CN109731562A - A kind of two-part regeneration method of porous carbon base desulfurizer - Google Patents
A kind of two-part regeneration method of porous carbon base desulfurizer Download PDFInfo
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Abstract
The invention discloses a kind of two-part regeneration methods of porous carbon base desulfurizer, and first using the sulfuric acid and sulfurous acid in washing removal desulfurizing agent, then heating removes the elemental sulfur in desulfurizing agent under nitrogen atmosphere.The Sulfur capacity of porous carbon base desulfurizer after regeneration can efficiently restore the desulphurizing activated of desulfurizing agent up to the 80~99% of unused desulfurizing agent；And the method provided through the invention can be realized the multiple regeneration of porous carbon base desulfurizer, be conducive to the recycling of desulfurizing agent, reduce desulphurization cost, have huge application prospect in this field.
Description
Technical field
The invention belongs to environmental technology field, it is related to the desulfurizer regeneration technology for removing hydrogen sulfide, and in particular to one
The regeneration method of the porous carbon base desulfurizer of kind.
Background technique
Biogas, natural gas etc. are the important component and key link of energy-saving and emission-reduction as important clean energy resource,
Reply climate change and development low-carbon economy promote to have played huge effect in terms of new countryside construction.However, in the life of biogas
It produces with during gas extraction, is usually associated with H2The generation of S gas.H2S is a kind of harmful hypertoxic gas, works as air
Middle concentration is more than 28mg/m3When, people just can not work normally；More than 1000mg/m3When, so that it may cause acute poisoning, causes personnel
It is dead.In addition, H2S is to the also strong corrosiveness such as pipeline, burner and instrument and meter, the SO generated after burning2It will cause
Environmental pollution, and lead to the pollution problems such as serious acid rain, haze.In general, the H in biogas2S concentration is 100~15000mg/
m3, and H in China's natural gas2S content is more than 10000mg/m3Natural gas account for the 25% of gross reserves, significantly larger than Environmental Protection in China
The regulation 20mg/m of standard3.To realize the environmental protection of energy source gas, high level, efficiently utilizing, the research and development of desulfurization technology are especially compeled
It cuts.
Therefore, the desulfurizing agent for being largely used to removing hydrogen sulfide is had developed both at home and abroad.Common desulfurizing agent be mainly iron oxide,
Zinc oxide and porous charcoal.Ferric oxide desulfurizer is extremely difficult to fine de-sulfur, and ferric oxide desulfurizer due to being limited by chemical balance
It is influenced by the water vapour carried secretly, desulfurization effect is not good enough, and regenerates difficult.Zinc oxide can fine de-sulfur, the disadvantage is that high-temperature operation, making
With at high cost.Porous charcoal desulfurization is absorption, the catalysis oxidation H using its flourishing pore structure and surface active groups2S reaches
To the purpose of desulfurization, has many advantages, such as that low energy consumption, equipment be simple, ambient operation, be widely used in removing hydrogen sulfide.
In sweetening process, hydrogen sulfide in gas can by the active component on porous carbon material surface such as metal oxide,
The catalysis oxidations such as oxygen-containing functional group, nitrogen-containing functional group are elemental sulfur, and have a small amount of sulfuric acid and sulfurous acid to generate.Sweetening process produces
Raw elemental sulfur and sulfurous acid, sulfuric acid can be attached in the duct of porous carbon material, and covering desulphurizing activated point loses desulfurizing agent
It is living, cause desulfuration efficiency to decline, it is necessary to be replaced or be regenerated.In general, inactivation porous charcoal desulfurizing agent as hazardous waste into
Enter landfill yard to be filled, not only increase the burden of landfill yard, and also greatly increases the use cost of desulfurizing agent.Cause
This, removes its internal desulfurization product adhered to by certain regeneration method to the desulfurizing agent of inactivation and restores desulphurizing activated to be very
It is necessary.
The regeneration method of common porous carbon base desulfurizer (i.e. active carbon class desulfurizing agent) has hot recycling and solvent reclamation.
Hot recycling is to heat the porous carbon base desulfurizer of adsorption saturation in nitrogen or air atmosphere, and release is wherein deposited
The desulfurization products such as the elemental sulfur and sulfuric acid of storage, sulfurous acid, so that it is desulphurizing activated to restore its.However, during heating, being attached to
Sulfuric acid on porous carbon base desulfurizer can react with carbon matrix, can not only destroy the pore structure of porous carbon material, make more
SO is largely lost and generate to the quality of hole Carbon Materials2Gas (formula (1) and (2)), but also will increase the table of porous carbon material
Face is acid.The increase of porous carbon base desulfurizer surface acidity can greatly weaken it to the absorption of sour gas hydrogen sulfide and urge
Change ability causes its hot recycling efficiency lower.Therefore, the hot recycling method of porous carbon base desulfurizer uses less.
C+H2SO4→CO(g)+SO2(g)+H2O(g) (1)
C+2H2SO4→CO2(g)+2SO2(g)+2H2O(g) (2)
Solvent reclamation is the desulfurization products such as the elemental sulfur being stored on desulfurizing agent after being inactivated using solvent dissolution, elution, from
And restore the activity of desulfurizing agent.Since sulphur simple substance is insoluble in water, it is slightly soluble in alcohol, is soluble in carbon disulfide, therefore, solvent reclamation
Mainly use carbon disulfide as solvent.Patent publication No. is " a kind of vulcanization disclosed in the patent document of 102489278 A of CN
The regeneration method of hydrogen desulfurizing agent " is configured to eluent, desulfurizing agent using carbon disulfide as primary raw material, by diluent of organic reagent
It is impregnated with eluent, after elution desulfurization, is filtered, dries successfully recycling desulfurizer can be realized.But this method largely makes
Carbon disulfide is volatile, and high poison, inflammable, explosive, very harmful to environmental and human health impacts, is national regulatory drug,
And higher cost.Meanwhile the sulphur simple substance in the eluent after this method recycling desulfurizer needs further distillation that could be enriched with benefit
With process is complicated, and energy consumption is higher.On the other hand, this method is difficult to remove sulfuric acid, the sulfurous acid of sweetening process generation, leads to this
The regeneration efficiency of method is not high, and only 8~78%.
Therefore, realize key is how effectively to go to the highly efficient regeneration of the porous carbon base desulfurizer after removing hydrogen sulfide
Except leading to its desulphurizing activated reduced desulfurization product, such as sulphur simple substance, sulfurous acid and sulfuric acid, while porous carbon base desulfurizer is not changed
Pore structure and surface chemical property.
Summary of the invention
Low, the at high cost, desulfurization product for regeneration efficiency existing for existing porous charcoal base hydrogen sulfide desulphurization agent regeneration techniques
The problems such as hardly possible recycling, complex process, the purpose of the present invention is intended to provide a kind of regeneration method of porous carbon base desulfurizer, Neng Gouyou
Effect removes the desulfurization product of porous carbon base desulfurizer, efficiently restores desulphurizing activated, desulfurization product (such as sulphur isolated of desulfurizing agent
Simple substance, sulfuric acid and sulfurous acid) classification recycling can be carried out, realize the regeneration of Sulphur ressource.
By the desulfurization product such as physicochemical properties of elemental sulfur, sulfurous acid and sulfuric acid it is found that sulfurous acid and sulfuric acid are soluble in
Water, and elemental sulfur easy distillation not soluble in water.Based on this, the invention proposes be segmented regenerated side using washing-heating two-stage
The desulfurization product of porous carbon base desulfurizer after method removal inactivation, is removed in inactivation desulfurizing agent to be processed first by washing
Sulfurous acid and sulfuric acid to efficiently restore the desulphurizing activated of desulfurizing agent, while realizing desulfurization then by heating removal sulphur simple substance
The classification resource utilization of product.
The two-part regeneration method of porous carbon base desulfurizer provided by the invention, comprising the following steps:
(1) it washs: being washed using porous carbon base desulfurizer of the water to inactivation to washing lotion pH value >=6.5；
(2) dry: the porous carbon base desulfurizer after washing is dry at a temperature of not higher than 60 DEG C；
(3) it heats: the porous carbon base desulfurizer after drying being heated to 300~450 DEG C under nitrogen atmosphere, and in the temperature
Degree is lower to be kept for 10~60 minutes.
The two-part regeneration method of above-mentioned porous carbon base desulfurizer, the purpose of step (1) are to remove desulfurizing agent by washing
In sulfurous acid and sulfuric acid.Washing specific implementation can are as follows: at least one in the modes such as elution, oscillation washing and supersound washing
Kind, generally use one such mode.It is washed with water the porous carbon base desulfurizer of inactivation, removes sulfuric acid and sulfurous therein
Acid is filtered or is filtered removal washing lotion after washing；In washing process aforesaid operations can be repeated to washing lotion by replacing water
PH value >=6.5 (for elution, can periodically measure the pH value of washing lotion).Washing Water usage is 5~50mL/g porous charcoal every time
Base desulfurizer (i.e. water is 5~50mL/g metering according to the volume mass of porous carbon base desulfurizer ratio).Wash the water used
It can be deionized water, distilled water or tap water.Elute concrete operations are as follows: the desulfurizing agent of inactivation is placed in elution device, with water
Desulfurizing agent is eluted as leacheate.Oscillation washing concrete operations are as follows: desulfurizing agent and water are placed in after container mixes, then
Container is placed in shaking table or oscillation case and vibrates washing；Oscillation wash time is generally 5~30min.Supersound washing concrete operations
Are as follows: desulfurizing agent and water are placed in after container mixes, container is then placed in supersound washing in ultrasonic device again, supersound washing when
Between generally 2~10min.
The two-part regeneration method of above-mentioned porous carbon base desulfurizer in step (2), is preferentially taken at 40~60 DEG C to porous
24~48h is dried in carbon base desulfurizer.
The purpose of the two-part regeneration method of above-mentioned porous charcoal base hydrogen sulfide desulphurization agent, step (3) is to pass through heating sublimation
Mode remove the elemental sulfur in desulfurizing agent, in order to avoid the physicochemical property of desulfurizing agent changes, the present invention is in nitrogen atmosphere
Enclose middle progress.The heating ramp rate that the present invention uses is 5~20 DEG C/min.10 are kept after being heated to 300~450 DEG C
~60min can remove the elemental sulfur on desulfurizing agent, while can be by the sulphur simple substance enriching and recovering after distillation.
Compared with prior art, the two-part regeneration method of porous carbon base desulfurizer provided by the invention has following ten
Divide prominent advantage and advantageous effects:
1, the present invention uses two-part regeneration method, first using the sulfuric acid and sulfurous acid in washing removal desulfurizing agent, so
The elemental sulfur in heating removal desulfurizing agent, the hydrogen sulfide Sulfur capacity of the porous carbon base desulfurizer after regeneration are reachable under nitrogen atmosphere afterwards
The 80~99% of desulfurizing agent are not used, the desulphurizing activated of desulfurizing agent can be efficiently restored.
2, the present invention can be realized the multiple regeneration of porous carbon base desulfurizer, be conducive to the recycling of desulfurizing agent, reduce
Desulphurization cost has huge application prospect in this field.
3, desulfurization product such as sulfuric acid, sulfurous acid, elemental sulfur generated in regenerative process of the present invention etc. can further effectively
It separates, convenient for the recycling and utilization of desulfurization product.
4, the present invention will not destroy the pore structure of porous carbon material and charcoal is caused to damage compared to the method for simple hot recycling
It loses, material surface chemistries will not be changed.
5, the present invention does not use poisonous and hazardous carbon disulfide equal solvent compared to solvent regenerated from washing method, will not be right
Environment generates secondary pollution, can satisfy environmentally friendly production requirement.
Detailed description of the invention
Fig. 1 is the thermal gravimetric analysis curve of N doping porous charcoal desulfurizing agent after desulfurization in the embodiment of the present invention 1.
Fig. 2 is desulfurization product X-ray energy spectrum high-resolution in N doping porous charcoal desulfurizing agent after desulfurization in the embodiment of the present invention 1
Figure.
Fig. 3 be the embodiment of the present invention 1 in N doping porous charcoal desulfurizing agent washed, dried after thermal gravimetric analysis curve.
Fig. 4 is the X-ray of the N doping porous charcoal and regenerated N doping porous charcoal of desulfurization inactivation in the embodiment of the present invention 1
Energy spectrum diagram.
Fig. 5 is N doping porous charcoal desulfurizing agent desulfurization-regeneration cycle test analysis figure in the embodiment of the present invention 2.
Specific embodiment
The embodiment of the present invention is provided below with reference to attached drawing, and technical solution of the present invention is carried out into one by embodiment
Clear, the complete explanation of step.Obviously, the embodiment is only a part of the embodiments of the present invention, instead of all the embodiments.
Based on the content of present invention, those of ordinary skill in the art are obtained all other without making creative work
Embodiment belongs to the range that the present invention is protected.
Embodiment 1
N doping porous charcoal is used to remove hydrogen sulfide, simulation biogas by hydrogen sulfide gas, nitrogen, air mixed preparing,
Wherein concentration of hydrogen sulfide is 1000ppmv, and oxygen concentration 10000ppmv, relative humidity 10%, reaction temperature is when desulfurization
25 DEG C, when exporting concentration of hydrogen sulfide and reaching 50ppm, experiment stops, it is believed that desulfurizing agent has inactivated, the working curve obtained at this time
For calculating desulfurizing agent Sulfur capacity.
The porous carbon base desulfurizer that the present embodiment uses provides for national flue-gas desulfurizing engineering Technical Research Center laboratory
N doping porous charcoal, test obtain N doping porous charcoal desulfurizing agent Sulfur capacity be 420mg/g.The preparation of N doping porous charcoal
Journey are as follows: using cypress bits as raw material, KOH is activator, and melamine is nitrating agent, is that 1:1:1 waits bodies in water according to mass ratio
It is dried after product dipping 12h, drying products therefrom activates 2h under the conditions of 800 DEG C and obtains N doping porous charcoal.
To after desulfurization N doping porous charcoal carry out thermogravimetric analysis, and to the desulfurization product adhered in N doping porous charcoal into
Row X-ray energy spectrum high resolution analysis, analysis result are as depicted in figs. 1 and 2.
Shown in Fig. 1, weightless peak of the N doping porous charcoal between 190~280 DEG C is mainly the decomposition of sulfurous acid after desulfurization
With mass loss caused by the reacting of sulfuric acid and carbon base body, the mass loss between 280~430 DEG C is mainly the liter of elemental sulfur
China.
Shown in Fig. 2, the X-ray energy spectrum High-Resolution Map of desulfurization product shows that the desulfurization product of porous carbon base desulfurizer is mainly
Sulfuric acid, sulfurous acid and elemental sulfur.
The cleaning solution that the present embodiment uses is tap water.
It takes the N doping porous charcoal desulfurizing agent inactivated after 10g desulfurization to be placed in the ground conical flask of 250mL, is added later
100mL originally water immersion desulfurizing agent, places into supersound washing 10min in ultrasonic device, then filters, and is measured and is filtered using pH meter
Washing lotion pH value.Replacement tap water repeats aforesaid operations and washs to N doping porous charcoal, the washing lotion pH of washing to filtering
Value >=6.5 stops washing, the N doping porous charcoal after being washed；By the N doping porous charcoal desulfurizing agent after washing at 60 DEG C
Drying is for 24 hours.N doping porous charcoal desulfurizing agent after taking drying is placed in tube furnace, under nitrogen protection, with the heating of 5 DEG C/min
Rate is heated to 400 DEG C and keeps 60min to get regenerated N doping porous charcoal desulfurizing agent.
Thermogravimetric analysis is carried out to the N doping porous charcoal desulfurizing agent after washing-drying, analysis result is as shown in Figure 3.From figure
In as can be seen that the heat decomposition curve of desulfurizing agent after washing-drying only remains next weightless peak, the liter of Master Home elemental sulfur
China, this shows that water washing process has removed sulfuric acid and sulfurous acid substantially.
X-ray energy spectrum analysis is carried out respectively to the N doping porous charcoal and regenerated N doping porous charcoal of desulfurization inactivation, point
Result is analysed as shown in figure 4, it can be seen from the figure that the desulfurization product on desulfurizing agent is stored in after desulfurization, by washing-heating two
It has been substantially removed after the regeneration of segmentation regeneration method, also, washing-heating two-part regenerative process and to have not been changed N doping more
The chemical property of hole charcoal desulfurizing agent.
Nitrogen adsorption desorption analysis is carried out respectively to the N doping porous charcoal after the N doping porous charcoal and regeneration of desulfurization inactivation,
The results are shown in Table 1 for analysis.From table 1 it follows that regeneration after desulfurizing agent pore structure and specific surface area with it is not used
Desulfurizing agent (not carrying out desulphurization reaction) is closer to, and shows washing-heating two-part regenerative process to the pore structure of desulfurizing agent
Influence is smaller, can restore the pore structure of desulfurizing agent.
The pore structure of table 1 desulfurizing agent and recycling desulfurizer
N doping porous charcoal after taking regeneration carries out desulfurization again, and experiment condition is identical as initial desulfurization condition, tests
The Sulfur capacity of N doping porous charcoal desulfurizing agent is 415mg/g after to regeneration, is 99% that N doping porous charcoal desulfurizing agent is not used.This
The regeneration method that real invention provides can efficiently restore the desulphurizing activated of desulfurizing agent.
Embodiment 2
Porous carbon base desulfurizer that the present embodiment uses, the desulfurization test of progress are same as Example 1, no longer superfluous here
It states.
The cleaning solution that the present embodiment uses is tap water.
It takes the N doping porous charcoal desulfurizing agent inactivated after 10g desulfurization to be placed in the ground conical flask of 250mL, is added later
100mL originally water immersion desulfurizing agent, places into supersound washing 10min in ultrasonic device, then filters, and is measured and is filtered using pH meter
Washing lotion pH value.Replacement tap water repeats aforesaid operations and washs to N doping porous charcoal, the washing lotion pH of washing to filtering
Value >=6.5 stops washing, the N doping porous charcoal after being washed；By the N doping porous charcoal desulfurizing agent after washing at 60 DEG C
Drying is for 24 hours.N doping porous charcoal desulfurizing agent after taking drying is placed in tube furnace, under nitrogen protection, then with 5 DEG C/min's
Heating rate is heated to 400 DEG C and keeps 60min to get regenerated N doping porous charcoal desulfurizing agent.
N doping porous charcoal after taking regeneration carries out desulfurization according to the sweetening process that embodiment 1 provides, after desulfurization, then
Desulfurizer regeneration is carried out according to the regenerative process that front provides.Entire desulfurization-regenerative process recycles 5 times.
The Sulfur capacity and time of break-through of N doping porous charcoal desulfurizing agent in each sweetening process are measured, as a result as shown in Figure 5.
From figure 5 it can be seen that the Sulfur capacity of regeneration N doping porous charcoal desulfurizing agent is 415mg/g for the first time, it is unused
The 99% of desulfurizing agent.The Sulfur capacity that the 5th regenerates N doping porous charcoal desulfurizing agent is 360mg/g, is that N doping porous charcoal is not used
The 86% of desulfurizing agent, it can thus be seen that the two-stage regeneration realizes the highly efficient regeneration of N doping porous charcoal desulfurizing agent.
Embodiment 3
The desulfurizing agent that the present embodiment uses is the wooden mesoporous carbon of N doping of laboratory preparation, preparation process are as follows: with biology
Matter waste cypress bits are raw material, and phosphoric acid is activator, are that 1.2:1 is isometric in water according to phosphoric acid and the mass ratio that cypress is considered to be worth doing
Dipping activates 2h at 600 DEG C and obtains mesoporous carbon after 12 hours；Then use urea for nitrating agent again, according to urea and preparation
The mass ratio of mesoporous carbon is 2:1 in water after incipient impregnation 12 hours, N doping is prepared within 1 hour in 700 DEG C small reaction
Mesoporous carbon.
The wooden mesoporous carbon of the N doping of preparation is subjected to desulfurization test according to the desulfurized step that embodiment 1 provides, is tested
The wooden mesoporous carbon desulfurizing agent Sulfur capacity of the N doping arrived is 365mg/g, and desulfurization product mainly has sulphur simple substance, sulfurous acid, sulfuric acid.
The cleaning solution that the present embodiment uses is tap water.
The wooden mesoporous carbon desulfurizing agent of N doping after taking 10g desulfurization is placed in the ground conical flask of 250mL, is added later
The 50mL originally wooden mesoporous carbon desulfurizing agent of water immersion N doping places into shaking table oscillation washing 30min, then filters, using pH
The pH value for the washing lotion for measuring to filter is 4.3.Replacement tap water repeats aforesaid operations and washs three times to porous charcoal, measures most
The pH value of the washing lotion once filtered afterwards is 6.7, stops washing, the wooden mesoporous carbon desulfurizing agent of N doping after being washed；By water
The wooden mesoporous carbon desulfurizing agent of N doping after washing is in 50 DEG C of dry 48h.Take it is dry after the wooden mesoporous carbon desulfurizing agent of N doping in
In tube furnace under nitrogen protection, 450 DEG C are heated to the heating rate of 5 DEG C/min and 10min is kept to mix to get regenerated nitrogen
Weedtree matter mesoporous carbon desulfurizing agent.
Desulfurization is carried out according to the sweetening process that front provides with the wooden mesoporous carbon desulfurizing agent of regenerated N doping, test obtains
The Sulfur capacity of the wooden mesoporous carbon desulfurizing agent of N doping is 320mg/g, is 88% that desulfurizing agent is not used.
Embodiment 4
The desulfurizing agent that the present embodiment uses is industrial common business porous charcoal desulfurizing agent.
Porous charcoal desulfurizing agent is subjected to desulfurization test, the porous charcoal tested according to the desulfurized step that embodiment 1 provides
The Sulfur capacity of desulfurizing agent is 250mg/g, and desulfurization product mainly has sulphur simple substance, sulfurous acid, sulfuric acid.
The cleaning solution that the present embodiment uses is distilled water.
It takes the porous charcoal desulfurizing agent inactivated after 10g desulfurization to be placed in the conical flask of 1L, 500mL is added later and distills water immersion
Desulfurizing agent places into supersound washing 2min in ultrasonic device, after rear filtering, use pH meter measure the pH value of the washing lotion of filtering for
5.6.Replacement distilled water repeats to wash modified porous charcoal desulfurizing agent aforesaid operations 1 time, measures washing for last time filtering
The pH value of liquid is 6.9, stops washing, the porous charcoal desulfurizing agent after being washed；By the porous charcoal desulfurizing agent after washing at 60 DEG C
Drying is for 24 hours.Porous charcoal desulfurizing agent after taking drying is placed in tube furnace, under nitrogen protection, with the heating rate of 20 DEG C/min
It is heated to 300 DEG C and keeps 60min to get regenerated porous charcoal desulfurizing agent.
Desulfurization is carried out according to the sweetening process that front provides with regenerated porous charcoal desulfurizing agent, porous charcoal desulfurization is calculated
The Sulfur capacity of agent is 212mg/g, is 85% that desulfurizing agent is not used.
Embodiment 5
The desulfurizing agent that the present embodiment uses is the N doping of national flue-gas desulfurizing engineering Technical Research Center laboratory preparation
Mesoporous carbon, preparation process are as follows: select NH3For nitrogen source, centring hole charcoal carries out N doping under the high temperature conditions.Weigh 0.4g mesoporous carbon
It is placed in quartz boat, in N2Target spray NH is warming up to the heating rate of 20 DEG C/min in atmosphere3Temperature (600 DEG C) turns gas
It is changed to the NH that concentration is 1%3(N2For balanced gas), it is passed through in high temperature process furnances with the flow velocity of 100mL/min and keeps 1h, then
Close NH3, continue to be passed through N2, it is cooled to room temperature to sample, i.e. acquisition high temperature NH3(see reference text for treated N Doped Mesoporous charcoal
It offers: the preparation of the novel N Doped Mesoporous charcoal of Zhou Qiying and its desulfurization and decarburization performance study Sichuan University 2018).
N doping mesoporous carbon desulfurizing agent is subjected to desulfurization test according to the desulfurized step that embodiment 1 provides, is tested
The Sulfur capacity of mesoporous carbon desulfurizing agent is 130mg/g, and desulfurization product mainly has sulphur simple substance, sulfurous acid, sulfuric acid.
The cleaning solution that the present embodiment uses is tap water.
Take the mesoporous carbon desulfurizing agent inactivated after 10g desulfurization to be placed in the Buchner funnel of diameter 50mm, using 50mL/min from
Water elution, after the pH value of the washing lotion of 5min acquisition filter, 12min, the pH value for measuring the washing lotion of filtering is 6.5, is stopped
Washing, the mesoporous carbon after being washed；Mesoporous carbon desulfurizing agent after washing is dried for 24 hours at 60 DEG C.Mesoporous carbon after taking drying
Desulfurizing agent is placed in tube furnace, under nitrogen protection, is heated to 400 DEG C with the heating rate of 10 DEG C/min and is kept 40min, i.e.,
Obtain regenerated mesoporous carbon desulfurizing agent.
Desulfurization is carried out according to the sweetening process that front provides with regenerated N doping mesoporous carbon desulfurizing agent, test obtains nitrogen and mixes
The Sulfur capacity of miscellaneous mesoporous carbon desulfurizing agent is 114mg/g, is 88% that desulfurizing agent is not used.
Claims (9)
1. a kind of two-part regeneration method of porous carbon base desulfurizer, it is characterised in that the following steps are included:
(1) it washs: being washed using porous carbon base desulfurizer of the water to inactivation to washing lotion pH value >=6.5；
(2) dry: the porous carbon base desulfurizer after washing is dry at a temperature of not higher than 60 DEG C；
(3) it heats: the porous carbon base desulfurizer after drying being heated to 300~450 DEG C under nitrogen atmosphere, and at this temperature
It is kept at least 10 minutes.
2. the two-part regeneration method of porous carbon base desulfurizer according to claim 1, it is characterised in that in step (1), lead to
It crosses at least one of elution, oscillation washing and supersound washing mode to wash the porous carbon base desulfurizer of inactivation, removes it
In sulfuric acid and sulfurous acid, filtered or filtered removal washing lotion after washing.
3. the two-part regeneration method of porous carbon base desulfurizer according to claim 2, it is characterised in that use water when washing
Amount is the porous carbon base desulfurizer of 5~50mL/g.
4. the two-part regeneration method of porous carbon base desulfurizer according to claim 2, it is characterised in that elution concrete operations
Are as follows: the desulfurizing agent of inactivation is placed in elution device, desulfurizing agent is eluted using water as leacheate；The specific behaviour of oscillation washing
As: desulfurizing agent is placed in container with water and is mixed, then container is placed in shaking table or oscillation case again and carries out oscillation washing；Ultrasound
Wash concrete operations are as follows: desulfurizing agent is placed in container with water and is mixed, container is then placed in progress ultrasound in ultrasonic device again and is washed
It washs.
5. the two-part regeneration method of porous carbon base desulfurizer according to claim 4, it is characterised in that the oscillation treatment time
For 5~30min；Sonication treatment time is 2~10min.
6. according to claim 1 to the two-part regeneration method of 5 any porous carbon base desulfurizers, it is characterised in that washing makes
Water is deionized water, distilled water or tap water.
7. the two-part regeneration method of porous carbon base desulfurizer according to claim 1, which is characterized in that porous after washing
Carbon base desulfurizer dry 24~48h at 40 DEG C~60 DEG C.
8. the two-part regeneration method of porous carbon base desulfurizer according to claim 1, it is characterised in that heating in step (3)
Heating rate is 5~20 DEG C/min.
9. the two-part regeneration method of porous carbon base desulfurizer according to claim 1 or 8, it is characterised in that in step (3),
10~60min will be kept after the heating of porous carbon base desulfurizer.
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| CN111116278A (en) * | 2019-12-19 | 2020-05-08 | 西安近代化学研究所 | Method for flow type ultrasonic treatment of intercrystalline acid of elemental explosive |
| CN114272755A (en) * | 2021-12-30 | 2022-04-05 | 北京北科环境工程有限公司 | Method for inhibiting heating and spontaneous combustion of active carbon desulfurizer |
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| CN111116278B (en) * | 2019-12-19 | 2022-02-22 | 西安近代化学研究所 | Method for flow type ultrasonic treatment of intercrystalline acid of elemental explosive |
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