CN101062480A - Catalyst for removing carbon oxides in gas - Google Patents
Catalyst for removing carbon oxides in gas Download PDFInfo
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- CN101062480A CN101062480A CN 200610078651 CN200610078651A CN101062480A CN 101062480 A CN101062480 A CN 101062480A CN 200610078651 CN200610078651 CN 200610078651 CN 200610078651 A CN200610078651 A CN 200610078651A CN 101062480 A CN101062480 A CN 101062480A
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Abstract
The invention relates to the catalyst for removing impurities from gases to solve existing issue like high temperature and poor stability, improving adding catalyst element Tin and Mn, or La, Ce, or Yt or sodium with high reactive feature and fine stability.
Description
Technical field
The present invention relates to a kind of catalyst that removes oxycarbide in the gas, specifically, the present invention relates to a kind of catalyst that removes the small amount of carbon oxide in ammonia-preparing device process gas or the ethylene unit hydrogen-rich gas.
Background technology
Remove in the catalyst of oxycarbide (methanation) existing, generally adopt nickel or add other on this basis and help catalyst component, for example RU 2185240 and RU 2186623 disclose and have helped catalyst component chromium, potassium, sodium, silicon, iron, calcium, magnesium; CN 1043639A discloses and has helped catalyst component barium, sodium; CN 1016146B discloses and has helped catalyst component rare earth element and magnesium; US 4,132, and the nickel content of 672 open catalyst is 25%, and helping catalyst component is iridium, and its content is 0.1%～1%, serviceability temperature 350-500 ℃.In addition, the disclosed catalyst component that helps also has chromium, cobalt, zirconium, copper at present, but the serviceability temperature of above-mentioned catalyst is high temperature.
Though above-mentioned document adds the effect that helps catalyst component to have to improve catalyst activity, its main purpose is in order to improve the high-temperature heat-resistance performance of catalyst, to make catalyst have long service life.
Although existing methanation catalyst added above-mentioned help catalyst component after, active and hear resistance all there is certain facilitation, but still there is following shortcoming: one, at low temperatures active relatively low of existing methanation catalyst, in order to obtain high reaction activity and high, reaction temperature must be increased to about 300 ℃.Yet the nickel crystallite in the nickel catalyst is at high temperature grown up easily, thereby influences life of catalyst.Two, from the angle of technology, raw material is heated to 280～350 ℃ step by step from-160 ℃ must uses the high steam heat exchanger, the requirement height to equipment easily produces problems such as run, drip, leak, influences the normal operation of device, the running cost height.Three, high-temperature methanation catalyst must have the shortcoming of high energy consumption, yet the energy is more and more nervous, so high-temperature methanation catalyst can not adapt to the requirement of modern energy saving technique.
Summary of the invention
The problem of the present invention's and poor stability high for the serviceability temperature that solves the existing catalyst that removes oxycarbide in the gas and exist proposes a kind of methanation catalyst that has activity height and good stability under lower temperature and high-speed.
The present invention adopts nickel-base catalyst, adds some metallic elements and help catalyst component in catalyst, improves the activity of catalyst under low temperature and high-speed, and adds these and help catalyst component can improve the stability of catalyst.
Concrete technical scheme is as follows.
Of the present inventionly remove the component that the catalyst of oxycarbide in the gas comprises following weight percentage, based on the gross weight of described catalyst:
5%～60% nickel, 0.25%～15% tin, 2%～20% manganese, 30%～90% carrier.
Catalyst of the present invention preferably also comprises 0%～15% lanthanum, cerium, yttrium or their mixture.Can be independent lanthanum, cerium, yttrium, also can be any combination of two kinds in them, can also be their any combinations of three kinds.Described any combination is meant that there is no particular limitation to the component ratio in the combination.
Catalyst of the present invention preferably also comprises 0%～5% alkali metal and/or alkaline-earth metal.Can be a kind of separately in alkali metal and the alkaline-earth metal, also can be two or more any combination in them.Described alkali metal is preferably sodium or potassium; Described alkaline-earth metal is preferably magnesium, calcium, strontium or barium.
Employed carrier is preferably aluminium oxide, silica, titanium dioxide, zirconium dioxide or their mixture among the present invention.If using their mixture can be the mixture of the arbitrary proportion composition of the carrier of any kind in the above-mentioned carrier.For example the carrier of Shi Yonging can be the mixture of aluminium oxide and silica, and the proportion of composing between aluminium oxide and the silica is arbitrarily.
There is no particular limitation to the shape of catalyst of the present invention.For example catalyst component of the present invention can be loaded on difform aluminium oxide, silica, titanium dioxide, zirconium dioxide or its mixture, for example sphere, strip, sheet, clover shape, tooth are spherical.Catalyst component of the present invention also can with above-mentioned carrier coprecipitation, be shaped to difformity then.There is no particular limitation to size of catalyst, and those skilled in the art can select its size according to general knowledge.For example, when catalyst of the present invention was spherical, the diameter of catalyst granules can be 2～6mm, is preferably 2～4mm.When catalyst of the present invention was bar shaped, preferred diameter was 2～4mm, and bar length is 3～10mm.
Preparation of catalysts method of the present invention is not had special requirement, can use the method for preparing catalyst that those skilled in the art will know that.Be that example makes an explanation below with the infusion process.
Catalyst component of the present invention is more, can adopt the single-steeping method, once all catalyst components is immersed on the carrier, also can adopt the graded impregnation method, different catalyst components progressively is immersed on the carrier, and perhaps with these component groupings, graded impregnation is on carrier.
At first according to the concrete dipping method of taking, parent wiring solution-forming with catalyst component, porous carrier is contacted with the solution of preparation, remove excess liquid, each dipping back is dry down at 110～300 ℃, again 350～600 ℃ of high-temperature roastings, under hydrogen atmosphere, reduce at last behind each dipping or the whole dipping.
The parent of described catalyst component is to dissolve in the solvent, and at high temperature can be decomposed into the parent of metal oxide, is generally the salt of the catalytic metal component of catalyst.
The parent of described nickel can be various inorganic salts or organic salt, for example is nickel nitrate, nickel acetate, basic nickel carbonate, nickelous carbonate, nickel formate etc.The parent of described tin can be a nitric acid tin.The parent of described manganese can be a manganese nitrate.The parent of rare earth metal can be a nitrate, as lanthanum nitrate, and cerous nitrate, yttrium nitrate etc.; It also can be the mixture of several rare earths.The parent of described alkali metal and alkaline-earth metal can be their hydroxide, nitrate, carbonate etc.
The employed solvent of the parent of catalytic dissolution component can be any solvent that can dissolve these compounds, for example water, ethanol, methyl alcohol, acetone, acetate etc., preferred water or ethanol.
Because the particular components of above-mentioned catalyst of the present invention particularly because catalyst of the present invention has added tin and these two kinds of active components of manganese, makes catalyst of the present invention have high low temperature active and stability.
Catalyst of the present invention can be used for removing ammonia-preparing device process gas or ethylene unit hydrogen-rich gas small amount of carbon oxide.
Catalyst of the present invention also can be used for other hydrogenation reaction, the hydrogenation of C2-C10 unsaturated hydrocarbons for example, and specifically, for example diolefin is hydrogenated to monoolefine, hydrogenation of olefins is alkane, alkynes hydrogenation and nitro compound hydrogenation system amines.
Description of drawings
Fig. 1 is the figure of stability assessment result of the test of the catalyst of expression embodiments of the invention 3.
The specific embodiment
Further explain the present invention in the mode of embodiment below, but the present invention is not limited to these embodiment.In the following embodiments, percentage all is that the gross weight with catalyst is the percentage by weight of benchmark, the ppm of unit represents * and 10
-6(v/v).
Take by weighing through commercially available BYAC-206 alumina support 120 grams of 600 ℃ of roastings after 4 hours, with 8 gram stannous chloride (SnCl
22H
2O) be dissolved in 120 milliliters the ethanol and make ethanolic solution, this solution impregnation to above-mentioned carrier, 110 ℃ of oven dry 4 hours down, is obtained A.
With 450 gram nickel nitrate [Ni (NO
3)
26H
2O] and 52 gram manganese nitrates be dissolved in 60 milliliters the water, make solution, with this solution impregnation to A.Dried 5 hours down at 110 ℃, obtain B.
B is placed in the stainless steel tube that is connected with air, and decomposition obtained C in 5 hours under 300 ℃, made the catalyst 1 of present embodiment like this.This catalyst 1 contains 40% nickel, 5% manganese, 2% tin, and surplus is an alumina support.
Embodiment 2
Take by weighing through alumina support 240 gram of 500 ℃ of roastings after 4 hours, this carrier is identical with carrier among the embodiment 1, and different is with 6.5 gram stannous chloride (SnCl
22H
2O) be dissolved in 260 milliliters the ethanol, 345 gram nickel nitrates and 160 gram manganese nitrates be dissolved in 310 milliliters the water and make solution respectively, the method for dipping stannous chloride, nickel nitrate and manganese nitrate is identical with embodiment 1, obtains the catalyst 2 of present embodiment.After the identical decomposition and reduction of embodiment 1, this catalyst 2 contains 20% nickel, 1% tin, 10% manganese, and surplus is an alumina support.
Embodiment 3
Take by weighing through alumina support 160 gram of 580 ℃ of roastings after 4 hours, this carrier is identical with carrier among the embodiment 1, with the lanthanum nitrate [La (NO of 32 grams
3)
36H
2O] be dissolved in 160 milliliters the water and make solution, be impregnated into then on the carrier, 110 ℃ of oven dry 4 hours down, obtain D.
With 12 gram stannous chloride (SnCl
22H
2O) be dissolved in 160 milliliters the ethanol and make solution, be impregnated into then on the D,, obtain E 110 ℃ of oven dry 4 hours down.
With 450 gram nickel nitrate [Ni (NO
3)
26H
2O] and 140 gram manganese nitrates be dissolved in 100 milliliters the water and make solution, be impregnated on the E then.Dried 5 hours down at 110 ℃, obtain F.
F is placed in the stainless steel tube that is connected with air, decomposed 5 hours in 350 ℃.After the reduction, this catalyst 3 contains 30% nickel, 10% manganese, 3% tin, 5% lanthanum, and surplus is an alumina support.
Embodiment 4
Take by weighing through alumina support 160 gram of 500 ℃ of roastings after 4 hours, this carrier is identical with carrier among the embodiment 1,3.8 gram potassium hydroxide is dissolved in 180 milliliters the water and makes solution, it is impregnated on the carrier, 110 ℃ of oven dry down,, obtain G 600 ℃ of following roastings 4 hours.
10 gram stannous chlorides are dissolved in 175 milliliters the ethanol make solution, flood G, obtain H with it.
23 gram yttrium nitrates, 330 gram nickel nitrates and 120 gram manganese nitrates are dissolved in 180 milliliters the water make solution, be divided into twice and be impregnated on the H, obtain I.I is placed in the stainless steel tube that is connected with air, and in 350 ℃ of decomposition 5 hours, this catalyst contained 25% nickel, 10% manganese, 2% tin, 2% yttrium, 1% potassium, and surplus is an alumina support.
Embodiment 5
Take by weighing through alumina support 160 grams of 800 ℃ of roastings after 4 hours, this carrier is identical with carrier among the embodiment 1, at first be dissolved in 135 milliliters the water and make solution impregnation to carrier with the magnesium nitrates of 59 grams, flood stannous chloride, yttrium nitrate, nickel nitrate and manganese nitrate with the same way as of embodiment 4 then, 400 ℃ of following roastings 4 hours, the catalyst that makes contains 25% nickel, 10% manganese, 1% tin, 2% yttrium, 2% magnesium, and surplus is an alumina support.
Comparative Examples 1
Take by weighing 480 gram nickel nitrates, 15 gram copper nitrates, 2.4 gram chromic nitrates and 3.0 gram ferric nitrates, be dissolved in water, be made into the solution of 1.5 mol, then this mixed solution is joined under constantly stirring in excessive 5% the 4 mol sodium carbonate liquors and carry out co-precipitation.The control precipitation temperature is 80～85 ℃, and endpoint pH is controlled to be neutrality, and after the material of post precipitation was removed nitrate anion through filtration, washing, oven dry was 5 hours under 110 ℃.400 ℃ of following roastings, granulation mixes with 100 gram silica supports by proportioning, and last compression molding, the catalyst that makes contain 48% nickel, 2% copper, 0.2% iron and 0.15% chromium, and all the other are silica supports.
Comparative Examples 2
Prepare Ni-La-Mg/Al according to CN 1016146B
2O
3Catalyst, this catalyst contain 30% nickel, 14% magnesia, 10% lanthana.
Comparative Examples 3
Take by weighing through alumina support 160 grams of 500 ℃ of roastings after 4 hours, this carrier is identical with carrier among the embodiment 1,1.8 gram potassium hydroxide is dissolved in 100 milliliters the water and makes solution, and it is impregnated on the carrier, 110 ℃ of oven dry down, obtained H in 4 hours 600 ℃ of following roastings.
370 gram nickel nitrates and 55 gram yttrium nitrates are dissolved in 60 milliliters the water make solution, this solution is impregnated on the H at twice.
Dried 5 hours down at 110 ℃, 400 ℃ of following roastings 4 hours, the catalyst that makes contained 30% nickel, 5% yttrium, 0.5% potassium, and all the other are carrier.
Embodiment 6
Present embodiment is the evaluating catalyst example.
The catalyst of top embodiment and Comparative Examples preparation is respectively charged into fixed-bed tube reactor, under 400 ℃ of temperature and pressure 3.0MPa, uses hydrogen reducing 6 hours, the hydrogen volume air speed is 2500h
-1, be cooled to reaction temperature, feed unstripped gas, this unstripped gas contains 95% H
2, 0.4% oxycarbide and the methane of surplus, the feed gas volume air speed is 10000h
-1, carry out evaluation test, the results are shown in table 1.
Table 1
| Embodiment | The content of oxycarbide (weight %) in the unstripped gas | Reaction temperature (℃) | Oxycarbide content (ppm by weight) in the |
| Embodiment | |||
| 1 | 0.4 | 170 | Less than 1 |
| Embodiment 2 | 0.4 | 170 | Less than 1 |
| Embodiment 3 | 0.4 | 170 | Less than 1 |
| Embodiment 4 | 0.4 | 170 | Less than 1 |
| Embodiment 5 | 0.4 | 170 | Less than 1 |
| Comparative example 1 | 0.4 | 170 | 113 |
| Comparative example 2 | 0.4 | 170 | 817 |
| Comparative example 3 | 0.4 | 170 | 820 |
As can be seen from Table 1, catalyst of the present invention has high catalytic activity at low temperatures, at 10000h
-1Oxycarbide in the unstripped gas can be removed under the 1ppm under the air speed, and the catalyst of Comparative Examples can not effectively remove the oxycarbide in the gas.
Embodiment 7
Present embodiment is the catalytic performance of the catalyst of the catalyst of comparative example 3 under different reaction temperatures and Comparative Examples 1.
Concrete test method is identical with embodiment 6 with condition, and different is to change reaction temperature, the catalytic performance of evaluate catalysts under different reaction temperatures.Result of the test is illustrated in the table 2.
Table 2 catalyst of the present invention and comparative example 1 comparison of test results
| Catalyst | Material carbon oxide content % | Reaction condition | Oxycarbide conversion ratio % | |
| Temperature ℃ | Air speed h -1 | |||
| Embodiment 3 | 0.42 | 140 | 10000 | 30.66 |
| 150 | 10000 | 50.24 | ||
| 160 | 10000 | 94.99 | ||
| 170 | 10000 | 100.00 | ||
| Comparative Examples 1 | 0.42 | 140 | 10000 | 19.37 |
| 150 | 10000 | 27.88 | ||
| 160 | 10000 | 50.60 | ||
| 170 | 10000 | 91.00 | ||
From the result of table 2 as can be seen, in 140 ℃～170 ℃ scopes of temperature, under identical reaction condition, the catalytic performance of catalyst of the present invention is apparently higher than the catalyst of Comparative Examples 1.
Embodiment 8
Present embodiment is the stability test of examination catalyst of the present invention.
With the catalyst of embodiment 3 fixed-bed tube reactor of packing into, fed hydrogen reducings 6 hours down for 400 ℃ in temperature, the hydrogen volume air speed is 2500h
-1, be cooled to 170 ℃ then, under the 3.0MPa pressure condition, feed unstripped gas, this unstripped gas contains 95% H
2, 0.4% oxycarbide and the methane of surplus, the feed gas volume air speed is 10000h
-1, carry out stability test.Reaction result is illustrated among Fig. 1.In Fig. 1, abscissa is represented the accumulated time of evaluating catalyst test, and unit be hour, and the ordinate on the left side is CO and export CH in the unstripped gas
4Content, unit is ppm, the ordinate on the right be the outlet CO content, unit is ppm.
Find out obviously that from Fig. 1 catalyst of the present invention has good stable.
Claims (5)
1. a catalyst that removes oxycarbide in the gas is characterized in that, based on the gross weight of described catalyst, it comprises the component of following weight percentage:
5%～60% nickel, 0.25%～15% tin, 2%～20% manganese, 30%～90% carrier.
2. catalyst as claimed in claim 1 is characterized in that, it also comprises 0%～15% lanthanum, cerium, yttrium or their mixture.
3. catalyst as claimed in claim 1 or 2 is characterized in that, it also comprises 0%～5% alkali metal and/or alkaline-earth metal.
4. catalyst as claimed in claim 3 is characterized in that, described alkali metal is sodium or potassium; Described alkaline-earth metal is magnesium, calcium, strontium or barium.
5. catalyst as claimed in claim 1 is characterized in that, described carrier is aluminium oxide, silica, titanium dioxide, zirconium dioxide or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100786518A CN100490972C (en) | 2006-04-29 | 2006-04-29 | Catalyst for removing carbon oxides in gas |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100786518A CN100490972C (en) | 2006-04-29 | 2006-04-29 | Catalyst for removing carbon oxides in gas |
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|---|---|
| CN101062480A true CN101062480A (en) | 2007-10-31 |
| CN100490972C CN100490972C (en) | 2009-05-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100786518A Active CN100490972C (en) | 2006-04-29 | 2006-04-29 | Catalyst for removing carbon oxides in gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105289622A (en) * | 2015-11-11 | 2016-02-03 | 中国石油大学(华东) | Catalyst used for dehydrogenation preparation of monoolefine by saturated alkane |
| CN105413700A (en) * | 2014-09-17 | 2016-03-23 | 中国石油化工股份有限公司 | Catalyst for preparing ethylidene diacetate |
-
2006
- 2006-04-29 CN CNB2006100786518A patent/CN100490972C/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105413700A (en) * | 2014-09-17 | 2016-03-23 | 中国石油化工股份有限公司 | Catalyst for preparing ethylidene diacetate |
| CN105413700B (en) * | 2014-09-17 | 2018-01-09 | 中国石油化工股份有限公司 | For preparing the catalyst of ethylidene diacetate |
| CN105289622A (en) * | 2015-11-11 | 2016-02-03 | 中国石油大学(华东) | Catalyst used for dehydrogenation preparation of monoolefine by saturated alkane |
| CN105289622B (en) * | 2015-11-11 | 2019-01-08 | 中国石油大学(华东) | Saturated alkane dehydrogenation prepares the application of the catalyst of monoolefine |
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| Publication number | Publication date |
|---|---|
| CN100490972C (en) | 2009-05-27 |
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