CN1297344C - 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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CN1297344C
CN1297344C CNB2004100645741A CN200410064574A CN1297344C CN 1297344 C CN1297344 C CN 1297344C CN B2004100645741 A CNB2004100645741 A CN B2004100645741A CN 200410064574 A CN200410064574 A CN 200410064574A CN 1297344 C CN1297344 C CN 1297344C
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catalyst
temperature
synthesizing methanol
zro2
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CN1651139A (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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    • 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
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    • 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

The present invention relates to a Cu/ZrO2-base synthesized methanol catalyst modified by precious metal, which is prepared from the raw materials of the proportion by weight: 9 to 24% of Cu, 75 to 90% of Zr and 0.1 to 1.0% of Pd or Ag. The Cu/ZrO2-base synthesized methanol catalyst modified by precious metals is prepared by that a mixed solution of copper nitrate and zirconium oxychloride, and a sodium carbonate solution are coprecipitated at a temperature of 60 to 90 DEG C in a stirring state, and the pH value is kept at 9 to 11; the precipitates are washed in distilled water until no chlorine ion can be detected, dried, calcined at a temperature of 350 to 550 DEG C, naturally cooled to the room temperature, formed by tabletting, pulverized and sieved into 40 to 60 meshes; Pa or Ag auxiliary agents are introduced by an immersion method, and added in a nitrate form, immersion time lasts for 12 to 24 hours, the processed materials are dried through infrared lamp irradiation, and thus, the catalyst is prepared. The present invention has the advantages of good mechanical strength of the catalyst, good repeatability of properties, simple preparation method and easy operation.

Description

The Cu/ZrO of modified with noble metals 2Radical synthesizing methanol catalyst and its production 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 alternative to oil, the development of catalst for synthesis of methanol thereby be subjected to attracting attention of people.The catalyst of present industrial synthesizing methanol mainly is Cu/ZnO/Al 2O 3Catalyst system and catalyzing, but this catalyst still exists some weakness, relatively poor as hear resistance, in reduction and course of reaction, need 3-12%CO 2Keeping its catalytic activity, and operating 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 and catalyzing receives much attention at catalytic field with its stable catalyst structure and unique synthol activity and selectivity.
Noble metal since to the hydrogen molecule strong solution from adsorption capacity and promote hydrogen overflow effect between component, to stable and promote other activated 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 catalyst.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 oxidation of catalyst activity phase, thereby improved activity of such catalysts.This shows that a little P d can reach good effect as catalyst promoter, but to Cu/ZrO 2The modification of catalyst system and catalyzing 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 condition gentleness, good stability 2Radical synthesizing methanol catalyst.
The weight of catalyst 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 catalyst composition, mixed solution with copper nitrate and zirconium oxychloride, 60-90 ℃ of following and sodium carbonate liquor stirring co-precipitation, keep the pH value at 9-11, precipitation through distilled water washing 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 infusion process, with the form adding of nitrate, dip time is 12-24 hour, makes catalyst after infrared lamp irradiation oven dry.
The suitable reaction condition of the catalyst 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
Catalyst provided by the invention has following characteristics:
(1) each uniform component distribution of catalyst, and have strong interaction between each component, anti-agglutinatting property is relatively good.
(2) but catalyst straight forming before dry need not other adding additives, and catalyst is after roasting, mechanical strength is better.
(3) the required temperature and pressure of catalytic reaction is lower.
(4) in Fan Ying the liquid product, accessory substance is fewer, and the content of senior alcohol and water is all lower.
(5) this method for preparing catalyst is simple, easy operating, and catalyst performance good reproducibility.
The specific embodiment:
Embodiment 1
With copper 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 control temperature and pH=9 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate liquor 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical agitator, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and spend deionised water to detecting less than till the chlorion with liquor argenti nitratis ophthalmicus, 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 liquor argenti nitratis ophthalmicus dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 24 hours,, obtain catalyst 1#, each weight metal percentage composition Cu:24.0%, Zr:75.0%, Ag:1.0% with the infrared lamp oven dry.
Embodiment 2
With copper 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 control temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate liquor 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical agitator, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and spend deionised water to detecting less than till the chlorion with liquor argenti nitratis ophthalmicus, 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 liquor argenti nitratis ophthalmicus dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 12 hours,, obtain catalyst 2#, each weight metal percentage composition Cu:24.0%, Zr:74.9%, Ag:0.1% with the infrared lamp oven dry.
Embodiment 3
With copper 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 control temperature and pH=11 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate liquor 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical agitator, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and spend deionised water to detecting less than till the chlorion with liquor argenti nitratis ophthalmicus, 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 catalyst 3#, each weight metal percentage composition Cu:24.0%, Zr:75.0%, Pd:1.0% with the infrared lamp oven dry.
Embodiment 4
With copper 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 control temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate liquor 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical agitator, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and spend deionised water to detecting less than till the chlorion with liquor argenti nitratis ophthalmicus, 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 liquor argenti nitratis ophthalmicus dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 18 hours,, obtain catalyst 4#, each weight metal percentage composition Cu:24.0%, Zr:74.9%, Pd:0.1% with the infrared lamp oven dry.
Embodiment 5
With copper 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 control temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate liquor 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical agitator, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and spend deionised water to detecting less than till the chlorion with liquor argenti nitratis ophthalmicus, 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 liquor argenti nitratis ophthalmicus dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 20 hours,, obtain catalyst 5#, each weight metal percentage composition Cu:14.77%, Zr:84.48%, Ag:0.5% with the infrared lamp oven dry.
Embodiment 6
With copper 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 control temperature and pH=10 condition, (takes by weighing the 63.6g anhydrous Na with sodium carbonate liquor 2CO 3Be dissolved in the 800mL deionized water) charging simultaneously and fully stir with mechanical agitator, make precipitation evenly mixed, post precipitation continues to stir aging 2 hours at 70 ℃, filter and spend deionised water to detecting less than till the chlorion with liquor argenti nitratis ophthalmicus, 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 liquor argenti nitratis ophthalmicus dipping 3.20g (2.2mL) of 0.0015g/mL is above-mentioned made the copper Zirconium oxide 24 hours,, obtain catalyst 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 catalyst 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 flowmenter (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 catalyst is estimated, catalyst is reduced.Hydrogen nitrogen mixed gas (H is adopted in the reduction of catalyst 2Content 5-10%, N 2Content 90-95%) as reducing gases, the condition of reduction is: pressure 0.1MPa, air speed is 3000h -1, adopt temperature programmed reduction, be elevated to 300 ℃ gradually from room temperature, reduction is 6 hours under this temperature, be cooled to room temperature then after, switch to synthesis 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 operating data, the catalyst operation began sampling after 48 hours.Representative for guaranteeing the coercibility 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) (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 percentage by weight of OH, its chromatographic column use carbon molecular sieve and the GDX401 packed column of 2m respectively, and column temperature is 110 ℃.Hydrocarbon in the gas and the mixed alcohol 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
Embodiment Reaction pressure MPa Reaction temperature ℃ Raw material air speed h -1 H 2/CO CO conversion ratio % Alcohol space-time yield g/mlh Product distribution (wt%) Selectivity (mol%)
H 2O ROH ROH CH x
1 2 3 4 5 6 4.0 6.0 8.0 6.0 4.0 4.0 230 250 250 280 230 250 2000 6000 10000 6000 6000 1000 2.0 2.2 1.8 2.2 1.5 2.2 23.74 31.88 35.45 34.19 28.35 30.40 0.41 0.53 0.98 0.57 0.42 0.27 3.33 4.02 2.59 3.86 1.71 2.41 96.67 95.98 97.41 96.14 98.29 97.59 97.39 98.03 96.79 98.45 93.57 89.99 2.61 1.97 3.21 1.55 6.43 10.01

Claims (3)

1, a kind of Cu/ZrO of modified with noble metals 2Radical synthesizing methanol catalyst is characterized in that the weight of catalyst consists 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 mixed solution of usefulness copper nitrate and zirconium oxychloride is 60-90 ℃ of following and sodium carbonate liquor stirring co-precipitation, keep the pH value at 9-11, precipitation through distilled water washing 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 infusion process, with the form adding of nitrate, dip time is 12-24 hour, makes catalyst 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 of radical synthesizing methanol catalyst is characterized in that reaction condition 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 (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

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* Cited by examiner, † Cited by third party
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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
CN103480376B (en) * 2013-10-14 2015-01-14 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
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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US4567160A (en) * 1982-07-09 1986-01-28 The British Petroleum Company P.L.C. Catalyst composition 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
US6048820A (en) * 1997-03-11 2000-04-11 Agency Of Industrial Of Sciences And Technology Copper-based catalyst and method for production thereof

Patent Citations (4)

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US4567160A (en) * 1982-07-09 1986-01-28 The British Petroleum Company P.L.C. Catalyst composition for the production of alcohols from synthesis gas
US4576968A (en) * 1982-07-09 1986-03-18 The British Petroleum Company P.L.C. Catalyst composition 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
US6048820A (en) * 1997-03-11 2000-04-11 Agency Of Industrial Of Sciences And Technology Copper-based catalyst and method for production thereof

Cited By (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

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