CN102350355A - Iron-based water gas transformation catalyst and preparation method thereof - Google Patents
Iron-based water gas transformation catalyst and preparation method thereof Download PDFInfo
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- CN102350355A CN102350355A CN201110254193XA CN201110254193A CN102350355A CN 102350355 A CN102350355 A CN 102350355A CN 201110254193X A CN201110254193X A CN 201110254193XA CN 201110254193 A CN201110254193 A CN 201110254193A CN 102350355 A CN102350355 A CN 102350355A
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Abstract
The invention relates to an iron-based water gas transformation catalyst and a preparation method thereof. The catalyst is a water gas transformation catalyst which is composed of oxides of iron, aluminum and copper, wherein the mol ratio of all the metal elements is as follows: n(F) to n(Al) to n(Cu) is equal to 1:(0.5-1):(0.1-1). The preparation method of the catalyst comprises the following steps of: firstly mixing soluble inorganic acid iron salt, aluminum salt and copper salt solutions with alkali liquor to be neutralized to obtain sediment; and carrying out operations such as filtering, washing, drying, roasting, granulating and the like on the sediment to obtain the finished catalyst. Compared with the prior art, the catalyst provided by the invention has the advantages of high water gas transformation activity, wide usage temperature range, low vapor/gas ratio, good heat stability, low production cost, environmental friendliness, no chromium harm and the like. In a normal-pressure fixed bed reactor, the catalyst is used for carrying out a water gas transformation reaction at a hydrogen-enriched atmosphere (hydride VH2 is not less than 72%) and the carbon monoxide conversion rate at a temperature of 250-550 DEG C reaches 83-97%.
Description
Technical field
The invention discloses a kind of new sections is water gas converting catalyst and preparation method thereof, belongs to catalysis technical field, is specifically related to a kind of Fe-Al-Cu water gas converting catalyst that is used for the hydrogen rich gas atmosphere.
Background technology
The a large amount of coke oven crude gas that produce in iron and steel enterprise or the coking plant coking process obtain coke-stove gas through purified treatment, and its main component is: 53 ~ 59%H
2, 25% ~ 30%CH
4, 6%CO, 2.5%CO
2, 4%N
2, 0.5% O
2And 2.5%C
mH
n, this coke-stove gas that contains a large amount of hydrogen is a kind of hydrogen feedstock of high-quality.Technological through transformation absorption (PSA) at present to the original H in the coke-stove gas
2Component is separated purification, and separative efficiency can reach more than 90%.This technology has only reclaimed the original H in the coke-stove gas
2Component, all the other compositions or quilt directly emptying burn, and have caused certain wasting of resources and environmental pollution.Hydrogen production from coke oven gas technology then carries out steam reforming to the small molecule hydrocarbon in the coke-stove gas or partial oxygen changes into carbon monoxide, obtains highly purified hydrogen through processes such as Water gas shift/WGS then.This technology can make hydrogen output increase considerably, and has both made full use of resource and has also protected environment, also helps the problem of producing of the cheap hydrogen of solution scale simultaneously.Hydrogen production from coke oven gas technology comprises impurity desulfurization, coke tar cracking, CH
4Partial oxidation, Water gas shift/WGS steps such as (generally being divided into high temperature shift and low-temperature conversion).Wherein, the hydrogen content in work off one's feeling vent one's spleen (inlet gas of high-temperature water gas conversion just) of methane portion oxidation is greater than 72 vol%.
At above-mentioned hydrogen rich gas atmosphere (H
2>=72 vol%) in, the activity of traditional Fe-Cr HTS high-temperature water gas conversion catalyst can be suppressed.In addition, the chromated oxide in the catalyst has toxicity and carcinogenic, and human body and environment are all had very big harm.Therefore, develop under the hydrogen rich gas atmosphere high activity that uses, pollution-free, long-life water gas converting catalyst seems very important to the coke-stove gas process for making hydrogen.The active constituent of Fe-series catalyst is Fe
3O
4, separately by Fe
3O
4When using, there is activity low as catalyst, easy-sintering, serviceability temperature height and warm area are narrow, and the operating condition of high steam-to-gas ratio is to keep the shortcomings such as stable existence of active phase.Therefore, must add auxiliary agent to improve activity of such catalysts and stability, the active promotion and eco-friendly principle followed in the selection of auxiliary agent.For this reason, the various countries scientist has carried out extensive studies in the no chromaking process of Fe-Cr HTS high conversion catalyst:
U.S. Pat 5830425 (A) discloses a kind of Chrome-free high temperature conversion catalyst, and it is the Fe of 30 ~ 98 wt% that its group is wanted composition
2O
3, the CuO of 0.1 ~ 20 wt%, the rare earth oxide of 0.1 ~ 20 wt% and ZrO
2, 0.1 ~ 30 wt% ionic radius is one or more oxides (except the chromium element) of 50 ~ 72 pm, one or more platinum family metal oxide containing precious metals of 0 ~ 0.1wt% and the barium monoxide of 0 ~ 30 wt%.
Japan Patent JP2006122793A has reported a kind of wide warm water gas conversion catalyst; It is the oxide of calcium and aluminium that its group is wanted composition; Also can add the ferro element that accounts for aluminium content 0.001 ~ 10 mol%, account for one or both oxides additives among Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Os and the Ru of catalyst gross mass 0.001 ~ 10wt% in addition in addition.
Korean Patent KR100847443 (B1) discloses a kind of iron-based chrome-free high conversion catalyst, and its component is two kinds of elements and the ferro element in nickel, cobalt, the zinc, does not contain chromium element and noble metal.Wherein the catalyst of 5%Zn-75%Fe-20%Ni is 77% at 400 ℃ CO conversion ratio.
Chinese patent CN101227975A discloses a kind of Chrome-free high temperature conversion catalyst.Adopt aluminium oxide and cupric oxide replaced C r
2O
3, the mol ratio of its Fe/Al is 5:1 ~ 15:1, the mol ratio of Fe/Cu is 5:1 ~ 25:1.Prepared catalyst is at H
2O/CO=1, the initial activity under 250 ℃ ~ 400 ℃ the condition is 30 ~ 60%.
Summary of the invention
The object of the present invention is to provide that catalytic activity in a kind of hydrogen rich gas atmosphere is high, serviceability temperature is wide, steam-to-gas ratio is low, Heat stability is good, production cost is low and the Fe-Al-Cu water gas converting catalyst of environmental protection Chrome-free evil.
New sections of the present invention is a water gas converting catalyst, it is characterized in that being made up of the oxide of iron, aluminium, copper, and the mol ratio of each metallic element is n (Fe): n (Al): n (Cu)=1: (0.5 ~ 1): (0.1 ~ 1).
Its preparation method is a coprecipitation, mainly may further comprise the steps:
A) element of pressing catalyst is formed, and disposes a certain amount of Fe
3+, Al
3+And Cu
2+Mixed aqueous solution, the metal ion molar concentration is 0.25 ~ 0.26 mol/L; Said Fe
3+Lead compound be in ferric nitrate, ferric sulfate, the iron chloride any; Described Al
3+Lead compound be in aluminum nitrate, aluminum sulfate, the aluminium chloride any; Described Cu
2+Be in copper nitrate, copper sulphate, the copper chloride any;
B) the configuration precipitating reagent aqueous solution: the mass concentration of the precipitating reagent aqueous solution is 1 mol/L; Precipitating reagent is any in NaOH, potassium hydroxide, sodium acid carbonate, the carbonic hydroammonium;
C) above-mentioned metal ion mixed aqueous solution and the alkaline precipitating agent aqueous solution and drip are gone into carrying out neutralization precipitation in the beaker of agitating device; Mixing speed is 150 rev/mins; Precipitation reaction is carried out under 5 ~ 30 ℃ of room temperatures, the pH value that keeps mixed liquor in the N-process between 9 ~ 12, neutralize finish after with sediment the boiling of heat that heat up; Curing temperature is controlled between 40 ~ 75 ℃, and the curing time is 5 ~ 24 hours;
D) the above-mentioned sediment for preparing is carried out decompress filter, cakes with deionized water washing to filtrating is neutral, and drying is 12 ~ 24 hours in 100 ~ 150 ℃ drying box; Grind to form fine powder then, roasting is 2 ~ 5 hours in 300 ~ 450 ℃ Muffle furnace; Powder after the roasting is extrusion modling in mould under the pressure of 20 ~ 35 kN; With after broken, sieve, obtaining particle diameter is 20～40 purpose particles, is Fe-Al-Cu water gas converting catalyst finished product.
Description of drawings
Fig. 1 is the initial activity figure of catalyst under different temperatures in the embodiment of the invention 1,2,3,4.
Fig. 2 be in the embodiment of the invention 3 catalyst through 530 ℃ heat-resisting after behind the 15h, at 350 ℃ heat-resisting activity and time relation figure.
Fig. 3 is that catalyst in the embodiment of the invention 3 is at different H
2Initial activity variation diagram under the O/CO ratio.
The specific embodiment
Through following examples the present invention is further specified, but the present invention is not limited in these embodiment.
Embodiment 1:N (Fe): n (Al): n (Cu)=1:1:0.1 takes by weighing 50.6g Fe (NO respectively in molar ratio
3)
39H
2O, 47.0g Al (NO
3)
39H
2O and 3.1g Cu (NO
3)
23H
2O is dissolved in the 1000 mL deionized waters.Simultaneously, take by weighing 32g NaOH and be dissolved in the 810 mL deionized waters, with metal salt solution and precipitating reagent at room temperature and flow co-precipitation, keeping the pH value of solution value in the precipitation process is 9.After deposition finishes, handled 5 hours in 60 ℃ of constant temperature, the gained sedimentation and filtration; Spend deionised water to filtrating and be neutral; And 110 ℃ of dryings 24 hours, grind into powder placed 400 ℃ Muffle furnace roasting 3 hours; After extrusion modling under the pressure of 25kN, with its fragmentation, sieving obtains 20～40 purpose catalyst granules.
Embodiment 2:N (Fe): n (Al): n (Cu)=1:1:0.2 takes by weighing 50.6g Fe (NO respectively in molar ratio
3)
39H
2O, 47.0g Al (NO
3)
39H
2O and 6.1g Cu (NO
3)
23H
2O is dissolved in the 1100 mL deionized waters.Simultaneously, take by weighing 33g NaOH and be dissolved in the 825 mL deionized waters, with metal salt solution and precipitating reagent at room temperature and flow co-precipitation, keeping the pH value of solution value in the precipitation process is 10.After deposition finishes, handled 5 hours in 60 ℃ of constant temperature, the gained sedimentation and filtration; Spend deionised water to filtrating and be neutral; And 110 ℃ of dryings 18 hours, grind into powder placed 400 ℃ Muffle furnace roasting 3 hours; After extrusion modling under the pressure of 25kN, with its fragmentation, sieving obtains 20～40 purpose catalyst granules.
Embodiment 3:N (Fe): n (Al): n (Cu)=1:1:0.5 takes by weighing 50.6g Fe (NO respectively in molar ratio
3)
39H
2O, 47.0g Al (NO
3)
39H
2O and 15.1g Cu (NO
3)
23H
2O is dissolved in the 1250 mL deionized waters.Simultaneously, take by weighing 50g KOH and be dissolved in the 900 mL deionized waters, with metal salt solution and precipitating reagent at room temperature and flow co-precipitation, keeping the pH value of solution value in the precipitation process is 9.After deposition finishes, handled 5 hours in 60 ℃ of constant temperature, the gained sedimentation and filtration; Spend deionised water to filtrating and be neutral; And 120 ℃ of dryings 12 hours, grind into powder placed 400 ℃ Muffle furnace roasting 3 hours; After extrusion modling under the pressure of 25kN, with its fragmentation, sieving obtains 20～40 purpose catalyst granules.
Embodiment 4:N (Fe): n (Al): n (Cu)=1:1:1 takes by weighing 50.6g Fe (NO respectively in molar ratio
3)
39H
2O, 47.0g Al (NO
3)
39H
2O and 30.3g Cu (NO
3)
23H
2O is dissolved in the 1500 mL deionized waters.Simultaneously, take by weighing 85g NaHCO
3Be dissolved in the 1000 mL deionized waters, with metal salt solution and precipitating reagent at room temperature and flow co-precipitation, keeping the pH value of solution value in the precipitation process is 11.After deposition finishes, handled 4 hours in 70 ℃ of constant temperature, the gained sedimentation and filtration; Spend deionised water to filtrating and be neutral; And 120 ℃ of dryings 12 hours, grind into powder placed 400 ℃ Muffle furnace roasting 3 hours; After extrusion modling under the pressure of 25kN, with its fragmentation, sieving obtains 20～40 purpose catalyst granules.
Embodiment 5:N (Fe): n (Al): n (Cu)=1:0.5:0.5 takes by weighing 50.6g Fe (NO respectively in molar ratio
3)
39H
2O, 23.5g Al (NO
3)
39H
2O and 15.1g Cu (NO
3)
23H
2O is dissolved in the 1000 mL deionized waters.Simultaneously, take by weighing 56g NH
4HCO
3Be dissolved in the 700 mL deionized waters, with metal salt solution and precipitating reagent at room temperature and flow co-precipitation, keeping the pH value of solution value in the precipitation process is 12.After deposition finishes, handled 4 hours in 70 ℃ of constant temperature, the gained sedimentation and filtration; Spend deionised water to filtrating and be neutral; And 130 ℃ of dryings 8 hours, grind into powder placed 450 ℃ Muffle furnace roasting 2 hours; After extrusion modling under the pressure of 25kN, with its fragmentation, sieving obtains 20～40 purpose catalyst granules.
The assessment experiment:Activity of such catalysts is evaluated in the atmospheric fixed bed reactor carries out, catalyst amount 1.0 mL, and the dry gas air speed is 2500 h
-1, H
2O/CO=2.The unstripped gas composition is seen table 1, and catalyst at 200 ℃ of reductase 12 h, is surveyed its activity with unstripped gas then between 250 ~ 550 ℃, and activity representes that with the CO conversion ratio experimental result is as shown in table 2.Water gas shift reaction CO (g)+H
2O (g) CO
2(g)+H
2(g) CO conversion ratio is meant that CO changes into CO
2Percentage, computing formula is following:
The CO conversion ratio=(1-
Y CO, out /
Y CO, in ) * 100%/(1+
Y CO, out )
In the formula,
Y CO, in The mole percent of CO in the expression original gas,
Y CO, out The mole percent of CO in the gas after the expression conversion.
Table 1
| Form | H 2 | CO | CO 2 | CH 4 |
| Volumn concentration, % | 72.25 | 25.21 | 1.69 | 0.85 |
Can obtain from Fig. 1, the catalyst of different proportionings (250 ~ 550 ℃) in wider temperature range all has catalytic activity preferably, explains that this catalyst not only is applicable to low temperature shift reaction but also can be applied to high temperature shift technology.As can beappreciated from fig. 2 catalyst is heat-resisting back in 350 ℃, H
2The heat-resisting activity of operation after 110 hours still maintains more than 86% under the condition of O/CO=2, has CO conversion ratio advantage (activity of patent CN101227975A report is about 60%) clearly; Heat-resisting activity is along with the trend of rising gradually that is of test, and this is because catalyst is restored in its activity of lower temperature spot after heat-resisting gradually.As can beappreciated from fig. 3 catalyst can be under the low steam carbon ratio condition can be good operation, under the prerequisite that guarantees greater activity, this helps reducing the required significant amount of energy of vaporize water steam.Catalyst of the present invention has advantages of high catalytic activity and heat endurance and can be applied under the flexible and changeable water gas shift conditions, so this catalyst has the favorable industrial application prospect.
Table 2
| Embodiment | Catalyst is formed | The CO conversion ratio, % (450 ℃) |
| Embodiment 1 | n(Fe):n(Al):n(Cu)=1:1:0.1 | 88.16 |
| Embodiment 2 | n(Fe):n(Al):n(Cu)=1:1:0.2 | 91.68 |
| Embodiment 3 | n(Fe):n(Al):n(Cu)=1:1:0.5 | 91.15 |
| Embodiment 4 | n(Fe):n(Al):n(Cu)=1:1:1 | 92.82 |
| Embodiment 5 | n(Fe):n(Al):n(Cu)=1:0.5:0.5 | 90.42 |
Claims (2)
1. an iron is water gas converting catalyst, it is characterized in that being made up of the oxide of iron, aluminium, copper, and the mol ratio of each metallic element is n (Fe): n (Al): n (Cu)=1: (0.5 ~ 1): (0.1 ~ 1).
2. one kind prepares the method that iron according to claim 1 is water gas converting catalyst, it is characterized in that preparation technology adopts coprecipitation, mainly comprises following steps:
Press the element of catalyst and form, dispose a certain amount of Fe
3+, Al
3+And Cu
2+Mixed aqueous solution, the metal ion molar concentration is 0.25 ~ 0.26 mol/L; Said Fe
3+Lead compound be in ferric nitrate, ferric sulfate, the iron chloride any; Described Al
3+Lead compound be in aluminum nitrate, aluminum sulfate, the aluminium chloride any; Described Cu
2+Be in copper nitrate, copper sulphate, the copper chloride any;
The configuration precipitating reagent aqueous solution: the mass concentration of the precipitating reagent aqueous solution is 1 mol/L; Precipitating reagent is any in NaOH, potassium hydroxide, sodium acid carbonate, the carbonic hydroammonium;
Above-mentioned metal ion mixed aqueous solution and the alkaline precipitating agent aqueous solution and drip are gone into carrying out neutralization precipitation in the beaker of agitating device; Mixing speed is 150 rev/mins; Precipitation reaction is carried out under 5 ~ 30 ℃ of room temperatures, the pH value that keeps mixed liquor in the N-process between 9 ~ 12, neutralize finish after with sediment the boiling of heat that heat up; Curing temperature is controlled between 40 ~ 75 ℃, and the curing time is 5 ~ 24 hours;
The above-mentioned sediment for preparing is carried out decompress filter, and cakes with deionized water washing to filtrating is neutral, and drying is 12 ~ 24 hours in 100 ~ 150 ℃ drying box; Grind to form fine powder then, roasting is 2 ~ 5 hours in 300 ~ 450 ℃ Muffle furnace; Powder after the roasting is extrusion modling in mould under the pressure of 20 ~ 35 kN; With after broken, sieve, obtaining particle diameter is 20～40 purpose particles, is Fe-Al-Cu water gas converting catalyst finished product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055865A (en) * | 2013-01-04 | 2013-04-24 | 福州大学 | Cu-Fe coupled carbon monoxide wide-temperature shift catalyst and preparation method thereof |
| CN108264081A (en) * | 2016-12-30 | 2018-07-10 | 海门市源美美术图案设计有限公司 | A kind of aluminium oxide and oxidation carbon/carbon-copper composite material and preparation method thereof |
| CN108479785A (en) * | 2018-04-16 | 2018-09-04 | 深圳市国能环保科技有限公司 | A kind of anti-applications catalyst of high-temperature water gas conversion and its manufacturing method |
| CN109847748A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of water-gas shift catalyst and preparation method |
| CN110562913A (en) * | 2019-09-30 | 2019-12-13 | 内蒙古大学 | method for producing hydrogen by using methane and water as raw materials |
| CN112839736A (en) * | 2018-10-15 | 2021-05-25 | 浦项产业科学硏究院 | Medium-temperature water gas shift reaction catalyst, preparation method thereof and method for preparing hydrogen by using same |
| CN114534784A (en) * | 2022-02-21 | 2022-05-27 | 浙江师范大学 | High-temperature water-gas shift catalyst, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101227975A (en) * | 2005-06-15 | 2008-07-23 | 俄亥俄州立大学 | Catalyst for hydrogen production from water gas shift reaction |
| CN101518737A (en) * | 2009-03-26 | 2009-09-02 | 上海大学 | Catalyst for shifting carbon monoxide by water gas reaction in hydrogen-rich fuel gas and preparation method thereof |
-
2011
- 2011-08-31 CN CN201110254193XA patent/CN102350355A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101227975A (en) * | 2005-06-15 | 2008-07-23 | 俄亥俄州立大学 | Catalyst for hydrogen production from water gas shift reaction |
| CN101518737A (en) * | 2009-03-26 | 2009-09-02 | 上海大学 | Catalyst for shifting carbon monoxide by water gas reaction in hydrogen-rich fuel gas and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103055865A (en) * | 2013-01-04 | 2013-04-24 | 福州大学 | Cu-Fe coupled carbon monoxide wide-temperature shift catalyst and preparation method thereof |
| CN108264081A (en) * | 2016-12-30 | 2018-07-10 | 海门市源美美术图案设计有限公司 | A kind of aluminium oxide and oxidation carbon/carbon-copper composite material and preparation method thereof |
| CN109847748A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院大连化学物理研究所 | A kind of water-gas shift catalyst and preparation method |
| CN108479785A (en) * | 2018-04-16 | 2018-09-04 | 深圳市国能环保科技有限公司 | A kind of anti-applications catalyst of high-temperature water gas conversion and its manufacturing method |
| CN112839736A (en) * | 2018-10-15 | 2021-05-25 | 浦项产业科学硏究院 | Medium-temperature water gas shift reaction catalyst, preparation method thereof and method for preparing hydrogen by using same |
| CN110562913A (en) * | 2019-09-30 | 2019-12-13 | 内蒙古大学 | method for producing hydrogen by using methane and water as raw materials |
| CN114534784A (en) * | 2022-02-21 | 2022-05-27 | 浙江师范大学 | High-temperature water-gas shift catalyst, and preparation method and application thereof |
| CN114534784B (en) * | 2022-02-21 | 2023-10-20 | 浙江师范大学 | High-temperature water-gas shift catalyst and preparation method and application thereof |
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Application publication date: 20120215 |