CN115608320B - Preparation method of mercury removal agent with desulfurization effect - Google Patents
Preparation method of mercury removal agent with desulfurization effect Download PDFInfo
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- CN115608320B CN115608320B CN202211138485.1A CN202211138485A CN115608320B CN 115608320 B CN115608320 B CN 115608320B CN 202211138485 A CN202211138485 A CN 202211138485A CN 115608320 B CN115608320 B CN 115608320B
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 64
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 26
- 230000023556 desulfurization Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000000694 effects Effects 0.000 title abstract description 14
- 230000003213 activating effect Effects 0.000 claims abstract description 37
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 229910000278 bentonite Inorganic materials 0.000 claims description 23
- 239000000440 bentonite Substances 0.000 claims description 23
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 23
- 239000007822 coupling agent Substances 0.000 claims description 20
- 238000005470 impregnation Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- 229940116318 copper carbonate Drugs 0.000 claims description 15
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims description 15
- 230000001105 regulatory effect Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- 150000004682 monohydrates Chemical class 0.000 claims description 10
- 150000001282 organosilanes Chemical class 0.000 claims description 10
- 238000000967 suction filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000004321 preservation Methods 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- -1 naphtha Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dispersion Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a preparation method of a mercury removal agent with a desulfurization effect, which relates to the technical field of mercury removal agents and comprises the following steps: (1) obtaining a suspension; (2) obtaining a sol solution; (3) obtaining a mixed sol solution; (4) obtaining a composite carrier; (5) activating the composite carrier; (6) obtaining an impregnated body; (7) drying the impregnated body to obtain a dried body; (8) Roasting the dried body in a crucible for 40-50min, and naturally cooling to room temperature; the mercury removal agent prepared by the method has excellent structural stability, can be suitable for being used in various complex environments, has excellent mercury removal efficiency, has excellent desulfurization efficiency, can remove mercury and sulfur at the same time, greatly reduces the content of mercury and sulfur in treated substances, and reduces the pollution to the environment.
Description
Technical Field
The invention belongs to the technical field of mercury removal agents, and particularly relates to a preparation method of a mercury removal agent with a desulfurization effect.
Background
Small amounts of mercury are present in all hydrocarbon feedstocks such as natural gas, liquefied petroleum gas, liquid hydrocarbons (e.g., naphtha, condensate, distillate oil, etc.), and the presence of mercury causes the following problems: the aluminum heat exchanger is damaged due to amalgamation; poisoning the expensive catalyst of the downstream device, greatly reducing its lifetime; contaminating the shipping container. In addition, mercury is one of the most important toxic substances in oil gas, and the mercury enters the atmosphere after the oil gas is combusted to cause environmental pollution, so that the mercury in the materials must be removed before the materials are used.
The invention belongs to the technical field of mercury removal agents, and particularly relates to a mercury removal agent and a mercury removal method, wherein the prior art CN 107487888A discloses a mercury removal agent and a mercury removal method; the mercury removal agent consists of aluminum powder and iron powder, wherein the mass ratio of the aluminum powder to the iron powder is 1.5:1-9:1. The mercury removing agent in the technical scheme of the invention can realize the high-efficiency removal of mercury in the polluted acid with high and low mercury concentration, has less side reaction with other heavy metal ions in the polluted acid, good mercury removing selectivity and high mercury extraction rate; the mercury removing agent has good adaptability to the acidity of the polluted acid, is suitable for removing mercury in the polluted acid wastewater with the pH value of 0.8-4.0, and compared with the traditional mercury removing method, the mercury removing agent consumes acid in the wastewater in the reduction process so as to reduce the acidity of the wastewater without adding alkali for neutralization. The method is simple and easy to operate, and can meet the industrial application. However, the mercury removal effect is more general and the desulfurization effect is not achieved.
Accordingly, there is a need for further improvements in the art.
Disclosure of Invention
The invention aims at solving the existing problems and provides a preparation method of a mercury removal agent with a desulfurization effect.
The invention is realized by the following technical scheme:
The invention aims to provide a preparation method of a mercury removal agent with a desulfurization effect, which aims to solve the defects in the prior art.
The technical scheme adopted by the invention is as follows:
the preparation method of the mercury removal agent with the desulfurization effect comprises the following steps:
(1) Sequentially adding alumina monohydrate and water into a stirrer, and uniformly stirring to obtain a suspension;
(2) Dropwise adding a nitric acid solution into the suspension, regulating the pH to 5.5, stopping dropwise adding the nitric acid solution, regulating the temperature to 80 ℃, and carrying out heat preservation and stirring for 40min to obtain a sol solution;
(3) Adding nano bentonite into the sol solution, and performing ultrasonic dispersion treatment for 10min to obtain a mixed sol solution;
(4) Spray drying the mixed sol solution to obtain a composite carrier;
(5) Activating the composite carrier:
firstly, preparing an activating solution, then adding a composite carrier into the activating solution, adjusting the temperature to 70-80 ℃, preserving the heat for 10 hours, then filtering, washing with clear water to be neutral, and drying to constant weight to obtain the activating carrier;
(6) Sequentially adding the activated carrier and the basic copper carbonate solution into a vacuum impregnation reaction kettle, carrying out vacuum impregnation treatment for 1-2 hours, and then carrying out suction filtration to obtain an impregnated body;
(7) Drying the impregnated body to obtain a dried body;
(8) And (3) placing the dried body in a crucible, roasting for 40-50min, and naturally cooling to room temperature.
As a further technical scheme: the mixing mass ratio of the alumina monohydrate to the water is 1:10-12.
As a further technical scheme: the mass fraction of the nitric acid solution is 1.5%.
As a further technical scheme: the mixing mass ratio of the sol solution to the nanometer bentonite is 15:1, a step of;
the nanometer bentonite is treated by a coupling agent.
As a further technical scheme: the coupling agent treatment is as follows:
Preparing an organosilane coupling agent solution with the mass fraction of 10%;
Nanometer bentonite is prepared according to the following proportion of 1: adding 10 mass ratio into organosilane coupling agent solution, adjusting temperature to 85 ℃, preserving heat and stirring for 2 hours, carrying out suction filtration, washing to neutrality, and drying to constant weight.
As a further technical scheme: the preparation method of the activating solution comprises the following steps:
Sequentially adding 1,3, 5-trimesic acid and maleic anhydride into deionized water, and uniformly stirring to obtain an activating solution;
The mixing mass ratio of the 1,3, 5-trimesic acid, the maleic anhydride and the deionized water is 3-5:1:30.
As a further technical scheme: the mixing mass ratio of the activating carrier to the basic copper carbonate solution is 1:20-30 parts;
the concentration of the basic copper carbonate solution is 1.2mol/L.
As a further technical scheme: the vacuum impregnation temperature was 68 ℃.
As a further technical scheme: the vacuum degree of the vacuum impregnation was 0.25Pa.
The composite carrier prepared by the invention can be soaked by the impregnating solution more quickly due to the porous structural characteristic, and capillary force generated in the composite carrier in the impregnating process can ensure that the impregnating solution enters all porous structures, so that active ingredients are fully and uniformly dispersed in the composite carrier, the prepared mercury removal agent can be fully contacted with a medium to be treated, the mercury removal efficiency and the desulfurization efficiency are greatly improved, and the mercury removal agent prepared by the invention has higher mechanical stability, does not generate dust pollution to the environment, and can maintain good mercury removal and desulfurization stability even under a special high-pressure high-humidity environment.
The composite carrier prepared by the sol spraying method can obviously improve the specific surface area and the adsorption capacity of the composite carrier, and has higher removal efficiency for elemental mercury.
Through the activation treatment, the microstructure of the composite carrier can be obviously improved by activation, the adsorption capacity of the active site of the surface of the composite carrier to mercury is improved, and the catalyst has obvious promotion effect on the mercury removal and desulfurization efficiency.
Compared with the prior art, the invention has the following advantages:
The mercury removal agent prepared by the method has excellent structural stability, can be suitable for being used in various complex environments, has excellent mercury removal efficiency, has excellent desulfurization efficiency, can remove mercury and sulfur at the same time, greatly reduces the content of mercury and sulfur in treated substances, and reduces the pollution to the environment.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the mercury removal agent with the desulfurization effect comprises the following steps:
(1) Sequentially adding alumina monohydrate and water into a stirrer, and uniformly stirring to obtain a suspension;
(2) Dropwise adding a nitric acid solution into the suspension, regulating the pH to 5.5, stopping dropwise adding the nitric acid solution, regulating the temperature to 80 ℃, and carrying out heat preservation and stirring for 40min to obtain a sol solution;
(3) Adding nano bentonite into the sol solution, and performing ultrasonic dispersion treatment for 10min to obtain a mixed sol solution;
(4) Spray drying the mixed sol solution to obtain a composite carrier;
(5) Activating the composite carrier:
Firstly, preparing an activating solution, then adding a composite carrier into the activating solution, regulating the temperature to 70 ℃, preserving the heat for 10 hours, then filtering, washing with clear water to be neutral, and drying to constant weight to obtain the activating carrier;
(6) Sequentially adding the activated carrier and the basic copper carbonate solution into a vacuum impregnation reaction kettle, carrying out vacuum impregnation treatment for 1 hour, and then carrying out suction filtration to obtain an impregnated body;
(7) Drying the impregnated body to obtain a dried body;
(8) And (3) placing the dried body into a crucible for roasting for 40min, and then naturally cooling to room temperature.
The mixing mass ratio of the alumina monohydrate to the water is 1:10.
The mass fraction of the nitric acid solution is 1.5%.
The mixing mass ratio of the sol solution to the nanometer bentonite is 15:1, a step of;
the nanometer bentonite is treated by a coupling agent.
The coupling agent treatment is as follows:
Preparing an organosilane coupling agent solution with the mass fraction of 10%;
Nanometer bentonite is prepared according to the following proportion of 1: adding 10 mass ratio into organosilane coupling agent solution, adjusting temperature to 85 ℃, preserving heat and stirring for 2 hours, carrying out suction filtration, washing to neutrality, and drying to constant weight.
The preparation method of the activating solution comprises the following steps:
Sequentially adding 1,3, 5-trimesic acid and maleic anhydride into deionized water, and uniformly stirring to obtain an activating solution;
the mixing mass ratio of the 1,3, 5-trimesic acid, the maleic anhydride and the deionized water is 3:1:30.
The mixing mass ratio of the activating carrier to the basic copper carbonate solution is 1:20, a step of;
the concentration of the basic copper carbonate solution is 1.2mol/L.
The vacuum impregnation temperature was 68 ℃.
The vacuum degree of the vacuum impregnation was 0.25Pa.
Example 2
The preparation method of the mercury removal agent with the desulfurization effect comprises the following steps:
(1) Sequentially adding alumina monohydrate and water into a stirrer, and uniformly stirring to obtain a suspension;
(2) Dropwise adding a nitric acid solution into the suspension, regulating the pH to 5.5, stopping dropwise adding the nitric acid solution, regulating the temperature to 80 ℃, and carrying out heat preservation and stirring for 40min to obtain a sol solution;
(3) Adding nano bentonite into the sol solution, and performing ultrasonic dispersion treatment for 10min to obtain a mixed sol solution;
(4) Spray drying the mixed sol solution to obtain a composite carrier;
(5) Activating the composite carrier:
Firstly, preparing an activating solution, then adding a composite carrier into the activating solution, adjusting the temperature to 80 ℃, preserving the heat for 10 hours, then filtering, washing with clear water to be neutral, and drying to constant weight to obtain the activating carrier;
(6) Sequentially adding the activated carrier and the basic copper carbonate solution into a vacuum impregnation reaction kettle, carrying out vacuum impregnation treatment for 2 hours, and then carrying out suction filtration to obtain an impregnated body;
(7) Drying the impregnated body to obtain a dried body;
(8) And (3) placing the dried body in a crucible, roasting for 40-50min, and naturally cooling to room temperature.
The mixing mass ratio of the alumina monohydrate to the water is 1:12.
The mass fraction of the nitric acid solution is 1.5%.
The mixing mass ratio of the sol solution to the nanometer bentonite is 15:1, a step of;
the nanometer bentonite is treated by a coupling agent.
The coupling agent treatment is as follows:
Preparing an organosilane coupling agent solution with the mass fraction of 10%;
Nanometer bentonite is prepared according to the following proportion of 1: adding 10 mass ratio into organosilane coupling agent solution, adjusting temperature to 85 ℃, preserving heat and stirring for 2 hours, carrying out suction filtration, washing to neutrality, and drying to constant weight.
The preparation method of the activating solution comprises the following steps:
Sequentially adding 1,3, 5-trimesic acid and maleic anhydride into deionized water, and uniformly stirring to obtain an activating solution;
The mixing mass ratio of the 1,3, 5-trimesic acid, the maleic anhydride and the deionized water is 5:1:30.
The mixing mass ratio of the activating carrier to the basic copper carbonate solution is 1:30;
the concentration of the basic copper carbonate solution is 1.2mol/L.
The vacuum impregnation temperature was 68 ℃.
The vacuum degree of the vacuum impregnation was 0.25Pa.
Example 3
The preparation method of the mercury removal agent with the desulfurization effect comprises the following steps:
(1) Sequentially adding alumina monohydrate and water into a stirrer, and uniformly stirring to obtain a suspension;
(2) Dropwise adding a nitric acid solution into the suspension, regulating the pH to 5.5, stopping dropwise adding the nitric acid solution, regulating the temperature to 80 ℃, and carrying out heat preservation and stirring for 40min to obtain a sol solution;
(3) Adding nano bentonite into the sol solution, and performing ultrasonic dispersion treatment for 10min to obtain a mixed sol solution;
(4) Spray drying the mixed sol solution to obtain a composite carrier;
(5) Activating the composite carrier:
Firstly, preparing an activating solution, then adding a composite carrier into the activating solution, adjusting the temperature to 72 ℃, preserving the heat for 10 hours, then filtering, washing with clear water to be neutral, and drying to constant weight to obtain the activating carrier;
(6) Sequentially adding the activated carrier and the basic copper carbonate solution into a vacuum impregnation reaction kettle, carrying out vacuum impregnation treatment for 1.5 hours, and then carrying out suction filtration to obtain an impregnated body;
(7) Drying the impregnated body to obtain a dried body;
(8) And (3) placing the dried body into a crucible for roasting for 45min, and then naturally cooling to room temperature.
As a further technical scheme: the mixing mass ratio of the alumina monohydrate to the water is 1:11.
As a further technical scheme: the mass fraction of the nitric acid solution is 1.5%.
The mixing mass ratio of the sol solution to the nanometer bentonite is 15:1, a step of;
the nanometer bentonite is treated by a coupling agent.
The coupling agent treatment is as follows:
Preparing an organosilane coupling agent solution with the mass fraction of 10%;
Nanometer bentonite is prepared according to the following proportion of 1: adding 10 mass ratio into organosilane coupling agent solution, adjusting temperature to 85 ℃, preserving heat and stirring for 2 hours, carrying out suction filtration, washing to neutrality, and drying to constant weight.
The preparation method of the activating solution comprises the following steps:
Sequentially adding 1,3, 5-trimesic acid and maleic anhydride into deionized water, and uniformly stirring to obtain an activating solution;
The mixing mass ratio of the 1,3, 5-trimesic acid, the maleic anhydride and the deionized water is 4:1:30.
The mixing mass ratio of the activating carrier to the basic copper carbonate solution is 1:25, a step of selecting a specific type of material;
the concentration of the basic copper carbonate solution is 1.2mol/L.
The vacuum impregnation temperature was 68 ℃.
The vacuum degree of the vacuum impregnation was 0.25Pa.
Test
Detecting the specific surface area and pore volume of the mercury removing agent in the embodiment;
TABLE 1
| Specific surface area/cm 2/g | Pore volume/cm 2/g | |
| Example 1 | 1108.3 | 0.53 |
| Example 2 | 1110.5 | 0.55 |
| Example 3 | 1103.7 | 0.51 |
As can be seen from Table 1, the mercury removal agent prepared by the invention has higher specific surface area and larger pore volume, so that the reaction activity of the mercury removal agent can be improved, and meanwhile, the reaction capacity is higher, and the desulfurization and mercury removal treatment capacity is larger.
Detecting and comparing mercury removal efficiency;
The reaction condition is that O 2 is 5.2 percent, hg 0 is 35 mug/m 3, and the reaction temperature is 200 ℃;
TABLE 2
| Mercury removal efficiency/% | |
| Example 1 | 88.5 |
| Example 2 | 86.2 |
| Example 3 | 87.6 |
| Comparative example 1 | 65.3 |
| Comparative example 2 | 59.7 |
Comparative example 1: the difference from example 1 is that no nano bentonite is added;
Comparative example 2: the difference from example 1 is that the composite support is not subjected to an activation treatment;
As can be seen from Table 2, the mercury removal agent prepared by the invention has higher mercury removal efficiency, and the mercury removal efficiency can be greatly improved by introducing nano bentonite and activating the composite carrier.
Detecting and comparing desulfurization efficiency;
comparative example 1: the difference from example 1 is that no nano bentonite is added;
Comparative example 2: the difference from example 1 is that the composite support is not subjected to an activation treatment;
as can be seen from table 3, the mercury removal agent prepared by the present invention also has an excellent desulfurization function.
The foregoing description of the preferred embodiments of the invention should not be taken as limiting the scope of the invention, which is defined by the appended claims, but rather by the description of the preferred embodiments, all changes and modifications that come within the meaning and range of equivalency of the claims are intended to be embraced therein.
Claims (7)
1. A preparation method of a mercury removal agent with desulfurization function is characterized by comprising the following steps: the method comprises the following steps:
(1) Sequentially adding alumina monohydrate and water into a stirrer, and uniformly stirring to obtain a suspension;
(2) Dropwise adding a nitric acid solution into the suspension, regulating the pH to 5.5, stopping dropwise adding the nitric acid solution, regulating the temperature to 80 ℃, and carrying out heat preservation and stirring for 40min to obtain a sol solution;
(3) Adding nano bentonite into the sol solution, and performing ultrasonic dispersion treatment for 10min to obtain a mixed sol solution;
the mixing mass ratio of the sol solution to the nanometer bentonite is 15:1, treating the nano bentonite by a coupling agent;
(4) Spray drying the mixed sol solution to obtain a composite carrier;
(5) Activating the composite carrier:
firstly, preparing an activating solution, then adding a composite carrier into the activating solution, adjusting the temperature to 70-80 ℃, preserving the heat for 10 hours, then filtering, washing with clear water to be neutral, and drying to constant weight to obtain the activating carrier;
The preparation method of the activating solution comprises the following steps:
Sequentially adding 1,3, 5-trimesic acid and maleic anhydride into deionized water, and uniformly stirring to obtain an activating solution;
The mixing mass ratio of the 1,3, 5-trimesic acid, the maleic anhydride and the deionized water is 3-5:1:30;
(6) Sequentially adding the activated carrier and the basic copper carbonate solution into a vacuum impregnation reaction kettle, carrying out vacuum impregnation treatment for 1-2 hours, and then carrying out suction filtration to obtain an impregnated body;
(7) Drying the impregnated body to obtain a dried body;
(8) And (3) placing the dried body in a crucible, roasting for 40-50min, and naturally cooling to room temperature.
2. The method for preparing the mercury removal agent with desulfurization function according to claim 1, which is characterized in that: the mixing mass ratio of the alumina monohydrate to the water is 1:10-12.
3. The method for preparing the mercury removal agent with desulfurization function according to claim 1, which is characterized in that: the mass fraction of the nitric acid solution is 1.5%.
4. The method for preparing the mercury removal agent with desulfurization function according to claim 2, which is characterized in that: the coupling agent treatment is as follows:
preparing an organosilane coupling agent solution with the mass fraction of 10%;
Nanometer bentonite is prepared according to the following proportion of 1: adding 10 mass ratio into organosilane coupling agent solution, adjusting temperature to 85 ℃, preserving heat and stirring for 2 hours, carrying out suction filtration, washing to neutrality, and drying to constant weight.
5. The method for preparing the mercury removal agent with desulfurization function according to claim 1, which is characterized in that: the mixing mass ratio of the activating carrier to the basic copper carbonate solution is 1:20-30 parts;
the concentration of the basic copper carbonate solution is 1.2mol/L.
6. The method for preparing the mercury removal agent with desulfurization function according to claim 1, which is characterized in that: the vacuum impregnation temperature was 68 ℃.
7. The method for preparing the mercury removal agent with desulfurization function according to claim 6, wherein the method comprises the following steps: the vacuum degree of the vacuum impregnation was 0.25Pa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211138485.1A CN115608320B (en) | 2022-09-19 | 2022-09-19 | Preparation method of mercury removal agent with desulfurization effect |
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