CN103203254B - Methylamine catalyst regenerating method and device - Google Patents
Methylamine catalyst regenerating method and device Download PDFInfo
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- CN103203254B CN103203254B CN201310120770.5A CN201310120770A CN103203254B CN 103203254 B CN103203254 B CN 103203254B CN 201310120770 A CN201310120770 A CN 201310120770A CN 103203254 B CN103203254 B CN 103203254B
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- methylamine
- catalyst
- methylamine catalyst
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Abstract
The invention relates to a methylamine catalyst regenerating method comprising the following steps of: stacking a methylamine catalyst without activity in a reactor, and opening steam at the bottom of the reactor, wherein ammonia, methylamine and methanol remaining in the methylamine catalyst are blown into an absorption tower by using the steam and absorbed and discharged by using an alkaline solution; then, starting a compressor and a heating furnace, introducing air into the reactor through the heating furnace, and meanwhile, introducing nitrogen gas to the reactor; and heating to 550 DEG C at the speed smaller than 25 DEG C/h, keeping the temperature for 5-6h, and when the oxygen content of the discharged air is up to 20-22%, stopping the heating furnace, and continuing to introduce air for cooling the methylamine catalyst. The invention also discloses a device for realizing the method. Residues and deposited carbon in the methylamine catalyst are removed, and water combined in the residues and the deposited carbon is completely released, so that the methylamine catalyst is regenerated, the service life of the methylamine catalyst is prolonged, and the production cost of methylamine is reduced.
Description
Technical field
The present invention relates to a kind of regeneration cycle operation technique and device of catalyst, relate in particular to methylamine catalyst regneration method and device thereof that a kind of methylamine production is used.
Background technology
At present, methylamine production method is more, the technique of comparative maturity is " the continuous gas phase catalysis ammoniation process of methyl alcohol ", utilize methyl alcohol and liquefied ammonia for raw material, by a certain percentage, under uniform temperature and pressure, pass through catalyst layer, fully contact with methylamine catalyst (catalyst), at gas phase catalytic reaction, obtain one, two, trimethylamine.Methylamine catalyst is mainly with γ-AL
2o
3be main, then the compound that adds the elements such as magnesium, silicon, zinc, titanium, tungsten, chromium is made.
At present, after a catalysis of the general employing of methylamine catalyst, be waste treatment, can not recycle, consume larger.The domestic methylamine catalyst operating period generally adopting is about 1 year, import BASF(company) SI-1221T catalyst uses 2 years.Reach after the time limit service time of methylamine catalyst, needs waste treatment and again buy and change.Expensive due to methylamine catalyst, if can make methylamine catalyst regneration, extends the service life of methylamine catalyst, will greatly reduce production costs, and increases the methylamine competitiveness of product in market.
Because methylamine catalyst is to use in methanol amination, it is subject to the impact of three aspects: reason below and makes its active decline:
One, be the easy carbon distribution in surface of methylamine catalyst and the activity that hinders catalyst produces;
Two, be that the hydrocarbon of macromolecule has stopped up the micropore in methylamine catalyst, make its active decline;
Three, methylamine catalyst is in long-term use, due in reaction raw materials methyl alcohol and liquefied ammonia in various degree contain moisture content, in process of production, most of along with temperature in reaction rises and discharges, but still have small part to be combined generation hydrate AL with methylamine catalyst
2o
3.3H
2o; And this hydrate need to just can change into γ-AL under 400-450 ℃ of condition
2o
3,thereby make the holomorphosis of methylamine catalyst, recover it as the activity of catalyst.
Four, the methylamine catalyst that other compounds cause poisoning.
Methylamine catalyst activity that wherein first three reasons causes declines, and can regenerate and continues to use, and the 4th kind is permanent losing activity, and generally cannot regenerate.
Summary of the invention
Object of the present invention will solve above-mentioned deficiency exactly, and a kind of renovation process of methylamine catalyst is provided, and makes deactivated methylamine catalyst also manage former process dehydration regeneration by regeneration, reaches the object that extends its service life, reduces use cost.
Another object of the present invention is to provide a kind of regenerating unit of realizing the method.
In order to achieve the above object, the invention provides a kind of renovation process of methylamine catalyst, comprise the following steps:
(1) deactivated methylamine catalyst is deposited in reactor, opens the steam that is positioned at reactor bottom, steam is blown into ammonia residual in methylamine catalyst, methylamine and methyl alcohol in absorption tower;
(2), by the waste gas alkali liquor absorption in absorption tower, then distinguish discharging waste gas, waste liquid;
(3) open compressor and heating furnace, air passes in reactor through heating furnace, passes into nitrogen in reactor simultaneously;
(4) in reactor, the temperature of methylamine catalyst heats up by being less than 25 ℃/h, and temperature keeps 5-6h while rising to 550 ℃, when the content of oxygen is 20-22% in the waste gas of discharge, closes heating furnace, continues to pass into air methylamine catalyst is lowered the temperature.
The preferred version of such scheme is, in described step (1), steam is 120-160 ℃, 0.3MPa saturated vapor, and the time that steam passes into is 5-6 hour.
In described step (4), the temperature rise period of methylamine catalyst is divided into double teacher:
A, de-free water stage: in 30-110 ℃, by heating rate, be less than 5 ℃/h, intensification 5-7h;
B, transition stage: in 110-220 ℃, by heating rate, be less than 15 ℃/h, intensification 8-10h;
C, methylamine catalyst water smoking: in 220-450 ℃, by heating rate, be less than 15 ℃/h, intensification 15-17h;
D, methylamine catalyst regneration stage: in 450-550 ℃, by heating rate, be less than 10 ℃/h, intensification 10-12h;
E, coal stage: temperature is that 550 ℃ of constant temperature keep 6-8h.
In described step (4), methylamine catalyst is cooled to below 200 ℃.
In order to realize above-mentioned renovation process, the device that the present invention adopts, comprises reactor, absorption tower, and described reactor bottom is provided with steam inlet, air intlet and nitrogen inlet, and described air intlet is connected with heating furnace and compressor in turn; The top of described reactor is connected with the bottom on absorption tower by pipeline, and the top on described absorption tower is provided with exhaust outlet, bottom is provided with leakage fluid dram, and the middle part on absorption tower is provided with alkali liquor inlet.
In order to control the reaction temperature in reactor, regulate the inlet of nitrogen, described nitrogen inlet is provided with control valve.
In order to control air, add equably, in the middle of the pipeline on described coupled reaction device and absorption tower, be provided with pressure-control valve.
When the present invention regenerates to methylamine catalyst, first ammonia residual in methylamine catalyst, methylamine and methyl alcohol will be blown in absorption tower through steam, then by alkali liquor absorption, waste gas and waste liquid discharge from the gas outlet, top on absorption tower and the leakage fluid dram of bottom respectively.Rear unlatching compressor, heating furnace have been blown, air passes into the catalyst bed in reactor through heating furnace heating after compressor compression again, and pass into nitrogen simultaneously, methylamine catalyst surface and inner carbon distribution (C), hydrocarbon (CnHm) progressively react with airborne oxygen, its course of reaction is exothermic reaction, the temperature of catalyst layer is raise gradually, when reaching under 550 ℃ of high temperature, maintain 6 hours the carbon and the hydrocarbon that accumulate on methylamine catalyst are burnt completely, recover the catalyst activity of methylamine catalyst.Its heated oxide reduction reaction has five courses of reaction:
The completing combustion reaction of methylamine catalyst carbon distribution: C+O
2--→ CO
2(completing combustion)
The imperfect combustion reaction of methylamine catalyst carbon distribution: C+O
2--→ CO (imperfect combustion)
The combustion reaction of the inner hydrocarbon of methylamine catalyst: CnHm+O2--→ CO
2+ H
2o
Methylamine catalyst dehydration: AL
2o
33H
2o--→ AL
2o
3h
2o(225 ℃)
Methylamine catalyst regneration reaction: AL
2o
3h
2o--→ γ-AL
2o
3(400--450 ℃)
Illustrate in reactor and pass into after air, the carbon distribution in airborne oxygen and methylamine catalyst carries out combustion reaction and generates CO, CO
2in hydrocarbon, heat release rising temperature, its gas continues to enter in absorption tower and discharges.When the temperature in reactor reaches 225 ℃, methylamine catalyst hydrate starts dehydration, sloughs most of water; Continue to pass into air, when continuation generation heat is warming up to 400 ℃-450 ℃, methylamine catalyst holomorphosis regeneration γ-AL
2o
3and continue to use as methylamine catalyst in methylamine production.
Methylamine catalyst regneration reduction process is exothermic reaction, and the key of its regeneration is to control the speed of reacting, and requirement heats up steadily, water outlet is even, prevents that the violent liter of temperature and water outlet are too fast, otherwise can affect activity, intensity and the life-span of catalyst.
And the speed of reaction speed and the concentration of oxygen and reaction temperature have substantial connection, therefore will suitably control air addition, evenly pass into air, by regulating the control valve of nitrogen inlet to regulate the inlet of nitrogen, prevent that catalyst layer each point temperature-difference is excessive simultaneously.Adding of nitrogen is mainly to control airborne oxygen content, to control programming rate, the effect of nitrogen is to reduce airborne oxygen concentration, in temperature rising situation suddenly, adds rapidly nitrogen to reach reduction reaction temperature, prevents that methylamine overtemperature from damaging.This is because methylamine catalyst is porous adsorbent, the moisture content of its inner bore surface and other compositions, if it is too fast to heat up, the rapid effusion of moisture content can damage the pore structure of methylamine catalyst, makes its active decline.
If it is too fast that the temperature in reactor rises, should stand and reduce air inlet; Or by pressure-control valve by system unload and strengthen the inlet of nitrogen, also can close valve heating furnace simultaneously and stop heating.
So in methylamine catalyst regneration process, need slowly to improve the temperature in reactor, according to the methylamine catalyst heating curve (see figure 2) that heats up, in figure:
A, de-free water stage: in 30-110 ℃, by heating rate, be less than 5 ℃/h, intensification 5h;
B, transition stage: in 110-220 ℃, by heating rate, be less than 15 ℃/h, intensification 8h;
C, methylamine catalyst water smoking: in 220-450 ℃, by heating rate, be less than 15 ℃/h, intensification 15h;
D, methylamine catalyst regneration stage: in 450-550 ℃, by heating rate, be less than 10 ℃/h, intensification 10h;
E, coal stage: temperature is that 550 ℃ of constant temperature keep 6h.
Its heating rate specifically sees the following form:
Illustrate that the moisture content in methylamine catalyst volatilizees substantially 120 ℃ of left and right substantially from methylamine catalyst, in methylamine catalyst, the water of combination discharges with interior completely at 450 ℃.Continuing to be warming up to 550 ℃, is mainly that the carbon in methylamine catalyst and hydrocarbon are burnt, and the purity of methylamine catalyst is improved.Methylamine catalyst after regeneration, for avoiding catalyst ash that system after regenerating is produced and stopped up, is tackled its processing of sieving.
Beneficial effect of the present invention has:
1, first at the lose activity reactor bottom of methylamine catalyst of stacking, pass into steam, steam is blown into ammonia residual in methylamine catalyst, methylamine and methyl alcohol in absorption tower, makes to be blocked in material in the micropore of methylamine catalyst and cleans out.
2, the present invention is by adding air, and in air, synthetic reaction occurs for oxygen and methylamine catalyst surface and inner carbon distribution (C), by the carbon cleaning on methylamine catalyst surface, to improve the activity of methylamine catalyst.
3, because reactor temperature constantly raises, the moisture content in methylamine catalyst volatilizees substantially 120 ℃ of left and right from methylamine catalyst, and in methylamine catalyst, the water of combination discharges with interior completely at 450 ℃, changes into γ-AL
2o
3,thereby make the holomorphosis of methylamine catalyst, recover it as the activity of catalyst.
4, continue to be warming up to 550 ℃ and keep 5-6 hour, the carbon in methylamine catalyst and hydrocarbon are burnt, improve the purity of methylamine catalyst.
5, the regeneration due to methylamine catalyst realizes under hot conditions, and the present invention reaches raising temperature by the exothermic reaction of carbon distribution on air and methylamine catalyst, makes the object of methylamine catalyst dehydration, energy-conserving and environment-protective; And by regulating the inlet of air and nitrogen to control the temperature in reactor, simple to operate, easily realize.
6, in methylamine catalyst, residual ammonia, methylamine and methyl alcohol is processed discharge by alkali lye in absorption tower; Meanwhile, in reactor, burning gases continue to enter in absorption tower and discharge, and have protected environment.
7, the present invention has extended the service life of methylamine catalyst and has reduced methylamine production cost.
8, the equipment that methylamine catalyst regneration of the present invention is used all can adopt equipment in methylamine production, and wherein reactor can replace with synthetic tower, does not additionally increase equipment investment.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 realizes device schematic diagram of the present invention.
Fig. 2 is methylamine catalyst heating curve figure of the present invention.
In figure: 1-reactor, 2-control valve, 3-compressor, 4-heating furnace, 5-nitrogen inlet, 6-air intlet, 7-steam inlet, 8-leakage fluid dram, 9-absorption tower, 10-alkali liquor inlet, 11-exhaust outlet, 12-pipeline, 13-pressure-control valve.
The specific embodiment
Embodiment mono-:
The renovation process that the invention provides a kind of methylamine catalyst, comprises the following steps:
(1) deactivated methylamine catalyst is deposited in reactor, open the steam that is positioned at reactor bottom, steam is blown into ammonia residual in methylamine catalyst, methylamine and methyl alcohol in absorption tower, and steam is 120 ℃, the saturated vapor of 0.3MPa, and the time of logical steam is 5 hours;
(2) by the waste gas alkali liquor absorption being blown in absorption tower, row discharge when then gas is from the exhaust outlet on top, absorption tower, liquid is disposed to Sewage Disposal from the leakage fluid dram of bottom, absorption tower and processes;
(3) open compressor and heating furnace, air passes in reactor through heating furnace, passes into nitrogen in reactor simultaneously;
(4) temperature of methylamine catalyst heats up by being less than 25 ℃/h in reactor, and temperature keeps 5h while rising to 550 ℃, when the content of oxygen is 20% in emission gases, closes heating furnace and continues to pass into air methylamine catalyst is cooled to 180 ℃.
Embodiment bis-:
A renovation process for methylamine catalyst, comprises the following steps:
(1) deactivated methylamine catalyst is deposited in reactor, open the steam that is positioned at reactor bottom, steam is blown into ammonia residual in methylamine catalyst, methylamine and methyl alcohol in absorption tower, and steam is that 160 ℃, 0.3MPa have saturated vapor, and the time of logical steam is 6 hours;
(2) by the waste gas alkali liquor absorption being blown in absorption tower, row discharge when then gas is from the exhaust outlet on top, absorption tower, liquid is disposed to Sewage Disposal from the leakage fluid dram of bottom, absorption tower and processes;
(3) open compressor and heating furnace, air passes in reactor through heating furnace, passes into nitrogen in reactor simultaneously;
(4) temperature of methylamine catalyst heats up by being less than 25 ℃/h in reactor, and temperature keeps 6h while rising to 550 ℃, when the content of oxygen is 21% in emission gases, closes heating furnace and continues to pass into air methylamine catalyst is cooled to 100 ℃.
Embodiment tri-:
As shown in Figure 2, the temperature rise period of methylamine catalyst is divided into double teacher:
A, de-free water stage: in 30-110 ℃, by heating rate, be less than 5 ℃/h, intensification 5h;
B, transition stage: in 110-220 ℃, by heating rate, be less than 15 ℃/h, intensification 8h;
C, methylamine catalyst water smoking: in 220-450 ℃, by heating rate, be less than 15 ℃/h, intensification 15h;
D, methylamine catalyst regneration stage: in 450-550 ℃, by heating rate, be less than 10 ℃/h, intensification 10h;
E, coal stage: temperature is that 550 ℃ of constant temperature keep 6h.
Methylamine catalyst regneration reduction process is exothermic reaction, by controlling the addition of air, simultaneously by regulating the inlet of nitrogen, reduce airborne oxygen concentration, control airborne oxygen content, to control the speed that reaction heats up, prevent that catalyst layer each point temperature-difference is excessive and make its active decline.If it is too fast that the temperature in reactor rises, should reduce air inlet; Or by pressure-control valve by system unload and strengthen the inlet of nitrogen, also can close valve heating furnace simultaneously and stop heating.
Embodiment tetra-:
As shown in Figure 1 be the regenerating unit of methylamine catalyst of the present invention, comprise reactor 1, absorption tower 9, reactor 1 bottom is provided with steam inlet 7, air intlet 6 and nitrogen inlet 5, nitrogen inlet 5 is provided with control valve 2; Air intlet 6 is connected with heating furnace 4 and compressor 3 in turn; The top of reactor 1 is connected with the bottom on absorption tower 9 by pipeline 12, in the middle of pipeline 12, is provided with pressure-control valve 13, and the top on absorption tower 9 is provided with exhaust outlet 11, bottom is provided with leakage fluid dram 8, and the middle part on absorption tower 9 is provided with alkali liquor inlet 10.
When methylamine catalyst of the present invention is regenerated, first ammonia residual in methylamine catalyst, methylamine and methyl alcohol will be blown in absorption tower through steam, then by alkali liquor absorption, waste gas and waste liquid discharge from the gas outlet, top on absorption tower and the leakage fluid dram of bottom respectively.Rear unlatching compressor, heating furnace have been blown, the methylamine catalyst bed that air heats in backward reactor through heating furnace after compressor compression again passes into, and pass into nitrogen simultaneously, methylamine catalyst surface and inner carbon distribution (C), hydrocarbon (CnHm) progressively react with airborne oxygen, its course of reaction is exothermic reaction, the temperature of catalyst layer is raise gradually, when reaching under 550 ℃ of high temperature, maintain 6 hours the carbon and the hydrocarbon that accumulate on methylamine catalyst are burnt completely, recover the catalyst activity of methylamine catalyst.
Above embodiment is not limited only to protection scope of the present invention, all based on basic thought of the present invention and all belonging in protection scope of the present invention of modifying or change.
Claims (3)
1. a renovation process for methylamine catalyst, is characterized in that: comprise the following steps:
(1) deactivated methylamine catalyst is deposited in reactor, opens the steam that is positioned at reactor bottom, steam is blown into ammonia residual in methylamine catalyst, methylamine and methyl alcohol in absorption tower;
(2), by the waste gas alkali liquor absorption in absorption tower, then distinguish discharging waste gas, waste liquid;
(3) open compressor and heating furnace, air passes in reactor through heating furnace, passes into nitrogen in reactor simultaneously;
(4) in reactor, the temperature of methylamine catalyst heats up by double teacher:
A, de-free water stage: in 30-110 ℃, by heating rate, be less than 5 ℃/h, intensification 5-7h;
B, transition stage: in 110-220 ℃, by heating rate, be less than 15 ℃/h, intensification 8-10h;
C, methylamine catalyst water smoking: in 220-450 ℃, by heating rate, be less than 15 ℃/h, intensification 15-17h;
D, methylamine catalyst regneration stage: in 450-550 ℃, by heating rate, be less than 10 ℃/h, intensification 10-12h;
E, coal stage: temperature is that 550 ℃ of constant temperature keep 5-6h;
When the content of oxygen is 20-22% in the waste gas of discharge, close heating furnace, continue to pass into air methylamine catalyst is lowered the temperature.
2. the renovation process of a kind of methylamine catalyst according to claim 1, is characterized in that: in described step (1), steam is 120-160 ℃, 0.3MPa saturated vapor, and the time that steam passes into is 5-6 hour.
3. the renovation process of a kind of methylamine catalyst according to claim 1, is characterized in that: in described step (4), methylamine catalyst is cooled to below 200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310120770.5A CN103203254B (en) | 2013-04-09 | 2013-04-09 | Methylamine catalyst regenerating method and device |
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|---|---|---|---|
| CN201310120770.5A CN103203254B (en) | 2013-04-09 | 2013-04-09 | Methylamine catalyst regenerating method and device |
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| CN103203254A CN103203254A (en) | 2013-07-17 |
| CN103203254B true CN103203254B (en) | 2014-12-10 |
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| CN110721645B (en) * | 2019-10-21 | 2022-01-25 | 山东京博石油化工有限公司 | Environment-friendly purging device and method for ethylbenzene reactor |
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| CN101172263B (en) * | 2006-10-31 | 2010-12-01 | 中国石油化工股份有限公司 | Regeneration method of copper base hydrodearsenic catalyst |
| CN100525901C (en) * | 2008-01-23 | 2009-08-12 | 昆明理工大学 | Regeneration method of dead catalyst |
| CN102407170B (en) * | 2010-09-21 | 2013-03-20 | 中国石油化工股份有限公司 | Device for simultaneously scorching at multiple sections in catalyst device of fixed bed reactor and process thereof |
| CN102698817B (en) * | 2012-05-28 | 2014-06-18 | 清华大学 | Pure oxygen regeneration process for fluid catalytic cracking catalyst and hydrogen preparation method |
| CN203220909U (en) * | 2013-04-09 | 2013-10-02 | 高玉华 | Regeneration device of methylamine catalyst |
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