CN111330439A - Catalytic oxidation desulfurization method for ship flue gas - Google Patents

Catalytic oxidation desulfurization method for ship flue gas Download PDF

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CN111330439A
CN111330439A CN202010216878.4A CN202010216878A CN111330439A CN 111330439 A CN111330439 A CN 111330439A CN 202010216878 A CN202010216878 A CN 202010216878A CN 111330439 A CN111330439 A CN 111330439A
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flue gas
catalytic
desulfurization method
ship
absorption liquid
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韩建英
黄献
褚华珍
张永柱
韩建平
李海永
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/73—After-treatment of removed components
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05C—NITROGENOUS FERTILISERS
    • C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
    • C05D5/00—Fertilisers containing magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B01D2251/102—Oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/102—Ammonia
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/103—Water
    • B01D2252/1035—Sea water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/20—Organic absorbents
    • B01D2252/204—Amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/012—Diesel engines and lean burn gasoline engines
    • 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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  • Chemical Kinetics & Catalysis (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

A catalytic oxidation desulfurization method for ship flue gas utilizes a smoke exhaust pipeline and flue gas purification equipment of the existing ship power machine, and specifically comprises the following steps: (1) preparing flue gas absorption liquid by adopting seawater or alkaline metal compounds or ammonia or amine compounds; (2) preparing a catalytic aqueous solution containing a metal catalyst by adopting a metal compound; (3) atomized and sprayed into a smoke exhaust pipeline or/and smoke purification equipment, and the catalytic water agent and the absorption liquid in the smoke are instantly and fully and uniformly mixed with the smoke; (4) absorbing particles in liquid and SO in flue gas2Molecule, O2The molecules are fast under the action of the catalytic water agentQuickly carrying out desulfurization reaction to generate stable sulfate compound particles; (5) the generated sulfate compound particles are collected by a flue gas purification device and then directly discharged into rivers and seas or comprehensively utilized and treated. The invention has the advantages of small occupied area, low investment cost, stable and reliable operation, high desulfurization efficiency and the like.

Description

Catalytic oxidation desulfurization method for ship flue gas
Technical Field
The invention relates to the field of air pollution prevention and control, in particular to a catalytic oxidation desulfurization method for ship flue gas.
Background
In recent years, with the development of global shipping trade, tail gas emitted by marine diesel engines becomes one of the main sources of air pollution, and has a greater influence on inland river regions, coastal regions and ports. The International Maritime Organization (IMO) has issued the international public convention for preventing ship pollution (MARPOL 73/78) standard for pollutants generated by current marine diesel engines, and mainly controls nitrogen oxides (NOx), sulfur oxides (S0 x), carbon monoxide (C0), Hydrocarbons (HC), Particulate Matters (PM) and the like discharged by ships. At present, compression ignition engines are used in most ships, and particularly, low-quality heavy oil is mostly adopted as fuel in international ocean-going ships, so that serious pollution and damage are caused to the atmospheric environment.
Because low-sulfur heavy oil or liquefied natural gas is used as fuel, the running cost is high, and the sulfur content in the flue gas of the main stream control ship engine at present is mainly realized by installing a waste gas desulfurization device; the desulfurization technology mainly adopts industrial measures such as thermal power and the like. However, due to the characteristics of the ship such as load, gravity center, available area and space, limestone-gypsum wet desulphurization and circulating fluidized bed semi-dry desulphurization are less in use, and magnesium desulphurization and seawater desulphurization are mainly used. The magnesium desulfurization method comprises the steps of preparing a magnesium hydroxide solution by using a magnesium oxide pulping system, carrying out contact reaction with flue gas in a desulfurization tower to generate magnesium sulfite, and dehydrating the magnesium sulfite to realize comprehensive utilization. Compared with a limestone-gypsum method, the method has the advantages of small floor area, stable and reliable operation and difficult blockage; the reaction end product is dissolved in water and can be used as a non-pollution discharge in a large water body or a sea area; but has large investment and high desulfurizing agent costHigh cost, etc., resulting in high practical cost. The seawater desulfurization method utilizes the alkalinity (main component is Na) of natural seawater+、Mg2+、Ca2+、K+、Cl-、SO4 2-Etc.) to prepare a sulfur dioxide absorbent, and the sulfur dioxide absorbent and the flue gas are discharged into the seawater after contact reaction in a desulfurizing tower; the process saves fresh water resources and has low construction and operation costs, but has the following problems: firstly, the equipment volume and the occupied area are large; secondly, the method is only suitable for the smoke with lower sulfur content; thirdly, the impurities in the flue gas pollute the seawater; fourth, it cannot be tried on coastal and inland riverways.
Meanwhile, other ship desulfurization and purification technologies exist, for example, in the patent application with the application number of 201610286160.6, the methods of photocatalysis, aeration and the like are adopted to realize tail gas purification in the flue gas seawater desulfurization and denitration process integrating photocatalytic oxidation and photocatalytic aeration; in the patent application with the application number of 201611256827.4, the SCR desulfurization, denitrification, dedusting and denoising composite device is combined with a low-temperature plasma technology to realize tail gas purification, but the 2 types of technologies are not mature, so that the use is less. In addition, catalytic desulfurization technologies are adopted in other industries at present, and the technologies can be mainly divided into a solid-supported catalytic desulfurization technology, a liquid-phase catalytic desulfurization technology and an unsupported catalytic desulfurization technology, but the technologies are immature or high in cost, and technical research on operation on ship flue gas is not available.
In conclusion, no catalytic oxidation desulfurization technology which occupies a small area, is low in investment cost and runs stably and reliably exists for the ship flue gas desulfurization at present.
Disclosure of Invention
The invention aims to solve the technical problem of providing a catalytic oxidation desulfurization method for ship flue gas, which has the advantages of small floor area, low investment cost and stable and reliable operation.
The technical scheme adopted by the invention for solving the technical problems is as follows: a catalytic oxidation desulfurization method for ship flue gas utilizes a smoke exhaust pipeline and flue gas purification equipment of the existing ship power machine, and specifically comprises the following steps:
(1) preparing flue gas absorption liquid by adopting seawater or alkaline metal compounds or ammonia or amine compounds;
(2) preparing a catalytic water agent containing a metal catalyst by using a metal compound, wherein the metal compound is a transition metal compound or/and an aluminum metal compound;
(3) atomizing and spraying the flue gas absorption liquid obtained in the step (1) and the catalytic water agent obtained in the step (2) into a smoke exhaust pipeline or/and flue gas purification equipment, and instantly and uniformly mixing the catalytic water agent and the absorption liquid in the flue gas with the flue gas;
(4) wherein the particles in the absorption liquid and SO in the flue gas2Molecule, O2The molecules rapidly carry out desulfurization reaction under the action of a catalytic water agent to generate stable sulfate compound particles;
(5) the generated sulfate compound particles are collected by a flue gas purification device and then directly discharged into rivers and seas or comprehensively utilized and treated.
Further, in the step (2), the transition metal compound is preferably a compound of a transition metal element of the fourth or fifth period, more preferably a compound of manganese, iron, copper or zinc, and the operation is economical.
Further, in the step (2), the aqueous catalytic agent may be a solution or a suspension, preferably a soluble metal compound solution, and may be spray-dried to form the nano-scale catalyst.
Further, in the step (2), when the catalytic aqueous solution is a suspension, the micron-sized metal compound is preferably used for preparing the catalytic aqueous solution, and the micron-sized catalyst can be prepared by spray drying.
Further, in the step (1), the flue gas absorption liquid is preferably prepared by urea in ammonia and amine compounds or magnesium oxide in alkaline metal compounds, so that the desulfurization efficiency per unit weight is high, the occupied area is small, and the comprehensive economy is good. When urea in ammonia or amine compounds is used, desulfurization products (NH) can be treated4)2SO4The conversion treatment is carried out, the internal circulation of the ammonia desulfurizer is realized, and the storage space and the cost of the desulfurizer are reduced.
Further, an oxidant can be added into the flue gas absorption liquid prepared in the step (1) and/or the catalytic water agent prepared in the step (2), so that the removal efficiency of sulfur dioxide is improved.
Further, adding a surfactant and/or an agglomerating agent into the flue gas absorption liquid prepared in the step (1) and/or the catalytic water agent prepared in the step (2); or in the step (3), the surfactant and/or the agglomerating agent are independently sprayed, so that the dust collection effect of the flue gas purification device is improved.
Further, in the step (3), the smoke exhaust pipeline refers to a smoke conveying pipeline from smoke generated by the diesel engine to smoke exhausted out of the atmosphere; the flue gas purification equipment comprises equipment such as a flue gas strip washing tower, a dust collector, denitration equipment and a desulfurization tower, wherein the dust collector can be a water mist dust collector, a cloth bag dust collector, a cyclone dust collector and an electric dust collector, and the cloth bag dust collector is preferably used.
Further, the flue gas absorption liquid prepared in the step (1) and the catalytic water agent prepared in the step (2) can be mixed and sprayed into a smoke exhaust pipeline or/and flue gas purification equipment.
Further, in the step (3), the desulfurization catalysis water agent is sprayed into the high-temperature flue gas, wherein the spraying amount of the effective catalyst is 0.01-5 mol/(preferably 0.1-3 mol) per ten thousand cubic meters of flue gas; the specific injection concentration is determined according to the initial SO of the kiln tail flue gas2The concentration is adjusted.
Further, in the step (3), one or more than two catalytic water agent injection points can be arranged and arranged in the smoke exhaust pipeline or/and the smoke purification equipment; the injection points can be arranged in a shape surrounding the pipeline and can be more than two layers, so that the catalyst and the absorbent are fully mixed with the smoke.
Further, the flue gas absorption liquid prepared in the step (1) and the catalytic water aqua prepared in the step (2) need to be filtered by a filter to obtain seawater or fresh water, so that the cost is reduced.
The technical principle is as follows:
heavy oil is generally adopted as fuel by ships, and pollutants in emissions mainly comprise CO and NOX、SO2、CXHXPM-based, especiallyDischarging SO when using high-sulfur heavy oil2The emission requirement is seriously exceeded. The invention mainly utilizes the catalytic property of metals (particularly transition metals); atomizing and spraying a catalyst water agent containing a metal catalyst and an alkaline absorbent in a high-temperature flue gas environment, and realizing rapid and uniform mixing with the flue gas; in the high-temperature flue gas of every 1 cubic millimeter, hundreds of millions of H exist2O molecules, billions of particles of desulfurizing agent, thousands of metal catalyst particles, which rapidly react with SO at high temperatures2Molecule, O2Molecules contact and catalyze reaction to generate stable sulfate compound particles; while the sulfate compound particles may be in H2O and some adsorbents, etc., and collecting in a flue gas purification device, and discharging the final product into water or as fertilizer (such as MgSO 2) according to product characteristics and ship navigation characteristics4、(NH4)2SO4Etc.) to the shore for sale.
The invention only needs to use the existing smoke exhaust pipeline and the existing flue gas purification facility for modification treatment, and the desulfurizer can preferably select light magnesium oxide, ammonia or urea for treatment, so that the modification cost is low on the whole, and the occupied area is small; meanwhile, the efficiency of converting sulfur dioxide into sulfate is improved through the catalyst, the generation chance of unstable sulfurous acid is reduced, the desulfurization effect is improved, and the requirement on the sulfur content of fuel oil is greatly reduced.
The invention has the beneficial effects that:
1. compared with a seawater desulphurization method, the method adopts the flue gas catalytic oxidation desulphurization, is not limited by sea areas, and can navigate inland rivers; the energy consumption of using a large amount of seawater is not needed, and simultaneously, pollution-free discharge to a water area is realized; the discharged smoke has no problems of white smoke, feather flying and the like.
2. The invention preferentially adopts MgO or urea for desulfurization, and MgSO in the desulfurization product4Or (NH)4)2SO4The economic value of the fertilizer is high, and the fertilizer can be used as an agricultural fertilizer; greatly reduces the operation cost and simultaneously desulfurizes the product (NH)4)2SO4And the waste heat can be utilized to circularly prepare ammonia, so that the ship loading space and the cost of the desulfurizer are greatly reduced.
3. Compared with the magnesium desulphurization technology, the invention does not need to build a large-scale desulphurization tower, greatly reduces the weight of the ship desulphurization facility, reduces the utilization of the ship space, and simultaneously reduces the influence on the gravity center of the ship.
4. The invention adopts the metal catalyst and the alkaline absorbent to improve the desulfurization efficiency and the desulfurization effect, and the desulfurization efficiency is more than 98 percent.
5. The catalyst added by the invention can react with NOX、CXHXCatalytic oxidation to remove part of NOX、CXHXThe emission of (2) reduces the pollution to the atmosphere, and when a dust collector is adopted for collection, a large amount of PM can be removed, so that the phenomenon that the smoke of the ship emits black smoke is reduced.
Drawings
FIG. 1 is a schematic view of the working conditions of embodiment 1 of the catalytic oxidation desulfurization method for marine flue gas according to the present invention;
1-a smoke exhaust pipeline, 11-a smoke exhaust pipeline I, 12-a chimney, 13-an electromagnetic valve I, 14-an electromagnetic valve II, 15-an electromagnetic valve III, 16-an injection point I, 17-an injection point II; 2-flue gas purification equipment (cloth bag dust collector), 21-dust collector frame, 22-filter bag, 23-dust collecting hopper, and 24-conveying screw; 3-catalytic desulfurization system, 31-catalyst system, 311-catalyst loading tank, 312-flowmeter III, 313-catalyst dilution tank, 314-catalyst pump, 315-nozzle I, 32-absorbent system, 321-absorbent loading tank, 322-absorbent dilution tank, 323-absorbent pump, 324-flowmeter II, 325-nozzle II, 33-seawater system, 331-flowmeter I, 332-water pump, 333-filter; 4-desulfurization product treatment system, 41-desulfurization product warehouse, 42-electromagnetic valve IV, 43-discharge purifier, and 44-discharge tailing tank.
Detailed Description
The invention is further explained with reference to the drawings and the embodiments.
Example 1
A4100 KW freight ship adopts a flue gas catalytic oxidation desulfurization method, as shown in figure 1, and utilizes a smoke exhaust pipeline 1 and a flue gas purification device 2 of an existing ship power machine 5 to carry out related transformation; the method comprises the following implementation steps:
(1) seawater or river water is used as water for desulfurization (the seawater or river water is filtered by a filter 333, pumped by a water pump 332 and distributed into a related tank body through a flowmeter I331 and an electromagnetic valve for use), MgO powder is used for preparing flue gas absorption liquid (the MgO powder is added from a feed inlet of an absorbent feeding tank 321 and is prepared into stock solution, and then the stock solution is diluted into the flue gas absorption liquid through an absorbent diluting tank 322);
(2) adopting manganese sulfate and ferric sulfate to prepare Fe-containing material3+、Mn2+The metal catalyst solution (manganese sulfate and ferric sulfate powder are added from the feed inlet of the catalyst charging tank 311, and the raw solution is prepared and then diluted into the flue gas desulfurization catalyst by the catalyst dilution tank 313);
(3) the absorption liquid is pumped to an injection point II 17 by an absorbent pump 323 and atomized and injected into the smoke exhaust pipeline I11 through 4 annularly arranged nozzles II 325, the catalyst solution is pumped to an injection point I16 by a catalyst pump 314 and atomized and injected into the smoke exhaust pipeline I11 through 4 annularly arranged nozzles I315, and therefore the catalyst solution, the absorption liquid and the smoke are fully mixed; the catalyst presents a nano-scale molecular state, and is helpful for being fully mixed with the flue gas;
(4) fine particles in the absorption liquid (MgO \ Mg (OH)2Etc.) and SO in flue gas2Molecule, O2Molecular in catalyst (Fe)3+、Mn2+) Quickly desulfurizing to obtain stable MgSO4Microparticles;
(5) the MgSO produced by the separation of the filter bag 22 in the flue gas cleaning apparatus 24The particles are collected in an ash collecting hopper 23 and discharged to a desulfurization product treatment system 4 through a conveying screw 24, wherein a desulfurization product warehouse can be selected for collection, and ships can arrive at the shore after arriving at a case and sell as chemical fertilizers, and can also be directly discharged into seawater after being filtered during long-term voyage.
Catalysis of SO with catalysts2The solid wastes in the whole process can be converted into chemical fertilizers with economic value for use, and when the heavy oil with the concentration of 3.5 percent is used for sailing, the discharged flue gas SO is used2The concentration is 30mg/NM3Wherein the dust discharge meansTarget 10mg/NM3And the air pollution emission is greatly reduced.
Example 2
A3725 KW freight ship adopts a flue gas catalytic oxidation desulfurization method, and specifically comprises the following steps:
(1) preparing a flue gas absorption liquid by adopting urea and seawater/river water according to a mass ratio of 1: 50;
(2) preparing a catalytic aqueous solution by adopting micron-sized cerium oxide powder, micron-sized manganese oxide and seawater/river water according to a mass ratio of 1:5:200, wherein the cerium oxide has oxidability and catalytic property and is beneficial to improving the desulfurization effect;
(3) atomizing and spraying the flue gas absorption liquid obtained in the step (1) and the catalytic water agent obtained in the step (2) into a smoke exhaust pipeline according to 1.1t/h and 0.2t/h respectively, and instantly and fully mixing the catalytic water agent and the absorption liquid in the flue gas with the flue gas;
(4) wherein each 1mm3About 5 × 10 is present in the flue gas of (1)6Micron-sized metal catalytic particles, about 1.4 × 1011A SO2Molecule and about 5.5 × 108A H2O gas molecular particles for absorbing CO (NH) in liquid in high-temperature flue gas environment2)2SO in molecules and flue gases2Molecule, NOXMolecule, O2The molecules are quickly subjected to desulfurization reaction under the action of a catalyst to generate stable ammonium sulfate and ammonium nitrate particles;
(5) the generated ammonium sulfate and ammonium nitrate particles are collected by a cyclone dust collector and then are sent to a circulating treatment system for treatment, and part of ammonium sulfate solution is prepared to be used as an absorbent for secondary absorption so as to reduce the dosage of the absorbent; and after the absorption effect is deteriorated, the collected desulfurization product is subjected to a tailing warehouse and sold as a fertilizer to shore.
Catalysis of SO with catalysts2The solid waste can be converted into ammonium sulfate and ammonium nitrate fertilizers with economic value for use in the whole process, and the discharged flue gas SO2The concentration is 25mg/NM3NOx concentration 151mg/NM3Wherein the dust emission index is 15mg/NM3Greatly decreaseThe air pollution emission is reduced.
Example 3
A5960 KW super oil tanker is technically improved by a flue gas catalytic oxidation desulfurization method in order to reduce investment cost and operation cost, and specifically comprises the following steps:
(1) preparing flue gas absorption liquid by adopting liquid ammonia and seawater (after filtering) according to the mass ratio of 1: 25; cold energy generated in the preparation process is used as marine refrigeration energy;
(2) preparing a nano-scale catalytic water agent by adopting copper sulfate and seawater according to the mass ratio of 1: 50;
(3) mixing the flue gas absorption liquid obtained in the step (1) and the catalytic aqueous solution obtained in the step (2) according to a mass ratio of 8:1, spraying the mixture into a smoke exhaust pipeline behind an exhaust heat boiler, and instantly and uniformly mixing the catalytic aqueous solution and the absorption liquid in the flue gas with the flue gas;
(4) preparing a surfactant solution by adopting sodium dodecyl benzene sulfonate and seawater according to the mass ratio of 1:100, and spraying the surfactant solution into a smoke exhaust pipeline in front of a bag dust collector to improve the agglomeration of reaction products;
(5) wherein each 1mm3About 8 × 10 is present in the flue gas6Micron-sized metal catalytic particles, about 1.4 × 1011A SO2Molecule and about 4.8 × 108A H2O gas molecular particles and thousands of surfactant particles absorb NH in the liquid under the environment of high-temperature flue gas3SO in molecules and flue gases2Molecule, NOXMolecule, O2The molecules are subjected to desulfurization reaction rapidly under the action of a catalytic water agent to generate stable ammonium sulfate particles;
(6) the generated ammonium sulfate particles are collected by the cyclone dust collector and then are sent to a circulating treatment system for treatment, and part of ammonium sulfate solution can be prepared to be used as an absorbent for secondary absorption so as to reduce the dosage of the absorbent; and after the absorption effect is deteriorated, the collected desulfurization product is subjected to a tailing warehouse and sold as a fertilizer to shore.
The whole process adopts catalyst to catalyze SO2Conversion into stable ammonium sulfate, and not only greatly reduces unstable sulfurous acid productsThe solid wastes in the whole process can be converted into ammonium sulfate fertilizer with economic value for use, and the discharged flue gas SO2The concentration is 18mg/NM3And the air pollution emission is greatly reduced.
Various modifications and variations of the present invention may be made by those skilled in the art, and they are also within the scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents. And are not limited to the details of the foregoing exemplary embodiments, nor to the details of the drawings.
What is not described in detail in the specification is prior art that is well known to those skilled in the art.

Claims (10)

1. A catalytic oxidation desulfurization method for ship flue gas utilizes a smoke exhaust pipeline and flue gas purification equipment of the existing ship power machine, and is characterized by comprising the following steps:
(1) preparing flue gas absorption liquid by adopting seawater or alkaline metal compounds or ammonia or amine compounds;
(2) preparing a catalytic water agent containing a metal catalyst by using a metal compound, wherein the metal compound is a transition metal compound or/and an aluminum metal compound;
(3) atomizing and spraying the flue gas absorption liquid obtained in the step (1) and the catalytic water agent obtained in the step (2) into a smoke exhaust pipeline or/and flue gas purification equipment, and instantly and uniformly mixing the catalytic water agent and the absorption liquid in the flue gas with the flue gas;
(4) absorbing particles in liquid and SO in flue gas2Molecule, O2The molecules rapidly carry out desulfurization reaction under the action of a catalytic water agent to generate stable sulfate compound particles;
(5) the generated sulfate compound particles are collected by a flue gas purification device and then directly discharged into rivers and seas or comprehensively utilized and treated.
2. The catalytic oxidative desulfurization method for marine flue gas according to claim 1, wherein in the step (2), the transition metal compound is a compound of a transition metal element of the fourth or fifth period.
3. The catalytic oxidative desulfurization method for marine flue gas according to claim 2, characterized in that the transition metal compound is a compound of manganese, iron, copper or zinc.
4. The catalytic oxidative desulfurization method for the ship flue gas according to claim 1 or 2, wherein in the step (2), the catalytic water agent is a solution or a suspension.
5. The catalytic oxidative desulfurization method for the ship flue gas according to claim 4, wherein the catalytic water agent is a soluble metal compound solution.
6. The catalytic oxidative desulfurization method for marine flue gas according to claim 4, wherein the catalytic water agent is prepared from micron-sized metal compounds
Preparing a suspension.
7. The catalytic oxidative desulfurization method for marine flue gas according to claim 1 or 2, wherein in the step (1), the flue gas absorption liquid is prepared from urea in amine compounds or magnesium oxide in alkali metal compounds.
8. The catalytic oxidative desulfurization method for the ship flue gas according to claim 1 or 2, characterized in that a surfactant and/or an aggregating agent is added into the flue gas absorption liquid prepared in the step (1) and/or the catalytic water agent prepared in the step (2); or in the step (3), the surfactant and/or the agglomerating agent are sprayed in separately.
9. The catalytic oxidative desulfurization method for the ship flue gas as claimed in claim 1 or 2, wherein in the step (3), the flue gas discharge pipeline refers to a flue gas conveying pipeline from the flue gas generated by the diesel engine to the flue gas discharge atmosphere; the flue gas purification equipment comprises a flue gas strip washing tower, a dust collector, denitration equipment, a desulfurization tower and other equipment.
10. The catalytic oxidative desulfurization method for the ship flue gas according to claim 1 or 2, characterized in that the flue gas absorption liquid prepared in the step (1) and the catalytic aqueous solution prepared in the step (2) are mixed and sprayed into a smoke exhaust pipeline or/and flue gas purification equipment.
CN202010216878.4A 2020-03-25 2020-03-25 Catalytic oxidation desulfurization method for ship flue gas Pending CN111330439A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113634587A (en) * 2021-08-25 2021-11-12 昆明理工大学 Resource utilization method for desulfurization and sulfur by using magnesite

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1466481A (en) * 2000-10-05 2004-01-07 Fl Method for reducing the sox emission from a plant for manufacturing cement clinker and such plant
CN1565709A (en) * 2003-06-27 2005-01-19 北京紫光威肯环境工程有限公司（中美合资） Technique for catalytic oxidating desulfurizing products of flue gas
CN1712115A (en) * 2005-05-09 2005-12-28 刘汉东 High-efficient catalyzing smoke desulfurizing and denitrifying method and apparatus thereof
CN1986032A (en) * 2005-12-23 2007-06-27 浙江大学 Alkali earth metal compound enhanced wet combined urea desulfurizing and denitrifying process
CN101195097A (en) * 2007-12-12 2008-06-11 浙江工商大学 Liquid-phase oxidation catalyst for fire coal flue gas desulfurization
CN101259376A (en) * 2007-12-17 2008-09-10 昆明理工大学 Method for purifying reducing inorganic waste gases
CN101773778A (en) * 2010-01-04 2010-07-14 云南亚太环境工程设计研究有限公司 Method for integration of desulphurization and denitration of coal-fired flue gas by wet method
CN102580497A (en) * 2012-01-17 2012-07-18 浙江工商大学 Method for desulfuring flue gas in cooperation with pulse discharge and liquid phase catalytic oxidation
CN103551031A (en) * 2013-10-31 2014-02-05 昆明理工大学 Method and device for purifying phosphorus, sulfur and cyanogen under synergetic action of electrochemical oxidation and liquid phase catalytic oxidation
US20150104365A1 (en) * 2010-06-23 2015-04-16 Baoquan Zhang Flue-Gas Purification and Reclamation System and Method Thereof
CN106178865A (en) * 2016-09-14 2016-12-07 湖南省小尹无忌环境能源科技开发有限公司 Industrial furnace smoke heavy metal and fluorine chlorine sulfur nitre purify and resource utilization method
CN106178909A (en) * 2016-09-14 2016-12-07 湖南省小尹无忌环境能源科技开发有限公司 Preparation oxidation soil release agent is for removing heavy metal in flue gas and the system of fluorine chlorine sulfur nitre
CN106334442A (en) * 2016-11-11 2017-01-18 焦作和信冶金科技有限责任公司 Liquid-phase desulphurization device and method for electrolytic aluminum flue gas
CN107174934A (en) * 2017-06-01 2017-09-19 严生 A kind of new dry process rotary kiln liquid nano catalytic desulfurizing agent and preparation method thereof
CN107497259A (en) * 2017-08-30 2017-12-22 昆明理工大学 A kind of ultrasonic atomization catalytic oxidative desulfurization low concentration SO2Method

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1466481A (en) * 2000-10-05 2004-01-07 Fl Method for reducing the sox emission from a plant for manufacturing cement clinker and such plant
CN1565709A (en) * 2003-06-27 2005-01-19 北京紫光威肯环境工程有限公司（中美合资） Technique for catalytic oxidating desulfurizing products of flue gas
CN1712115A (en) * 2005-05-09 2005-12-28 刘汉东 High-efficient catalyzing smoke desulfurizing and denitrifying method and apparatus thereof
CN1986032A (en) * 2005-12-23 2007-06-27 浙江大学 Alkali earth metal compound enhanced wet combined urea desulfurizing and denitrifying process
CN101195097A (en) * 2007-12-12 2008-06-11 浙江工商大学 Liquid-phase oxidation catalyst for fire coal flue gas desulfurization
CN101259376A (en) * 2007-12-17 2008-09-10 昆明理工大学 Method for purifying reducing inorganic waste gases
CN101773778A (en) * 2010-01-04 2010-07-14 云南亚太环境工程设计研究有限公司 Method for integration of desulphurization and denitration of coal-fired flue gas by wet method
US20150104365A1 (en) * 2010-06-23 2015-04-16 Baoquan Zhang Flue-Gas Purification and Reclamation System and Method Thereof
CN102580497A (en) * 2012-01-17 2012-07-18 浙江工商大学 Method for desulfuring flue gas in cooperation with pulse discharge and liquid phase catalytic oxidation
CN103551031A (en) * 2013-10-31 2014-02-05 昆明理工大学 Method and device for purifying phosphorus, sulfur and cyanogen under synergetic action of electrochemical oxidation and liquid phase catalytic oxidation
CN106178865A (en) * 2016-09-14 2016-12-07 湖南省小尹无忌环境能源科技开发有限公司 Industrial furnace smoke heavy metal and fluorine chlorine sulfur nitre purify and resource utilization method
CN106178909A (en) * 2016-09-14 2016-12-07 湖南省小尹无忌环境能源科技开发有限公司 Preparation oxidation soil release agent is for removing heavy metal in flue gas and the system of fluorine chlorine sulfur nitre
CN106334442A (en) * 2016-11-11 2017-01-18 焦作和信冶金科技有限责任公司 Liquid-phase desulphurization device and method for electrolytic aluminum flue gas
CN107174934A (en) * 2017-06-01 2017-09-19 严生 A kind of new dry process rotary kiln liquid nano catalytic desulfurizing agent and preparation method thereof
CN107497259A (en) * 2017-08-30 2017-12-22 昆明理工大学 A kind of ultrasonic atomization catalytic oxidative desulfurization low concentration SO2Method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
宁平等: "《大宗工业固体废物综合利用-矿浆脱硫》", 31 January 2018, 冶金工业出版社 *
朱德庆等: "过渡金属离子液相催化氧化低浓度烟气脱硫", 《中南大学学报(自然科学版)》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113634587A (en) * 2021-08-25 2021-11-12 昆明理工大学 Resource utilization method for desulfurization and sulfur by using magnesite

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