CN1515530A - New process for protecting methyl alcohol catalyst - Google Patents
New process for protecting methyl alcohol catalyst Download PDFInfo
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- CN1515530A CN1515530A CNA031253148A CN03125314A CN1515530A CN 1515530 A CN1515530 A CN 1515530A CN A031253148 A CNA031253148 A CN A031253148A CN 03125314 A CN03125314 A CN 03125314A CN 1515530 A CN1515530 A CN 1515530A
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- scavenging
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- methyl alcohol
- methanol
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Abstract
The present invention relates to a purification process of raw material gas for synthesizing methyl alcohol, and it relates to a production process for producing methyl alcohol in coal gas-making ammonia synthesis plant. After fine desulfurizing process or before methyl alcohol catalyst one or two kinds of purifying agents (ET-7 type carbonyl metal purifying agent and ET-8 type methyl alcohol catalyst protecting agent, they are developed by Hubei prov. research inst. of chemistry, China) are added. Its use temp. is normal temp.-300 deg.C, operation pressure is normal pressure to 25MPa. After the purifying agent is used, the micro chlorine, sulfur and carbonyl metal poison in the raw material gas can be bemoved to below 0.01 ppm.
Description
Technical field
The present invention relates to coal generating gas and produce the technical process of methyl alcohol.
Technical background
Along with the exploitation of methyl alcohol Application Areas, derived product such as the technical progress of methanol-to-olefins, preparing gasoline by methanol, methanol fuel and industrialization breakthrough and acetic acid, methyl-formiate, methylcarbonate, dme are continually developed, particularly as C
1The methyl alcohol of chemical industry foundation stone, its market outlook are with boundless.China's methanol industry had obtained developing by leaps and bounds in recent years, and by adding Cu, Zn, Al element in addition, the different copper base catalyst for methanol of many performances constantly is applied to obtain remarkable economic efficiency among the industrial production.
Yet, in use, because the influence of various factors, reach design requirements the work-ing life of catalyst for methanol far away, China has only 6～9 months with the catalyst for methanol of the medium and small synthesis ammonia plant of coal generating gas work-ing life usually at present, short less than 3 months with regard to inactivation, this with domestic big nitrogen fertilizer plant or abroad Methanol Plant tangible distance is arranged.According to decaying catalyst is discovered, except that agglomerating agent, sulphur, chlorine and metallic carbonyls etc. are fatal to the influence of catalyst for methanol.
Though the popularization of smart desulfurization technology makes the copper-based catalysts industrial application life-span increase about one times, yet remaining Determination of Trace Sulfur remains and influences one of active major reason of catalyst for methanol.
For catalyst for methanol, chlorine is the poisonous substance more severe than sulphur, and the Cu in chlorine and the catalyzer, Zn generate low melting point CuCl and ZnCl
2, accelerator activator surface sintering causes poisoning of catalyst.0.01ppm chlorine will the remarkably influenced activity of such catalysts, 0.01%～0.03% inhales chlorine dose and will cause activity to decline to a great extent in the catalyzer.
The metallic carbonyls main source is that CO contacts with equipment, pipeline table wall or impurity such as Fe in CO and the raw material and Ni reaction and generating in the gas making process in the unstripped gas.Metallic carbonyls decomposes in methyl alcohol synthetic reactor, is deposited on catalyst surface, the blocking catalyst micropore, cause the active and selectivity decline of catalyst reaction, side reaction increases, and quickens synthetic paraffin class material, high chain hydrocarbon, ether and higher alcohols, and the foreign matter content in the thick methyl alcohol increases.Millionth carbonyl compound just can cause the poisoning of catalyst inactivation in the synthetic gas.
The separating effect of the enterprise's oil separator that has is bad, and the lubricating oil of high-pressure unit and circulator is often brought synthetic tower into, and at catalyst surface knot charcoal, the blocking catalyst hole makes the serious inactivation of catalyzer.According to one's analysis, also contain 0.02～0.04% sulphur in the lubricating oil, also can increase the weight of murder by poisoning catalyzer.
Yet in the quite a long time, above-mentioned impurity is not paid attention to by manufacturing enterprise the harm of catalyst for methanol up till now, does not more take corresponding measure to solve, thereby causes the work-ing life of catalyst for methanol short partially.
Summary of the invention
Purpose of the present invention is exactly to increase a kind of refining plant in methanol process; with the impurity removals such as micro-chlorine, residual sulfur and metallic carbonyls in the synthetic gas below 0.01ppm; can protect catalyst for methanol better, prolong its work-ing life, improve the business economic benefit.This technology has the wide temperature region of use, the applying pressure scope is big, the impurity capacity is big, degree of purification is high and easy to use, flexible characteristic.
The present invention adopts following method to realize; according to S in the operating mode unstripped gas; the content of Cl and metallic carbonyls; a kind of scavenging agent (ET-8 type catalyst for methanol protective material that ET-7 type metallic carbonyls scavenging agent that the Hubei Inst. of Chemistry development and production are commercially available or Hubei Inst. of Chemistry development and production are commercially available is adopted in suitable position in the technological process of production; together following) or two kinds of scavenging agents (ET-7 type metallic carbonyls scavenging agent+ET-8 type catalyst for methanol protective material); according to processing condition decision scavenging agent loading amount; above-mentioned trace impurity in the gas is removed, and concrete technology is provided with as follows:
1, with scavenging agent (ET-7 type metallic carbonyls scavenging agent or ET-8 type catalyst for methanol protective material; or ET-7 type metallic carbonyls scavenging agent+ET-8 type catalyst for methanol protective material) is contained in after carbonization or the decarburization in last thionizer of smart desulfurization; use temperature is normal temperature～100 ℃, and the use air speed is 3000～5000h
-1This method need not increase any equipment.Fig. 1 is seen in technical process.
2, behind last thionizer of smart desulfurization, increase a scavenging tower; built-in purifying agent (ET-7 type metallic carbonyls scavenging agent or ET-8 type catalyst for methanol protective material; or ET-7 type metallic carbonyls scavenging agent+ET-8 type catalyst for methanol protective material); use temperature is from normal temperature～300 ℃, and the use air speed is 3000～5000h
-1This method is owing to adopt the independent scavenging tower that meets aspect ratio, and decontamination effect improving is better.Fig. 2 is seen in technical process.
3, between oil separator and methyl alcohol synthetic reactor, increase a scavenging tower; built-in purifying agent (ET-7 type metallic carbonyls scavenging agent or ET-8 type catalyst for methanol protective material; or ET-7 type metallic carbonyls scavenging agent+ET-8 type catalyst for methanol protective material); use temperature is normal temperature～300 ℃, and the use air speed is 5000～10000h
-1This method can be given full play to the usefulness of scavenging agent owing to dechlorinating agent can be arranged on the high-temperature zone, can reduce the protective material consumption and reduces investment outlay.Fig. 3 is seen in technical process.
4, at the top of catalyst for methanol filling scavenging agent (ET-7 type metallic carbonyls scavenging agent or ET-8 type catalyst for methanol protective material; or ET-7 type metallic carbonyls scavenging agent+ET-8 type catalyst for methanol protective material); use temperature is 200～300 ℃, and the use air speed is 10000～20000h
-1This method can be given full play to the usefulness of scavenging agent because the temperature of reaction height, can reduce the protective material consumption and reduces investment outlay.Fig. 4 is seen in technical process.
After adopting technical process of the present invention, have the following advantages:
1, the catalyst for methanol life-span can be enhanced about more than once on existing basis, reduces catalyzer running cost;
2, reduce improper shutdown period and catalyzer and change number of times, reduce the loss that causes owing to stopping:
3, because the catalyst activity decline is slow, in the identical time, can improve methanol output;
4, after trace impurity reduces in the unstripped gas, also can alleviate equipment corrosion.
Description of drawings:
Fig. 1 is a filling scavenging agent process flow sheet in the thionizer
Fig. 2 is provided with the scavenging tower process flow sheet for behind the thionizer
Fig. 3 is provided with the scavenging tower technical process for before the methyl alcohol synthetic reactor
Fig. 4 is catalyst for methanol top filling scavenging agent process flow sheet
In the schema shown in Figure 1; with scavenging agent (ET-7 type metallic carbonyls scavenging agent or ET-8 type catalyst for methanol protective material; or ET-7 type metallic carbonyls scavenging agent and ET-8 type catalyst for methanol protective material) be seated in last thionizer of smart desulfurization; unstripped gas reaches the purification purpose by scavenging agent of the present invention again through behind the sweetening agent; air speed 3000～5000h is used in use temperature normal temperature～100 ℃
-1
In the schema shown in Figure 2, in last thionizer of smart desulfurization workshop section, increase a scavenging tower, interior dress (ET-7 type metallic carbonyls scavenging agent), unstripped gas enters the present invention after thionizer comes out, use temperature normal temperature～300 ℃, air speed 3000～5000h
-1Described scavenging tower reaches the purification purpose.
In the schema shown in Figure 3, between oil separator and methyl alcohol synthetic reactor, increase a scavenging tower, built-in purifying agent (ET-7 type metallic carbonyls scavenging agent), unstripped gas enters scavenging tower after coming out from oil separator, purifies back gas and enters methyl alcohol synthetic reactor.200～300 ℃ of scavenging tower service temperatures are used air speed 5000～10000h
-1
In the schema shown in Figure 4, the catalyst for methanol top filling scavenging agent (ET-7 type metallic carbonyls scavenging agent) in synthetic tower, unstripped gas enters the methanol synthesis catalyst bed through behind the scavenging agent.230～300 ℃ of use temperatures, applying pressure 25MPa.
Embodiment
Embodiment 1
Certain factory adopts Φ 800mm double-column in series synthesizing methanol, do not adopt this technology before, only 4～5 months work-ing life of catalyst for methanol, when sweetening agent is changed in the back at the second thionizer bottom device 5.0M
3ET-8 type catalyst for methanol protective material.The dechlorinating agent use temperature is a normal temperature, and applying pressure is a normal pressure, the back operation 1 year of driving, and catalyst activity is still good, and the bed focus does not move down, and can not detect poisonous substances such as S, Cl and metallic carbonyls behind the thionizer in the gas.
Embodiment 2
Loaded the Hubei Inst. of Chemistry in the scavenging tower of certain nitrogen fertilizer plant after smart desulfurization and produced commercially available ET-8 type catalyst for methanol protective material, used forward and backward catalyst life to change and see the following form 1:
Table 1
| Poison type | The scavenging tower inlet | The scavenging tower outlet | Life-span before using | Use the back life-span |
| ??Cl/ppm | ????0.87 | Do not detect (＜0.01ppm) | 3 months | 17 months (still using) |
| ??S/ppm | ????0.09 | Do not detect (＜0.01ppm) | ||
| Metallic carbonyls/ppm | ????0.12 | Do not detect (＜0.01ppm) |
Embodiment 3
Certain joins pure factory 4 * 10
4T/a synthetic ammonia coproducing 1 * 10
4T/a methyl alcohol.Synthesizing methanol adopts Φ 600mm double tower flow process in parallel, and pressure is 13.5MPa.This factory's catalyst for methanol was changed once in original per 5～6 months, contained 0.84ppmCl in the synthetic raw gas by analysis
-, 0.07ppmH
2S.A scavenging tower is set up in the back before methyl alcohol synthetic reactor; interior dress Hubei Inst. of Chemistry produces commercially available ET-8 type catalyst for methanol protective material and ET-7 type metallic carbonyls scavenging agent; working conditions normal temperature; pressure is 13.0MPa; after driving to move; the scavenging tower outlet can not detect Cl, S always, and catalyst for methanol used 9 months, is still using at present.
Embodiment 4
Certain Methanol Plant adopts Φ 10000 synthetic towers, produces 2 * 10 per year
4Methyl alcohol; system pressure 25.0MPa; the each use of 280 ℃～300 ℃ catalyst for methanol of temperature of reaction promptly changed in 6 months; increase the Hubei Inst. of Chemistry on the catalyst for methanol of back in synthetic tower and produced commercially available ET-8 type catalyst for methanol protective material scavenging agent; now used 6 months; catalyst activity is good, still in use at present.
Claims (3)
1. produce in the technical process of methyl alcohol at coal generating gas, a kind of novel process of protecting catalyst for methanol is characterized in that at one or both scavenging agents of desulfurizing agent bottom filling; Or behind desulfurizing agent, increase a scavenging tower, one or both scavenging agents of interior dress; Or before methyl alcohol synthetic reactor, increase a scavenging tower, one or both scavenging agents of interior dress.Purify in the technology of back residual sulfur, micro-chlorine and metallic carbonyls all＜0.01ppm.
2. scavenging tower as claimed in claim 1, the system pressure that it is characterized in that this tower is at normal pressure～25MPa.
3. scavenging agent as claimed in claim 1, the use temperature that it is characterized in that this scavenging agent are normal temperature～300 ℃, and it is the commercially available ET-7 type metallic carbonyls scavenging agent of Hubei Inst. of Chemistry development and production, ET-8 type catalyst for methanol protective material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031253148A CN1515530A (en) | 2003-08-22 | 2003-08-22 | New process for protecting methyl alcohol catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031253148A CN1515530A (en) | 2003-08-22 | 2003-08-22 | New process for protecting methyl alcohol catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1515530A true CN1515530A (en) | 2004-07-28 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031253148A Pending CN1515530A (en) | 2003-08-22 | 2003-08-22 | New process for protecting methyl alcohol catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219186A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Removing method of carbonyl iron and carbonyl nickel in syngas |
| CN106090612B (en) * | 2016-08-17 | 2018-07-24 | 智胜化工股份有限公司 | A kind of catalyst safety guard and methanol-fueled CLC Tower System |
-
2003
- 2003-08-22 CN CNA031253148A patent/CN1515530A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219186A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Removing method of carbonyl iron and carbonyl nickel in syngas |
| CN102219186B (en) * | 2010-04-15 | 2012-11-14 | 中国石油化工股份有限公司 | Removing method of carbonyl iron and carbonyl nickel in syngas |
| CN106090612B (en) * | 2016-08-17 | 2018-07-24 | 智胜化工股份有限公司 | A kind of catalyst safety guard and methanol-fueled CLC Tower System |
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