CN102218295A - Removing agent for removing carbonyl iron and carbonyl nickel in syngas and preparation method thereof - Google Patents
Removing agent for removing carbonyl iron and carbonyl nickel in syngas and preparation method thereof Download PDFInfo
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- CN102218295A CN102218295A CN2010101470646A CN201010147064A CN102218295A CN 102218295 A CN102218295 A CN 102218295A CN 2010101470646 A CN2010101470646 A CN 2010101470646A CN 201010147064 A CN201010147064 A CN 201010147064A CN 102218295 A CN102218295 A CN 102218295A
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Abstract
The invention relates to a removing agent for removing carbonyl iron and carbonyl nickel in syngas and a preparation method thereof, and mainly solves the problem in the prior art that carbonyl iron and carbonyl nickel in raw material syngas can cause catalyst poisoning and thereby influence the product yield and the catalyst life. Through the technical scheme that carbonyl iron and carbonyl nickel in syngas are removed by using a removing agent with copper or its oxides as main metal components and alkali metal magnesium, potassium, calcium, or their oxides and mixtures as auxiliary metal components, the invention solves the problem well, and is applicable to the industrial production of preparing C2+-oxygenates by syngas.
Description
Technical field
The present invention relates to a kind of remove carbonyl iron and carbonyl nickel in the synthesis gas remove agent and preparation method thereof.
Background technology
Carbonyl iron in the synthesis gas and carbonyl nickel generally are by wherein CO stainless steel equipment and corrosive pipeline to be formed.Li Xuanzhi etc. are at " Industrial Catalysis " (Oct.2006, Vol.14, No.10, P28～30) reported in " carbonyl metal compound is to the influence and the countermeasure of catalyst in the methyl methanol syngas " literary composition in methanol industry is produced, under low relatively temperature and extra high pressure, the stainless steel pipes surface component that a large amount of CO that contain in the unstrpped gas can be contacted with it reacts and forms carbonyl iron Fe (CO)
5, carbonyl nickel (CO)
4After these carbonyl irons and carbonyl nickel enter reaction system; can under reaction temperature, decompose; and finally cause catalyst activity to descend fast; shorten catalyst life; and influence the methanol product quality; therefore material synthesis gas enters and uses before the reaction system adsorbent to remove wherein carbonyl iron, carbonyl nickel earlier in the industrial production, to play the effect of guard catalyst.
Laboratory synthesis gas system C
2Above oxygenatedchemicals (C
2Material synthesis gas in the catalytic reaction of+-oxygenates) can contain carbonyl iron and carbonyl nickel equally, generally all comes from the corrosion of high pressure CO to the steel cylinder inner surface.If these carbonyl irons and carbonyl nickel do not remove before reaction, the iron that decomposes under reaction temperature, nickel not only can progressively be deposited on catalyst surface, destroy catalyst active center, make catalyst activity reduction; More because synthesis gas system C
2Above oxygenatedchemicals is a hydrogenation reaction, and iron, nickel are good hydrogenation activity components, therefore can the transition hydrogenation and produce serious side reaction, generates a large amount of hydrocarbon products, reduction C
2The selectivity of above oxygenatedchemicals and space-time yield; The iron, nickel that cover catalyst surface simultaneously can the blocking catalyst holes, not only influence activity of such catalysts, and the heat that reaction is generated can not in time be taken away and influence life of catalyst.Therefore, first preliminary treatment synthesis gas is very necessary to remove carbonyl iron and carbonyl nickel before reacting, and at present for synthesis gas system C
2The removal methods of carbonyl iron and carbonyl nickel rarely has report in the unstripped gas of above oxygenatedchemicals.
Summary of the invention
One of technical problem to be solved by this invention is existing synthesis gas system C
2Above oxygenatedchemicals (C
2Carbonyl iron and carbonyl nickel can cause catalyst poisoning in the material synthesis gas that exists in the technology of+-oxygenates), thereby influence the problem of product yield and catalyst life, and a kind of new agent that removes that removes carbonyl iron and carbonyl nickel in the synthesis gas is provided.This remove agent have carbonyl iron and carbonyl nickel removal effect good, thereby the synthesis gas system of making C
2In the course of reaction of above oxygenatedchemicals, the purpose product C
2Above oxygenatedchemicals (C
2The yield height of+-oxygenates), the advantage of catalyst long service life.Two of technical problem to be solved by this invention provides one of a kind of and the technical solution problem corresponding preparation method who removes agent.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of agent that removes that removes carbonyl iron and carbonyl nickel in the synthesis gas comprises following component by weight percentage:
A) 0.5～20% copper or its oxide;
B) 0.5～30% magnesium, potassium, calcium or its oxide and composition thereof;
C) γ-Al of 50～99%
2O
3Carrier.
In the technique scheme, the consumption preferable range of copper or its oxide is 0.8～15% by weight percentage; The consumption preferable range of magnesium, potassium, calcium or its oxide and composition thereof is 0.8～20%; Carrier γ-Al
2O
3The consumption preferable range be 65～98.4%%.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method who removes agent who removes carbonyl iron and carbonyl nickel in the synthesis gas may further comprise the steps:
A) salt with magnesium, potassium, calcium or its mixture of the mantoquita of aequum and aequum is mixed with solution I;
B) with the γ-Al of aequum
2O
3Carrier with the dipping method, with the activity component impregnation in the solution I to γ-Al
2O
3On the carrier, obtain removing agent presoma I;
C) will remove agent presoma I dry under 80～150 ℃ of conditions, roasting obtains the required agent product that removes under 300～600 ℃ of conditions.
In the technique scheme, preparation removes that the salt preferred version that removes the needed mantoquita of agent and magnesium, potassium, calcium or its mixture of carbonyl iron and carbonyl nickel is a nitrate in the synthesis gas; The dipping method preferred version is with equal-volume method dipping, and places 2～7 hours in room temperature; Remove agent presoma I preferred version and be under 80～130 ℃ of conditions dry 1～36 hour; Roasting is 2～6 hours under 320～550 ℃ of conditions.
Of the present invention to remove its active main metal component copper of agent be the group vib metal, and high degree of dispersion is at the γ-Al of high-ratio surface
2O
3On the carrier, come complexing absorption carbonyl iron and carbonyl nickel mutually with its activity, thereby from synthesis gas, remove carbonyl iron, carbonyl nickel effectively.This class removes the synthetic and hydrogenation reaction of catalysis does not take place when agent removes carbonyl iron and carbonyl nickel from synthesis gas, thereby not only solved effectively in the reaction and constantly be adsorbed in the problem that catalyst surface causes catalyst performance decline, shortening in service life because carbonyl iron and carbonyl nickel decompose the iron, the nickel that produce, the existence that has also solved owing to carbonyl iron in the unstripped gas and carbonyl nickel produces serious side reaction, thereby causes the purpose product C
2The problem that above oxygenatedchemicals yield descends.
Using the agent that removes that removes carbonyl iron and carbonyl nickel in the synthesis gas provided by the invention, is being unstripped gas with the synthesis gas, and the reaction pressure that removes carbonyl iron and carbonyl nickel is that 2～5MPa, reaction velocity are 9000h
-1～15000h
-1, to remove temperature be under 150～200 ℃ the condition, to be used for synthesis gas system C
2The catalytic reaction of above oxygenatedchemicals, reaction pressure and reaction velocity and the reacting phase that removes carbonyl iron, carbonyl nickel with, the catalytic reaction temperature is 320 ℃, the result and the reacting phase that need not remove agent are relatively, the CO conversion ratio can rise to more than 14.8% target product C from 5.6% in the material synthesis gas
2Above oxygenatedchemicals (C
2The space-time yield of+-oxygenates) is risen to more than the 353.7g/kg.h by 85.2g/kg.h, and catalyst life rose to more than 200 hours by 50.2 hours, obtained better technical effect.
The invention will be further described below by example, but do not limit its scope.
The specific embodiment
Following example is all according to γ-Al
2O
3The mixed aqueous solution of water absorption rate preparation dipping usefulness, adopt equal-volume method dipping, each constituent content is the percentage with respect to catalyst weight in the catalyst.
[embodiment 1]
Take by weighing 1.65g potassium nitrate, 3.1g copper nitrate (containing 6 crystallizations water), add the 4.5g deionized water, after copper nitrate, potassium nitrate dissolving mix, add 5.0g γ-Al again
2O
3, flood and put into baking oven after 5 hours in 100 ℃ of dryings 18 hours, at last in 600 ℃ of roastings 2 hours.Obtain Cu (10.5%)-K (10.1%)/γ-Al
2O
3(79.4%) removes agent, be numbered T-1.
[embodiment 2]
Take by weighing 19.1g magnesium nitrate (containing 6 crystallizations water), 7.4g copper nitrate (containing 6 crystallizations water) is dissolved in the 3.0g deionized water, mix the back and add 5.0g γ Al
2O
3, flood and put into baking oven after 2 hours in 80 ℃ of dryings 36 hours, at last in 500 ℃ of roastings 4.Obtain CuO (20%)-MgO (30%)/γ-Al
2O
3(50%) removes agent, be numbered T-2.
[embodiment 3]
Take by weighing 9.9g magnesium nitrate (containing 6 crystallizations water), 1.45g copper nitrate (containing 6 crystallizations water) is dissolved in the 2.3g deionized water, mix the back and add 5.0g γ Al
2O
3, flood and put into baking oven after 7 hours in 150 ℃ of dryings 1 hour, at last in 300 ℃ of roastings 6 hours.Obtain Cu (5%)-Mg (15%)/γ-Al
2O
3(80%) removes agent, be numbered T-3.
[embodiment 4]
Take by weighing 0.31g magnesium nitrate (containing 6 crystallizations water), 4.13g copper nitrate (containing 6 crystallizations water) is dissolved in the 4.0g deionized water, mix the back and add 5.0g γ Al
2O
3, flood and put into baking oven after 5 hours in 100 ℃ of dryings 12 hours, at last in 550 ℃ of roastings 3 hours.Obtain Cu (15%)-Mg (0.5%)/γ-Al
2O
3(84.5%) removes agent, be numbered T-4.
[embodiment 5]
Take by weighing 3.8g magnesium nitrate (containing 6 crystallizations water), 4.4g copper nitrate (containing 6 crystallizations water) is dissolved in the 3.0g deionized water, mix the back and add 5.0g γ-Al
2O
3, flood and put into baking oven after 4 hours in 120 ℃ of dryings 16 hours, at last in 400 ℃ of roastings 5 hours.Obtain Cu (15%)-Mg (5.7%)/γ-Al
2O
3(79.3%) removes agent, be numbered T-5.
[embodiment 6]
Take by weighing 0.27g magnesium nitrate (containing 6 crystallizations water), 0.12g copper nitrate (containing 6 crystallizations water) is dissolved in the 5.5g deionized water, mix the back and add 5.0g γ-Al
2O
3, flood and put into baking oven after 5 hours in 100 ℃ of dryings 18 hours, at last in 450 ℃ of roastings 4 hours.Obtain Cu (0.5%)-Mg (0.5%)/γ-Al
2O
3(99%) removes agent, be numbered T-6.
[embodiment 7]
Take by weighing 3.62g magnesium nitrate (containing 6 crystallizations water), 2.94g copper nitrate (containing 6 crystallizations water), 0.14g potassium nitrate and be dissolved in the 3.1g deionized water, mix the back and add 5.0g γ-Al
2O
3, flood and put into baking oven after 5 hours in 100 ℃ of dryings 18 hours, at last in 450 ℃ of roastings 4 hours.Obtain Cu (10.5%)-Mg (5.7%)-K (0.85%)/γ-Al
2O
3(82.95%) removes agent, be numbered T-7.
[embodiment 8]
Take by weighing 3.62g magnesium nitrate (containing 6 crystallizations water), 2.94g copper nitrate (containing 6 crystallizations water), 0.30g calcium nitrate (containing 4 crystallizations water) and be dissolved in the 3.0g deionized water, mix the back and add 5.0g γ-Al
2O
3, flood and put into baking oven after 5 hours in 100 ℃ of dryings 18 hours, at last in 450 ℃ of roastings 4 hours.Obtain Cu (10.5%)-Mg (5.7%)-Ca (0.85%)/γ-Al
2O
3(82.95%) removes agent, be numbered T-8.
[embodiment 9]
Take by weighing 3.62g magnesium nitrate (containing 6 crystallizations water), 2.94g copper nitrate (containing 6 crystallizations water), 0.10g barium nitrate and be dissolved in the 3.1g deionized water, mix the back and add 5.0g γ-Al
2O
3, flood and put into baking oven after 5 hours in 100 ℃ of dryings 18 hours, at last in 450 ℃ of roastings 4 hours.Obtain Cu (10.5%)-Mg (5.7%)-Ba (0.85%)/γ-Al
2O
3(82.95%) removes agent, be numbered T-9.
[embodiment 10]
To prepare C
2Above oxygenatedchemicals (C
2The synthesis gas of the usefulness of+-oxygenates) (CO30%, H
260, N
210%) remove agent by above-mentioned 9 respectively under 3.0MPa pressure, reaction velocity is controlled at 9000h
-1, reaction temperature is controlled at 180 ℃.Stop test after 18 hours, 9 iron, the nickel content that remove in the agent are measured in fluorescence analysis respectively, and remove agent with blank and compare, and result of the test sees Table-1.
[embodiment 11]
To remove agent T-1～T-9 and be respectively applied for synthesis gas system C
2Above oxygenatedchemicals (C
2In the catalystic converter system of+-oxygenates), synthesis gas is earlier by being equipped with the reaction tube that removes agent, and reaction pressure is 3.0MPa, and reaction velocity is 9000h
-1, remove 180 ℃ of temperature; The synthesis gas that removes behind carbonyl iron and the carbonyl nickel enters catalytic reaction tube again, and reaction pressure and air speed are with to remove conversion zone identical, and the catalytic reaction temperature is 320 ℃, and compares with not loading the reaction result that removes agent, and comparative result sees Table-2.
[embodiment 12]
To remove agent T-7 and be used for synthesis gas system C
2Above oxygenatedchemicals (C
2In the catalystic converter system of+-oxygenates), the course of reaction of synthesis gas in system is with [embodiment 11].Remove reaction and be all 2.0MPa mutually with catalytic reaction pressure, reaction velocity also is all 9000h mutually
-1, removing reaction temperature is 180 ℃, 320 ℃ of catalytic reaction temperature, and compare with not loading the reaction result that removes agent, comparative result sees Table-3.
[embodiment 13]
To remove agent T-7 and be used for synthesis gas system C
2Above oxygenatedchemicals (C
2In the catalystic converter system of+-oxygenates), the course of reaction of synthesis gas in system is with [embodiment 11].Remove reaction and be all 3.0MPa mutually with catalytic reaction pressure, reaction velocity also is all 12000h mutually
-1, removing reaction temperature is 150 ℃, 320 ℃ of catalytic reaction temperature, and compare with not loading the reaction result that removes agent, comparative result sees Table-3.
[embodiment 14]
To remove agent T-7 and be used for synthesis gas system C
2Above oxygenatedchemicals (C
2In the catalystic converter system of+-oxygenates), the course of reaction of synthesis gas in system is with [embodiment 11].Remove reaction and be all 5.0MPa mutually with catalytic reaction pressure, reaction velocity also is all 15000h mutually
-1, removing reaction temperature is 200 ℃, and the catalytic reaction temperature is 320 ℃, and compares with not loading the reaction result that removes agent, and comparative result sees Table-3.
Table-1 removes iron and nickel content (fluorescence analysis) in the agent before and after removing reaction
(representing) with oxide form
Table-2 removes agent to synthesis gas system C
2The influence of above oxygenatedchemicals catalyst performance
| Remove agent | CO conversion ratio (%) | C 2+-oxygenates yield (g/kg.h) | Catalyst life (hour) |
| T-1 | 14.8 | 353.7 | ＞200 |
| T-2 | 15.0 | 362.1 | ＞200 |
| T-3 | 15.6 | 370.2 | ＞200 |
| T-4 | 15.9 | 375.0 | ＞200 |
| T-5 | 17.9 | 401.3 | ＞200 |
| T-6 | 15.2 | 368.2 | ＞200 |
| T-7 | 19.1 | 450.6 | ＞200 |
| T-8 | 18.2 | 422.9 | ＞200 |
| T-9 | 17.6 | 395.4 | ＞200 |
| Do not have and remove agent | 5.6 | 85.2 | 50.2 |
Remove the influence of agent under table-3 differential responses conditions to catalyst performance
Claims (8)
1. agent that removes that removes carbonyl iron and carbonyl nickel in the synthesis gas comprises following component by weight percentage:
A) 0.5～20% copper or its oxide;
B) 0.5～30% magnesium, potassium, calcium or its oxide and composition thereof;
C) γ-Al of 50～99%
2O
3Carrier.
2. according to the described agent that removes that removes carbonyl iron and carbonyl nickel in the synthesis gas of claim 1, it is characterized in that the consumption of copper by weight percentage or its oxide is 0.8～15%.
3. according to the described agent that removes that removes carbonyl iron and carbonyl nickel in the synthesis gas of claim 1, it is characterized in that the consumption of magnesium, potassium, calcium or its oxide and composition thereof is 0.8～20% by weight percentage.
4. according to the described agent that removes that removes carbonyl iron and carbonyl nickel in the synthesis gas of claim 1, it is characterized in that carrier γ-Al by weight percentage
2O
3Consumption be 65～98.4%.
5. the described preparation method who removes agent who removes carbonyl iron and carbonyl nickel in the synthesis gas of claim 1 may further comprise the steps:
A) salt with magnesium, potassium, calcium or its mixture of the mantoquita of aequum and aequum is mixed with solution I;
B) with the γ-Al of aequum
2O
3Carrier with the dipping method, with the activity component impregnation in the solution I to γ-Al
2O
3On the carrier, obtain removing agent presoma I;
C) will remove agent presoma I dry under 80～150 ℃ of conditions, after roasting under 300～600 ℃ of conditions, obtain the required agent product that removes.
6. the preparation method who removes agent who removes carbonyl iron and carbonyl nickel in the synthesis gas according to claim 5, the salt that it is characterized in that mantoquita and magnesium, potassium, calcium or its mixture is nitrate.
7. the preparation method who removes agent who removes carbonyl iron and carbonyl nickel in the synthesis gas according to claim 5 is characterized in that dipping method with equal-volume method dipping, and room temperature was placed 2～7 hours.
8. the preparation method who removes agent who removes carbonyl iron and carbonyl nickel in the synthesis gas according to claim 5 is characterized in that removing the agent presoma under 80～130 ℃ of conditions dry 1～36 hour; Roasting is 2～6 hours under 320～550 ℃ of conditions.
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|---|---|---|---|
| CN2010101470646A CN102218295A (en) | 2010-04-15 | 2010-04-15 | Removing agent for removing carbonyl iron and carbonyl nickel in syngas and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973716A (en) * | 2018-01-04 | 2018-05-01 | 西南化工研究设计院有限公司 | A kind of method of dimethyl ether carbonyl synthesis of acetic methyl esters |
| CN112705157A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | For removing Fe (CO)5And/or Ni (CO)4Purifying agent and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272395A (en) * | 1999-04-29 | 2000-11-08 | 中国石化集团齐鲁石油化工公司 | Adsorbing agent for removing carbonyl metal compound from gas and its preparation method |
| CN1180885C (en) * | 2001-11-29 | 2004-12-22 | 中国石化集团齐鲁石油化工公司 | Protection agent of catalyst for methanol synthesis and preparation method thereof |
| CN1569329A (en) * | 2003-07-15 | 2005-01-26 | 四川大学 | Novel catalyst for methanol cracking reaction to produce CO and H2 |
-
2010
- 2010-04-15 CN CN2010101470646A patent/CN102218295A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272395A (en) * | 1999-04-29 | 2000-11-08 | 中国石化集团齐鲁石油化工公司 | Adsorbing agent for removing carbonyl metal compound from gas and its preparation method |
| CN1180885C (en) * | 2001-11-29 | 2004-12-22 | 中国石化集团齐鲁石油化工公司 | Protection agent of catalyst for methanol synthesis and preparation method thereof |
| CN1569329A (en) * | 2003-07-15 | 2005-01-26 | 四川大学 | Novel catalyst for methanol cracking reaction to produce CO and H2 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973716A (en) * | 2018-01-04 | 2018-05-01 | 西南化工研究设计院有限公司 | A kind of method of dimethyl ether carbonyl synthesis of acetic methyl esters |
| CN112705157A (en) * | 2019-10-24 | 2021-04-27 | 中国石油化工股份有限公司 | For removing Fe (CO)5And/or Ni (CO)4Purifying agent and preparation method and application thereof |
| CN112705157B (en) * | 2019-10-24 | 2023-06-06 | 中国石油化工股份有限公司 | For removing Fe (CO) 5 And/or Ni (CO) 4 Purifying agent of (2), preparation method and application thereof |
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Application publication date: 20111019 |