CN1363424A - Nano-Cr iron-series catalyst for high-temp conversion of CO and its preparing process - Google Patents

Nano-Cr iron-series catalyst for high-temp conversion of CO and its preparing process Download PDF

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Publication number
CN1363424A
CN1363424A CN01138010A CN01138010A CN1363424A CN 1363424 A CN1363424 A CN 1363424A CN 01138010 A CN01138010 A CN 01138010A CN 01138010 A CN01138010 A CN 01138010A CN 1363424 A CN1363424 A CN 1363424A
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oxide
iron
manganese
nickel
catalyst
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CN01138010A
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CN1173780C (en
Inventor
魏士新
张天胜
高峰
彭波
陈长新
蔡成伟
黄建明
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Research Institute of Sinopec Nanjing Chemical Industry Co Ltd
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Research Institute of Nanjing Chemical Industry Group Co Ltd
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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
    • 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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Abstract

A novel non-Cr Fe-series catalyst for high-temp cnversion of CO is prepared by co-deposition and wet mixing, and features that more metallic oxides replace chromium oxide, eliminating Cr harm. Its advantages include no Cr pollution, low density, and high strength and activity.

Description

Novel nano-Cr iron-series catalyst for high-temp conversion of CO and preparation method thereof
Technical field: belong to catalysis technical field, relate to a kind of novel nano-Cr iron-series catalyst for high-temp conversion of CO and preparation method thereof.
Background technology: carbon monoxide and water vapour transformationreation hydrogen manufacturing are very important chemical processes, in industrial production, usually high temperature conversion catalyst and low temperature conversion catalyst series connection are used, high temperature shift can obtain higher reaction rate, and reaction heat can be reclaimed by-product high-pressure steam, it is more thorough that low-temperature conversion gets the CO conversion, reduces the remaining CO content in the conversion exit gas.
Carbon-oxide high-temperature conversion catalyst is to use a kind of chemical fertilizer catalyst of the widest consumption maximum, and traditional high conversion catalyst is structural promoter based on iron oxide with the chrome green.Chromium adds with the form of chromic anhybride (chromium trioxide) and bichromate usually in high conversion catalyst is produced, and is reduced into nontoxic chrome green in the use, can be oxidized to chromium trioxide with the chrome green in the discarded catalyst in back again in air.Chromium trioxide and bichromate all have severe toxicity, and are very strong carcinogens, cause serious harm all can for human body and environment in catalyst manufacturing, filling process and after discarding.Therefore, development Cr iron-series high conversion catalyst has very important significance.
In order to solve the pollution problem of chromium, the research of Chrome-free high conversion catalyst has extensively been carried out in countries in the world:
United States Patent (USP) 4,540,563 disclose a kind of Chrome-free high conversion catalyst, except Main Ingredients and Appearance Fe 2O 3, contain a kind of simple substance that is difficult for being reduced at least outward, have+oxide of divalent above valent metal, as alkaline-earth metal Ca, Sr, Ba, rare earth metal Ce, and Zr, Hf etc.
Chinese patent 95121834.4 adds CeO based on iron oxide 2Or CoO is main auxiliary agent, eliminated the chromium evil.
Chinese patent 1256966A discloses a kind of Chrome-free high conversion catalyst, adopts ferrous nitrate, ferric nitrate, bismuth nitrate and ammoniacal liquor co-precipitation, adds TiO simultaneously 2, MnO 2, ZnO, CeO 2, Al 2O 3, CuO, K 2MnO 4Deng auxiliary agent, prepared activity of such catalysts is better than existing industrial catalyst.
The disclosed Chrome-free high conversion catalyst of Chinese patent 1265340A is made up of chemical compositions such as composite oxides such as iron oxide, ferro-aluminum silicon or aluminum silica gel, barium oxide, magnesium oxide, nickel oxide, potassium oxides.
Summary of the invention: the objective of the invention is to adopt nontoxic metal oxide to substitute the CrO of severe toxicity 3Make a kind of novel non-chrome high conversion catalyst, this catalyst has good activity, heat endurance and mechanical strength and low bulk density.
Chromium is by entering active constituent Fe in the high conversion catalyst at iron-chromium 3O 4The lattice of cubic system in, substitute the part Fe in octahedral voids or the tetrahedral holes 3+, form spinel structure (Fe 2+Fe 3+Cr 3+O 4) solid solution.Chromium atom has played the effect of interval iron atom therein, thereby slows down growing up of iron crystallite effectively, can improve activity of such catalysts and heat endurance significantly.
Theoretically, except chromium, also have many metals, all may enter Fe as Ca, Ba, Bi, Al, Mn, Mg, Mo, Co, Ni, Pb, Ce etc. 3O 4Lattice forms M 2+Fe 2 3+O 4, M 2+M 3+Fe 3+O 4, Fe 2+Fe 3+M 3+O 4, M 4+Fe 2 2+O 4Spinel structure (M wherein etc. type N+The above-mentioned metal ion of acute pyogenic infection of finger tip), reach the heat endurance purpose that improves catalyst.
Although have many auxiliary agents can play the effect of substitute chromium theoretically, up to the present also do not find a kind of oxide can play the effect of complete substitute chromium separately.
Chrome-free high conversion catalyst of the present invention adopts the synergistic methods of many auxiliary agents such as manganese oxide, nickel oxide, magnesia, cerium oxide, cupric oxide, aluminium oxide to reach the purpose of substitute chromium based on iron oxide.Its (wt%) mainly composed as follows: iron oxide 60%-90%, manganese oxide (or aluminium oxide, magnesia, cerium oxide etc.) 1%-20%, nickel oxide 0.5%-5%, cupric oxide 0.5%-5%, potassium oxide 0.1%-1.0%.Primary structure auxiliary agent manganese oxide and nickel oxide add by the mode with the molysite co-precipitation with the form of manganese salt, nickel salt, and promoter cupric oxide and potassium oxide adopt the mode of wet-mixing to add.
Purpose of the present invention can realize by following measure:
With above-mentioned component amount FeSO 4[or Fe (NO 3) 2], MnSO 4[or Mn (NO 3) 2], NiSO 4[or Ni (NO 3) 2] the water-soluble mixed solution that is mixed with, solution carries out neutralization precipitation in the adding alkali lye precipitating reagent under the condition of stirring, blowing air, the control temperature is 50-80 ℃ in the N-process, after finishing, neutralization continues aging 2-6h subject to the foregoing, precipitation concentrates through separating with the qualified back of washing facility washing, and substep adds aluminium oxide, copper sulphate (or copper nitrate) and potassium hydroxide, drying, granulation, roasting then, add compressing tablet behind a small amount of graphite and the water again, obtain the catalyst finished product after the tablet roasting.The alkali lye precipitating reagent can be a kind of in NaOH, sodium carbonate, sodium acid carbonate, carbonic hydroammonium, the ammoniacal liquor, preferably adopts NaOH or ammoniacal liquor.
Purpose of the present invention can also reach by following measure:
The MnSO that adds in the coprecipitation process 4[or Mn (NO 3) 2] can also replace with the sulfate (or nitrate) of Al, Mg, Ce.
The specific embodiment: the present invention is described in detail below in conjunction with embodiment.
Embodiment 1:
4000g ferrous sulfate (FeSO 47H 2O), 145.7g manganese sulfate (MnSO 4H 2O), 105.6g nickelous sulfate (NiSO 46H 2O) the water-soluble solution A that is mixed with, wherein Fe 2O 3Content is 120-150g/L, and solution A is carried out neutralization precipitation with 15% ammonia spirit B under the condition that stirs, feeds air in certain amount, in finishing control pH7-8.Neutralization is warmed up to 50-80 ℃ after finishing, and is stirring and feeding the crystal formation conversion of finishing ferric hydroxide precipitate under an amount of conditions of air, and the crystal formation transformation time is 1-8h.Precipitation is allocated 70.7g copper nitrate (Cu (NO into after washing, concentrating 3) 25H 2O) and 2.4g potassium hydroxide (KOH), mix back drying, granulation, roasting, allocate compressing tablet behind the 10g graphite into, obtain catalyst I through 400 ℃ of roasting 1h.
Embodiment 2:
1300g NaOH is dissolved in 8L water wiring solution-forming B, replaces ammoniacal liquor to make catalyst I I according to embodiment 1 described condition with solution B.
Embodiment 3:
4000g ferrous sulfate (FeSO 47H 2O), 97.1g manganese sulfate (MnSO 4H 2O), 140.8g nickelous sulfate (NiSO 46H 2O) the water-soluble solution A that is mixed with, wherein Fe 2O 3Content is 120-150g/L, and solution A is carried out neutralization precipitation by the ammoniacal liquor of embodiment 1 described condition and 15%, makes catalyst I II.
Embodiment 4:
Change the manganese sulfate among the embodiment 1 into 305.8g magnesium sulfate (MgSO 4H 2O) obtain solution A makes catalyst I V according to embodiment 1 described condition.
Embodiment 5:
Change the manganese sulfate among the embodiment 1 into 326.7g aluminum sulfate (Al 2(SO 4) 39H 2O) obtain solution A makes catalyst V according to embodiment 1 described condition.
Embodiment 6:
Change the manganese sulfate among the embodiment 1 into 68.6g (Ce (SO 4) 2) obtain solution A, make catalyst V I according to embodiment 1 described condition.
Embodiment 7:
Ferrous nitrate, ferric nitrate, nickel nitrate, water-soluble being mixed with of manganese nitrate contain 1000g Fe 2O 3, 75g MnO 2, 30g NiO solution A, 1300g NaOH is dissolved in 8L water wiring solution-forming B, solution A and B make catalyst V II by embodiment 1 described condition.
Above-mentioned catalyst detects according to HG/T 3544-1989 standard detection condition, obtains following result:
Catalyst Anti-crushing power N/cm radially Bulk density kg/L 350 ℃ of activity (CO interconversion rate), %
Initial activity Heat-resisting back is active
????I ????266 ????1.38 ????79.9 ????54.4
????II ????468 ????1.24 ????84.7 ????59.5
????III ????260 ????1.34 ????75.0 ????50.1
????IV ????250 ????1.27 ????86.4 ????52.3
????V ????283 ????1.46 ????76.3 ????54.3
????VI ????267 ????1.35 ????76.3 ????55.0
????VII ????394 ????1.11 ????87.0 ????63.7

Claims (3)

1, novel nano-Cr iron-series catalyst for high-temp conversion of CO, based on iron oxide, adopt many auxiliary agents such as manganese oxide, nickel oxide, magnesia, cerium oxide, cupric oxide, aluminium oxide to act synergistically to substitute chromium oxide, (wt%) mainly composed as follows that it is characterized in that it: iron oxide 60%-90%, manganese oxide (or aluminium oxide, magnesia, cerium oxide) 1%-20%, nickel oxide 0.5%-5%, cupric oxide 0.5%-5%, potassium oxide 0.1%-1.0%.
2, the preparation method of novel nano-Cr iron-series catalyst for high-temp conversion of CO, it is characterized in that primary structure auxiliary agent manganese oxide and nickel oxide are with manganese salt, the form of nickel salt, add by mode with the molysite co-precipitation, promoter cupric oxide and potassium oxide adopt the mode of wet-mixing to add: ferrous sulfate or ferrous nitrate solution are mixed with the sulfate or the nitrate solution of manganese and nickel, stirring, adopt the neutralization of alkali lye precipitating reagent under the condition of blowing air, make iron, manganese, the nickel co-precipitation, the control temperature is 50-80 ℃ in the N-process, continues aging 2-6h after neutralization finishes subject to the foregoing; Precipitation concentrates through separating with the qualified back of washing facility washing, substep adds promoter copper sulphate (or copper nitrate) and potassium hydroxide, making beating mixes back drying, granulation, roasting, adds compressing tablet behind a small amount of graphite and the water again, and tablet obtains the catalyst finished product through roasting.
3, a kind of Preparation of catalysts method as claimed in claim 2 is characterized in that the alkali lye precipitating reagent can be a kind of in NaOH, sodium carbonate, sodium acid carbonate, carbonic hydroammonium, the ammoniacal liquor, preferably adopts NaOH or ammoniacal liquor.
CNB011380101A 2001-12-20 2001-12-20 Nano-Cr iron-series catalyst for high-temp conversion of CO and its preparing process Expired - Fee Related CN1173780C (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2175989A1 (en) * 2007-08-10 2010-04-21 Rentech, Inc. Precipitated iron catalyst for hydrogenation of carbon monoxide
CN101954286A (en) * 2010-09-25 2011-01-26 东华大学 Rare earth catalyst for eliminating carbon monoxide at normal temperature and preparation method thereof
CN104107688A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Sheet metal oxide catalyst and preparation method thereof
CN111617769A (en) * 2020-07-02 2020-09-04 四川亚联高科技股份有限公司 Preparation method of chromium-free wide-temperature water-gas shift catalyst, catalyst and application

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100450625C (en) * 2005-12-22 2009-01-14 南化集团研究院 Preparing method of high stability high conversion catalyst

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2175989A1 (en) * 2007-08-10 2010-04-21 Rentech, Inc. Precipitated iron catalyst for hydrogenation of carbon monoxide
EP2175989A4 (en) * 2007-08-10 2012-02-01 Rentech Inc Precipitated iron catalyst for hydrogenation of carbon monoxide
CN101954286A (en) * 2010-09-25 2011-01-26 东华大学 Rare earth catalyst for eliminating carbon monoxide at normal temperature and preparation method thereof
CN101954286B (en) * 2010-09-25 2012-08-08 东华大学 Rare earth catalyst for eliminating carbon monoxide at normal temperature and preparation method thereof
CN104107688A (en) * 2013-04-16 2014-10-22 中国石油化工股份有限公司 Sheet metal oxide catalyst and preparation method thereof
CN104107688B (en) * 2013-04-16 2016-12-28 中国石油化工股份有限公司 Sheet metal oxide catalyst and preparation method thereof
CN111617769A (en) * 2020-07-02 2020-09-04 四川亚联高科技股份有限公司 Preparation method of chromium-free wide-temperature water-gas shift catalyst, catalyst and application

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