CN101972598B - Process method for desulphurizing smoke and co-producing hydrogen - Google Patents

Process method for desulphurizing smoke and co-producing hydrogen Download PDF

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Publication number
CN101972598B
CN101972598B CN2010105557263A CN201010555726A CN101972598B CN 101972598 B CN101972598 B CN 101972598B CN 2010105557263 A CN2010105557263 A CN 2010105557263A CN 201010555726 A CN201010555726 A CN 201010555726A CN 101972598 B CN101972598 B CN 101972598B
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desulfurizing tower
desulfurization
flue gas
hydrogen
solution
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CN101972598A (en
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胡国新
赵宇
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Abstract

The invention provides a process method for desulphurizing smoke and co-producing hydrogen in the technical field of smoke purification. The method comprises the following steps of: allowing humic acid sodium salt solution to react with SO2 in gas to be purified to generate a humic acid precipitate and sodium sulfite solution serving as a sacrifice agent; putting the sacrifice agent into a photocatalytic chemical reactor for a photocatalytic chemical reaction with a nano-titanium dioxide doped graphene catalyst so as to prepare the hydrogen which is a byproduct during desulphurization. The technical process is reasonably designed, can effectively utilize novel energy, co-produces clean gas, makes up for the defect that the conventional desulphurization technology only converts gaseous sulphur into solid sulphur, ensures that the whole system operates stably and reliably, and has low energy consumption and high economical benefit. The process realizes novel energy utilization and obtains clean energy simultaneously, and meets the requirement of energy conservation and exhaust reduction and sustainable development recommend by China.

Description

The process of flue gas desulfurization and by-product hydrogen
Technical field
What the present invention relates to is the method in a kind of air purifying process field, specifically is the process of a kind of flue gas desulfurization and by-product hydrogen.
Background technology
The present SO that contains 2The processing of gas mainly contains limestone-based process, two alkaline process and ammonia absorption process etc.Limestone-based process is with the SO in lime stone and the gas 2Reaction generates gypsum and fully utilizes; Two alkaline process are the aqueous solution absorption SO with alkaline metal salt of elder generation 2, in another reactor, will absorb SO then with lime stone 2After solution regeneration, the absorption liquid recirculation after the regeneration is used, end product is separated out with calcium sulfite and gypsum form; The ammonia absorption process is to adopt ammonia as desulfurizing agent, removes the SO in the flue gas 2, reclaim solid products such as producing sulfuric acid, ammonium sulfate, ammonium sulfite simultaneously.Patent CN1475298 discloses a kind of concentrated base double alkali method flue gas desulfurization technology; Flue gas is sent in the absorber in the absorption tower through discharging after the absorption liquid absorbing sulfur dioxide; Absorption liquid is extracted out at the bottom of tower; The most of entering in the absorber carried out desulfurization, and the absorption liquid after the absorbing sulfur dioxide is got back to the bottom on absorption tower; Another fraction gets into regenerated reactor, add regeneration alkali in the regenerated reactor and regenerate with supplementing water, the regeneration rear slurry through the depositing reservoir clarification after, clarified solution gets into the absorption tower again to the pump forebay and the additional alkali of adding, with the absorption liquid entering absorber that circulates; Calcium sulfite in the depositing reservoir and calcium sulfate precipitation thing after filtering, the filter residue otherwise processed; Filtrating is still sent absorption liquid circulatory system circulating and recovering back to.Patent CN1712113 discloses a kind of sulfur removal technology based on the ammonia absorption process; It is that a kind of deposed ammonia that utilizes is desulfurizing agent; Carbide slag is the desulphurization system of regenerative agent, by pump doctor solution is sent in the desulfurizing tower, with the flue gas adverse current haptoreaction through cooling and dedusting; Flue gas after the desulfurization drains into chimney through air-introduced machine then through the water spray demist; Reacted doctor solution is gone in the deposition adjusting regenerated reactor by tower bottom flow, adds carbide slag slurry and regenerates, precipitates; The circulation desulfurization hydrorrhea flows to the doctor solution mixing pit, adds ammoniacal liquor, regulates the pH value, and the cooling back is sent into desulfurizing tower again with pump and recycled.
Retrieval through to prior art is found, no matter is limestone-based process, two alkaline process or ammonia absorption process, and these technology all are only with SO 2Change solid-state sulphur-containing substance into and realize the sulphur recovery of resources.And the present invention can be in desulfurization by-product hydrogen, not only realize the recovery of sulphur resource but also can obtain clean energy resource, meet the requirement of current recycling economy and low carbon development.
Summary of the invention
The present invention is directed to the above-mentioned deficiency that prior art exists, the process of a kind of flue gas desulfurization and by-product hydrogen be provided, can be in desulfurization by-product hydrogen; Technical flow design is reasonable, can effectively utilize new forms of energy, and the by-product clean air; Remedied the deficiency that existing desulfur technology only changes gaseous sulfur into solid-state sulphur merely; The whole system stable and reliable operation, consuming little energy, economic benefit is high.This technology has realized that the utilization of new forms of energy has also obtained clear energy sources simultaneously, meets the energy-saving and emission-reduction of country's promotion and the requirement of sustainable development.
The present invention realizes that through following technical scheme the present invention passes through the SO in sodium humate salting liquid and the gas to be clean 2Reaction generates the humic acid deposition and as the sodium sulfite solution of sacrifice agent; Place photocatalysis chemical reactor and nano titanium oxide doped graphene catalyst to carry out the photocatalysis chemical reaction sacrifice agent then, prepare hydrogen.
The mass concentration of described sodium humate salting liquid is 3%~5%;
SO in the gas described and to be clean 2Reaction is meant: the sodium humate salting liquid is sprayed in the tower with nozzle from desulfurizing tower top; With air-introduced machine gas to be clean is got into desulfurizing tower through sending into after the deduster dedusting after heat exchanger is cooled to 80 ℃ from boiler then, utilize to spray into humate solution counter current contacting desulfurization in desulfurizing tower;
Solution after the first desulfurization in the described counter current contacting desulfurization is collected the Buffer Pool from the desulfurizing tower bottom, in pump input desulfurizing tower, recycles, and be 3-4 until the pH value;
The component of described nano titanium oxide doped graphene catalyst and mass percentage content are Nano titanium dioxide 70~99%, doped graphene 1~30%.
Described photocatalysis chemical reaction is meant: the photocatalysis chemical reactor is placed intensity of illumination 0.35~0.65W/m in the open 2, 0~45 ℃ of environment temperature.
Adopt technical scheme of the present invention, can reach following technique effect:
1, present technique technology desulfuration efficiency reaches more than 98%, and by-product hydrogen purity 99% has considerable economic value.
2, the present technique power consumption is few, and can effectively utilize solar energy, and the integrated operation cost is very low, and the no waste discharging meets the requirement of the sustainable development of country's promotion.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Among the figure: the 1-desulfurizing tower; The 2-Buffer Pool; The 3-photo catalysis reactor; The 4-hydrogen container; The 5-cyclone hydraulic separators; The 6-evaporimeter.
The specific embodiment
Elaborate in the face of embodiments of the invention down, present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
As shown in Figure 1; The implement device of following examples comprises: desulfurizing tower 1, Buffer Pool 2, photo catalysis reactor 3, hydrogen container 4, cyclone hydraulic separators 5 and evaporimeter 6; Wherein: the bottom output of desulfurizing tower 1 links to each other with Buffer Pool 2; Air-introduced machine gets into desulfurizing tower 1 with gas to be clean from boiler after sending into heat exchanger after the deduster dedusting to be cooled to 80 ℃, through with the SO in sodium humate salting liquid and the gas to be clean 2Reaction generates the humic acid deposition and as the sodium sulfite solution of sacrifice agent and export Buffer Pool 2 to; The output of Buffer Pool 2 links to each other with photo catalysis reactor 3 and desulfurizing tower 1 respectively; Sacrifice agent places photocatalysis chemical reactor 3 and nano titanium oxide doped graphene catalyst to carry out the photocatalysis chemical reaction; The hydrogen that the output of photo catalysis reactor 3 links to each other and prepares with storage with hydrogen container 4 and cyclone hydraulic separators 5 respectively, cyclone hydraulic separators 5 outputs link to each other with evaporimeter 6.
Embodiment 1
N with 78% 2, 18%CO 2, 1000ppm SO 2And the flue gas of 3.9% steam feeding desulfurizing tower, flue gas flow is 1Nm 3/ min sprays into concentration and is 3% sodium humate salting liquid simultaneously, and flow is 150ml/min; Collect in the surge tank after the first desulfurization of doctor solution; Spray into desulfurizing tower with the pump circulation, pH value of solution value to 3.5 in surge tank feeds solution after this desulfurization in the photochemical reactor then; Adopt nano titanium oxide doped graphene catalyst and produce hydrogen, intensity of illumination 0.35W/m with solar light irradiation 2, 0 ℃ of environment temperature, hydrogen output is 20 μ mol/h.
Embodiment 2
N with 78% 2, 18%CO 2, 2000ppm SO 2And the flue gas of 3.8% steam feeding desulfurizing tower, flue gas flow is 1Nm 3/ min sprays into concentration and is 4% sodium humate salting liquid simultaneously, and flow is 300ml/min; Collect in the surge tank after the first desulfurization of doctor solution; Spray into desulfurizing tower with the pump circulation, pH value of solution value to 3 in surge tank feeds solution after this desulfurization in the photochemical reactor then; Adopt nano titanium oxide doped graphene catalyst and produce hydrogen, intensity of illumination 0.45W/m with solar light irradiation 2, 30 ℃ of environment temperatures, hydrogen output is 30 μ mol/h.
Embodiment 3
N with 78% 2, 18%CO 2, 1000ppm SO 2And the flue gas of 3.9% steam feeding desulfurizing tower, flue gas flow is 1Nm 3/ min sprays into concentration and is 3% sodium humate salting liquid simultaneously, and flow is 150ml/min; Collect in the surge tank after the first desulfurization of doctor solution; Spray into desulfurizing tower with the pump circulation, pH value of solution value to 4 in surge tank feeds solution after this desulfurization in the photochemical reactor then; Adopt nano titanium oxide doped graphene catalyst and produce hydrogen, intensity of illumination 0.55W/m with solar light irradiation 2, 35 ℃ of environment temperatures, hydrogen output is 20 μ mol/h.
Embodiment 4
N with 78% 2, 18%CO 2, 1000ppm SO 2And the flue gas of 3.9% steam feeding desulfurizing tower, flue gas flow is 1Nm 3/ min sprays into concentration and is 5% sodium humate salting liquid simultaneously, and flow is 150ml/min; Collect in the surge tank after the first desulfurization of doctor solution; Spray into desulfurizing tower with the pump circulation, pH value of solution value to 3.5 in surge tank feeds solution after this desulfurization in the photochemical reactor then; Adopt nano titanium oxide doped graphene catalyst and produce hydrogen, intensity of illumination 0.65W/m with solar light irradiation 2, 45 ℃ of environment temperatures, hydrogen output is 25 μ mol/h.
Embodiment 5
N with 78% 2, 18%CO 2, 1000ppm SO 2And the flue gas of 3.9% steam feeding desulfurizing tower, flue gas flow is 1Nm 3/ min sprays into concentration and is 4% sodium humate salting liquid simultaneously, and flow is 100ml/min; Collect in the surge tank after the first desulfurization of doctor solution; Spray into desulfurizing tower with the pump circulation, pH value of solution value to 4 in surge tank feeds solution after this desulfurization in the photochemical reactor then; Adopt nano titanium oxide doped graphene catalyst and produce hydrogen, intensity of illumination 0.5W/m with solar light irradiation 2, 40 ℃ of environment temperatures, hydrogen output is 25 μ mol/h.

Claims (4)

1. the process of flue gas desulfurization and by-product hydrogen is characterized in that, through with the SO in sodium humate salting liquid and the gas to be clean 2Reaction generates the humic acid deposition and as the sodium sulfite solution of sacrifice agent; Place photocatalysis chemical reactor and nano titanium oxide doped graphene catalyst to carry out the photocatalysis chemical reaction this sodium sulfite solution then, prepare hydrogen;
The component of described nano titanium oxide doped graphene catalyst and mass percentage content are Nano titanium dioxide 70~99%, doped graphene 1~30%;
Described photocatalysis chemical reaction is meant: the photocatalysis chemical reactor is placed intensity of illumination 0.35~0.65W/m in the open 2, 0~45 ℃ of environment temperature.
2. the process of flue gas desulfurization according to claim 1 and by-product hydrogen is characterized in that, the mass concentration of described sodium humate salting liquid is 3%~5%.
3. the process of flue gas desulfurization according to claim 1 and by-product hydrogen is characterized in that, the SO in the gas described and to be clean 2Reaction is meant: the sodium humate salting liquid is sprayed in the tower with nozzle from desulfurizing tower top; With air-introduced machine gas to be clean is got into desulfurizing tower through sending into after the deduster dedusting after heat exchanger is cooled to 80 ℃ from boiler then, utilize to spray into humate solution counter current contacting desulfurization in desulfurizing tower.
4. the process of flue gas desulfurization according to claim 3 and by-product hydrogen; It is characterized in that; Solution after the first desulfurization in the described counter current contacting desulfurization is collected the Buffer Pool from the desulfurizing tower bottom, in pump input desulfurizing tower, recycles, and be 3-4 until the pH value.
CN2010105557263A 2010-11-24 2010-11-24 Process method for desulphurizing smoke and co-producing hydrogen Expired - Fee Related CN101972598B (en)

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CN104474894B (en) * 2014-11-20 2019-01-25 王在仕 A kind of cyclone cylinder dry fume catalytic desulfurization device and technique

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CN101620935A (en) * 2009-07-21 2010-01-06 华中师范大学 TiO2-based composite film material with functions of solar energy storage and release

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101620935A (en) * 2009-07-21 2010-01-06 华中师范大学 TiO2-based composite film material with functions of solar energy storage and release

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* Cited by examiner, † Cited by third party
Title
Zhiguo Sun et al..Removal of SO2 from Flue Gas by Sodium Humate Solution.《Energy Fuels》.2010,第24卷第1014页,图1,图3. *

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