CN108057462B - Regeneration method of carbon-based non-metallic desulfurizer - Google Patents
Regeneration method of carbon-based non-metallic desulfurizer Download PDFInfo
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Abstract
The invention provides a regeneration method of a carbon-based non-metal desulfurizer, which is characterized in that the inactivated carbon-based non-metal desulfurizer after desulfurization is placed in a container, deionized water is sequentially added to soak the desulfurizer, a water-insoluble organic solvent which is insoluble in sulfuric acid is added to immerse the desulfurizer, and then the steps of vacuum leaching regeneration, drying and filtrate recovery are sequentially carried out to obtain the regenerated carbon-based non-metal desulfurizer and a byproduct dilute sulfuric acid.
Description
Technical Field
The invention belongs to the technical field of desulfurizer, and particularly relates to a regeneration method of a carbon-based nonmetal desulfurizer.
Background
In recent years, the total sulfur dioxide emission amount in China is continuously at the first position in the world, and currently, flue gas desulfurization technologies (FGD) researched and developed at home and abroad are more than 200, and typically, the desulfurization technologies mainly comprise a lime-gypsum method, a spray drying method, a seawater desulfurization method, a furnace calcium spraying tail humidifying and activating method, active coke desulfurization, a novel catalytic method and the like. The lime-gypsum method, which is a mainstream technology, is simple and easy to implement, but has the problems that the quality of gypsum as a byproduct is not high and difficult to utilize, and a scale layer is formed on a pipeline easily due to the precipitation of calcium sulfite, so that the transportation pipeline is blocked. The novel catalytic flue gas desulfurization technology developed by the national flue gas desulfurization engineering research center is a desulfurization technology which uses a catalyst to catalyze and oxidize sulfur dioxide into sulfur trioxide, absorbs the sulfur trioxide to obtain dilute sulfuric acid, stores and recycles the dilute sulfuric acid, and easily recycles the dilute sulfuric acid as a desulfurization byproduct, so that the novel catalytic flue gas desulfurization technology is regarded as a desulfurization technology with a wide application prospect.
The core of the novel catalytic desulfurization technology is a desulfurizer, and the carbon-based nonmetal desulfurization catalyst developed by the national flue gas desulfurization engineering technology research center is simple in preparation method and high in desulfurization activity. But the method for desulfurizing and regenerating the carbon-based non-metal catalyst has no deep research, and the market application of the carbon-based non-metal catalyst is restricted. The existing regeneration method aiming at the saturated deactivated carbon-based desulfurizer after desulfurization can be divided into two types according to the principle: one is trying to desorb adsorbates adsorbed in the desulfurizer, so that the surface of the desulfurizer is updated, such as medicine regeneration, water washing regeneration and the like; the second type is that the structure of the adsorbate is destroyed by oxidation-reduction reaction or thermal decomposition so that the surface of the desulfurizing agent is renewed, such as high-temperature thermal regeneration, high-temperature thermal reduction regeneration, and the like.
Among them, water washing regeneration and thermal regeneration are the mainstream methods for regenerating carbon-based desulfurizing agents at present. The sulfuric acid is removed by washing and concentration difference of water in the water washing regeneration, but the regeneration method has large water consumption and long regeneration time, dilute sulfuric acid contained in the eluate is difficult to utilize, and the regeneration rate of the inactivated carbon-based desulfurizer is not high; the thermal regeneration method needs to strictly control the temperature and time, consumes a large amount of energy, and has the defects of carbon loss, reduced mechanical strength and changed surface chemical structure of the carbon-based catalyst. Therefore, if a regeneration method which does not affect the use of the regenerated carbon-based desulfurizer, has high regeneration rate, low cost and economic benefit of byproducts is provided, the method is beneficial to the popularization and application of the novel catalytic flue gas desulfurization technology.
Disclosure of Invention
The invention aims to solve the problems of the background technology and provide a regeneration method for regenerating a carbon-based desulfurizer and by-producing dilute sulfuric acid by using a mixed solution of water and an organic solvent as a medium and utilizing vacuum pressure. The method has the advantages of high regeneration rate, low cost, economic benefit of byproducts, simple process, suitability for popularization and benefit for popularization and application of the novel catalytic flue gas desulfurization technology.
A regeneration method of a carbon-based non-metallic desulfurizer comprises the following steps:
(1) soaking a desulfurizing agent:
placing the desulfurized inactivated carbon-based non-metal desulfurizer in a container, adding deionized water to soak the desulfurizer, and adding a water-insoluble organic solvent which is insoluble in sulfuric acid to immerse the desulfurizer;
(2) vacuum leaching regeneration:
putting the desulfurizer soaked in the step (1) into an environment with a vacuum degree of 0.04-0.08MPa for regeneration treatment for at least 8 min;
(3) and (3) drying:
carrying out solid-liquid separation on the solid-liquid mixture obtained by the treatment in the step (2), collecting a separation liquid, and drying a solid phase obtained by the separation to obtain a regenerated carbon-based non-metallic desulfurizer;
(4) and (3) recovering a separation liquid:
and (4) standing the separated liquid collected in the step (3) to separate the separated liquid into layers, and respectively collecting the water-insoluble organic solvent on the upper layer and the dilute sulfuric acid on the lower layer.
Wherein the mass of the inactivated carbon-based non-metallic desulfurizer is as follows: the dosage of deionized water is as follows: the dosage of the water-insoluble organic solvent is 1 g: (0.75-1.15) ml: (2.5-3.85) ml. Generally, the container for holding the desulfurized inactivated carbon-based non-metallic desulfurizer has the characteristic of pressure resistance, and the size of the container is selected according to the quality of the regenerated inactivated carbon-based non-metallic desulfurizer, so that the container is suitable for the above-mentioned limited conditions and can achieve the aims of soaking the desulfurizer with deionized water and soaking the desulfurizer with a water-insoluble organic solvent.
Wherein the water-insoluble organic solvent which is difficult to dissolve in sulfuric acid is butyl acetate, amyl acetate, butanol, toluene or cyclohexane. Note that, in general, the water-insoluble organic solvent is recyclable, and therefore, in a preferred embodiment, a water-insoluble organic solvent having a high boiling point and being difficult to volatilize and being difficult to dissolve in sulfuric acid is selected, which is advantageous in reducing the recycling cost.
Wherein, the drying in the step (3) is naturally dried, and then dried for 10-14h at the temperature of 100-110 ℃.
Wherein, the collected upper layer water-insoluble organic solvent in the step (4) is returned to the step (1) for recycling.
And (3) taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1-3 times in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration times of 2-4 times.
Typically, the lower dilute sulfuric acid from step (4) is recovered and its concentration is measured and used as a by-product in make-up water for the sulfuric acid dry cleaning tower.
To better illustrate the industrial applicability of the byproduct dilute sulfuric acid obtained by the present invention, for example, when the present invention is used to regenerate the saturated deactivated carbon-based non-metallic desulfurizing agent (sulfur atom doped carbon-based non-metallic catalyst), the vacuum leaching regeneration treatment time is 8-16min, the regeneration times are 2 times, the concentration of the obtained dilute sulfuric acid is 9-12%, the regeneration rate of the desulfurizing agent is 28-33%, and the activity recovery rate is 56.3-64.1%.
The dilute sulfuric acid with the concentration of 9-12% has low concentration, heavy weight and high transportation cost, and the novel catalytic method is suitable for factories needing to recycle dilute sulfuric acid in the process, so the specific application of the dilute sulfuric acid recycled by the regeneration method can be changed according to the production process and the process of the factories.
The invention is characterized in that firstly the desulfurized inactivated carbon-based non-metal desulfurizer is soaked by a small amount of deionized water, namely, the deionized water is introduced into the pore channels of the desulfurizer with the porous morphology, and then a proper amount of water-insoluble organic solvent is added to immerse the desulfurizer integrally, namely, the water-insoluble organic solvent is used for integrally coating the porous desulfurizer containing the deionized water. And then directly placing the desulfurizer in a negative pressure environment for regeneration treatment, sucking out air in pores of the desulfurizer by negative pressure, and interacting with deionized water in the sucking-out process to form the effect similar to mixing and stirring the deionized water, so that the air reacts with sulfur dioxide adsorbed in the channels of the inactivated desulfurizer to generate sulfuric acid, and then continuously sucking out air in the desulfurizer, so that dilute sulfuric acid generated by dissolving the generated sulfuric acid in the deionized water is continuously taken out of the desulfurizer to be mixed with an organic solvent outside the desulfurizer to form turbid liquid. And after the regeneration treatment is finished, carrying out solid-liquid separation to obtain the desulfurizing agent, wherein the separation liquid is a mixed turbid liquid of a water-insoluble organic solvent and dilute sulfuric acid, standing and layering the separation liquid, the upper layer is the water-insoluble organic solvent and can be recycled, and the lower layer is the dilute sulfuric acid and can be used as a byproduct for supplementing water for a sulfuric acid dry cleaning tower.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with water washing, the regeneration activity recovery rate of the inactivated carbon-based non-metal desulfurizer treated by the regeneration method is relatively improved by over 25 percent, the regeneration time is shortened by 80 percent, and the method does not cause the reduction of the mechanical strength of the desulfurizer, does not obviously cause the side effects of carbon loss, change of surface chemical structure and the like, and does not influence the use effect of the regenerated carbon-based non-metal desulfurizer.
(2) The concentration of the by-product dilute sulfuric acid can reach 18.4%, and the method can be used for industrial purposes such as water replenishment of a sulfuric acid dry cleaning tower and the like, and effectively reduces industrial cost.
(3) The water-insoluble organic solvent can be repeatedly used, the recovery rate can reach more than 90 percent, and the regeneration cost is reduced.
Drawings
FIG. 1 is a schematic diagram of the apparatus for regenerating a carbon-based non-metallic desulfurizing agent according to the present invention.
FIG. 2 is a graph showing the desulfurization efficiency comparison of the regenerated carbon-based non-metallic desulfurization agents obtained in examples 1 to 4 of the present invention.
FIG. 3 is a column diagram comparing the mass concentration of the by-product sulfuric acid obtained in examples 1-4 of the present invention with the regeneration rate of the regenerated carbon-based non-metallic desulfurizing agent.
FIG. 4 is a graph showing a comparison of desulfurization efficiencies of the regenerated carbon-based non-metallic desulfurizing agents obtained in examples 5 to 7 of the present invention and comparative example 3.
FIG. 5 is a bar graph comparing the mass concentration of the by-product sulfuric acid obtained in examples 5 to 7 of the present invention and comparative example 3 with the regeneration rate of the regenerated carbon-based non-metallic desulfurizing agent.
In the figure, 1 a circulating water type vacuum pump, 2 a connecting pipe, 3 a pressure-resistant regeneration vessel.
Detailed Description
The present invention will be described in further detail by way of examples with reference to the accompanying drawings. It should be noted that the examples given are not to be construed as limiting the scope of the invention, and that those skilled in the art, on the basis of the teachings of the present invention, will be able to make numerous insubstantial modifications and adaptations of the invention without departing from its scope.
The embodiment of the following example of the invention is shown in fig. 1, the desulfurized inactive carbon-based non-metal desulfurizer is placed in a pressure-resistant regeneration container 3, deionized water is sequentially added to soak the desulfurizer, a water-insoluble organic solvent which is insoluble in sulfuric acid is added to immerse the desulfurizer, the pressure-resistant regeneration container 3 is sealed, the pressure-resistant regeneration container 3 is communicated with a circulating water type vacuum pump 1 through a connecting conduit 2, so that vacuum leaching regeneration is carried out, after the vacuum leaching regeneration time is up, the connecting conduit 2 is taken down, the content of the pressure-resistant regeneration container 3 is filtered, filtrate is collected, and filter cakes are dried, so that the regenerated desulfurizer is obtained.
The desulfurization efficiency, sulfuric acid concentration, regeneration rate and activity recovery rate described in the following examples and drawings were measured and calculated by a conventional desulfurization evaluation method under the following conditions:
the correlation calculation formula is:
(1) desulfurization efficiency:
in the formula
Measured by a flue gas analyzer, and an outlet
For the sulfur dioxide concentration at the outlet of the desulfurization evaluation device, the flue gas analyzer selects the one produced by Wuhan tetragonal photoelectric technology LimitedThe model is Gasdoard-3000 on-line infrared smoke gas analyzer.
(2) Concentration of sulfuric acid:
the concentration of the sulfuric acid is determined by a titration method: titrating the sulfuric acid solution by using NaOH standard solutions with the concentrations of 1mol/L and 0.1mol/L, and designating the titration end point by using phenolphthalein as an indicator.
The sulfuric acid concentration calculation formula:
wherein ξ is the mass percent concentration of sulfuric acid, and the unit is%;
VNaOHthe volume of standard NaOH consumed for titration is in ml;
(3) Regeneration rate:
the regeneration rate of the desulfurizer is obtained by sulfur balance calculation, and the calculation formula is as follows:
in the formula, omega is the regeneration rate of the desulfurizer, and the unit is percent;
Moriginal sourceThe mass of sulfur element in the desulfurizer is mg;
Moriginal sourceThe unit is the mass of the sulfur element regenerated from the desulfurizer in the regeneration process, and is mg.
(4) The activity recovery rate:
the activity recovery of the desulfurizing agent is represented by the ratio of the sulfur capacity:
in the formula (I), the compound is shown in the specification,
activity recovery in%;
Ssulfur capacity i +1The unit is mg of desulfurization sulfur capacity after the i +1 th regeneration of the desulfurizer;
Ssulfur capacity iIs the desulfurization sulfur capacity after the i-th regeneration of the desulfurizing agent, mg
Example 1
(1) Soaking a desulfurizing agent: selecting a carbon-based non-metal desulfurizer, marked as NS-AC (A), using the carbon-based non-metal desulfurizer to be an inactivated carbon-based non-metal desulfurizer after desulfurization, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to soak the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 16min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a 105 ℃ drying oven for drying for 12 hours to obtain the carbon-based non-metal desulfurizer which is regenerated for 1 time and is recorded as NS-AC-C1;
(4) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 2
(1) Soaking a desulfurizing agent: selecting the same carbon-based non-metal desulfurizer as the carbon-based non-metal desulfurizer in the embodiment 1, using the carbon-based non-metal desulfurizer to be an inactivated carbon-based non-metal desulfurizer after desulfurization, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to immerse the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 16min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 105 ℃ for drying for 12 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1 time in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration frequency of 2 times, which is marked as NS-AC-C2;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 3
(1) Soaking a desulfurizing agent: selecting the same carbon-based non-metal desulfurizer as the carbon-based non-metal desulfurizer in the embodiment 1, using the carbon-based non-metal desulfurizer to be an inactivated carbon-based non-metal desulfurizer after desulfurization, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to immerse the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 16min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 105 ℃ for drying for 12 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) in sequence for 2 times to obtain the carbon-based non-metal desulfurizer with the regeneration times of 3 times, which is marked as NS-AC-C3;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 4
(1) Soaking a desulfurizing agent: selecting the same carbon-based non-metal desulfurizer as the carbon-based non-metal desulfurizer in the embodiment 1, using the carbon-based non-metal desulfurizer to be an inactivated carbon-based non-metal desulfurizer after desulfurization, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to immerse the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 16min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 105 ℃ for drying for 12 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) in sequence for 3 times to obtain the carbon-based non-metal desulfurizer with the regeneration times of 4 times, which is marked as NS-AC-C4;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 5
(1) Soaking a desulfurizing agent: selecting a carbon-based non-metal desulfurizer, marked as NS-AC (B), using the carbon-based non-metal desulfurizer to be an inactivated carbon-based non-metal desulfurizer after desulfurization, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to soak the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 8min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 105 ℃ for drying for 12 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1 time in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration frequency of 2 times, which is recorded as NS-AC-8 min;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 6
(1) Soaking a desulfurizing agent: selecting the same carbon-based non-metal desulfurizer as the carbon-based non-metal desulfurizer prepared in the embodiment 5, using the carbon-based non-metal desulfurizer to desulfurize to obtain an inactivated carbon-based non-metal desulfurizer, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to immerse the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 12min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 105 ℃ for drying for 12 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1 time in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration frequency of 2 times, which is recorded as NS-AC-12 min;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 7
(1) Soaking a desulfurizing agent: selecting the same carbon-based non-metal desulfurizer as the carbon-based non-metal desulfurizer prepared in the embodiment 5, using the carbon-based non-metal desulfurizer to desulfurize to obtain an inactivated carbon-based non-metal desulfurizer, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to immerse the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 16min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 105 ℃ for drying for 12 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1 time in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration frequency of 2 times, which is recorded as NS-AC-16 min;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 8
(1) Soaking a desulfurizing agent: selecting a carbon-based non-metal desulfurizer which is used as an inactivated carbon-based non-metal desulfurizer after desulfurization, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 12ml of distilled water to soak the desulfurizer, and pouring 38ml of toluene to soak the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 20min under the vacuum degree of 0.04 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 100 ℃ for drying for 10 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1 time in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration time of 2 times;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is toluene, and recycling the toluene; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Example 9
(1) Soaking a desulfurizing agent: selecting a carbon-based non-metal desulfurizer which is used as an inactivated carbon-based non-metal desulfurizer after desulfurization, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 17ml of distilled water to soak the desulfurizer, and pouring 57ml of butanol to soak the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 25min under the vacuum degree of 0.08 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 110 ℃ for drying for 14h to obtain the regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1 time in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration time of 2 times;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is toluene, and recycling the toluene; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
Comparative example 1
Washing and regenerating: selecting the same carbon-based non-metal desulfurizer as the carbon-based non-metal desulfurizer in the embodiment 1, using the carbon-based non-metal desulfurizer in desulfurization to be the inactivated carbon-based non-metal desulfurizer, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, pouring 200ml of distilled water, soaking for 40min, filtering and drying the desulfurizer, placing the desulfurizer in a drying oven at 105 ℃ for drying for 12h to obtain the carbon-based non-metal desulfurizer which is regenerated for 1 time, using the carbon-based non-metal desulfurizer as the inactivated carbon-based non-metal desulfurization catalyst, and repeating the step 1 time to obtain the carbon-based.
Comparative example 2
(1) Soaking a desulfurizing agent: selecting the same carbon-based non-metal desulfurizer as the carbon-based non-metal desulfurizer prepared in the embodiment 5, using the carbon-based non-metal desulfurizer to desulfurize to obtain an inactivated carbon-based non-metal desulfurizer, weighing 15g of the inactivated carbon-based non-metal desulfurizer, placing the inactivated carbon-based non-metal desulfurizer in a regeneration container, adding 15ml of distilled water to soak the desulfurizer, and pouring 50ml of butyl acetate to immerse the desulfurizer;
(2) vacuum leaching regeneration: sealing the regeneration container obtained in the step (1), opening a circulating water type vacuum pump, and treating the regeneration container obtained in the step (1) for 4min under the vacuum degree of 0.06 MPa;
(3) and (3) drying: filtering the content of the regeneration container obtained in the step (2), collecting filtrate, placing a filter cake in a fume hood for drying, and then transferring the filter cake to a drying oven at 105 ℃ for drying for 12 hours to obtain a regenerated carbon-based non-metal desulfurizer;
(4) and (3) repeating regeneration: taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1 time in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration frequency of 2 times, which is recorded as NS-AC-4 min;
(5) recovering the filtrate: standing and layering the filtrate collected in the step (3), wherein the upper layer of the filtrate is butyl acetate and recycling; the lower layer of the filtrate is dilute sulfuric acid, and the mass concentration of the dilute sulfuric acid is measured by acid-base titration for recycling.
The above examples and comparative examples were subjected to conventional desulfurization evaluation, and the results were as follows:
the sulfur penetration capacity, penetration time and activity recovery of the regenerated carbon-based non-metallic desulfurizing agents obtained in examples 1 to 4 are shown in the following table:
it can be seen that the regeneration was performed 3 times at the best, and that the activity recovery rate decreased when the regeneration was performed too much.
The sulfur breakthrough capacity, the breakthrough time, and the activity recovery of the regenerated carbon-based non-metallic desulfurizing agents obtained in examples 5 to 7 and comparative example 2 are as follows:
it can be seen that the regeneration effect increases with the length of the vacuum treatment, but if the vacuum treatment time is too short, the regeneration is incomplete and the activity recovery rate decreases.
The sulfur penetration capacity, penetration time and activity recovery rate of the regenerated carbon-based non-metallic desulfurizing agent obtained in comparative example 1 are as follows:
as can be seen from the breakthrough sulfur capacity and the activity recovery rate of comparative example 1, the regeneration method of the present invention has a significantly better regeneration effect than the water washing regeneration. Similar regeneration conditions are selected for comparison, and it can be seen from the following table that the regeneration method of the present invention can achieve a better regeneration effect within a shorter regeneration time by performing the same regeneration twice.
The above examples are only selected embodiments of the present invention, and are not to be construed as limiting the present invention, and those skilled in the art should, in light of the present disclosure, make modifications and alterations without departing from the scope of the present invention.
Claims (9)
1. A regeneration method of a carbon-based non-metallic desulfurizer is characterized by comprising the following steps:
(1) soaking a desulfurizing agent:
placing the desulfurized inactivated carbon-based non-metal desulfurizer in a container, adding deionized water to soak the desulfurizer, and then adding a water-insoluble organic solvent which is insoluble in sulfuric acid to immerse the desulfurizer, wherein the mass of the inactivated carbon-based non-metal desulfurizer is as follows: the dosage of deionized water is as follows: the dosage of the water-insoluble organic solvent is 1 g: (0.75-1.15) mL: (2.5-3.85) mL;
(2) vacuum leaching regeneration:
putting the desulfurizer soaked in the step (1) into an environment with a vacuum degree of 0.04-0.08MPa for regeneration treatment for at least 8 min;
(3) and (3) drying:
carrying out solid-liquid separation on the solid-liquid mixture obtained by the treatment in the step (2), collecting a separation liquid, and drying a solid phase obtained by the separation to obtain a regenerated carbon-based non-metallic desulfurizer;
(4) and (3) recovering a separation liquid:
and (4) standing the separated liquid collected in the step (3) to separate the separated liquid into layers, and respectively collecting the water-insoluble organic solvent on the upper layer and the dilute sulfuric acid on the lower layer.
2. The method for regenerating a carbon-based non-metallic desulfurizing agent according to claim 1, wherein: the water insoluble organic solvent insoluble in sulfuric acid is butyl acetate, amyl acetate, butanol, toluene or cyclohexane.
3. The method for regenerating the carbon-based non-metallic desulfurizing agent according to claim 1 or 2, characterized in that: the drying in the step (3) is naturally dried, and then dried for 10-14h at the temperature of 100-.
4. The method for regenerating the carbon-based non-metallic desulfurizing agent according to claim 1 or 2, characterized in that: and (4) returning the collected upper-layer water-insoluble organic solvent to the step (1) for recycling.
5. The method for regenerating a carbon-based non-metallic desulfurizing agent according to claim 3, wherein: and (4) returning the collected upper-layer water-insoluble organic solvent to the step (1) for recycling.
6. The method for regenerating the carbon-based non-metallic desulfurizing agent according to claim 1 or 2, characterized in that: and (3) taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1-3 times in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration times of 2-4 times.
7. The method for regenerating a carbon-based non-metallic desulfurizing agent according to claim 3, wherein: and (3) taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1-3 times in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration times of 2-4 times.
8. The method for regenerating a carbon-based non-metallic desulfurizing agent according to claim 4, wherein: and (3) taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1-3 times in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration times of 2-4 times.
9. The method for regenerating a carbon-based non-metallic desulfurizing agent according to claim 5, wherein: and (3) taking the regenerated carbon-based non-metal desulfurizer obtained in the step (3) as the inactivated carbon-based non-metal desulfurizer in the step (1), and repeating the steps (1), (2) and (3) for 1-3 times in sequence to obtain the carbon-based non-metal desulfurizer with the regeneration times of 2-4 times.
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