CN114558624B - Mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst and application thereof - Google Patents
Mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst and application thereof Download PDFInfo
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- CN114558624B CN114558624B CN202210294452.XA CN202210294452A CN114558624B CN 114558624 B CN114558624 B CN 114558624B CN 202210294452 A CN202210294452 A CN 202210294452A CN 114558624 B CN114558624 B CN 114558624B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 239000004005 microsphere Substances 0.000 title claims abstract description 32
- QETNDERBWLTKFA-UHFFFAOYSA-N [Mg].[Ca].[Ni] Chemical compound [Mg].[Ca].[Ni] QETNDERBWLTKFA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 87
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 42
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 38
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 34
- 150000002815 nickel Chemical class 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 19
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 19
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 8
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001291 vacuum drying Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 230000009467 reduction Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000011261 inert gas Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- 229920000742 Cotton Polymers 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 8
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 8
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 1
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 16
- 229910021641 deionized water Inorganic materials 0.000 description 16
- 241000282326 Felis catus Species 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 230000018109 developmental process Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910017976 MgO 4 Inorganic materials 0.000 description 2
- 229910002642 NiO-MgO Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst and application thereof. The preparation method comprises the following specific steps: (1) preparing nickel salt and magnesium salt into aqueous solution; (2) Adding a high molecular surfactant into the solution, and preparing the nano microsphere nickel-magnesium composite oxide after hydrothermal treatment; (3) preparing calcium salt into an aqueous solution; (4) And (3) dipping the calcium salt aqueous solution into the nano microsphere nickel magnesium calcium composite oxide to obtain the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst. The mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst provided by the invention can catalyze the co-conversion of methane and carbon dioxide to prepare acetic acid, and has good catalytic activity and selectivity.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to a mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst and application thereof.
Background
With the rapid development of modern industry, a large amount of fossil fuel is consumed, and CO in the atmosphere 2 The content of (2) increases. Too high CO in the atmosphere 2 The content has extremely negative effects on ecological balance and climate, and CO 2 Is a great concern in society. Meanwhile, people face the problem of gradually lacking fuel resources, the energy is gradually lacking, and especially the absolute shortage of petroleum resources becomes an important factor for preventing the sustainable development of economy. CO 2 As a potential carbon source substance, is a renewable resource with great potential. However, CO is to 2 The direct exhaust of the amplified gas not only wastes resources but also causes environmental pollution, thus developing CO 2 Is rich in CO from nature through separation, fixation and conversion 2 The method can reduce greenhouse effect, generate organic fuel, other organic chemical raw materials or chemical products, and reduce environmental pollution caused by the reaction of other chemical raw materials. Of course, the current industrial emission of CO 2 Quantity andby using CO 2 Consumed CO 2 There is a considerable gap between the amounts, however, carbon dioxide is an inexpensive and abundant carbon resource, thus enhancing the CO 2 The transformation and utilization of (a) have various meanings such as resources, environment and economic benefits (CatalToday., 2015,256,88).
CO 2 And CH (CH) 4 As main greenhouse gases, CH 4 、CO 2 The method is a reaction with 100 percent of atomic utilization rate for directly converting raw materials into acetic acid, and can comprehensively utilize CO 2 And CH (CH) 4 A resource. CH (CH) 4 、CO 2 Direct conversion into acetic acid can realize the activation of small molecular substance CO difficult to activate 2 And CH (CH) 4 Simultaneously reduces the influence of the two main greenhouse gases on the environment, and has various research values (ACS catalyst, 2021,11,3384) of environmental protection, science, economy and the like. Wilcox et al first utilized AspenPlus TM Gibbs free energy minimization calculations were performed and showed that the conversion of methane increased with increasing pressure and temperature, even though the reaction feed composition was 95% CO 2 And 5% CH 4 And under the most favorable thermodynamic conditions of 1000K and 100atm, the conversion rate of methane is only 1.6X10 -6 . At the same time, the team developed 5% Pd/C and 5% Pd/Al 2 O 3 Catalyst, CO 2 And CH (CH) 4 In 5% Pd/Al 2 O 3 Catalyst, gas phase acetic acid produced at 400 deg.c and acetic acid yield of 1.5×10 -6 μg·g -1 ·h -1 (Catal today, 2003,88,83). Huang Wei professor et al developed V 2 O 5 -PdCl 2 /Al 2 O 3 Catalyst, O is introduced in the reaction process 2 So that the highest production rate of the acetic acid directly prepared by methane and carbon dioxide is 180 mug.g -1 ·h -1 ，O 2 The introduction of (c) can lower the reaction energy barrier, allowing the reaction to proceed at lower temperatures (j. Nat. Gas. Chem.,2004,2,13). However, pd and other noble metal catalysts have high preparation cost and poor catalytic activity, so that development of the catalyst for CO is urgently required 2 And CH (CH) 4 Novel high-efficiency non-noble metal catalyst for directly preparing acetic acid.
Disclosure of Invention
The invention aims to provide a mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst, and another aim of the invention is to utilize the application of the catalyst in synthesizing acetic acid so as to realize activation of CH 4 With CO 2 Co-conversion to acetic acid.
The technical scheme of the invention is as follows: magnesium oxide (MgO) is a common oxide with a rock salt structure and plays an important role in the fields of chemistry and chemical engineering and nanotechnology. CO by using magnesium oxide 2 Chemical adsorption is carried out to help reduce atmospheric CO 2 The content is roughly estimated to eliminate more than 2GtCO each year 2 . Nickel (Ni) -based catalysts are commonly used active components for methane activation, and have the advantages of low price, high affinity, and the like, compared with noble metal catalysts. However, nickel-based catalysts have the problem of deactivation of carbon deposition, limiting their rapid development. It is well known that the crystal types of MgO and NiO belong to the cubic NaCl, mg 2+ (0.065 nm) and Ni 2+ The difference in ionic radius of (0.070 nm) is small. Thus, regardless of the compounding ratio of MgO and NiO, ni can be formed x Mg (1-x) O solid solution. Ni with alkaline surface produced by MgO and NiO combination x Mg (1-x) The O solid solution catalyst has the characteristics of MgO and NiO and is beneficial to inhibiting carbon deposition. Meanwhile, modification by adding a second metal is a good choice for further suppressing carbon deposition, and alkali metal oxides (such as K 2 O、Cs 2 O, etc.), alkaline earth metal oxides (e.g., caO, etc.) as modifiers. Therefore, the invention prepares the mesoporous Kong Niemei calcium composite oxide catalyst, and the introduction of the mesoporous can enhance the enrichment and activation of the reaction raw materials methane and carbon dioxide on the surface of the catalyst while ensuring high catalytic activity and stability.
The specific technical scheme of the invention is as follows: the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst is characterized by being prepared by the following steps:
(1) Preparing nickel salt and magnesium salt into aqueous solution;
(2) Adding a high molecular surfactant into the solution, stirring, cooling to room temperature after hydrothermal treatment, centrifuging, washing and vacuum drying;
(3) And (3) preparing calcium salt into aqueous solution, pouring the solid powder obtained in the step (2) into the prepared calcium salt aqueous solution, aging in water bath, centrifuging, washing and drying in vacuum to obtain the mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst. The catalyst obtained is marked as PE-CaO-NiO-MgO.
Preferably, the nickel salt in step (1) is one of nickel nitrate, nickel chloride, nickel carbonate or nickel sulfate; the magnesium salt is one of magnesium nitrate, magnesium chloride, magnesium sulfate or magnesium oxalate; the mass ratio of the nickel salt to the magnesium salt is 1 (1-20).
Preferably, the polymer surfactant in the step (2) is one of polyvinylpyrrolidone, carboxymethyl cellulose or sodium polyacrylate; the mass ratio of the nickel salt to the macromolecular surfactant is 1 (1-8).
Preferably, the hydrothermal temperature in the step (2) is 100-200 ℃ and the hydrothermal time is 6-30 h; the vacuum drying temperature is 50-80 ℃ and the vacuum drying time is 4-12 h.
Preferably, the calcium salt in step (3) is one of calcium nitrate, calcium sulfate, calcium chloride, calcium carbonate or calcium oxide; the mass ratio of the calcium salt to the nickel salt is 1 (1-16).
Preferably, the water bath temperature in the step (3) is 40-80 ℃, and the aging time is 4-16 h; the vacuum drying temperature is 40-80 ℃, and the vacuum drying time is 8-20 h.
The invention also provides an application of the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst in synthesizing acetic acid, which comprises the following specific steps: mixing a catalyst and high-temperature-resistant fiber cotton, loading the mixture into a fixed bed reactor, introducing inert gas, purging, heating to a required reduction temperature, switching the inert gas into reducing gas at the required reduction temperature for starting reduction, and switching the reducing gas into methane and carbon dioxide for reaction after the reduction is finished.
Preferably, the mass ratio of the catalyst to the high temperature resistant fiber cotton is (1-8): 1; the inert gas may be one of nitrogen, argon or helium; the reducing gas is hydrogen or mixed gas of hydrogen and nitrogen, wherein the volume fraction of the hydrogen is 5-100%; the reduction temperature is 300-500 ℃; the reduction time is 1-5 h; the volume ratio of methane to carbon dioxide is 1-6, the reaction pressure is 1-30 atm, and the reaction temperature is 450-700 ℃.
The beneficial effects are that:
the invention prepares the mesoporous Kong Niemei calcium composite oxide catalyst, and the introduction of the mesoporous can enhance the enrichment and activation of the reaction raw materials methane and carbon dioxide on the surface of the catalyst while ensuring high catalytic activity and stability. The catalyst can catalyze the co-conversion of methane and carbon dioxide to prepare acetic acid, and has good catalytic activity and selectivity.
Detailed Description
The present invention will be described in more detail with reference to examples. These examples are merely illustrative of the best modes of carrying out the invention and do not limit the scope of the invention in any way.
Example 1
Step 1, adding 2.9079g of nickel nitrate and 2.9079g of magnesium nitrate into 100mL of deionized water, and stirring;
step 2, adding polyvinylpyrrolidone (the mass ratio of nickel salt to polyvinylpyrrolidone is 1:1), stirring, hydrothermal for 30h at 100 ℃, centrifuging, washing, and vacuum drying at 50 ℃ for 12h;
and 3, adding calcium nitrate (the mass ratio of calcium salt to nickel salt is 1:1) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the prepared calcium salt aqueous solution into the solid obtained in the step 2, centrifuging, washing, and vacuum drying at 40 ℃ for 20 hours after water bath at 40 ℃ to obtain the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst, wherein the catalyst obtained in the four steps is named as PE-CaO-NiO-MgO-1.
Example 2
Step 1, adding 2.3769g of nickel chloride and 11.8845g of magnesium chloride into 100mL of deionized water, and stirring;
step 2, adding polyvinylpyrrolidone (the mass ratio of nickel salt to polyvinylpyrrolidone is 1:3), stirring, carrying out hydrothermal treatment at 130 ℃ for 24 hours, centrifuging, washing, and carrying out vacuum drying at 60 ℃ for 10 hours;
and 3, adding calcium carbonate (the mass ratio of calcium salt to nickel salt is 1:4) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the solid obtained in the step 2 into the prepared calcium salt aqueous solution, centrifuging, washing, and vacuum drying at 60 ℃ for 16 hours after water bath at 50 ℃ to obtain the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst, wherein the catalyst obtained in the four steps is PE-CaO-NiO-MgO-2.
Example 3
Step 1, adding 1.187g of nickel carbonate and 11.87g of magnesium sulfate into 100mL of deionized water, and stirring;
step 2, adding carboxymethyl cellulose (the mass ratio of nickel salt to carboxymethyl cellulose is 1:4) into the solution, stirring, carrying out hydrothermal treatment at 150 ℃ for 12 hours, centrifuging, washing, and carrying out vacuum drying at 70 ℃ for 8 hours;
and 3, adding calcium sulfate (the mass ratio of the calcium salt to the nickel salt is 1:7) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the solid obtained in the step 2 into the prepared calcium salt aqueous solution, centrifuging, washing, and vacuum drying at the temperature of 70 ℃ for 10 hours after water bath at the temperature of 60 ℃ to obtain the mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst, wherein the catalyst obtained in the four steps is PE-CaO-NiO-MgO-3.
Example 4
Step 1, adding 2.6285g of nickel sulfate and 13.1425g of magnesium oxalate into 100mL of deionized water, and stirring;
step 2, adding carboxymethyl cellulose (the mass ratio of nickel salt to carboxymethyl cellulose is 1:6) into the solution, stirring, carrying out hydrothermal treatment at 180 ℃ for 10 hours, centrifuging, washing, and carrying out vacuum drying at 80 ℃ for 4 hours;
and 3, adding calcium chloride (the mass ratio of calcium salt to nickel salt is 1:10) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the solid obtained in the step 2 into the prepared calcium salt aqueous solution, centrifuging and washing after water bath at 70 ℃ for 6 hours, and vacuum drying at 80 ℃ for 8 hours to obtain the mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst, wherein the catalyst obtained in the four steps is PE-CaO-NiO-MgO-4.
Example 5
Step 1, adding 1.187g of nickel carbonate and 17.805g of magnesium sulfate into 100mL of deionized water, and stirring;
step 2, adding sodium polyacrylate (the mass ratio of nickel salt to sodium polyacrylate is 1:8) into the solution, stirring, carrying out hydrothermal treatment at 200 ℃ for 6 hours, centrifuging, washing, and carrying out vacuum drying at 80 ℃ for 4 hours;
and 3, adding calcium oxide (the mass ratio of calcium salt to nickel salt is 1:13) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the solid obtained in the step 2 into the prepared calcium salt aqueous solution, centrifuging and washing after water bath at 80 ℃ for 4 hours, and vacuum drying at 80 ℃ for 12 hours to obtain the mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst, wherein the catalyst obtained in the four steps is PE-CaO-NiO-MgO-5.
Example 6
Step 1, adding 1.4540g of nickel nitrate and 24.7180g of magnesium chloride into 100mL of deionized water, and stirring;
step 2, adding sodium polyacrylate (the mass ratio of nickel salt to sodium polyacrylate is 1:7) into the solution, stirring, carrying out hydrothermal treatment at 180 ℃ for 10 hours, centrifuging, washing, and carrying out vacuum drying at 60 ℃ for 8 hours;
and 3, adding calcium sulfate (the mass ratio of the calcium salt to the nickel salt is 1:12) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the solid obtained in the step 2 into the prepared calcium salt aqueous solution, centrifuging, washing, and vacuum drying at 60 ℃ for 16 hours after water bath at 70 ℃ to obtain the mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst, wherein the catalyst obtained in the four steps is PE-CaO-NiO-MgO-6.
Example 7
Step 1, adding 1.1871g of nickel carbonate and 20.1807g of magnesium oxalate into 100mL of deionized water, and stirring;
step 2, adding polyvinylpyrrolidone (the mass ratio of nickel salt to polyvinylpyrrolidone is 1:6), stirring, carrying out hydrothermal treatment at 200 ℃ for 6 hours, centrifuging, washing, and carrying out vacuum drying at 80 ℃ for 4 hours;
and 3, adding calcium chloride (the mass ratio of calcium salt to nickel salt is 1:15) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the solid obtained in the step 2 into the prepared calcium salt aqueous solution, centrifuging, washing, and vacuum drying at 80 ℃ for 8 hours after water bath at 80 ℃ to obtain the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst, wherein the catalyst obtained in the four steps is PE-CaO-NiO-MgO-7.
Example 8
Step 1, adding 1.4539g of nickel nitrate and 29.0780g of magnesium chloride into 100mL of deionized water, and stirring;
step 2, adding carboxymethyl cellulose (the mass ratio of nickel salt to carboxymethyl cellulose is 1:8) into the solution, stirring, carrying out hydrothermal treatment at 160 ℃ for 15h, centrifuging, washing, and carrying out vacuum drying at 60 ℃ for 12h;
and 3, adding calcium nitrate (the mass ratio of calcium salt to nickel salt is 1:16) into 100ml of deionized water to prepare a calcium salt aqueous solution, adding the solid obtained in the step 2 into the prepared calcium salt aqueous solution, centrifuging and washing after water bath at 80 ℃ for 4 hours, and vacuum drying at 60 ℃ for 13 hours to obtain the mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst, wherein the catalyst obtained by the four steps is PE-CaO-NiO-MgO-8.
The mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst is used for catalyzing co-conversion of methane and carbon dioxide to synthesize acetic acid:
application example 1
Mixing 0.2g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-1 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas nitrogen for purging, heating to 300 ℃, and switching to hydrogen with the volume fraction of 5% for reduction for 5 hours; heating to 700 ℃, and introducing methane and carbon dioxide with the volume ratio of 1:1 under 1 atm. The selectivity of acetic acid is 80.41 percent, and the highest production rate of acetic acid is 232 mmol.kg cat -1 ·h -1 。
Application example 2
Mixing 0.4g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-2 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas helium for purging, heating to 400 ℃, and switching to hydrogen with volume fraction of 10% for reduction for 4 hours; heating to 600 ℃, and introducing methane and carbon dioxide with the volume ratio of 2:1 under 3 atm. Acetic acid selectivity was 85.51% with the highest acetic acid productionThe rate of formation is 294 mmol.kg cat -1 ·h -1 。
Application example 3
Mixing 0.6g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-3 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas argon for purging, heating to 400 ℃, and reducing for 3 hours by switching hydrogen with volume fraction of 20%; heating to 550 ℃, and introducing methane and carbon dioxide with the volume ratio of 3:1 under 6 atm. Acetic acid selectivity of 88.34% and maximum acetic acid formation rate of 319 mmol/kg cat -1 ·h -1 。
Application example 4
Mixing 0.8g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-4 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas nitrogen for purging, heating to 400 ℃, and reducing for 2.5 hours by switching hydrogen with the volume fraction of 50%; heating to 500 ℃, and introducing methane and carbon dioxide with the volume ratio of 4:1 under 10 atm. The selectivity of acetic acid is 87.26 percent, and the highest production rate of acetic acid is 301 mmol.kg cat -1 ·h -1 。
Application example 5
Mixing 1.0g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-5 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas nitrogen for purging, heating to 500 ℃, and switching to hydrogen with the volume fraction of 100% for reduction for 1h; cooling to 450 ℃, and introducing methane and carbon dioxide with the volume ratio of 5:1 under 30 atm. The selectivity of acetic acid was 95.16%, and the highest production rate of acetic acid was 399 mmol.kg cat -1 ·h -1 。
Application example 6
Mixing 1.2g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-6 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas nitrogen for purging, heating to 500 ℃, switching to 80% hydrogen by volume fraction, and reducing for 3 hours; methane and carbon dioxide were introduced at a volume ratio of 4.5:1 at 20atm while maintaining 500 ℃. Acetic acid selectivity is 93.53%, acetic acid highest production rateThe rate is 360 mmol/kg cat -1 ·h -1 。
Application example 7
Mixing 1.4g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-7 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas argon for purging, heating to 400 ℃, and switching to be 100% hydrogen for reduction for 2 hours; cooling to 450 ℃, and introducing methane and carbon dioxide with the volume ratio of 4:1 under 30 atm. Acetic acid selectivity of 90.24% and maximum acetic acid formation rate of 327 mmol/kg cat -1 ·h -1 。
Application example 8
Mixing 1.6g of mesoporous nano microsphere nickel magnesium calcium composite oxide PE-CaO-NiO-MgO-2 catalyst with 0.2g high temperature resistant fiber cotton, adding the mixture into a fixed bed reactor, introducing inert gas helium for purging, heating to 500 ℃, and switching to hydrogen with volume fraction of 100% for reduction for 1.5h; heating to 600 ℃, and introducing methane and carbon dioxide with the volume ratio of 6:1 under 30 atm. The selectivity of acetic acid was 97.89%, and the highest production rate of acetic acid was 424 mmol.kg cat -1 ·h -1 。
TABLE 1 comparison of catalytic Properties of PE-CaO-NiO-MgO catalysts
Note that: reference cat. Reference j.nat.gas.chem.,2004,2,13, comparative example 2.
Claims (6)
1. The application of the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst in synthesizing acetic acid comprises the following specific steps: mixing a catalyst and high-temperature-resistant fiber cotton, then filling the mixture into a fixed bed reactor, introducing inert gas for purging, then heating to a required reduction temperature, switching the inert gas into reducing gas for starting reduction at the temperature, and switching the reducing gas into methane and carbon dioxide for reaction after the reduction is finished; wherein the mass ratio of the catalyst to the high temperature resistant cellucotton is (1-8): 1; the inert gas may be one of nitrogen, argon or helium; the reducing gas is hydrogen or mixed gas of hydrogen and nitrogen, wherein the volume fraction of the hydrogen is 5-100%; the reduction temperature is 300-500 ℃; the reduction time is 1-5 h; the volume ratio of methane to carbon dioxide is (1-6), 1, the reaction pressure is 1-30 atm, and the reaction temperature is 450-700 ℃;
the mesoporous nano microsphere nickel magnesium calcium composite oxide catalyst is prepared by the following steps:
(1) Preparing nickel salt and magnesium salt into aqueous solution;
(2) Adding a high molecular surfactant into the solution, stirring, cooling to room temperature after hydrothermal treatment, centrifuging, washing and vacuum drying;
(3) And (3) preparing calcium salt into aqueous solution, pouring the solid powder obtained in the step (2) into the prepared calcium salt aqueous solution, aging in water bath, centrifuging, washing and drying in vacuum to obtain the mesoporous nano microsphere nickel-magnesium-calcium composite oxide catalyst.
2. The use according to claim 1, wherein: the nickel salt in the step (1) is one of nickel nitrate, nickel chloride, nickel carbonate or nickel sulfate; the magnesium salt is one of magnesium nitrate, magnesium chloride, magnesium sulfate or magnesium oxalate; the mass ratio of the nickel salt to the magnesium salt is 1 (1-20).
3. The use according to claim 1, wherein: the macromolecular surfactant in the step (2) is one of polyvinylpyrrolidone, carboxymethyl cellulose or sodium polyacrylate; the mass ratio of the nickel salt to the high molecular surfactant is 1 (1-8).
4. The use according to claim 1, wherein: the hydrothermal temperature in the step (2) is 100-200 ℃, and the hydrothermal time is 6-30 hours; the vacuum drying temperature is 50-80 ℃, and the vacuum drying time is 4-12 h.
5. The use according to claim 1, wherein: the calcium salt in the step (3) is one of calcium nitrate, calcium sulfate, calcium chloride, calcium carbonate or calcium oxide; the mass ratio of the calcium salt to the nickel salt is 1 (1-16).
6. The use according to claim 1, wherein: the water bath temperature in the step (3) is 40-80 ℃, and the aging time is 4-16 h; the vacuum drying temperature is 40-80 ℃, and the vacuum drying time is 8-20 h.
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