CN1651139A - Cu/ZrO2 radical synthesizing methanol catalyst and its making method and application - Google Patents

Cu/ZrO2 radical synthesizing methanol catalyst and its making method and application Download PDF

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CN1651139A
CN1651139A CNA2004100645741A CN200410064574A CN1651139A CN 1651139 A CN1651139 A CN 1651139A CN A2004100645741 A CNA2004100645741 A CN A2004100645741A CN 200410064574 A CN200410064574 A CN 200410064574A CN 1651139 A CN1651139 A CN 1651139A
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synthesizing methanol
catalyzer
catalyst
zro
methanol catalyst
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CN1297344C (en
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孙予罕
何鸣元
林明桂
李文怀
杨成
单永奎
魏伟
王太英
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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    • 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
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A noble metal modified Cu/ZrO2-based catalyst for synthesizing methanol contains proportionally Cu, Zr and Pd or Ag. It is prepared through mixing the mixed solution of copper nitrate and zirconium oxychloride with the solution of sodium carbonate, stirring, codepositing, keeping pH=9-11, washing with distilled water, drying, calcining, cooling, tabletting, pulverizing, immersing in the solution of palladium (or silver) nitrate, and infrared baking.

Description

Cu/ZrO 2Radical synthesizing methanol catalyst and method for making and application
Technical field
The invention belongs to a kind of catalst for synthesis of methanol, relate in particular to the copper Zirconium oxide catalst for synthesis of methanol of a kind of precious metal additive palladium or silver-colored modification.
Background technology
Methyl alcohol is a kind of important basic Organic Chemicals, in addition, also is expected to become novel liquid fuel and petroleum supplements, the development of catalst for synthesis of methanol thereby be subjected to attracting attention of people.The catalyzer of present industrial synthesizing methanol mainly is Cu/ZnO/Al 2O 3Catalyst system, but this catalyzer still exists some weakness, relatively poor as thermotolerance, in reduction and reaction process, need 3-12%CO 2Keeping its catalytic activity, and process cost is bigger.In order to overcome above-mentioned these weakness, people research and develop new copper-based catalysts system in succession in recent years, as Cu/ZrO 2Catalyst system receives much attention at catalytic field with its stable catalyst structure and unique synthol activity and selectivity.
Precious metal since to the hydrogen molecule strong solution from adsorptive power and promote hydrogen overflow effect between component, to stable and promote other active centre to have important effect, the existing in the recent period relevant bibliographical information of its auxiliary agent effect.Find that activity of such catalysts obviously improves studied the influence of metal pair Cu/ZnO base methanol synthetic catalysts such as Pd as Inui etc. after.Fujimoto and Yu also obtain similar conclusion, and think that Pd can weaken H 2O is to the toxic action of catalyzer.Melian-Cabrera etc. discover that Cu/ZnO activity of such catalysts phase has been stablized in the existence of Pd, has prevented CO in the unstripped gas 2To the oxygenizement of catalyst activity phase, thereby improved activity of such catalysts.This shows that a little P d can reach good effect as catalyst adjuvant, but to Cu/ZrO 2The modification of catalyst system does not appear in the newspapers.
Summary of the invention
The purpose of this invention is to provide a kind of active high, selectivity is high, the Cu/ZrO of the modified with noble metals of reaction conditions gentleness, good stability 2Radical synthesizing methanol catalyst.
The weight of catalyzer of the present invention institute containing metal consists of: Cu:9-24%, Zr:75-90%, Pd or Ag:0.1-1.0%.
Preparation of catalysts method provided by the invention is as follows:
Ratio according to above-mentioned catalyzer composition, mixing solutions with cupric nitrate and zirconium oxychloride, 60-90 ℃ of following and sodium carbonate solution whipped state co-precipitation, keep the pH value at 9-11, precipitation through distilled water wash till do not have chlorion and detect, after drying 350-550 ℃ of following roasting, naturally cool to room temperature after, compression molding, the broken 40-60 order that is sieved to.Introduce palladium or silver-colored auxiliary agent with pickling process, with the form adding of nitrate, dipping time is 12-24 hour, makes catalyzer after infrared lamp irradiation oven dry.
The suitable reaction conditions of the catalyzer of the present invention's preparation is: temperature=230-280 ℃, and pressure=4.0-8.0MPa, unstripped gas H 2/ CO=1.5-2.2, air speed=1000-10000h -1
Catalyzer provided by the invention has following characteristics:
(1) each uniform component distribution of catalyzer, and have strong interaction between each component, anti-agglutinatting property is relatively good.
(2) but catalyzer straight forming before dry need not other adding additives, and catalyzer is after roasting, physical strength is better.
(3) the required temperature and pressure of catalyst reaction is lower.
(4) in Fan Ying the liquid product, by product is fewer, and the content of senior alcohol and water is all lower.
(5) this method for preparing catalyst is simple, easy handling, and catalyst performance good reproducibility.
Embodiment:
Embodiment 1
With cupric nitrate (Cu (NO 3) 23H 2O) 22.53g and zirconium oxychloride (ZrOCl 28H 2O) 65.67g is dissolved in the deionized water of 800mL, behind the wiring solution-forming, under 70 ℃ of controlled temperature and pH=9 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate solution 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical stirrer, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and extremely detect less than till the chlorion with silver nitrate solution with deionized water wash, then with filter cake 120 ℃ of following dried overnight, place 350 ℃ of following roastings 3 hours at last, obtain copper Zirconium oxide powder agglomates.Behind the compression molding, pulverize order into 40-60.Pipette 16.5mL concentration and be that the silver nitrate solution dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 24 hours,, obtain catalyzer 1#, each weight metal percentage composition Cu:24.0%, Zr:75.0%, Ag:1.0% with the infrared lamp oven dry.
Embodiment 2
With cupric nitrate (Cu (NO 3) 23H 2O) 22.53g and zirconium oxychloride (ZrOCl 28H 2O) 65.67g is dissolved in the deionized water of 800mL, behind the wiring solution-forming, under 90 ℃ of controlled temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate solution 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical stirrer, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and extremely detect less than till the chlorion with silver nitrate solution with deionized water wash, then with filter cake 120 ℃ of following dried overnight, place 500 ℃ of following roastings 3 hours at last, obtain copper Zirconium oxide powder agglomates.Behind the compression molding, pulverize order into 40-60.Pipette 2.2mL concentration and be that the silver nitrate solution dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 12 hours,, obtain catalyzer 2#, each weight metal percentage composition Cu:24.0%, Zr:74.9%, Ag:0.1% with the infrared lamp oven dry.
Embodiment 3
With cupric nitrate (Cu (NO 3) 23H 2O) 22.53g and zirconium oxychloride (ZrOCl 28H 2O) 65.67g is dissolved in the deionized water of 800mL, behind the wiring solution-forming, under 70 ℃ of controlled temperature and pH=11 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate solution 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical stirrer, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and extremely detect less than till the chlorion with silver nitrate solution with deionized water wash, then with filter cake 120 ℃ of following dried overnight, place 350 ℃ of following roastings 3 hours at last, obtain copper Zirconium oxide powder agglomates.Behind the compression molding, pulverize order into 40-60.Pipette 16.5mL concentration and be that the palladium nitrate solution dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 24 hours,, obtain catalyzer 3#, each weight metal percentage composition Cu:24.0%, Zr:75.0%, Pd:1.0% with the infrared lamp oven dry.
Embodiment 4
With cupric nitrate (Cu (NO 3) 23H 2O) 22.53g and zirconium oxychloride (ZrOCl 28H 2O) 65.67g is dissolved in the deionized water of 800mL, behind the wiring solution-forming, under 80 ℃ of controlled temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate solution 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical stirrer, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and extremely detect less than till the chlorion with silver nitrate solution with deionized water wash, then with filter cake 120 ℃ of following dried overnight, place 550 ℃ of following roastings 3 hours at last, obtain copper Zirconium oxide powder agglomates.Behind the compression molding, pulverize order into 40-60.Pipette 2.2mL concentration and be that the silver nitrate solution dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 18 hours,, obtain catalyzer 4#, each weight metal percentage composition Cu:24.0%, Zr:74.9%, Pd:0.1% with the infrared lamp oven dry.
Embodiment 5
With cupric nitrate (Cu (NO 3) 23H 2O) 12.08g and zirconium oxychloride (ZrOCl 28H 2O) 64.45g is dissolved in the deionized water of 800mL, behind the wiring solution-forming, under 60 ℃ of controlled temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate solution 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical stirrer, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and extremely detect less than till the chlorion with silver nitrate solution with deionized water wash, then with filter cake 120 ℃ of following dried overnight, place 450 ℃ of following roastings 3 hours at last, obtain copper Zirconium oxide powder agglomates.Behind the compression molding, pulverize order into 40-60.Pipette 8.2mL concentration and be that the silver nitrate solution dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 20 hours,, obtain catalyzer 5#, each weight metal percentage composition Cu:14.77%, Zr:84.48%, Ag:0.5% with the infrared lamp oven dry.
Embodiment 6
With cupric nitrate (Cu (NO 3) 23H 2O) 12.08g and zirconium oxychloride (ZrOCl 28H 2O) 64.45g is dissolved in the deionized water of 800mL, behind the wiring solution-forming, under 90 ℃ of controlled temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate solution 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical stirrer, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and extremely detect less than till the chlorion with silver nitrate solution with deionized water wash, then with filter cake 120 ℃ of following dried overnight, place 350 ℃ of following roastings 3 hours at last, obtain copper Zirconium oxide powder agglomates.Behind the compression molding, pulverize order into 40-60.Pipette 8.2mL concentration and be that the silver nitrate solution dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 24 hours,, obtain catalyzer 6#, each weight metal percentage composition Cu:14.77%, Zr:84.47%, Pd:0.5% with the infrared lamp oven dry.
The evaluating catalyst experiment:
Experiment adopts the pressurization continuous flow fixed bed reactor to investigate catalyzer synthesizing methanol reactivity worth provided by the invention.Catalyst powder is broken to the 40-60 order, and loadings is 1.5ml.Unstripped gas makes through methanol decomposition.Gas enters reactor after purification, mass flowmeter (Chinese Academy of Sciences's Shanxi coalification is produced) metering.H in the unstripped gas 2Content be about 65.4%, the content of CO is about 32.5%, CO 2Content be about 0.8%, the content of hydro carbons is about 1.3%.Before catalyzer is estimated, catalyzer is reduced.Hydrogen nitrogen mixed gas (H is adopted in the reduction of catalyzer 2Content 5-10%, N 2Content 90-95%) as reducing gas, the reductive condition is: pressure 0.1MPa, air speed is 3000h -1, adopt temperature programmed reduction(TPR), be elevated to 300 ℃ gradually from room temperature, reduction is 6 hours under this temperature, be cooled to room temperature then after, switch to synthetic gas.Reactor outlet material is through cooling, gas-liquid separation, and tail gas is through metering emptying, regularly setting-out of liquid product.For guaranteeing the reliability of stationary state service data, the catalyzer operation began sampling after 48 hours.Representative for guaranteeing the condensability product of being got, each stationary state operation is all greater than 12 hours.Gas and product liquid adopt the analysis of Tianjin, island GC-8A gas chromatograph.Thermal conductivity detector (TCD) detects CO, the CO in the tail gas 2, H 2, CH 4Volume content and the H in the product liquid 2O, CH 3The weight percent of OH, its chromatographic column use carbonaceous molecular sieve and the GDX401 packed column of 2m respectively, and column temperature is 110 ℃.Hydrocarbon polymer in the gas and the alcohol mixture in the liquid then detect (FID) by hydrogen flame ionization detector, and its chromatographic column is Chrmosorb 101 and the Porapak Q packed column of 2m, and column temperature is 110 ℃.
Gas is that intermediate carries out related normalizing calculating by methane gas, and liquid is that the related normalizing of intermediate calculates by methyl alcohol.Table 1 is the example catalyst reaction result.
Table 1 embodiment catalyst reaction result
The products distribution selectivity
Real
Reaction pressure temperature of reaction raw material air speed CO transformation efficiency alcohol space-time yield (wt%) (mol%)
Execute
H 2/CO
MPa ℃ h -1
％ g/ml·h
Example
H 2O ROH ROH CH x
1 4.0 230 2000 2.0 23.74 0.41 3.33 96.67 97.39 2.61
2 6.0 250 6000 2.2 31.88 0.53 4.02 95.98 98.03 1.97
3 8.0 250 10000 1.8 35.45 0.98 2.59 97.41 96.79 3.21
4 6.0 280 6000 2.2 34.19 0.57 3.86 96.14 98.45 1.55
5 4.0 230 6000 1.5 28.35 0.42 1.71 98.29 93.57 6.43
6 4.0 250 1000 2.2 30.40 0.27 2.41 97.59 89.99 10.01

Claims (3)

1, a kind of Cu/ZrO of modified with noble metals 2Radical synthesizing methanol catalyst, it is characterized in that catalyzer weight consist of: Cu:9-24%, Zr:75-90%, Pd or Ag:0.1-1.0%.
2, the Cu/ZrO of a kind of modified with noble metals as claimed in claim 1 2The preparation method of radical synthesizing methanol catalyst is characterized in that comprising the steps:
Form Cu:9-24% by catalyst weight, Zr:75-90%, Pd or Ag:0.1-1.0%, the mixing solutions of usefulness cupric nitrate and zirconium oxychloride is 60-90 ℃ of following and sodium carbonate solution whipped state co-precipitation, keep the pH value at 9-11, precipitation through distilled water wash till do not have chlorion and detect, after drying 350-550 ℃ of following roasting, naturally cool to room temperature after, compression molding, the broken 40-60 order that is sieved to.Introduce palladium or silver-colored auxiliary agent with pickling process, with the form adding of nitrate, dipping time is 12-24 hour, makes catalyzer after infrared lamp irradiation oven dry.
3, the Cu/ZrO of a kind of modified with noble metals as claimed in claim 1 2The application method of radical synthesizing methanol catalyst is characterized in that reaction conditions is: temperature=230-280 ℃, and pressure=4.0-8.0MPa, unstripped gas H 2/ CO=1.5-2.2, air speed=1000-10000h -1
CNB2004100645741A 2004-11-30 2004-11-30 Cu/ZrO2 radical synthesizing methanol catalyst and its making method and application Expired - Fee Related CN1297344C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103007961A (en) * 2012-12-13 2013-04-03 北京化工大学常州先进材料研究院 Catalyst for eliminating CO in hydrogen source of fuel cell and preparation method of catalyst
CN103480376A (en) * 2013-10-14 2014-01-01 中国科学院山西煤炭化学研究所 Preparation method and application of synthetic carboxylate copper-mesoporous zirconium bifunctional catalyst
CN109999833A (en) * 2019-05-07 2019-07-12 盐城工学院 A kind of catalyst and preparation method thereof for synthesizing methanol by hydrogenating carbon dioxide
CN111939926A (en) * 2020-07-31 2020-11-17 扬州大学 Cu-Zr oxide nanoparticle loaded Pd (II) catalyst and preparation method and application thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102921420A (en) * 2012-11-09 2013-02-13 上海应用技术学院 Cu/ZrO2 catalytic agent, preparation method of Cu/ZrO2 catalytic agent and application of Cu/ZrO2 catalytic agent

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3369311D1 (en) * 1982-07-09 1987-02-26 British Petroleum Co Plc Catalyst compostion and its use in a process for the production of alcohols from synthesis gas
CN1153080A (en) * 1995-12-29 1997-07-02 中国科学院兰州化学物理研究所 Catalyst for direct preparation of dimethyl ether with synthetic gas
JP3232326B2 (en) * 1997-03-11 2001-11-26 経済産業省産業技術総合研究所長 Copper-based catalyst and method for producing the same

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103007961A (en) * 2012-12-13 2013-04-03 北京化工大学常州先进材料研究院 Catalyst for eliminating CO in hydrogen source of fuel cell and preparation method of catalyst
CN103480376A (en) * 2013-10-14 2014-01-01 中国科学院山西煤炭化学研究所 Preparation method and application of synthetic carboxylate copper-mesoporous zirconium bifunctional catalyst
CN109999833A (en) * 2019-05-07 2019-07-12 盐城工学院 A kind of catalyst and preparation method thereof for synthesizing methanol by hydrogenating carbon dioxide
CN111939926A (en) * 2020-07-31 2020-11-17 扬州大学 Cu-Zr oxide nanoparticle loaded Pd (II) catalyst and preparation method and application thereof
CN111939926B (en) * 2020-07-31 2023-03-24 扬州大学 Cu-Zr oxide nanoparticle loaded Pd (II) catalyst and preparation method and application thereof

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