CN108654567B - Medium-high temperature dechlorinating agent for removing HCl gas in flue gas and preparation method thereof - Google Patents

Medium-high temperature dechlorinating agent for removing HCl gas in flue gas and preparation method thereof Download PDF

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CN108654567B
CN108654567B CN201810457884.1A CN201810457884A CN108654567B CN 108654567 B CN108654567 B CN 108654567B CN 201810457884 A CN201810457884 A CN 201810457884A CN 108654567 B CN108654567 B CN 108654567B
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dechlorinating agent
drying
flue gas
stirring
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CN108654567A (en
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曹俊
金保昇
黄亚继
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Southeast University
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    • 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
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • 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
    • B01J20/16—Alumino-silicates
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • 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
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/204—Inorganic halogen compounds
    • B01D2257/2045—Hydrochloric acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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Abstract

The invention discloses a medium-high temperature dechlorinating agent for removing HCl gas in flue gas and a preparation method thereof, the dechlorinating agent is composed of 70-88% by mass of active ingredients, 10-25% by mass of carriers and auxiliaries and 2-5% by mass of adhesives, the active ingredients are obtained by high-temperature roasting of active precursor ingredients, and the active precursor ingredients are pretreated electrolytic stone and Ca (NO)3)2、Zn(NO3)2、NaHCO3Mixing above materials. The dechlorinating agent can efficiently and deeply remove HCl gas in flue gas within the temperature range of 273-1073K.

Description

Medium-high temperature dechlorinating agent for removing HCl gas in flue gas and preparation method thereof
The technical field is as follows:
the invention relates to a medium-high temperature dechlorinating agent for removing HCl gas in flue gas and a preparation method thereof, belonging to the technical field of flue gas purification treatment.
Background art:
according to statistics, the daily garbage yield of cities in the world is about 450-500 kg every year at present, and the cities grow year by year at a speed of 8-10% each year, China is taken as a developing country with fast economic growth, the influence of the urban household garbage is more remarkable, more than 600 cities in the country stack or bury various types of garbage for 80 hundred million tons, and the garbage accumulation amount accounts for 5 hundred million square meters of land. A large amount of domestic garbage not only destroys urban image, but also causes serious ecological environment pollution of atmosphere, soil, water, organisms and the like. The amount of the garbage which can be subjected to harmless treatment is only 60-70%, and the conventional garbage treatment methods mainly comprise three methods of landfill, composting and incineration. However, the traditional landfill treatment method has the problems of large floor area, secondary pollution caused by the fact that penetrating fluid damages the soil structure and the like, and the contradiction between the traditional landfill treatment method and the basic national conditions that the population density of large and medium-sized cities in China is large and the land resources are in short supply is increasingly intensified, and the incineration treatment method is used instead, the total number of domestic garbage incineration plants which are put into operation in China is more than 160 in 2015, and the total amount of municipal domestic garbage treated in 2015 is more than 4000 ten thousand tons. Project 44 of planning to be put into operation and building garbage incineration.
The incineration method has the advantages of reducing the volume by 90 percent and converting the chemical energy stored in the garbage into heat energy for utilizationThe method is widely applied. Because the components of the garbage are quite complex, the garbage incineration and gasification treatment can realize secondary utilization, and simultaneously, the problem of secondary pollution is also brought. According to detection, the waste incineration flue gas contains more than one hundred pollutants and also contains various toxic substances. Besides soot and heavy metal pollutants, it is mainly a large amount of gaseous pollutants (SO)2NOx, HCl, dioxin, etc.), the acidic gases in the flue gas not only cause high-temperature corrosion of the superheater and reheater in the boiler system and low-temperature corrosion of the heated surface at the tail, damage the monitoring instruments, and increase the operation and maintenance costs of the equipment; after being discharged into the atmosphere, the ozone layer can be damaged, and the environmental problems of photochemical smog, acid rain and the like are caused. Dioxin is an extremely difficult-to-decompose organic pollutant with continuous pollution, has damage to a plurality of organs and systems of a human body, has carcinogenicity, teratogenicity and mutagenicity, can migrate and spread in the environment, is gradually enriched along with a food chain, has extremely high harm to the environmental system and the human body, is listed as a pollutant needing priority control by all countries in the world, and is pointed out in a report incinerator and human health published by the United nations environmental planning agency at the end of the 20 th century that waste incineration is the largest source of dioxin. It is estimated that dioxin discharged from garbage incinerators accounts for about 10% to 40% of the total discharge amount on a global basis. The new construction of waste incineration plants in locations close to residential areas has been questioned by citizens and scholars at home and abroad. The problem of controlling secondary pollution from the incineration of refuse has been non-trivial. The nation also pays great attention to the environmental problem caused by waste incineration, after the emission of waste incineration is regulated by 'domestic waste incineration pollution control standard' (GB 18485-2001) firstly formulated in 2001, the standard is modified and perfected in 2014, the national standard GB18485-2014 is issued, and compared with the new and old standards, the national standard can find that the highest emission limit value of each pollutant is reduced in the new standard, and the sampling measurement method is further refined, wherein the emission limit value of dioxin with the largest change is reduced to 0.1 ng TEQ/m3 from 1 ng TEQ/m3, and the reduction amount reaches 99%.
According to statistics, SO in the flue gas at the hearth outlet of the domestic garbage incinerator2，NOXAnd the concentration of HCl is respectively150~1000mg/m3、300~500 mg/m3、815~1630mg/m3The prior art has the advantages that due to the wide application of coal-fired power plants, the control technology for the tail gas pollutants of the power plants at home and abroad is mainly focused on the fields of tail gas desulfurization, denitration and the like, the desulfurization and denitration process is very mature, most waste incineration power plants are also provided with perfect desulfurization and denitration systems, the removal efficiency reaches over 90 percent, and the emission standard can be met. However, almost all waste incineration plants do not have a separate HCl treatment unit, but only the influence of HCl is taken into account while desulfurizing and removing the spent waste, while removing a portion of the HCl. However, the waste incineration power plant is different from the common coal-fired power plant, and due to the existence of rich chlorine elements in PVC plastics, hard plastics and kitchen garbage, HCl gas becomes one of the main acidic pollution gases in the waste incineration furnace. Due to incomplete garbage classification and recovery measures, the average initial concentration of HCl in the outlet gas of the hearth of the domestic garbage incinerator is as high as 815-1630 mg/m3Is far higher than 163-815 mg/m of developed countries in the west3. HCl in the flue gas not only has damage of acid gas to incineration equipment and atmospheric environment, but also can form low-boiling-point metal chloride with heavy metal to intensify the enrichment of heavy metal in the fly ash; and researches show that the concentration of HCl in the high-temperature flue gas can directly influence the generation amount of dioxin, particularly at 400-700 ℃. The problem of HCl in acid gas generated in the process of garbage disposal is more and more drawing extensive attention of the international society, and dechlorination of garbage incineration flue gas is also one of research hotspots in the field in recent years.
The traditional HCl removing system, whether a wet method, a semi-dry method or a dry method, is mainly arranged at a low temperature section (< 250 ℃), and although the methods can greatly reduce the HCl emission concentration to meet increasingly strict emission standards, the method does not play a good role in controlling the influence of HCl gas at a high temperature section. In recent years, the focus of research has gradually shifted to the removal of HCl at medium and high temperatures, and thus dechlorinating agents are of particular importance. At present, more effort is put into the research of dechlorinating agents at home and abroad, and fruitful results are obtained. However, there still remain problems such as low chlorine capacity, narrow use range, high price and inability to regenerate. The development of a novel dechlorinating agent with high chlorine capacity and low price is the direction of further development and research.
The invention content is as follows:
the invention aims to provide a medium-high temperature dechlorinating agent for removing HCl gas in flue gas and a preparation method thereof, wherein the dechlorinating agent can efficiently and deeply remove HCl gas in flue gas within a temperature range of 273-1073K.
In order to solve the problems, the invention adopts the following technical scheme:
the medium-high temperature dechlorinating agent for removing HCl gas in flue gas comprises 70-88% by mass of active ingredients, 10-25% by mass of carriers and auxiliaries and 2-5% by mass of adhesives, wherein the active ingredients are obtained by high-temperature roasting of active precursor ingredients, and the active precursor ingredients are prepared from pretreated electrolytic stones and Ca (NO)3)2、Zn(NO3)2、NaHCO3Mixing above materials.
The medium-high temperature dechlorinating agent for removing HCl gas in the flue gas is prepared by the following steps of pretreating electrolytic stones according to the mass ratio of 1: 20-1: 30 is dissolved in acetic acid, stirred, filtered and dried to obtain the product.
The medium-high temperature dechlorinating agent for removing HCl gas in the flue gas, the pretreated electrolytic stone and Ca (NO)3)2、Zn(NO3)2、NaHCO3Mixing with one or more of the above components, and mixing with Ca (NO) in the course of mixing3)2、Zn(NO3)2、NaHCO315: 1 (15-30): 1.
the medium-high temperature dechlorinating agent for removing HCl gas in the flue gas is characterized in that the carrier and the auxiliary agent are activated carbon.
The medium-high temperature dechlorinating agent for removing HCl gas in the flue gas is carboxymethyl cellulose.
The preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in the flue gas comprises the following steps:
(1) pretreating electrolytic stones for later use;
(2) preparation of active precursor component: mixing the electrolytic stone pretreated in the step (1) with Ca (NO)3)2、Zn(NO3)2、NaHCO3Mixing with one or more of the above materials, and mixing with Ca (NO) in the course of mixing3)2、Zn(NO3)2、NaHCO315: 1 (15-30): 1, fully dissolving the mixture into deionized water; wherein the temperature of the deionized water is 333-358K, the solid-liquid mass ratio of the mixture to the deionized water is 1: 3-1: 10, and then drying and stirring are carried out to obtain a solid product, namely the active precursor component;
(3) preparing an active ingredient: roasting the active precursor prepared in the step (2) at high temperature;
(4) preheating the carrier and the auxiliary agent;
(5) mixing the active ingredient prepared in the step (3) with the preheated carrier and the auxiliary agent in the step (4); mixing and then fully mixing with the adhesive; the mass percent of the active component is 70-88%, the mass percent of the carrier and the auxiliary agent is 10-25%, and the mass percent of the adhesive is 2-5%;
(6) drying the product obtained in the step (5) and stirring to obtain a solid product;
(7) and (4) forming and granulating the solid product obtained in the step (6) to obtain the dechlorinating agent.
The preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in the flue gas comprises the following steps of (1): according to the mass ratio of 1: 20-1: 30 dissolving the electrolytic stone in acetic acid, stirring for 4 hours, filtering and drying, wherein the stirring speed is 50-100 rpm.
The preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in flue gas comprises the step (2) that the drying temperature is 358-373K, and the stirring speed is 50-100 rpm.
In the preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in the flue gas, the high-temperature roasting in the step (3) is carried out for 16 hours under 1123K.
According to the preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in the flue gas, the preheating treatment in the step (4) is preheating for 2-4 hours at the temperature of 333-358K.
According to the preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in flue gas, the drying and stirring conditions in the step (6) are that the drying temperature is 358-373K, and the stirring speed is 50-100 rpm.
Has the advantages that:
compared with the prior art, the medium-high temperature dechlorinating agent for removing HCl gas and the preparation method thereof provided by the invention have the following characteristics and advantages that:
1. the dechlorinating agent can efficiently and deeply remove HCl gas in flue gas within the temperature range of 273-1073K;
2. after a series of processing treatments, the active ingredients are decomposed at high temperature due to roasting, so that on one hand, a spinel structure with a stable structure in a wide temperature range is obtained, on the other hand, the active ingredients are decomposed to generate gas release, so that the specific surface area of the dechlorinating agent is large, pores are developed, and the adsorption activity of the surface of the dechlorinating agent can be effectively improved;
3. according to the preparation method of the dechlorinating agent, the specific surface area of the carrier is increased and the structure is stable by preheating the carrier and the auxiliary agent, so that the structure of the dechlorinating agent prepared tends to be more stable, and the prepared dechlorinating agent is stable in structure and large in specific surface area in a wide temperature range by roasting the active component precursor at high temperature, so that the prepared dechlorinating agent is ensured to have higher chlorine capacity and higher adsorption activity.
Detailed Description
The process of the present invention is further illustrated by the following specific examples.
Example 1
Weighing 750g of electrolytic stone, 30g of Ca (NO)3)2200g of activated carbon and 20g of carboxymethyl cellulose; dissolving the electrolytic stone in 15kg of acetic acid, stirring at 65rpm for 4 hours, and then drying at 358KDrying to obtain a solid; the electrolyte and Ca (NO) will be obtained3)2Fully and uniformly mixing, adding 4kg of 333K deionized water, stirring and rotating the obtained mixture at 65rpm, drying at 353K to obtain a solid, roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 350K for 4 hours, soaking the roasted mixture on a preheated molecular sieve, mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at 65rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 75.1% by test.
Example 2:
800g of electrolytic stone and 26g of Ca (NO) were weighed3)2144g of activated carbon and 30g of carboxymethyl cellulose; dissolving the electrolytic stone in 16kg of acetic acid, stirring at 65rpm for 4 hours, and drying at 358K to obtain a solid; the electrolyte and Ca (NO) will be obtained3)2Fully and uniformly mixing, adding 4kg of 333K deionized water, stirring and rotating the obtained mixture at 70rpm, drying at 353K to obtain a solid, roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 350K for 4 hours, soaking the roasted mixture on a preheated molecular sieve, mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at 70rpm, and drying at 333K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 74.3% by tests.
Example 3:
800g of electrolytic stone and 50g of NaHCO are weighed3120g of activated carbon and 30g of carboxymethyl cellulose; dissolving the electrolytic stone in 16kg of acetic acid, stirring at a rotational speed of 80rpm for 4 hours, and drying at 358K to obtain a solid; electrolytic stone and NaHCO are obtained3Fully and uniformly mixing, then adding 5kg of 353K deionized water, stirring and rotating the obtained mixture at 80rpm, and drying at 353K to obtain a solid, then roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 353K for 4 hours, then soaking the roasted mixture on a preheated molecular sieve, then mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at 80rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 76.6% through tests.
Example 4:
weighing 700g of electrolytic stone, 30g of Ca (NO)3)2，20g Zn(NO3)2200g of activated carbon and 50g of carboxymethyl cellulose; dissolving the electrolytic stone in 21kg of acetic acid, stirring at a rotating speed of 80rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Ca (NO) will be obtained3)2，Zn(NO3)2Mixing thoroughly, adding 6kg 343K deionized water, stirring at 80rpm, drying at 353K to obtain solid, calcining at 1123K for 16 hr, preheating activated carbon at 353K for 4 hr, soaking the calcined mixture in preheated molecular sieve, mixing with carboxymethyl cellulose, stirring at 80rpm, and drying at 353KDrying at 353K to obtain solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 76.1% through tests.
Example 5:
weighing 700g of electrolytic stone, 30g of Ca (NO)3)2，18g NaHCO3202g of activated carbon and 50g of carboxymethyl cellulose; dissolving the electrolytic stone in 20kg of acetic acid, stirring at a rotating speed of 100rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Ca (NO) will be obtained3)2，NaHCO3The mixture was mixed well, then 5kg of 343K deionized water was added, the resulting mixture was stirred at 100rpm and dried at 353K to obtain a solid, then the obtained solid was calcined at 1123K for 16 hours, activated carbon was preheated at 353K for 4 hours, then the calcined mixture was impregnated on a preheated molecular sieve and then mixed with carboxymethyl cellulose, the resulting mixture was stirred at 100rpm and dried at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 75.7% by tests.
Example 6:
800g of electrolytic stone and 20g of Ca (NO) were weighed3)2，20g NaHCO3140g of activated carbon and 20g of carboxymethyl cellulose; dissolving the electrolytic stone in 18kg of acetic acid, stirring at a rotating speed of 60rpm for 4 hours, and drying at 353K to obtain a solid;the electrolyte and Ca (NO) will be obtained3)2，NaHCO3Fully and uniformly mixing, then adding 4kg of 343K deionized water, stirring and rotating the obtained mixture at the speed of 60rpm, and drying at 353K to obtain a solid, then roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 353K for 4 hours, then soaking the roasted mixture on a preheated molecular sieve, then mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at the speed of 60rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 77.7% by tests.
Example 7:
800g of electrolytic stone, 22g of Zn (NO) are weighed3)2，20g NaHCO3128g of activated carbon and 30g of carboxymethyl cellulose; dissolving the electrolytic stone in 20kg of acetic acid, stirring at a rotating speed of 60rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Zn (NO) will be obtained3)2，NaHCO3Fully and uniformly mixing, then adding 4kg of 343K deionized water, stirring and rotating the obtained mixture at the speed of 60rpm, and drying at 353K to obtain a solid, then roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 353K for 4 hours, then soaking the roasted mixture on a preheated molecular sieve, then mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at the speed of 60rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 75.7% by tests.
Example 8:
785g of electrolytic stone and 26g of Zn (NO) are weighed3)2159g of activated carbon and 30g of carboxymethyl cellulose; dissolving the electrolytic stone in 19kg of acetic acid, stirring at a rotating speed of 70rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Zn (NO) will be obtained3)2Fully and uniformly mixing, then adding 4kg of 343K deionized water, stirring and rotating the obtained mixture at 70rpm, drying at 343K to obtain a solid, then roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 343K for 4 hours, then soaking the roasted mixture on a preheated molecular sieve, then mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at 70rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 74.4% by tests.
Example 9:
680g of electrolytic stone and 35g of Zn (NO) were weighed3)2160g of activated carbon and 25g of carboxymethyl cellulose; dissolving the electrolytic stone in 17kg of acetic acid, stirring at a rotation speed of 50rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Zn (NO) will be obtained3)2Mixing well, adding 3kg of 353K deionized water, stirring at 50rpm, drying at 343K to obtain solid, calcining at 1123K for 16 hr, preheating activated carbon at 353K for 4 hr, soaking the calcined mixture in preheated molecular sieve, mixing with carboxymethyl cellulose, stirring at 50rpm, and drying at 343KDrying at 353K to obtain solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 74.9% by tests.
Example 10:
675g of electrolytic stone and 40g of NaHCO were weighed3250g of activated carbon and 35g of carboxymethyl cellulose; dissolving the electrolytic stone in 14kg of acetic acid, stirring at a rotating speed of 60rpm for 4 hours, and drying at 353K to obtain a solid; electrolytic stone and NaHCO are obtained3Well mixing, then adding 4kg of 353K deionized water, stirring and rotating the obtained mixture at 60rpm, drying at 353K to obtain a solid, then roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 353K for 4 hours, then soaking the roasted mixture on a preheated molecular sieve, then mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at 60rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 78.9% through tests.
Example 11:
780g of electrolytic stone and 13g of Ca (NO) were weighed3)2，13g Zn(NO3)2，13g NaHCO3161g of activated carbon and 20g of carboxymethyl cellulose; dissolving the electrolytic stone in 24kg of acetic acid, stirring at a rotating speed of 60rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Ca (NO) will be obtained3)2，Zn(NO3)2，NaHCO3Fully and uniformly mixing, then adding 5kg of 353K deionized water, stirring and rotating the obtained mixture at 60rpm, drying at 353K to obtain a solid, then roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 353K for 4 hours, then soaking the roasted mixture on a preheated molecular sieve, then mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at 60rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 76.5% through tests.
Example 12:
730g of electrolytic stone and 20g of Ca (NO) are weighed3)2，15g Zn(NO3)2，20g NaHCO3195g of activated carbon and 20g of carboxymethyl cellulose; dissolving the electrolytic stone in 22kg of acetic acid, stirring at a rotating speed of 70rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Ca (NO) will be obtained3)2，Zn(NO3)2，NaHCO3Fully and uniformly mixing, then adding 5kg of 353K deionized water, stirring and rotating the obtained mixture at 70rpm, and drying at 353K to obtain a solid, then roasting the obtained solid at 1123K for 16 hours, preheating activated carbon at 353K for 4 hours, then soaking the roasted mixture on a preheated molecular sieve, then mixing with carboxymethyl cellulose, stirring and rotating the obtained mixture at 70rpm, and drying at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 77.5% by tests.
Example 13:
720g of electrolytic stone and 20g of Ca (NO) were weighed3)2，18g Zn(NO3)2210g of activated carbon and 32g of carboxymethyl cellulose; dissolving the electrolytic stone in 15kg of acetic acid, stirring at a rotating speed of 60rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Ca (NO) will be obtained3)2，Zn(NO3)2Well mixed, then 6kg of 343K deionized water is added, the obtained mixture is stirred at the rotating speed of 60rpm and dried at 353K to obtain a solid, then the obtained solid is roasted at 1123K for 16 hours, activated carbon is preheated at 353K for 4 hours, then the roasted mixture is soaked on a preheated molecular sieve and then mixed with carboxymethyl cellulose, and the obtained mixture is stirred at the rotating speed of 80rpm and dried at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 76.3% through tests.
Example 14:
810g of electrolytic stone and 17g of Zn (NO) are weighed3)2，10g NaHCO3143g of activated carbon and 20g of carboxymethyl cellulose; dissolving the electrolytic stone in 20kg of acetic acid, stirring at 75rpm for 4 hours, and drying at 353K to obtain a solid; the electrolyte and Zn (NO) will be obtained3)2，NaHCO3Mixing thoroughly, adding 5kg 343K deionized water, stirring at 75rpm, oven drying at 353K to obtain solid, and calcining at 1123K for 16 hrIn the preparation method, activated carbon is preheated at 353K for 4 hours, then the roasted mixture is soaked on a preheated molecular sieve and then mixed with carboxymethyl cellulose, the obtained mixture is stirred at the rotating speed of 60rpm and dried at 353K to obtain a solid. And molding and granulating the obtained solid to obtain the required dechlorinating agent.
The prepared dechlorination agent is subjected to dechlorination experiments, and the adsorbent reactor can be a moving bed, a fixed bed or a fluidized bed reactor and the like. The dechlorination reaction conditions are as follows: the amount of the introduced flue gas is 60L/h, wherein the amount of chlorine-containing gas is 100-3000 ppm, the reaction temperature is in the range of 273-1073K, the dechlorinating agent can reduce the amount of HCl contained in the outlet gas to below 0.5ppm, and the penetration chlorine capacity is 75.4% by tests.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
It should be noted that the above embodiments are only examples for clarity of illustration, and are not limiting, and all embodiments need not be exhaustive. All the components not specified in the present embodiment can be realized by the prior art. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (5)

1. A medium-high temperature dechlorinating agent for removing HCl gas in flue gas is characterized in that: the dechlorinating agent is composed of active ingredients, a carrier, an auxiliary agent and a binder, wherein the active ingredients are 70-88% by mass, the carrier and the auxiliary agent are 10-25% by mass and the binder is 2-5% by mass, the active ingredients are obtained by high-temperature roasting of active precursor ingredients, and the active precursor ingredients are prepared from pretreated electrolytic stone and Ca (NO)3)2、Zn(NO3)2、NaHCO3Mixing to obtain; the pretreated electrolytic stoneThe method comprises the following steps of mixing electrolytic stones according to the mass ratio of 1: 20-1: 30 is dissolved in acetic acid, stirred, filtered and dried to obtain the product; in the mixing process, pretreated electrolyte stone and Ca (NO)3)2、Zn(NO3)2、NaHCO315: 1 (15-30): 1; the carrier and the auxiliary agent adopt active carbon; the adhesive adopts carboxymethyl cellulose, and the high-temperature roasting refers to roasting at 1123K for 16 hours.
2. The preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in flue gas according to claim 1, characterized by comprising the following steps: the method comprises the following steps:
(1) pretreating electrolytic stones for later use;
(2) preparation of active precursor component: mixing the electrolytic stone pretreated in the step (1) with Ca (NO)3)2、Zn(NO3)2、NaHCO3Mixing thoroughly, during the mixing process, the pretreated electrolyte stone and Ca (NO)3)2、Zn(NO3)2、NaHCO315: 1 (15-30): 1, fully dissolving the mixture into deionized water; wherein the temperature of the deionized water is 333-358K, the solid-liquid mass ratio of the mixture to the deionized water is 1: 3-1: 10, and then drying and stirring are carried out to obtain a solid product, namely the active precursor component;
(3) preparing an active ingredient: roasting the active precursor prepared in the step (2) at high temperature;
(4) preheating the carrier and the auxiliary agent;
(5) mixing the active ingredient prepared in the step (3) with the preheated carrier and the auxiliary agent in the step (4); mixing and then fully mixing with the adhesive; the mass percent of the active component is 70-88%, the mass percent of the carrier and the auxiliary agent is 10-25%, and the mass percent of the adhesive is 2-5%;
(6) drying the product obtained in the step (5) and stirring to obtain a solid product;
(7) and (4) forming and granulating the solid product obtained in the step (6) to obtain the dechlorinating agent.
3. The preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in flue gas according to claim 2, characterized by comprising the following steps: the method for pretreating the electrolytic stone in the step (1) comprises the following steps: according to the mass ratio of 1: 20-1: 30 dissolving the electrolytic stone in acetic acid, stirring for 4 hours, filtering and drying, wherein the stirring speed is 50-100 rpm.
4. The preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in flue gas according to claim 2, characterized by comprising the following steps: the drying temperature in the step (2) is 358-373K, and the stirring speed is 50-100 rpm.
5. The preparation method of the medium-high temperature dechlorinating agent for removing HCl gas in flue gas according to claim 2, characterized by comprising the following steps: preheating for 2-4 h at 333-358K in the preheating treatment in the step (4); the drying and stirring conditions in the step (6) are that the drying temperature is 358-373K, and the stirring speed is 50-100 rpm.
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CN108654567B (en) * 2018-05-14 2020-02-07 东南大学 Medium-high temperature dechlorinating agent for removing HCl gas in flue gas and preparation method thereof
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