CN110013888B - Method for regenerating bifunctional catalyst - Google Patents
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Abstract
The invention discloses a regeneration method of a bifunctional catalyst, in particular to a regeneration method of a catalyst for synergistically removing dioxin elementary mercury, which comprises the following steps: (1) preparing a cleaning agent; (2) preparing an active supplementary liquid; (3) taking a catalyst to be regenerated, and purging the catalyst by using oil-free dry compressed air; (4) soaking the swept catalyst in a cleaning agent, and drying by hot air; (5) soaking the dried catalyst in an active supplementary solution, and drying by hot air; and roasting the catalyst loaded with the active ingredient precursor through a muffle furnace, cooling and finishing the regeneration process. The catalyst is not only suitable for the catalyst for removing dioxin and elementary mercury in a failure synergic manner, but also suitable for other types of exhaust gas treatment catalysts (SCR catalysts, VOCs catalysts for catalytic oxidation and the like), the catalyst has the performance of removing dioxin and elementary mercury in a synergic manner through regeneration, a catalyst carrier cannot be damaged, the regenerated catalyst is environment-friendly, secondary pollution cannot be generated, and the activity can be recovered to more than 90% of the original activity.
Description
Technical Field
The invention relates to catalyst regeneration, in particular to a regeneration method of a bifunctional catalyst (a catalyst for removing dioxin elementary mercury cooperatively).
Background
According to statistics, the urban garbage clearing amount per year in China reaches 1.78 hundred million tons, and the urban garbage is still growing at a speed of 2.6% per year, and the phenomenon of 'surrounding garbage' is increasingly serious. In the process of disposing urban garbage, the garbage incineration technology has advantages in the aspects of reducing, harmlessness and recycling of wastes, so that the garbage incineration technology is widely applied. However, a large amount of secondary pollution including dioxin and Nitrogen Oxide (NO) is generated during incinerationx) Dust, heavy metal Hg and the like become bottlenecks in development and application of incineration technology. Wherein the dioxin has strong carcinogenicity, teratogenicity and mutagenicity. And elemental mercury (Hg)0) The volatile water is difficult to dissolve in water, is a relatively stable form in an atmospheric environment, has an average residence time in the atmosphere of half to two years, can be transported in the atmosphere for a long distance to form large-range pollution, and can cause damage to the liver and the kidney and even failure and other serious consequences after entering a human body. Therefore, how to effectively control the dioxin and Hg generated in the incineration process0Is always the focus of research in the field of environmental protection.
Conventional dioxins and Hg0The desorption technique can only filter certain pollutant in a single direction, so that the required equipment structure is complex and the cost is increased when the mixed flue gas is treated. The catalyst (bifunctional catalyst) for synergistically removing the dioxin and the elemental mercury can simultaneously remove the dioxin and the Hg0The cost of treating the flue gas by enterprises is reduced, and the application prospect is wide.
When the dual-function catalyst is used, K, Na, As and other oxides and fly ash in the smoke can continuously abrade and poison the catalyst on the functional filter material, so that dioxin and Hg in the synergy of the catalyst are removed0The performance is reduced. The catalyst with reduced poisoning and activity can be reused by regeneration, the regeneration cost is only 30-50% of the updating cost, and the activity can be recovered to more than 90% of the original activity. Research catalystThe regeneration of the catalyst can prolong the service life of the bifunctional catalyst, and has important significance for large-scale popularization and application of the bifunctional catalyst. However, at present, domestic reports on a regeneration method of a catalyst for synergistically removing dioxin and elemental mercury are few.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a simple and efficient regeneration method of a bifunctional catalyst. The method can quickly complete the regeneration of the catalyst only by matching with a simple device, so that the regenerated active component of the bifunctional catalyst is environment-friendly and efficient, and secondary pollution can not be generated in the using process.
The above purpose of the invention is realized by the following technical scheme:
a method of regenerating a dual-function catalyst comprising the steps of:
(1) preparation of cleaning agent
Weighing appropriate amount of emulsifier polyacrylamide and acid, and performing ultrasonic treatment for 10-60min to mix them uniformly to obtain a cleaning agent;
(2) preparation of active supplementary liquid
Weighing a proper amount of active ingredient precursor, adding deionized water, mechanically stirring at the rotating speed of 100-1000r/min for 10-120min, uniformly mixing to prepare an active ingredient precursor solution, and marking as liquid A; weighing nitric acid, absolute ethyl alcohol and deionized water, mechanically stirring at the rotating speed of 100-; adding the solution A into the solution B, adding a promoter high-carbon fatty alcohol polyoxyethylene ether and a diffusant dinaphthylmethane disulfonic acid sodium, and mechanically stirring at the rotating speed of 100-1000r/min for 60-120min to prepare an active supplementary solution;
(3) taking a catalyst to be regenerated, purging for 10-60min by using 0.5-1MPa of oil-free dry compressed air, and removing dust accumulated on the surface and in holes;
(4) soaking the purged catalyst in the prepared cleaning agent for 100-300min to remove the alkali metal and the alkaline earth metal which are bonded on the catalyst and poison the catalyst, and then drying the catalyst for 12-24h by hot air at the temperature of 80-150 ℃ to remove the residual cleaning agent on the surface and in the catalyst;
(5) soaking the dried catalyst in the prepared active supplementary liquid for 30-120min to load the active component precursor on the catalyst, and then drying the catalyst by hot air at 70-150 ℃ for 360min to remove redundant active supplementary liquid on the surface and inside of the catalyst;
(6) roasting the catalyst loaded with the active component precursor for 3-6h at 1000 ℃ in a muffle furnace at 400-.
Further, in the step (1), the acid is any one of sulfuric acid, nitric acid or oxalic acid, the molar concentration is 0.018-3mol/L, and the acid accounts for 90-99.9% of the total mass of the cleaning solution. The acid is added to adjust the pH value to be 2-5.
Further, in the step (2), the active supplementary liquid comprises the following raw materials in percentage by mass:
0.1 to 10 percent of accelerator high-carbon fatty alcohol polyoxyethylene ether
0.1 to 10 percent of sodium dinaphthylmethane disulfonate serving as a diffusant
Active ingredient precursor 10-40%
0.1 to 20 percent of nitric acid
0.1 to 15 percent of absolute ethyl alcohol
The balance of deionized water.
Further, the active ingredient precursor is soluble tin salt, titanium salt, niobium salt, manganese salt, nickel salt, iron salt and copper salt.
Further, according to the molar ratio of Sn/Ti/Nb elements of 1: (0.1-1): (0.1-1), the molar ratio of Mn/Ni/Fe/Cu elements is 1: (0.1-1): (0-0.5): (0-0.5), weighing the active ingredient precursor.
Further, the soluble tin salt is tin oxalate; the titanium salt is any one of titanyl sulfate, tetrabutyl titanate or titanium tetrachloride; the niobium salt is niobium oxalate; the nickel salt is any one of nickel nitrate, nickel acetate or nickel sulfate; the ferric salt is any one of ferric sulfate, ferric nitrate or ferric chloride; the soluble copper salt is any one of copper nitrate, copper chloride or copper sulfate; the manganese salt is any one of manganese sulfate, potassium permanganate, manganese chloride or manganese nitrate.
Has the advantages that:
the method can effectively clean and regenerate the dual-function catalyst without damaging a catalyst carrier, and the regenerated catalyst is environment-friendly, does not generate secondary pollution in the using process, can recover the activity to more than 90 percent of the original activity, prolongs the service life of the catalyst, and has very important significance for popularization and application of the catalyst for cooperatively removing dioxin and elementary mercury. The catalyst is not only suitable for the catalyst for removing dioxin and elementary mercury in a failure synergic mode, but also suitable for other types of exhaust gas treatment catalysts (SCR catalysts, VOCs catalytic oxidation catalysts and the like), and the catalyst can achieve the performance of removing dioxin and elementary mercury in a synergic mode through regeneration.
Detailed Description
The following examples are given to illustrate the essence of the present invention, but not to limit the scope of the present invention.
Example 1:
(1) preparation of cleaning agent
0.05 Kg of polyacrylamide and 49.95Kg of oxalic acid with the molar concentration of 1.5mol/L are weighed, treated by ultrasonic for 10min and mixed evenly to prepare 50 Kg of cleaning agent.
(2) Preparation of active supplementary liquid
According to the molar ratio of Sn/Ti/Nb elements of 1: 0.1: 0.1, the molar ratio of Mn/Ni/Fe/Cu elements is 1: 0.1: 0.5: 0.5, weighing 5Kg of total amount of tin oxalate, titanyl sulfate, niobium oxalate, manganese sulfate, nickel nitrate, ferric sulfate and copper nitrate, adding 10.45 Kg of deionized water, mechanically stirring at the rotating speed of 100r/min for 120min, uniformly mixing to prepare an active ingredient precursor, and marking as liquid A; weighing 10 Kg of nitric acid, 7.5 Kg of absolute ethyl alcohol and 16.95 Kg of deionized water, and mechanically stirring at the rotating speed of 1000r/min for 10min to uniformly mix, wherein the mixture is marked as liquid B; adding the solution A into the solution B, adding 0.05 Kg of accelerator high-carbon fatty alcohol polyoxyethylene ether and 0.05 Kg of sodium dinaphthylmethane disulfonate serving as a diffusant, and mechanically stirring at the rotating speed of 500r/min for 90min to prepare 50 Kg of active supplementary solution.
(3) And (3) taking the catalyst which needs to be regenerated and is used for removing dioxin and elementary mercury cooperatively, and purging the catalyst for 60min by using 0.1MPa of oil-free dry compressed air to remove dust deposited on the surface and in the holes.
(4) Soaking the purged catalyst in the prepared cleaning agent for 20min to remove alkali metal and alkaline earth metal which are bonded on the catalyst and poison the catalyst, and then drying the catalyst for 2h by hot air at 100 ℃ to remove the residual cleaning agent on the surface and in the catalyst.
(5) And soaking the dried catalyst in the prepared active supplementary liquid for 15min to enable an active component precursor to be loaded on the catalyst, and then drying the catalyst by hot air at 100 ℃ for 120min to remove the redundant active supplementary liquid on the surface and in the catalyst.
(6) Roasting the catalyst loaded with the active ingredient precursor for 12 hours at 200 ℃ in a muffle furnace to convert the active ingredient precursor into an active ingredient, cooling, and finishing the regeneration process to obtain the regenerated environment-friendly synergistic dioxin and elemental mercury removal catalyst.
Example 2:
(1) preparation of cleaning agent
5Kg of polyacrylamide and 45Kg of nitric acid with the molar concentration of 3mol/L are weighed and subjected to ultrasonic treatment for 35min to be uniformly mixed to prepare 50 Kg of cleaning agent.
(2) Preparation of active supplementary liquid
According to the molar ratio of Sn/Ti/Nb elements of 1: 0.1: 0.1, the molar ratio of Mn/Ni/Fe/Cu elements is 1: 0.1: 0.5: 0.5, weighing 5Kg of total amount of tin oxalate, tetrabutyl titanate, niobium oxalate, potassium permanganate, nickel acetate, ferric nitrate and copper chloride, adding 10 Kg of deionized water, mechanically stirring at the rotating speed of 100r/min for 120min, uniformly mixing to prepare an active ingredient precursor, and marking as liquid A; weighing 0.05 Kg of nitric acid, 0.05 Kg of absolute ethyl alcohol and 34.8 Kg of deionized water, and mechanically stirring at the rotating speed of 100r/min for 120min to uniformly mix, wherein the mixture is marked as liquid B; adding the solution A into the solution B, adding 0.05 Kg of accelerator high-carbon fatty alcohol polyoxyethylene ether and 0.05 Kg of sodium dinaphthylmethane disulfonate serving as a diffusant, and mechanically stirring at the rotating speed of 100r/min for 120min to prepare 50 Kg of active supplementary solution.
(3) And (3) taking the catalyst which needs to be regenerated and is used for removing dioxin and elementary mercury cooperatively, and purging the catalyst for 60min by using 0.5MPa of oil-free dry compressed air to remove dust deposited on the surface and in the holes.
(4) Soaking the purged catalyst in the prepared cleaning agent for 100min to remove alkali metal and alkaline earth metal which are bonded on the catalyst and poison the catalyst, and then drying the catalyst in hot air at 150 ℃ for 24h to remove the residual cleaning agent on the surface and in the catalyst.
(5) And soaking the dried catalyst in the prepared active supplementary liquid for 30min to enable an active component precursor to be loaded on the catalyst, and then drying the catalyst for 360min by hot air at 70 ℃ to remove redundant active supplementary liquid on the surface and in the catalyst.
(6) Roasting the catalyst loaded with the active ingredient precursor for 3 hours at 1000 ℃ in a muffle furnace to convert the active ingredient precursor into an active ingredient, cooling, and finishing the regeneration process to obtain the regenerated environment-friendly synergistic dioxin and elemental mercury removal catalyst.
Example 3:
(1) preparation of cleaning agent
Weighing 15 Kg of polyacrylamide and 35Kg of sulfuric acid with the molar concentration of 0.018mol/L, and carrying out ultrasonic treatment for 60min to uniformly mix the polyacrylamide and the sulfuric acid to prepare 50 Kg of cleaning agent.
(2) Preparation of active supplementary liquid
According to the molar ratio of Sn/Ti/Nb elements of 1: 1: 1, wherein the molar ratio of Mn/Ni/Fe/Cu elements is 1: 1: 1: weighing 5Kg of total amount of tin oxalate, titanium tetrachloride, niobium oxalate, manganese nitrate, nickel sulfate, ferric chloride and copper sulfate, adding 30Kg of deionized water, mechanically stirring at the rotating speed of 100r/min for 120min, uniformly mixing to prepare an active ingredient precursor, and marking the active ingredient precursor as liquid A; weighing 2.5Kg of nitric acid, 2.5Kg of absolute ethyl alcohol and 5Kg of deionized water, and mechanically stirring at the rotating speed of 1000r/min for 60min to uniformly mix, wherein the mixture is marked as liquid B; adding the solution A into the solution B, adding 2.5Kg of accelerator higher fatty alcohol polyoxyethylene ether and 2.5Kg of sodium dinaphthylmethane disulfonate serving as a diffusant, and mechanically stirring at the rotating speed of 100r/min for 120min to prepare 50 Kg of active supplementary solution.
(3) And (3) taking the denitration catalyst which needs to be regenerated and is used for cooperatively removing dioxin and elementary mercury, and purging for 30min by using 0.5MPa of oil-free dry compressed air to remove dust deposited on the surface and in the holes.
(4) Soaking the purged catalyst in the prepared cleaning agent for 300min to remove alkali metal and alkaline earth metal which are bonded on the catalyst and poison the catalyst, and then drying the catalyst by hot air at 70 ℃ for 7h to remove the residual cleaning agent on the surface and in the catalyst.
(5) And soaking the dried catalyst in the prepared active supplementary liquid for 600min to enable an active component precursor to be loaded on the catalyst, and then drying the catalyst by hot air at 70 ℃ for 420min to remove the redundant active supplementary liquid on the surface and in the catalyst. (6) Roasting the catalyst loaded with the active ingredient precursor for 7 hours at 450 ℃ in a muffle furnace to convert the active ingredient precursor into an active ingredient, cooling, and finishing the regeneration process to obtain the regenerated environment-friendly synergistic dioxin and elemental mercury removal catalyst.
Example 4:
(1) preparation of cleaning agent
Weighing 2 Kg of polyacrylamide and 48Kg of oxalic acid with the molar concentration of 1mol/L, and carrying out ultrasonic treatment for 60min to uniformly mix the polyacrylamide and the oxalic acid to prepare 50 Kg of cleaning agent.
(2) Preparation of active supplementary liquid
According to the molar ratio of Sn/Ti/Nb elements of 1: 1: 1, wherein the molar ratio of Mn/Ni/Fe/Cu elements is 1: 1: 1: weighing 5Kg of total amount of tin oxalate, titanium tetrachloride, niobium oxalate, manganese chloride, nickel sulfate, ferric chloride and copper sulfate, adding 26.75 Kg of deionized water, mechanically stirring at the rotating speed of 100r/min for 120min, uniformly mixing to prepare an active ingredient precursor, and marking the precursor as liquid A; weighing 0.5 Kg of nitric acid, 0.5 Kg of absolute ethyl alcohol and 16.75Kg of deionized water, and mechanically stirring at the rotating speed of 500r/min for 60min to uniformly mix, wherein the mixture is marked as liquid B; adding the solution A into the solution B, adding 0.25Kg of accelerator high-carbon fatty alcohol polyoxyethylene ether and 0.25Kg of sodium dinaphthylmethane disulfonate serving as a diffusant, and mechanically stirring at the rotating speed of 100r/min for 120min to prepare 50 Kg of supplementary solution with activity.
(3) And (3) taking the catalyst which needs to be regenerated and is used for removing dioxin and elementary mercury cooperatively, and purging the catalyst for 60min by using 1MPa of oil-free dry compressed air to remove the dust on the surface and in the holes.
(4) Soaking the purged catalyst in the prepared cleaning agent for 240min to remove alkali metal and alkaline earth metal which are bonded on the catalyst and poison the catalyst, and then drying the catalyst by hot air at 85 ℃ for 8h to remove the residual cleaning agent on the surface and in the catalyst.
(5) And soaking the dried catalyst in the prepared active supplementary liquid for 240min to enable an active component precursor to be loaded on the catalyst, and then drying the catalyst for 480min by hot air at the temperature of 85 ℃ to remove redundant active supplementary liquid on the surface and in the catalyst.
(6) Roasting the catalyst loaded with the active ingredient precursor for 10 hours at 700 ℃ in a muffle furnace to convert the active ingredient precursor into an active ingredient, cooling, and finishing the regeneration process to obtain the regenerated environment-friendly synergistic dioxin and elemental mercury removal catalyst.
Example 5: evaluation of regenerated catalyst Activity
Dioxins and Hg0The removal efficiency test method comprises the following steps:
the experimental device consists of a gas distribution system, a flow control (mass flow meter), a gas mixer, a gas preheater, a catalytic reactor and a flue gas analysis system. The catalytic reactor was a quartz tube with an inner diameter of 10 mm, and then the reactor was placed in a fixed tube reactor. Simulation of flue gas from O2(8%), dioxins (3.2 ng I-TEQ Nm)-3）、Hg0And a carrier gas N2Composition, space velocity 20000 h-1The reaction temperature was controlled at 250 ℃ and the respective gas flow rates were controlled by mass flowmeters. Hg is a mercury vapor0Generated by Hg steam generator, and the concentration is controlled to be 450 μ g/m3. The gas is passed through the reactor before entering the reactorThe mixture is mixed by a gas mixer and then heated by a heater. Hg at air inlet and air outlet0And (3) measuring the concentration by a cold atom absorption spectrometry, wherein the concentration of dioxin at the air inlet and the air outlet is measured by high-resolution chromatography and high-resolution mass spectrometry. In order to eliminate the influence of surface adsorption, the system starts to collect and test after the aeration operation is stable for 20-30 min.
NO of catalystxCalculated from the following formula:
Hg0removal rate = [ (C)0-C)/C0]×100%
In the formula, C0Is Hg0Initial concentration, C is Hg in the treated gas0And (4) concentration.
The dioxin of the catalyst was calculated from the following formula:
dioxin removal rate = [ (X)0-X)/X0]×100%
In the formula, X0The initial concentration of dioxin is shown, and X is the concentration of dioxin in the treated gas.
Fresh samples, samples before regeneration and regenerated catalysts prepared by examples 1-4 were tested according to the test methods described above and the results are shown in table 1. As can be seen from Table 1, the catalyst prepared according to the regeneration method of the present invention (i.e., the regenerated catalyst prepared in example 2) synergistically removed dioxin and Hg0The efficiency of the method reaches 90 percent, and the removal rate of a fresh sample is basically achieved.
TABLE 1
The catalyst for removing the dioxin and the elemental mercury in a synergistic manner can be effectively cleaned and regenerated, a catalyst carrier is not damaged, the regenerated catalyst is environment-friendly, secondary pollution is not generated in the using process, the activity can be recovered to be more than 90% of the original activity, the service life of the catalyst is prolonged, and the catalyst has very important significance for popularization and application of the catalyst for removing the dioxin and the elemental mercury in a synergistic manner. The catalyst is not only suitable for the catalyst for removing dioxin and elementary mercury in a failure synergic mode, but also suitable for other types of exhaust gas treatment catalysts (SCR catalysts, VOCs catalytic oxidation catalysts and the like), and the catalyst can achieve the performance of removing dioxin and elementary mercury in a synergic mode through regeneration.
The above-described embodiments are intended to be illustrative of the nature of the invention, but those skilled in the art will recognize that the scope of the invention is not limited to the specific embodiments.
Claims (5)
1. A method for regenerating a bifunctional catalyst for synergistically removing dioxin and elemental mercury is characterized by comprising the following steps:
(1) preparation of cleaning agent
Weighing appropriate amount of emulsifier polyacrylamide and acid, and performing ultrasonic treatment for 10-60min to mix them uniformly to obtain a cleaning agent;
(2) preparation of active supplementary liquid
Weighing a proper amount of active ingredient precursor, adding deionized water, mechanically stirring at the rotating speed of 100-1000r/min for 10-120min, uniformly mixing to prepare an active ingredient precursor solution, and marking as liquid A; weighing nitric acid, absolute ethyl alcohol and deionized water, mechanically stirring at the rotating speed of 100-; adding the solution A into the solution B, adding a promoter high-carbon fatty alcohol polyoxyethylene ether and a diffusant dinaphthylmethane disulfonic acid sodium, and mechanically stirring at the rotating speed of 100-1000r/min for 60-120min to prepare an active supplementary solution; the active component precursor is soluble tin salt, titanium salt, niobium salt, manganese salt, nickel salt, iron salt and copper salt;
(3) taking a catalyst to be regenerated, purging for 10-60min by using 0.5-1MPa of oil-free dry compressed air, and removing dust accumulated on the surface and in holes;
(4) soaking the purged catalyst in the prepared cleaning agent for 100-300min to remove the alkali metal and the alkaline earth metal which are bonded on the catalyst and poison the catalyst, and then drying the catalyst for 12-24h by hot air at the temperature of 80-150 ℃ to remove the residual cleaning agent on the surface and in the catalyst;
(5) soaking the dried catalyst in the prepared active supplementary liquid for 30-120min to load the active component precursor on the catalyst, and then drying the catalyst by hot air at 70-150 ℃ for 360min to remove redundant active supplementary liquid on the surface and inside of the catalyst;
(6) roasting the catalyst loaded with the active component precursor for 3-6h at 1000 ℃ in a muffle furnace at 400-.
2. The regeneration method according to claim 1, characterized in that: in the step (1), the acid is any one of sulfuric acid, nitric acid or oxalic acid, the molar concentration is 0.018-3mol/L, and the acid accounts for 90-99.9% of the total mass of the cleaning solution.
3. The regeneration method according to claim 1, characterized in that: in the step (2), the active replenisher comprises the following raw materials in percentage by mass:
4. the regeneration method according to any one of claims 1 to 3, characterized in that: according to the molar ratio of Sn/Ti/Nb elements of 1: (0.1-1): (0.1-1), the molar ratio of Mn/Ni/Fe/Cu elements is 1: (0.1-1): (0-0.5): (0-0.5), weighing the active ingredient precursor.
5. The regeneration method according to claim 4, characterized in that: the soluble tin salt is tin oxalate; the titanium salt is any one of titanyl sulfate, tetrabutyl titanate or titanium tetrachloride; the niobium salt is niobium oxalate; the nickel salt is any one of nickel nitrate, nickel acetate or nickel sulfate; the ferric salt is any one of ferric sulfate, ferric nitrate or ferric chloride; the soluble copper salt is any one of copper nitrate, copper chloride or copper sulfate; the manganese salt is any one of manganese sulfate, potassium permanganate, manganese chloride or manganese nitrate.
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