CN104740987A - Recycling ammonia desulphurization process - Google Patents

Recycling ammonia desulphurization process Download PDF

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Publication number
CN104740987A
CN104740987A CN201510122614.1A CN201510122614A CN104740987A CN 104740987 A CN104740987 A CN 104740987A CN 201510122614 A CN201510122614 A CN 201510122614A CN 104740987 A CN104740987 A CN 104740987A
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liquid
ammonium
technique
pyrolusite
oxidation
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CN201510122614.1A
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CN104740987B (en
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杨有余
曾毅夫
叶明强
周益辉
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凯天环保科技股份有限公司
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Abstract

The invention discloses a recycling ammonia desulphurization process. According to the process, ammonium bicarbonate is used as an absorption agent to absorb sulfur dioxide smoke so as to generate an ammonium bisulfate intermediate product, the ammonium bisulfate intermediate product is used for reducing and carbonizing pyrolusite by utilizing the oxidization performance of the pyrolusite, and high-quality manganese carbonate and ammonium sulfide products are obtained; the sulfur dioxide smoke, ammonium bicarbonate and pyrolusite raw materials selected in the process are wide in source and cheap in price, the manganese carbonate and ammonium sulfide products with relatively high additional values are obtained, the economic benefit is remarkable, and the problems of low oxidization efficiency in the process of preparing ammonium sulfide from ammonium bisulfate and high production cost in the manganese carbonate preparation process can be overcome; moreover, the process is simple to operate, the process conditions are moderate, the reaction can be completed under a room temperature condition, the prepared product is high in quality, and the industrialized production requirement can be met.

Description

A kind of resource ammonia desulfurizing process

Technical field

The present invention relates to a kind of is that desulfurizing agent carries out sulfur dioxide FGD with carbonic hydroammonium, and the product obtained, for the technique of reducing pyrolusite co-producing manganese carbonate and ammonium sulfate simultaneously, belongs to flue gas desulfurization technique field.

Background technology

Wet Flue Gas Desulfurization Technique mainly comprises, limestone-based process, Dual alkali, ammonia process etc.Ammonia desulfurizing process is a kind of friendly process, and available liquefied ammonia, ammoniacal liquor, carbonic hydroammonium etc. are as desulfurizing agent, and the method has that desulfuration efficiency is high, without blocking, accessory substance ammonium sulfate can be used as the advantages such as chemical fertilizer products; But liquefied ammonia, ammoniacal liquor, carbonic hydroammonium etc., as desulfurizing agent, make the sulfur dioxide in itself and flue gas react, and blast air and make sulfite oxidation be ammonium sulfate, because the ammonium sulfate product quality that ammonium sulfite forced oxidation effect is poor, generate is not high.Therefore exploitation can solve the ammonia desulfurizing process of sulfite oxidation problem, will have very good market prospects.

China's pyrolusite resource is abundanter, but grade is lower.Pyrolusite is MnO containing manganese main component 2, sulfuric acid directly can not leach it, must it be reduced into manganese monoxide (MnO) could and sulfuric acid reaction generation manganese sulfate, the manganese sulfate of generation obtains manganese carbonate carrying out metathesis reaction with carbonate further.The method need consume a large amount of reducing agents and sulfuric acid, and production cost is higher, and resource utilization degree is not high.Such as, publication number is the technique that CN103553078A Chinese invention patent discloses a kind of high-efficiency ammonia desulfurization crystalline ammonium sulfate, this technique comprises desulfurization, oxidation, enrichment process, first flue gas, ammoniacal liquor are passed into desulfurizing tower desulfurization section, the slurries containing ammonium bisulfite and ammonium sulfite generated after reaction desulfuration enter regeneration storage tank; Ammoniacal liquor is passed into regeneration storage tank and ammonium bisulfite to react and generate ammonium sulfite, then ammonium sulfite solution is passed into desulfurizing tower oxidation panel, be oxidized with smoke reaction the slurries containing ammonium sulfate generated and enter concentrated storage tank; Ammonium sulfate is after crystallisation by cooling, and Separation of Solid and Liquid obtains ammonium sulfate product.It is high that this technique has sulfite oxidation efficiency, and effectively reduce the feature of equipment investment and energy consumption.But there is the escaping of ammonia in the method, the problems such as the sulfite oxidation time is long.

Publication number is the preparation method that the Chinese patent of 101704553A discloses a kind of manganese carbonate, slurry MnSO 4add H 2sO 4, adjust ph is 2 ~ 4; In 30 ~ 80 DEG C of temperature ranges, add carbonic hydroammonium and synthesize under stirring, control synthetic end point is reaction with same mole, obtains synthesis liquid; Above-mentioned synthesis solid and liquid be separated, solid phase 80 ~ 100 DEG C of hot washes, then dry to obtain manganese carbonate.This invention can obtain the manganese carbonate of the low magnesium of low calcium, but manganese sulfate is as a kind of industrial chemicals, and price is more expensive, poor by manganese sulfate production manganese carbonate economy.

Summary of the invention

There is oxidation efficiency production that is low and manganese carbonate and there is the problems such as cost is higher in the technique preparing ammonium sulfate for the ammonia process of desulfurization traditional in prior art, one is the object of the present invention is to provide to utilize carbonic hydroammonium to obtain desulfurization product as fume desulfurizing agent, utilize desulfurization product reducing pyrolusite dexterously again, obtain the technique of highly purified manganese carbonate and ammonium sulfate product simultaneously, this technological operation is simple, reaction condition is gentle, cost of material is low, manganese carbonate and the ammonium sulfate product added value of acquisition are higher, meet suitability for industrialized production.

The invention provides a kind of resource ammonia desulfurizing process, this technique comprises the following steps:

Step one: flue gas desulfurization

Using the solution containing carbonic hydroammonium as absorbing liquid, react with the smoke contacts containing sulfur dioxide in absorption tower, obtaining main component is liquid after the absorption of ammonium bisulfite;

Step 2: oxidation regeneration

After step one gained absorbs, liquid enters in oxidation regeneration reactor, regulate the pH of liquid after absorbing between 4.5 ~ 5.5, in oxidation regeneration reactor, add pyrolusite again carry out redox reaction, after having reacted, isolated by filtration, is separated the filtrate and the solid phase slag that obtain sulfur acid manganese and ammonium sulfite;

Step 3: produce MnCO 3

After step 2 gained filtrate enters and carries out sedimentation in sedimentation basin, after part sedimentation, liquid enters in precipitation reactor, in control precipitation reactor, solution ph is 6.8 ~ 7.2, pass into oxygen and add carbonic hydroammonium and carry out oxidation precipitation reaction, after having reacted, isolated by filtration, is separated and obtains manganese carbonate solid and ammonium sulfate;

Step 4: produce (NH 4) SO 4

Step 3 gained ammonium sulfate, by evaporative crystallization, obtains ammonium sulfate product.

The technique that ammonia process of desulfurization product based on carbonic hydroammonium of the present invention is used for reducing pyrolusite and co-producing manganese carbonate and ammonium sulfate also comprises following preferred version:

In preferred scheme, absorbing liquid also comprises ammonium sulfate and ammonium bisulfite composition, and in absorbing liquid, the mass percent concentration of carbonic hydroammonium is 15 ~ 30%, pH is 4.5 ~ 5.5.

Flue gas containing sulfur dioxide in step one in preferred scheme is 3 ~ 6m/s by the flow velocity on absorption tower, and liquid-gas ratio is at 5 ~ 18L/m 3between.

More preferably in scheme, absorption tower is spray column, packed tower or sieve-plate tower.

Time 1 ~ 3h that in preferred scheme, redox reaction is carried out.

In preferred scheme, pyrolusite granularity is not less than 200 orders, and Fe content is not less than 20%.

In preferred scheme in step 2 the solid phase slag of gained for the preparation of cement.

Mud in preferred scheme in step 3 bottom settling tank returns in oxidation regeneration reactor and reacts.

In preferred scheme, oxidation precipitation reacts the time 1 ~ 4h carried out.

After absorbing in step 2 in preferred scheme, liquid regulates pH by the flue gas containing sulfur dioxide.

The sulfuric acid solution being 5 ~ 10% by mass percent concentration in step 3 in preferred scheme regulates the pH value maintaining liquid after sedimentation 6.8 ~ 7.2.

In preferred scheme in step 3 after part sedimentation liquid enter as absorbing liquid regulate component return absorption tower use.

A kind of resource ammonia desulfurizing process of the present invention specifically comprises the following steps:

Step one: flue gas desulfurization

By carbonic hydroammonium by water (or the cleaning solution of washing manganese carbonate product, or precipitation after liquid) be configured to carbonic hydroammonium mass percent concentration 15 ~ 30% absorbing liquid, the pH of absorbing liquid controls 4.5 ~ 5.5, absorbing liquid enters absorption tower through transport pump and contacts with the flue gas containing sulfur dioxide is reverse, be 3 ~ 6m/s containing the flue gas of sulfur dioxide by the flow velocity on absorption tower, liquid-gas ratio is at 5 ~ 18L/m 3between, carbonic hydroammonium and SO 2react and generate ammonium bisulfite, acquisition main component is NH 4hSO 3absorption after liquid, the key reaction equation of generation is as follows:

NH 4HCO 3+SO 2→NH 4HSO 3+CO 2；

Step 2: oxidation regeneration

After absorbing, liquid is delivered to oxidation regeneration reactor, blasting a small amount of flue gas by air blast regulates the rear liquid pH of absorption between 4.5 ~ 5.5, and add pyrolusite and carry out redox reaction, preferred pyrolusite granularity is not less than 200 orders, Fe content is not less than 20%, and ammonium bisulfite is by MnO in pyrolusite 2oxidation, the liquid time of staying 1 ~ 3h in oxidation regeneration reactor after absorbing, generates the mixed solution of manganese sulfate and ammonium sulfite, by filtering to isolate the solid slag having neither part nor lot in reaction, solid slag is for the production of cement, and the key reaction equation occurred in course of reaction is as follows:

MnO 2+2NH 4HSO 3→MnSO 4+(NH 4) 2SO 3+H 2O；

Step 3: produce MnCO 3

The filtrate of isolated by filtration gained sulfur acid manganese and ammonium sulfite enters in sedimentation basin, and bottom sedimentation basin, mud returns oxidation regeneration reactor; The absorption tower that after partly precipitated, liquid returns step one recycles, after partly precipitated, liquid enters precipitation reactor, add a small amount of sulfuric acid and control the rear liquid pH value of precipitation between 6.8 ~ 7.2, pass into oxygen reaction 1 ~ 4h, manganese sulfate and carbonic hydroammonium and oxygen reaction generate manganese carbonate and precipitate and ammonium sulfate, isolated by filtration, washing, drying, obtains manganese carbonate product; The key reaction equation occurred in course of reaction is as follows:

2NH 4HCO 3+MnSO 4+(NH 4) 2SO 3+O 2→MnCO 3+2(NH 4)SO 4+H 2O+CO 2

Step 4: produce (NH 4) 2sO 4

In step 3, namely isolated by filtration gained filtrate obtain ammonium sulfate product after evaporative crystallization, isolated by filtration, drying; The steam that evaporative crystallization produces enters cooling tower and directly contacts mixing with clear water, generation temperature at the warm water of 60 ~ 70 DEG C, and for washing manganese carbonate.

Hinge structure, the beneficial effect that the present invention brings: the preparation technology of sulfur dioxide FGD technique and manganese carbonate ideally combines by the present invention first, with sulfur dioxide flue gas, carbonic hydroammonium and pyrolusite for raw material, complete absorption oxidation and the pyrolusite reduction and carbonization of sulfur dioxide simultaneously, obtain the higher manganese carbonate of surcharge and ammonium sulfate product.The present invention selects carbonic hydroammonium as desulfuration reagent, and carbonic hydroammonium not only has the effect of good sulfur dioxide absorption, and the midbody product that carbonic hydroammonium sulfur dioxide absorption produces has suitable reducing property; On this basis, the present invention selects cheap pyrolusite to be raw material further, two kinds of techniques combine by the oxidation susceptibility made full use of in the reducing property of desulfurization product and pyrolusite, overcome ammonium bisulfite to prepare ammonium sulfate and there is the low and manganese carbonate preparation process of oxidation efficiency and there is the high problem of production cost simultaneously, obtain manganese carbonate and ammonium sulfate product respectively.The sulfur dioxide flue gas of selection of the present invention, carbonic hydroammonium and pyrolusite raw material sources are wide, cheap, obtain the higher manganese carbonate of added value and ammonium sulfate product, remarkable in economical benefits.Technological operation of the present invention is simple, process conditions are gentle, substantially all at room temperature can complete reaction, obtains product quality high, meets industrialization production requirements.

Accompanying drawing explanation

[Fig. 1] is process chart of the present invention.

Detailed description of the invention

Following examples are intended to further illustrate content of the present invention, instead of the protection domain of restriction the claims in the present invention.

Embodiment 1

A, desulfurization: carbonic hydroammonium and part of sulfuric acid ammonium salt solution, certain proportion fresh water (FW) are configured to ammonium bicarbonate concentration at 20% ammonium bicarbonate soln, enter ammonium absorption tower through slush pump input and contact with flue gas is reverse, SO 2concentration is 2100mg/Nm 3flue gas be 5m/s by the flow velocity on absorption tower, liquid-gas ratio 10L/m in tower 3, the SO in carbonic hydroammonium and flue gas 2react and generate ammonium bisulfite.After desulfurization, SO 2removal efficiency is 97%, SO in neat stress 2concentration is 65mg/Nm 3.

B, oxidation regeneration: the slurries after desulfurization are delivered to oxidation regeneration reactor, ammonium bisulfite is wherein by the MnO in pyrolusite (Fe content 25%, 220 orders) 2oxidation regeneration, air blast blasts a small amount of flue gas and regulates slurries pH between 5 ~ 6, slurries time of staying 60min.

C, MnCO 3produce: the slurries after above-mentioned oxidation regeneration are filtered, solid phase slag is for the production of cement, filtrate enters in sedimentation basin, bottom sedimentation basin, mud returns band filter filtration, part staticly settles rear filtrate and returns ammonia absorber and recycle, and portion filtrate enters precipitation reactor, adds a small amount of sulfuric acid and controls solution ph 7.0, manganese sulfate wherein and carbonic hydroammonium and oxygen reaction about 2h generate manganese carbonate and precipitate and ammonium sulfate, and manganese carbonate product purity is 98.5%.Filtered by slurries after precipitation reaction, Separation of Solid and Liquid, solid phase obtains manganese carbonate product after washing drying.Filtrate enters filtrate tank and stores.

D, (NH 4) SO 4produce: in above-mentioned filtrate tank, clear liquid obtains ammonium sulfate product after evaporative crystallization, isolated by filtration, drying.The steam that evaporative crystallization produces enters cooling tower and directly contacts mixing with clear water, generates the warm water of 70 DEG C, and for washing manganese carbonate.Ammonium sulfate product purity is 98.6%.

Embodiment 2

A, desulfurization: carbonic hydroammonium and part of sulfuric acid ammonium salt solution, certain proportion fresh water (FW) are configured to ammonium bicarbonate concentration at 26% ammonium bicarbonate soln, enter ammonium absorption tower through slush pump input and contact with flue gas is reverse, SO 2concentration is 2400mg/Nm 3flue gas be 3.4m/s by the flow velocity on absorption tower, liquid-gas ratio 10L/m in tower 3, the SO in carbonic hydroammonium and flue gas 2react and generate ammonium bisulfite.After desulfurization, SO 2removal efficiency is 97%, SO in neat stress 2concentration is 72mg/Nm 3.

B, oxidation regeneration: the slurries after desulfurization are delivered to oxidation regeneration reactor, ammonium bisulfite is wherein by the MnO in pyrolusite (Fe content 30%, 220 orders) 2oxidation regeneration, air blast blasts a small amount of flue gas and regulates slurries pH between 5 ~ 6, slurries time of staying 120min.

C, MnCO 3produce: the slurries after above-mentioned oxidation regeneration are filtered, solid phase slag is for the production of cement, filtrate enters in sedimentation basin, bottom sedimentation basin, mud returns band filter filtration, part staticly settles rear filtrate and returns ammonia absorber and recycle, and portion filtrate enters precipitation reactor, adds a small amount of sulfuric acid and controls solution ph 7.0, manganese sulfate wherein and carbonic hydroammonium and oxygen reaction about 2h generate manganese carbonate and precipitate and ammonium sulfate, and manganese carbonate product purity is 98.1%.Filtered by slurries after precipitation reaction, Separation of Solid and Liquid, solid phase obtains manganese carbonate product after washing drying.Filtrate enters filtrate tank and stores.

D, (NH 4) SO 4produce: in above-mentioned filtrate tank, clear liquid obtains ammonium sulfate product after evaporative crystallization, isolated by filtration, drying.The steam that evaporative crystallization produces enters cooling tower and directly contacts mixing with clear water, generates the warm water of 70 DEG C, and for washing manganese carbonate.Ammonium sulfate product purity is 98.8%.

Embodiment 3

A, desulfurization: after the precipitation in carbonic hydroammonium and embodiment 2 step C, liquid and certain proportion fresh water (FW) are configured to ammonium bicarbonate concentration at 18% ammonium bicarbonate soln, enter ammonium absorption tower through slush pump input and contact with flue gas is reverse, SO 2concentration is 2000mg/Nm 3flue gas be 5m/s by the flow velocity on absorption tower, liquid-gas ratio 10L/m in tower 3, the SO in carbonic hydroammonium and flue gas 2react and generate ammonium bisulfite.After desulfurization, SO 2removal efficiency is 97%, SO in neat stress 2concentration is 60mg/Nm 3.

B, oxidation regeneration: the slurries after desulfurization are delivered to oxidation regeneration reactor, ammonium bisulfite is wherein by the MnO in pyrolusite (Fe content 30%, 220 orders) 2oxidation regeneration, air blast blasts a small amount of flue gas and regulates slurries pH between 5 ~ 6, slurries time of staying 70min.

C, MnCO 3produce: the slurries after above-mentioned oxidation regeneration are filtered, solid phase slag is for the production of cement, filtrate enters in sedimentation basin, bottom sedimentation basin, mud returns band filter filtration, part staticly settles rear filtrate and returns ammonia absorber and recycle, and portion filtrate enters precipitation reactor, adds a small amount of sulfuric acid and controls solution ph 7.0, manganese sulfate wherein and carbonic hydroammonium and oxygen reaction about 2h generate manganese carbonate and precipitate and ammonium sulfate, and manganese carbonate product purity is 98.0%.Filtered by slurries after precipitation reaction, Separation of Solid and Liquid, solid phase obtains manganese carbonate product after washing drying.Filtrate enters filtrate tank and stores.

D, (NH 4) SO 4produce: in above-mentioned filtrate tank, clear liquid obtains ammonium sulfate product after evaporative crystallization, isolated by filtration, drying.The steam that evaporative crystallization produces enters cooling tower and directly contacts mixing with clear water, generates the warm water of 70 DEG C, and for washing manganese carbonate.Ammonium sulfate product purity is 98.0%.

Claims (10)

1. a resource ammonia desulfurizing process, is characterized in that, comprises the following steps:
Step one: flue gas desulfurization
Using the solution containing carbonic hydroammonium as absorbing liquid, react with the smoke contacts containing sulfur dioxide in absorption tower, obtaining main component is liquid after the absorption of ammonium bisulfite;
Step 2: oxidation regeneration
After step one gained absorbs, liquid enters in oxidation regeneration reactor, regulate the pH of liquid after absorbing between 4.5 ~ 5.5, in oxidation regeneration reactor, add pyrolusite again carry out redox reaction, after having reacted, isolated by filtration, is separated the filtrate and the solid phase slag that obtain sulfur acid manganese and ammonium sulfite;
Step 3: produce MnCO 3
After step 2 gained filtrate enters and carries out sedimentation in sedimentation basin, after part sedimentation, liquid enters in precipitation reactor, in control precipitation reactor, solution ph is 6.8 ~ 7.2, pass into oxygen and add carbonic hydroammonium and carry out oxidation precipitation reaction, after having reacted, isolated by filtration, is separated and obtains manganese carbonate solid and ammonium sulfate;
Step 4: produce (NH 4) SO 4
Step 3 gained ammonium sulfate, by evaporative crystallization, obtains ammonium sulfate product.
2. technique according to claim 1, is characterized in that, described absorbing liquid also comprises ammonium sulfate and ammonium bisulfite composition, and in absorbing liquid, the mass percent concentration of carbonic hydroammonium is 15 ~ 30%, pH is 4.5 ~ 5.5.
3. technique according to claim 1, is characterized in that, be 3 ~ 6m/s containing the flue gas of sulfur dioxide by the flow velocity on absorption tower, liquid-gas ratio is at 5 ~ 18L/m 3between.
4. the technique according to claim 1 or 3, is characterized in that, described absorption tower is spray column, packed tower or sieve-plate tower.
5. technique according to claim 1, is characterized in that, time 1 ~ 3h that described redox reaction is carried out.
6. technique according to claim 1, is characterized in that, described pyrolusite granularity is not less than 200 orders, and Fe content is not less than 20%.
7. technique according to claim 1, is characterized in that, in step 2, the solid phase slag of gained is for the preparation of cement; Mud in step 3 bottom settling tank returns in oxidation regeneration reactor and reacts.
8. technique according to claim 1, is characterized in that, described oxidation precipitation reacts the time 1 ~ 4h carried out.
9. technique according to claim 1, is characterized in that, after absorbing in step 2, liquid regulates pH by the flue gas containing sulfur dioxide; Be that the pH value of liquid after the sulfuric acid solution adjustment sedimentation of 5 ~ 10% is 6.8 ~ 7.2 by mass percent concentration in step 3.
10. technique according to claim 1, is characterized in that, in step 3, after part sedimentation, liquid enters and returns absorption tower use as absorbing liquid adjustment component.
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CN108079776A (en) * 2017-11-24 2018-05-29 北京绿岩环保科技有限责任公司 A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application
CN109260928A (en) * 2018-10-22 2019-01-25 湘潭大学 A kind of ammonium hydrogen carbonate sulfur method and device that lead plaster desulfurization is cooperateed with flue gas desulfurization

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CN109260928A (en) * 2018-10-22 2019-01-25 湘潭大学 A kind of ammonium hydrogen carbonate sulfur method and device that lead plaster desulfurization is cooperateed with flue gas desulfurization

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