CN1061321C - Purifying method for metal carbonyl compound in synthetic gas - Google Patents
Purifying method for metal carbonyl compound in synthetic gas Download PDFInfo
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- CN1061321C CN1061321C CN 96119472 CN96119472A CN1061321C CN 1061321 C CN1061321 C CN 1061321C CN 96119472 CN96119472 CN 96119472 CN 96119472 A CN96119472 A CN 96119472A CN 1061321 C CN1061321 C CN 1061321C
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- Prior art keywords
- synthetic gas
- purifying method
- gac
- metal carbonyl
- acid
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a purifying method for metal carbonyl compounds in synthetic gas, which effectively removes the metal carbonyl compound in synthetic gas by using activated carbon and particularly to shell carbon with activity as a purifying agent under the conditions with the purification temperature of 0 DEG C to 200 DEG C, the airspeed of the synthetic gas which is lower than or equal to 5000h<-1> and the pressure of the synthetic gas of 0.01MPa to 20MPa. In order to improve the activity of the purifying agent, the acid and the alkali of the activated carbon are treated, or are treated in advance. The technology method has high removal activity of the carbonyl compound in synthetic gas, has the advantages of complete removal, simple technology and convenient operation, and is suitable for industrialization use.
Description
The present invention relates to the scavenging process of synthetic gas, specifically provide a kind of purifying method that is used for the synthetic gas metal carbonyl.
The purification requirement of synthetic gas and the purposes of synthetic gas are directly related.The method of US4572829 applied catalysis oxidation changes into CO to the CO in the synthetic gas
2, again CO
2Wash off, remaining detrimental impurity removes with sorbent material.DE3245463 has invented the method and apparatus that prevents the metallic sulfide blocking pipe in the synthetic gas production process.When the synthetic gas temperature of producing is reduced to below 250 ℃, in synthetic gas, replenish O
2, metal carbonyl is oxidized to metal oxide, reduced the possibility that generates metallic sulfide.In addition, generally all metal carbonyl can be arranged in the synthetic gas, as iron carbonyl, nickel, molybdenum etc., these carbonyl compound are very strong to noble metal catalyst toxicity, even measure littlely, also make catalyst deactivation easily.But, have not yet to see the practical and effective method for the elimination of the metal carbonyl in the synthetic gas.
The purifying method of metal carbonyl in the synthetic gas of the present invention is characterized in that adopting gac to eliminate metal carbonyl as scavenging agent, and preferably selects fruit shell carbon for use as the gac of scavenging agent.For improving the performance of scavenging agent, also can give processing to gac, obtain highly active gac.It gives one of the following method that adopts of handling:
(1) with diluted acid such as HCl, HNO
3Or H
2SO
4Carry out acid pickling, acid is boiled and pickling;
(2) use alkaline solution, as NaOH, KOH, Mg (OH)
2, Na
2CO
3Or K
2CO
3Carry out alkali steeping, soda boiling and alkali cleaning;
(3) at first use above-mentioned (1) to carry out using above-mentioned (2) to carry out alkaline purification again after diluted acid handles; Gac after treatment carries out drying according to a conventional method, can be purified agent.
Utilize the active carbon purifying agent of the invention described above, Liang difference as required, with above-mentioned scavenging agent pack into certain volume stainless steel tube or jar in, granularity is controlled to be 0.5mm～15mm, by following condition synthetic gas is purified.Purification condition is:
The temperature of purification pot: 0～200 ℃, optimum temps is 80～150 ℃;
Synthetic gas air speed :≤5000h
-1, best air speed is≤2000h
-1
Working pressure: 0.01～20MPa.
Below by example technology of the present invention is given to illustrate further.
Embodiment 1
Select the coal charcoal processing of 2-3mm, do not do and give processing, measure 10ml and pack in the stainless steel tube of φ 10mm, control active carbon bed temperature is at 100 ℃, synthetic gas pressure 3.0MPa, air speed 1000h
-1, the inlet synthetic gas contains O
2Amount 0.1%, the carbonyl metal compound total content is 3.5ppm.The content that records carbonyl metal compound in outlet is＜0.3ppm.
Embodiment 2
Select the coconut husk charcoal of 2-3mm, do not do pre-treatment and example 1 identical test conditions, record the outlet synthetic gas in the carbonyl metal compound total content be 0.08ppm.
Embodiment 3
Select the coconut husk charcoal of 5-8mm, with 0.1N NaOH dipping, drainage, oven dry, get 50L and pack in the stainless steel purification pot of 50L, the control bed temperature is at 100～110 ℃, synthetic gas pressure 8.0MPa, air speed 1000～1500h
-1, go into the O of implication
2Content is 0.1%～0.2%, carbonyl metal compound content 3.6～6.1ppm, and recording the middle carbonyl metal compound of working off one's feeling vent one's spleen is 0.02ppm.
Embodiment 4
Select the coal activated carbon of 2-3mm, soak, boil, washing, 2～3 times with 1N HCl.Use 0.5NK then
2CO
3Dipping, drainage, oven dry, test condition is intact consistent with example 1.Go into that carbonyl compound concentration is 3.5ppm in the implication, the concentration that records in working off one's feeling vent one's spleen is 0.05ppm.
Embodiment 5
Select the almond charcoal of 2-3mm, use 0.2N Na
2CO
3Dipping, oven dry.On the testing apparatus of example 1, the inlet synthetic gas contains O
2Be 620ppm, carbonyl metal compound is 3.6ppm, controls bed temperature at 120 ℃, pressure 3.0MPa, air speed 800h
-1Recording the middle carbonyl metal compound concentration of working off one's feeling vent one's spleen is 0.05ppm.
Embodiment 6
Select the coconut husk charcoal of 2-3mm, boil with the 1N HCl aqueous solution, water washes to pH=7, uses 0.1NNa then
2CO
3Flooded elimination moisture, oven dry one day.Test condition is removed air speed and is become 4000h
-1Outward, other is identical with example 1.The content that records carbonyl metal compound in the outlet synthetic gas is 0.08ppm.
Embodiment 7
Select the coconut husk charcoal of 2-3mm, with example 6 fully mutually give treatment condition.With embodiment 1 identical condition under, the carbonyl metal compound content that records the inlet synthetic gas is 3.5ppm, exports to be＜0.01ppm.
Comparative example 1
Select the Al of 2-3mm particle diameter
2O
3, test condition and embodiment 1 are identical.The carbonyl metal compound content that records the inlet synthetic gas is 3.5ppm, exports to be 1.2ppm.
The technology of the present invention has been used on 30 tons of/year pilot scale refining plants of natural gas via synthetic gas system ethanol, operation is after 1000 hours continuously, record the carbonyl metal compound content that purifies in the synthetic gas of back and be lower than 0.05ppm, guaranteed the normal operation of synthesizing alcohol rhodium base catalyst.
The activated-carbon catalyst that is adopted by above-mentioned example the present invention is active high to removing of metal carbonyl, and that takes off is clean, and technology is simple, easy to operate, is suitable for industrialization and adopts.
Claims (3)
1. the purifying method of metal carbonyl in the synthetic gas is characterized in that adopting gac as scavenging agent, and granularity of activated carbon is controlled to be 0.5mm～15mm; The purification process condition is: 0～200 ℃ of purification temperature, synthetic gas air speed :≤5000h
-1, synthetic gas pressure 0.01～20MPa.
2. according to the described purifying method of claim 1, it is characterized in that it being to adopt fruit shell carbon to make scavenging agent.
3. according to the described purifying method of claim 1, it is characterized in that it being to adopt the gac that gives processing to make scavenging agent, what is called is given and being handled is to adopt one of following method to carry out:
(1) with being selected from HCl, HNO
3, H
2SO
4Concentration be that the diluted acid of 1N carries out acid pickling, acid is boiled and pickling; (2) with being selected from NaOH, KOH, Mg (OH)
2, Na
2COO
3, K
2CO
3Concentration be that the alkaline solution of 0.1～0.2N carries out alkali steeping, soda boiling and alkali cleaning;
(3) at first use above-mentioned (1) to carry out using above-mentioned (2) to carry out alkaline purification again after diluted acid handles; Gac after treatment carries out drying according to a conventional method, can be purified agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96119472 CN1061321C (en) | 1996-10-09 | 1996-10-09 | Purifying method for metal carbonyl compound in synthetic gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96119472 CN1061321C (en) | 1996-10-09 | 1996-10-09 | Purifying method for metal carbonyl compound in synthetic gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1178766A CN1178766A (en) | 1998-04-15 |
| CN1061321C true CN1061321C (en) | 2001-01-31 |
Family
ID=5125725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96119472 Expired - Fee Related CN1061321C (en) | 1996-10-09 | 1996-10-09 | Purifying method for metal carbonyl compound in synthetic gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1061321C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408146C (en) * | 2003-01-28 | 2008-08-06 | 弗劳尔公司 | Configuration and process for carbonyl removal |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2007328925B2 (en) * | 2006-12-08 | 2010-12-02 | Shell Internationale Research Maatschappij B.V. | Process for producing a purified synthesis gas stream |
| CN103566708B (en) * | 2013-11-14 | 2016-06-15 | 西南化工研究设计院有限公司 | A kind of de-method except carbonyl metal compound in synthetic gas |
| CN103904328B (en) * | 2014-04-01 | 2016-04-27 | 华南师范大学 | A kind of preparation method of biomass lamella material with carbon element and application thereof |
| CN108152219A (en) * | 2017-12-29 | 2018-06-12 | 亚申科技研发中心（上海）有限公司 | The real-time detection method and device of impurity in synthesis gas |
| CN113198420A (en) * | 2021-04-25 | 2021-08-03 | 鲁西催化剂有限公司 | Modified activated carbon and preparation method and application thereof |
-
1996
- 1996-10-09 CN CN 96119472 patent/CN1061321C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408146C (en) * | 2003-01-28 | 2008-08-06 | 弗劳尔公司 | Configuration and process for carbonyl removal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1178766A (en) | 1998-04-15 |
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