O 2 -TPO, and the corresponding oxygen consumption peak area is a 3 ;
对O2-TPO曲线A进行分峰和峰面积积分处理得到Cu单质物质的量对应的耗氧峰面积为a1和Cu2O物质的量对应的耗氧峰面积为a2；The O 2 -TPO curve A is subjected to peak splitting and peak area integration processing to obtain that the oxygen consumption peak area corresponding to the amount of Cu elemental substance is a 1 and the oxygen consumption peak area corresponding to the amount of Cu 2 O substance is a 2 ;
对O2-TPO曲线B进行峰面积积分处理得到总积分面积为a0；由于氧化锌在程序升温还原H2-TPR测试中部分被还原，并且在O2-TPO过程这部分被还原的锌会被氧化，故，a0中包含了该部分锌氧化的耗氧峰，锌氧化温度为200℃左右，O2-TPO曲线B中锌氧化温度(200℃左右)时积分处理得到耗氧峰峰面积a4；Perform peak area integration processing on O 2 -TPO curve B to obtain a total integrated area of a 0 ; because zinc oxide was partially reduced in the temperature programmed reduction H 2 -TPR test, and this part of the zinc was reduced in the O 2 -TPO process It will be oxidized, so a 0 contains the oxygen consumption peak of this part of zinc oxidation. The zinc oxidation temperature is about 200°C. The oxygen consumption peak is obtained by integration at the zinc oxidation temperature (about 200°C) in the O 2 -TPO curve B. Peak area a 4 ;
计算出CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积为a3；CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积a3的计算公式为It is calculated that CuO is first reduced to Cu 0 in H 2 -TPR and then oxidized to CuO in O 2 -TPO, and the corresponding oxygen consumption peak area is a 3 ; CuO is first reduced to Cu 0 in H 2 -TPR and then O 2 -TPO For medium oxidation of CuO, the corresponding oxygen consumption peak area a 3 is calculated as:
a3＝a0-a1-2a2-a4 a 3 =a 0 -a 1 -2a 2 -a 4
再根据耗氧峰面积a1、耗氧峰面积为a2和耗氧峰面积a3计算出零价铜、氧化亚铜和氧化铜的摩尔比；Then calculate the molar ratio of zero-valent copper, cuprous oxide and copper oxide based on the oxygen consumption peak area a 1 , the oxygen consumption peak area a 2 and the oxygen consumption peak area a 3 ;
零价铜、氧化亚铜和氧化铜的摩尔比为The molar ratio of zerovalent copper, cuprous oxide and copper oxide is
Cu:Cu2O:CuO＝a1:a2:a3 Cu:Cu 2 O:CuO＝a 1 :a 2 :a 3
式中，a1为催化剂样品中Cu单质物质的量对应的耗氧峰面积，a2为Cu2O物质的量对应的耗氧峰面积；a3为CuO先在H2-TPR中还原为Cu0再O2-TPO中氧化CuO，对应的耗氧峰面积；a4为锌氧化温度时的耗氧峰峰面积；a0为O2-TPO曲线B进行峰面积积分处理得到总积分面积；In the formula, a 1 is the oxygen consumption peak area corresponding to the amount of Cu elemental substance in the catalyst sample, a 2 is the oxygen consumption peak area corresponding to the amount of Cu 2 O substance; a 3 is CuO first reduced in H 2 -TPR to Cu 0 oxidizes CuO in O 2 -TPO, corresponding oxygen consumption peak area; a 4 is the oxygen consumption peak area at the zinc oxidation temperature; a 0 is the peak area integration processing of O 2 -TPO curve B to obtain the total integrated area ;
(6)H2-TPR曲线A进行峰面积积分处理得到所有氢消耗峰拟合的总积分面积b0；对H2-TPR曲线C进行峰面积积分处理得到纯CuO的耗氢峰峰面积为b1；(6) Perform peak area integration processing on H 2 -TPR curve A to obtain the total integrated area b 0 of all hydrogen consumption peak fits; perform peak area integration processing on H 2 -TPR curve C to obtain the hydrogen consumption peak area of pure CuO: b1 ;
铜锌催化剂中，H2-TPR过程中还原温度为600℃以上，有部分氧化锌被还原，需要对耗氢峰进行校正，即需要扣除H2-TPR曲线A中氧化锌还原产生的耗氢峰，计算出校正后催化剂样品中铜对应的耗氢峰b′0；校正后催化剂样品中铜对应的耗氢峰b′0的计算公式为In copper-zinc catalysts, the reduction temperature during the H 2 -TPR process is above 600°C, and some zinc oxide is reduced. The hydrogen consumption peak needs to be corrected, that is, the hydrogen consumption generated by zinc oxide reduction in H 2 -TPR curve A needs to be deducted. Peak, calculate the hydrogen consumption peak b′ 0 corresponding to copper in the catalyst sample after correction; the calculation formula of the hydrogen consumption peak b′ 0 corresponding to copper in the catalyst sample after correction is:
计算出铜锌催化剂中Cu与Zn的摩尔比，铜锌催化剂中Cu与Zn的摩尔比为Calculate the molar ratio of Cu to Zn in the copper-zinc catalyst. The molar ratio of Cu to Zn in the copper-zinc catalyst is
Cu∶Zn＝b′0:(b1-b′0)Cu:Zn=b′ 0 : (b 1 -b′ 0 )
本实施例中a1＝223.52，a2＝45.49，a0＝780.43，b0＝14787.41，b1＝31877.62，a4＝16.62，计算出In this embodiment, a 1 =223.52, a 2 =45.49, a 0 =780.43, b 0 =14787.41, b 1 =31877.62, a 4 =16.62, calculated
Cu:Cu2O:CuO＝30.413:6.190:63.397Cu:Cu 2 O:CuO＝30.413:6.190:63.397
Cu:Zn＝0.4540:0.5460Cu:Zn＝0.4540:0.5460
等离子体发射光谱仪(ICP-AES)测定结果为Cu:Zn＝0.4403:0.5597，两者结果基本吻合。The measurement result of plasma optical emission spectrometer (ICP-AES) is Cu:Zn=0.4403:0.5597, and the two results are basically consistent.
以上对本发明的具体实施方式作了详细说明，但是本发明并不限于上述实施方式，在本领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。The specific embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above-described embodiments. Various changes can be made within the scope of knowledge of those of ordinary skill in the art without departing from the gist of the present invention. .
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