CN103349973A - Regeneration method of nitrogen-preparation carbon molecular sieve - Google Patents
Regeneration method of nitrogen-preparation carbon molecular sieve Download PDFInfo
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Abstract
The invention relates to the technical field of molecular sieve, and especially relates to a regeneration method of a nitrogen-preparation carbon molecular sieve. The method provided by the invention sequentially comprises the steps that: screening and washing are carried out, wherein poisoned carbon molecular sieve is screened by using a mesh, and the screened carbon molecular sieve is washed by using water, such that impurities are removed; nitrogen-based high-temperature charring is carried out, wherein the temperature is increased to 850-1000 DEG C under the protection of nitrogen gas, such that charring is carried out; mixed gas activation is carried out, wherein a mixed gas of CO2 and CO is delivered into a furnace cavity, wherein the proportion of CO2 is 85-90%, such that the charred carbon molecular sieve is activated, wherein the temperature in the furnace is 700-800 DEG C; carbon deposition is carried out, wherein activated carbon molecular sieve is placed in a furnace cavity of a converter; the temperature in the converter is 800-900 DEG C; xylene is delivered in under the protection of nitrogen gas; the temperature of the furnace is maintained at 300-500 DEG C, such that xylene is absorbed by the carbon molecular sieve; xylene is cracked under the temperature of 800-900 DEG C, such that pyrolytic carbon is deposited on the char material; the carbon molecular sieve is subjected to pore size adjustment, such that a regenerated finished product is obtained. With the method provided by the invention, deeply poisoned nitrogen-preparation carbon molecular sieve can be activated, and the pore sizes after activation is uniform.
Description
Technical field
The present invention relates to the sieve technology field, particularly a kind of renovation process of nitrogen-preparing carbon molecular sieves.
Background technology
Carbon molecular sieve (Carbon Molecular Sieves, CMS) is a kind of novel non-polar adsorbent, has under the normal temperature transformation performance of oxygen molecule in the absorbed air, thereby can obtain nitrogen-rich gas.Adopt carbon molecular sieve pressure-variable adsorption legal system nitrogen new technology, its outstanding feature is nitrogen (N
2) the product impurity content is lower, nitrogen gas concn and tolerance can be regulated arbitrarily as required, and can be by the refining oxygen (O that obtains
2) content is less than 5PPm, dew point is lower than-60 ℃ high-purity nitrogen.
Nitrogen-preparing carbon molecular sieves has the microstructure type that belongs to same with active carbon, carbon black, the a kind of of carbon element of graphite body structure space group, the character that its micropore size and microcellular structure show then is that the covalent bond coordination of carbon body becomes hexagonal dot matrix arrangement and determines.Because O
2Molecule and N
2Molecular diameter is quite approaching, N
2The molecule aperture is 3.0 dusts, O
2The molecule aperture is 2.8 dusts, and pressure-variable adsorption is the process of a complexity, and nitrogen-preparing carbon molecular sieves is to O
2And N
2Equilibrium adsorption increase along with the increase of adsorptive pressure, reduce along with the reduction of adsorptive pressure, general optimum pressure is controlled at 0.6-0.8Mpa.Simultaneously, nitrogen-preparing carbon molecular sieves is for O
2Adsorbed molecular velocity ratio N
2It is fast that molecule is wanted, and the micro-pore diameter because of nitrogen-preparing carbon molecular sieves is the scope that is controlled at the 2.8-3 dust again, is conducive to O
2By preferential adsorption.So when pressurization absorption, O
2Molecule is quickly in the solid phase enrichment, and N
2Molecule is at gas phase enrichment, and the nitrogen of generation higher degree.Nitrogen-preparing carbon molecular sieves (CMS) is the high-efficiency adsorbent of air separation by PSA nitrogen processed, because carbon molecular sieve has stronger affinity to water, wet goods molecule, this just requires the raw air must be very clean, must do to purify preliminary treatment.Because pressure-variable adsorption uses the factors such as air compressor, just in air, bring inevitably moisture content, oil vapour and other harmful chemical gas into simultaneously.Thereby cause the nitrogen-preparing carbon molecular sieves blockage of the micro orifice, separating effect gradually falls, until forfeiture effect, i.e. so-called nitrogen-preparing carbon molecular sieves " poisoning ".
The carbon molecular sieve making nitrogen by pressure swing adsorption comes oxygen separation and nitrogen by Van der Waals force, therefore the specific area of molecular sieve is larger, more even and the micropore of pore-size distribution or the more adsorbances of sub-micro hole number are just larger, when the micropore of molecular sieve is stopped up by moisture or oily matter, the adsorption capacity of molecular sieve weakens greatly, will show that nitrogen making machine nitrogen gas concn when identical aerogenesis flow descends or during identical gas product concentration productive rate descend molecular sieve that Here it is " poisoning ".Activation processing for " poisoning " nitrogen-preparing carbon molecular sieves mainly adopts two kinds of methods at present,
The one, as shown in Figure 1, remove the blockage of the micro orifice material by the heating carbon molecular sieve.600-900 ℃ of high temperature of industrial general employing comes the moisture content of minute desorption, and the charing dust is to reach the activation of " poisoning " carbon molecular sieve.
The 2nd, as shown in Figure 2, by reducing pressure and inert gas blowback, remove the blockage of the micro orifice material.Keep adsorbent temperature constant, by reducing pressure and inert gas through preheating, about reverse blow molecular sieve to 200 ℃, and take away the adsorbate that desorption gets off.
Above-mentioned these two kinds of methods, it is the domestic common activation processing technology to recovery poisoning carbon molecular sieve, these two kinds of technology all are simply carbon molecular sieve to be carried out activation processing, technique is comparatively simple, general carbon molecular sieve of only poisoning for shallow hierarchies such as water, dusts is effective, and the carbon molecular sieve aperture after, the activation poor for the activation effect of the darker nitrogen-preparing carbon molecular sieves (such as greasy dirt, chemical contamination) of poisoning is inhomogeneous, macropore is more.
Summary of the invention
The purpose of this invention is to provide a kind of renovation process that can activate and activate to the darker nitrogen-preparing carbon molecular sieves of poisoning the uniform nitrogen-preparing carbon molecular sieves of back aperture.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A kind of renovation process of nitrogen-preparing carbon molecular sieves, it comprises step successively:
(1) screening is cleaned: the poisoning carbon molecular sieve is screened through mesh screen, and impurity is removed in the carbon molecular sieve water flushing that again screening is obtained;
(2) nitrogen base high temperature carbonization: the carbon molecular sieve that will clean places flue, is warming up to 850-1000 ℃ and carries out charing under nitrogen protection;
(3) mist activation: behind the high temperature cabonization, in flue, pass into CO
2, CO mist, wherein CO
2Ratio is 85%-90%, and the carbon molecular sieve of charing is activated, and temperature is 700-800 ℃ in the stove;
(4) carbon deposition: the carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 800-900 ℃; under nitrogen protection, pass into dimethylbenzene; keep furnace temperature under 300-500 ℃, to make carbon molecular sieve absorption dimethylbenzene; then under 800-900 ℃, make the dimethylbenzene cracking; thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials, carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
The optimal adsorption effect of most of carbon molecular sieve was crossed three annual output nitrogen efficient and has progressively been descended i.e. so-called " poisoning " with regard to 2 or three years.The carbon molecular sieve aperture of gained is general also inhomogeneous after the carbonization of prior art process, the activation, and macropore is more, and generally about 0.5-0.55nm, it separates the indifferent of air to macropore diameter.
Carbon deposition of the present invention is to utilize dimethylbenzene as hole-blocking agent cracking in the macropore of carbon molecular sieve (Carbon Molecular Sieves, CMS), makes RESEARCH OF PYROCARBON be deposited on the porch of macropore, thereby dwindles macropore diameter, makes the homogenization of product aperture.Carbon deposition of the present invention transfers the key in hole to be to improve carbon in the deposition in aperture, improves optionally purpose to reach the reduced bore, can keep higher micropore volume to make it have higher adsorption capacity simultaneously." poisoning " nitrogen-preparing carbon molecular sieves that the present invention processes is because the H that adsorbs in the carbon molecular sieve micropore in nitrogen process processed
2The greasy dirt on O molecule and coated carbon molecular sieve surface and other chemical contaminations cause nitrogen-preparing carbon molecular sieves " poisoning ", and the reason of " poisoning " and degree are generally all darker, can't accomplish complete activating and regenerating during simple activation processing.This kind situation need be through after the clean processing in early stage, after high temperature carbonization, gas activation processing, just can guarantee to residue in the higher boiling composition that is in adsorbed state in the carbon molecular sieve micropore and be heated and decompose, the low molecule gasification of a part and desorb, remaining part becomes carbon.
The selection of hole-blocking agent is larger on the impact of regeneration effect of the present invention, and the inventor finds to use under carbon sedimentary condition of the present invention dimethylbenzene to carry out pyrolytic deposition through groping, can make the homogenization of product aperture, thereby carry out regeneration, reduce discharging so the present invention can be national energy-saving, it is precious that waste material becomes.
The present invention introduces the method for carbon deposition, by adding dimethylbenzene micropore adjusting agent, keep furnace temperature at 300-500 ℃ of lower absorption dimethylbenzene, under the Pintsch process condition, make RESEARCH OF PYROCARBON be deposited on the porch of macropore, thereby dwindle macropore diameter, make the homogenization of product aperture, can reach 0.28-0.3nm through the post-depositional micropore size of carbon, reach the purpose of activating and regenerating, so that the nitrogen-preparing carbon molecular sieves that the degree of depth is poisoned is realized activating and regenerating, making to recycle becomes possibility.
Because the nitrogen-preparing carbon molecular sieves factor of created gase of " poisoning " is down to below the 100L/hkg, and through the nitrogen-preparing carbon molecular sieves product of micropore recovery technique activating and regenerating after testing after, factor of created gase is more than or equal to the 280L/hkg(CMS-280 specification) more than, physicochemical property and technical indicator meet or the requirement that is above standard.
As preferably, described step (2) nitrogen base high temperature carbonization: the carbon molecular sieve that will clean places flue, is warming up to 900-950 ℃ and carries out charing under nitrogen protection.
More preferably, described carbonization time is 1-1.5 hour.
As preferably, described step (3) mist activation: behind the high temperature cabonization, in flue, pass into CO
2, CO mist, wherein CO
2Ratio is 88%, and the carbon molecular sieve of charing is activated 10-15min, and temperature is 740-780 ℃ in the stove.
The ratio of mist of the present invention and soak time are to nitrogen-preparing carbon molecular sieves activating and regenerating better effects if; If the time is too short, activation not exclusively; If the time is oversize, can cause pore size to differ, be difficult to make the final finished aperture even.
More preferably, described soak time is 0.3-0.8h.
As preferably; described step (4) carbon deposition: the carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 850-880 ℃; under nitrogen protection, pass into dimethylbenzene; keep furnace temperature under 330-350 ℃, pressure 0.02-0.05MPa, to make carbon molecular sieve absorption dimethylbenzene, then under 850-880 ℃, make the dimethylbenzene cracking, thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials; carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
Temperature and pressure condition of the present invention makes nitrogen-preparing carbon molecular sieves activating and regenerating better effects if, and this may be because this temperature and pressure makes the absorption property of carbon molecular sieve better.
As preferably, described step (4) dimethylbenzene is reinforced by accurate peristaltic pump, and reinforced flow is 50-80ml/min.
In activating and regenerating nitrogen-preparing carbon molecular sieves carbon depositing operation production practical operation, the feed liquor amount of dimethylbenzene and the control of feed liquor time are the difficult points of this technique.At the research initial stage, the inventor adopts simple separatory funnel feed liquor, when producing, because the separatory funnel feed liquor needs manually-operated, is difficult to hold at control feed liquor flow and the ratio of feed liquor time, easily causes excessive response.During excessive response, hole-blocking agent is excessive, so that excess deposition on the carbon molecular sieve of carbon atom in flue of reduction does not reach technological requirement, need reselect preceding working procedure and do to do over again processing, and this has just increased energy consumption and production cost.Find to adopt the auto feed pump to realize by research automatically accurately reinforced, charge pump can be realized evenly, accurate feed liquor to adopt novel precise to wriggle, and feed liquor amount and feed liquor time are effectively controlled, and improves the rate that once is up to the standards of processing, reduce secondary processing cost, also avoid potential safety hazard.With advancing, because accurately reinforced, the single process qualification rate is elevated to more than 95% from original about 80%, and production efficiency is corresponding improve approximately about 30% also.
More preferably, the reinforced flow of described step (4) dimethylbenzene is 66ml/min.
Description of drawings
Fig. 1 is a kind of activating treatment method of prior art nitrogen-preparing carbon molecular sieves;
Fig. 2 is the another kind of activating treatment method of prior art nitrogen-preparing carbon molecular sieves;
Fig. 3 is the regeneration method of nitrogen carbon molecular sieve of the present invention.
The specific embodiment
Embodiment one
As shown in Figure 3, the poisoning carbon molecular sieve with the CMS-200 specification screens the carbon molecular sieve water flushing that again screening is obtained 2-3 time, removal impurity through 15-30 purpose mesh screen; The carbon molecular sieve that has cleaned is placed flue, under nitrogen protection, be warming up to 850 ℃ and carry out charing; Mist activation: behind the high temperature cabonization, in flue, pass into CO
2, CO mist, wherein CO
2Ratio is 85%, and the carbon molecular sieve of charing is activated, and temperature is 700 ℃ in the stove; Carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 800 ℃; under nitrogen protection, pass into dimethylbenzene; dimethylbenzene is reinforced by accurate peristaltic pump, and reinforced flow is 50ml/min, keeps furnace temperature to make carbon molecular sieve absorption dimethylbenzene under 300 ℃; then under 800 ℃, make the dimethylbenzene cracking; thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials, carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
Because the nitrogen-preparing carbon molecular sieves factor of created gase after " poisoning " is down to below the 100L/hkg, and the nitrogen-preparing carbon molecular sieves product of process micropore recovery technique activating and regenerating is after authoritative department detects, factor of created gase is more than or equal to the 200L/hkg(CMS-200 specification) more than, physicochemical property and technical indicator (seeing Table 1) surpass the like product level.
Performance comparison before and after the table 1 embodiment one poisoning carbon molecular sieve activating and regenerating
Embodiment two
As shown in Figure 3, the poisoning carbon molecular sieve with the CMS-280 specification screens the carbon molecular sieve water flushing that again screening is obtained 2-3 time, removal impurity through mesh screen; The carbon molecular sieve that has cleaned is placed flue, under nitrogen protection, be warming up to 1000 ℃ and carry out charing; Mist activation: behind the high temperature cabonization, in flue, pass into CO
2, CO mist, wherein CO
2Ratio is 90%, and the carbon molecular sieve of charing is activated, and temperature is 800 ℃ in the stove; Carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 900 ℃; under nitrogen protection, pass into dimethylbenzene; dimethylbenzene is reinforced by accurate peristaltic pump, and reinforced flow is 80ml/min, keeps furnace temperature to make carbon molecular sieve absorption dimethylbenzene under 500 ℃; then under 900 ℃, make the dimethylbenzene cracking; thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials, carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
Because the nitrogen-preparing carbon molecular sieves factor of created gase after " poisoning " is down to below the 100L/hkg, and the nitrogen-preparing carbon molecular sieves product of process micropore recovery technique activating and regenerating is after authoritative department detects, factor of created gase is more than or equal to the 280L/hkg(CMS-280 specification) more than, bulk density reaches 0.68g/ml, and physicochemical property and technical indicator surpass the like product level.
Embodiment three
As shown in Figure 3, the poisoning carbon molecular sieve with the CMS-240 specification screens the carbon molecular sieve water flushing that again screening is obtained 2-3 time, removal impurity through mesh screen; The carbon molecular sieve that has cleaned is placed flue, under nitrogen protection, be warming up to 900 ℃ and carry out charing; Mist activation: behind the high temperature cabonization, in flue, pass into CO
2, CO mist, wherein CO
2Ratio is 88%, and the carbon molecular sieve of charing is activated, and temperature is 78 ℃ in the stove; Carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 850 ℃; under nitrogen protection, pass into dimethylbenzene; dimethylbenzene is reinforced by accurate peristaltic pump, and reinforced flow is 66ml/min, keeps furnace temperature to make carbon molecular sieve absorption dimethylbenzene under 400 ℃; then under 830 ℃, make the dimethylbenzene cracking; thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials, carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
Because the nitrogen-preparing carbon molecular sieves factor of created gase after " poisoning " is down to below the 100L/hkg, and the nitrogen-preparing carbon molecular sieves product of process micropore recovery technique activating and regenerating is after authoritative department detects, factor of created gase is more than or equal to the 240L/hkg(CMS-240 specification) more than, bulk density reaches 0.65-0.68g/ml, compression strength is greater than 100N/, physicochemical property and technical indicator surpass the like product level, specifically see Table 2.
Physicochemical property and technical indicator after table 2 embodiment three carbon molecular sieve activating and regeneratings are processed
Embodiment four
With embodiment one, different is nitrogen base high temperature carbonization: the carbon molecular sieve that will clean places flue, is warming up to 900-950 ℃ and carries out charing under nitrogen protection.
Embodiment five
With embodiment two, different be high temperature cabonization after, in flue, pass into CO
2, CO mist, wherein CO
2Ratio is 88%, and the carbon molecular sieve of charing is activated 10-15min, and temperature is 740-780 ℃ in the stove, and described soak time is 0.3-0.8h.
Embodiment six
With embodiment three; different is the carbon deposition: the carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 850-880 ℃; under nitrogen protection, pass into dimethylbenzene; keep furnace temperature under 330-350 ℃, pressure 0.02-0.05MPa, to make carbon molecular sieve absorption dimethylbenzene, then under 850-880 ℃, make the dimethylbenzene cracking, thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials; carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
The comparative example one
With embodiment three; different is that the carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 700 ℃; under nitrogen protection, pass into benzene; keep furnace temperature to make carbon molecular sieve absorption benzene at 600 ℃; then under 850-880 ℃, make the benzene cracking, carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
After testing, factor of created gase is the 180L/hkg(CMS-240 specification) more than, bulk density reaches 0.67g/ml, and compression strength is below 35N/, and physicochemical property and technical indicator are lower than the like product level.
This specific embodiment only is explanation of the invention; it is not limitation of the present invention; those skilled in the art can make the modification that does not have creative contribution to the present embodiment as required after reading this specification, but as long as all are subject to the protection of Patent Law in claim scope of the present invention.
Claims (9)
1. the renovation process of a nitrogen-preparing carbon molecular sieves is characterized in that: comprise successively step:
(1) screening is cleaned: the poisoning carbon molecular sieve is screened through mesh screen, and impurity is removed in the carbon molecular sieve water flushing that again screening is obtained;
(2) nitrogen base high temperature carbonization: the carbon molecular sieve that will clean places flue, is warming up to 850-1000 ℃ and carries out charing under nitrogen protection;
(3) mist activation: behind the high temperature cabonization, in flue, pass into CO
2, CO mist, wherein CO
2Ratio is 85%-90%, and the carbon molecular sieve of charing is activated, and temperature is 700-800 ℃ in the stove;
(4) carbon deposition: the carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 800-900 ℃; under nitrogen protection, pass into dimethylbenzene; keep furnace temperature under 300-500 ℃, to make carbon molecular sieve absorption dimethylbenzene; then under 800-900 ℃, make the dimethylbenzene cracking; thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials, carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
2. the renovation process of a kind of nitrogen-preparing carbon molecular sieves according to claim 1, it is characterized in that: described step (2) nitrogen base high temperature carbonization: the carbon molecular sieve that will clean places flue, is warming up to 900-950 ℃ and carries out charing under nitrogen protection.
3. the renovation process of a kind of nitrogen-preparing carbon molecular sieves according to claim 2, it is characterized in that: described carbonization time is 1-1.5 hour.
4. the renovation process of a kind of nitrogen-preparing carbon molecular sieves according to claim 1 is characterized in that: described step (3) mist activation: behind the high temperature cabonization, pass into CO in flue
2, CO mist, wherein CO
2Ratio is 88%, and the carbon molecular sieve of charing is activated 10-15min, and temperature is 740-780 ℃ in the stove.
5. the renovation process of a kind of nitrogen-preparing carbon molecular sieves according to claim 4, it is characterized in that: described soak time is 0.3-0.8h.
6. the renovation process of each described a kind of nitrogen-preparing carbon molecular sieves according to claim 1-5; it is characterized in that: described step (4) carbon deposition: the carbon molecular sieve after activated is placed in the converter flue; the converter temperature is 850-880 ℃; under nitrogen protection, pass into dimethylbenzene; keep furnace temperature under 330-350 ℃, pressure 0.02-0.05MPa, to make carbon molecular sieve absorption dimethylbenzene; then under 850-880 ℃, make the dimethylbenzene cracking; thereby RESEARCH OF PYROCARBON is deposited on the Carbon Materials; carbon molecular sieve is carried out aperture adjustment, obtain recycled product.
7. the renovation process of a kind of nitrogen-preparing carbon molecular sieves according to claim 6 is characterized in that: described step (4) dimethylbenzene is reinforced by accurate peristaltic pump, and reinforced flow is 50-80ml/min.
8. the renovation process of a kind of nitrogen-preparing carbon molecular sieves according to claim 6 is characterized in that: the reinforced flow of described step (4) dimethylbenzene is 66ml/min.
9. the renovation process of a kind of nitrogen-preparing carbon molecular sieves according to claim 7 is characterized in that: the reinforced flow of described step (4) dimethylbenzene is 66ml/min.
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Cited By (6)
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| CN104307479A (en) * | 2014-11-07 | 2015-01-28 | 威海华泰分子筛有限公司 | Regeneration method of invalid carbon molecular sieve |
| CN105944674A (en) * | 2016-06-17 | 2016-09-21 | 湖州南浔展辉分子筛厂 | Regeneration method of poisoned carbon molecular sieve |
| CN106076921A (en) * | 2016-06-15 | 2016-11-09 | 湖州南浔展辉分子筛厂 | A kind of cleaning device of carbon molecular sieve |
| CN107175091A (en) * | 2017-06-10 | 2017-09-19 | 湖州知维技术服务有限公司 | A kind of poison deactivation nitrogen-preparing carbon molecular sieves activating and regenerating Application way |
| CN107572521A (en) * | 2016-07-09 | 2018-01-12 | 王玲燕 | A kind of method that nitrogen carbon molecular sieve is prepared by bagasse |
| CN112337321A (en) * | 2019-08-08 | 2021-02-09 | 中国石油天然气股份有限公司 | Carbon molecular sieve membrane structure remodeling method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104307479A (en) * | 2014-11-07 | 2015-01-28 | 威海华泰分子筛有限公司 | Regeneration method of invalid carbon molecular sieve |
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| CN106076921A (en) * | 2016-06-15 | 2016-11-09 | 湖州南浔展辉分子筛厂 | A kind of cleaning device of carbon molecular sieve |
| CN105944674A (en) * | 2016-06-17 | 2016-09-21 | 湖州南浔展辉分子筛厂 | Regeneration method of poisoned carbon molecular sieve |
| CN107572521A (en) * | 2016-07-09 | 2018-01-12 | 王玲燕 | A kind of method that nitrogen carbon molecular sieve is prepared by bagasse |
| CN107175091A (en) * | 2017-06-10 | 2017-09-19 | 湖州知维技术服务有限公司 | A kind of poison deactivation nitrogen-preparing carbon molecular sieves activating and regenerating Application way |
| CN112337321A (en) * | 2019-08-08 | 2021-02-09 | 中国石油天然气股份有限公司 | Carbon molecular sieve membrane structure remodeling method |
| CN112337321B (en) * | 2019-08-08 | 2022-11-04 | 中国石油天然气股份有限公司 | Carbon molecular sieve membrane structure remodeling method |
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