CN110152482A - A kind of cement kiln flue gas desulfurizing agent and preparation method thereof - Google Patents
A kind of cement kiln flue gas desulfurizing agent and preparation method thereof Download PDFInfo
- Publication number
- CN110152482A CN110152482A CN201910524918.9A CN201910524918A CN110152482A CN 110152482 A CN110152482 A CN 110152482A CN 201910524918 A CN201910524918 A CN 201910524918A CN 110152482 A CN110152482 A CN 110152482A
- Authority
- CN
- China
- Prior art keywords
- carbonate
- ammonium
- catalyst
- flue gas
- oxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a kind of cement kiln flue gas desulfurizing agent and preparation method thereof, raw material compositions are as follows: ammonium carbonate 7~18%, oxidant 5 ~ 8%, catalyst 25~41%, ammonium oxalate 8~17%, urea 6~15%, sodium carbonate 8~26%, calcium oxide 5~17%, total amount 100%；The percentage is mass percent.According to formula rate, ammonium carbonate, oxidant, catalyst, ammonium oxalate, urea, sodium carbonate, calcium oxide are compounded, be uniformly mixed to get.Use that catalyst its chemical stability added according to demand is good, halide ion without containing corrosion equipment, under middle low-temperature condition, catalyst accelerates calcium carbonate fast decoupled to generate CaO, promotes SO2It is fully absorbed in preheater by CaO, reach solid sulphur and reduces SO2The purpose of discharge.
Description
Technical field
The present invention relates to a kind of cement kiln flue gas desulfurizing agents and preparation method thereof.
Background technique
China is that cement consumption big country is also manufacture of cement big country, and it is light that cement plays act foot to the development of the mankind and society
The effect of weight, while harm also is brought to the mankind and ecological environment, the discharge of dust and pernicious gas seriously destroys atmosphere
The sulfur dioxide environmental pollution being discharged into during environment and human health, especially Cement clinker buring in atmosphere
It is more serious.Sulfur dioxide will form sulfate aerosol after aoxidizing in air, so that its toxicity is increased 10 times or more, people's contact
After sucking these toxic gases, the symptoms such as cough, uncomfortable in chest, eye irritation, expiratory dyspnea can be caused, or even can seriously cause to exhale
Inhale functional failure.Sulfur dioxide is incessantly harmful to humans and animals, and sulfur dioxide can also corrode plant, inhibits plant growth, and
The acid rain of generation can reduce soil fertility, destroy soil texture.
American-European countries's cement production enterprise is to SO2The concern of discharge is earlier than Chinese Enterprise.GB 4915-2014 according to national standards
" cement industry atmosphere pollutants emission standards " regulation, from January 1st, 2010, existing cement kiln and kiln mill all-in-one machine exhaust
SO in cylinder2Highest allows concentration of emission to be 200mg/m3, unit product discharge amount must not exceed 0.6kg/t.The numerous cement in China
Enterprise SO2Emission reduction tasks are further arduous, some annual SO of enterprise2Blowdown expense is up to millions of members.
During Cement clinker buring other than can be with self-desulphurization, the conventionally used sulfur removal technology technology in cement plant be also wrapped
Include dry reactant insufflation, hot raw material insufflation, spray dry desulfurization method and wet desulfurization methods.
Although the desulfuration efficiency of dry reactant insufflation is higher, higher cost, the expense of white lime is mainly purchased.
The investment of spray dry desulfurization method is lower than wet processing, can be realized by improving to cement plant conditioning Tower, its advantage is that
Desulfuration efficiency is higher, there is no the processing problem of desulfurization product, but pipeline, valve, spray head, preheating in lime slurry insufflating procedure
The blockage problem of device blower is than more serious, repair and maintenance larger workload；Desulfurizer slurry solid content is more than that 13% will cause
Nozzle atomization is difficult, this series of operational issue gives it to propose challenge in the application of cement industry.Wet desulfurization methods effect
Preferably, desulfuration efficiency can achieve 80%~95%, and slurry solids content can reach 30%, and blocking and maintenance problem are less, but
By equipment investment, operating cost and technical requirements are high is limited, it is difficult to be suitble to the national conditions in China；Comparatively, hot raw material spray
Its desulfurization effect of method is not satisfactory, SO urgently to be solved for the cement industry in current China2Emission reduction problem is unable to complete not
It is suitble to the concrete condition of China's cement industry.Moreover, desulfurizing agent currently on the market it is generally existing to operation and equipment requirement very
High, many shortcomings such as energy consumption is high, at high cost, desulfurization effect is undesirable.
Summary of the invention
Purpose: to solve the deficiencies in the prior art, the present invention provides a kind of cement kiln flue gas desulfurizing agent and preparation method thereof.
Technical solution: in order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of cement kiln flue gas desulfurizing agent, it is characterised in that: the desulfurizing agent is by ammonium carbonate, oxidant, catalyst, oxalic acid
Ammonium, urea, sodium carbonate, calcium oxide compounding mixing composition, raw material composition are as follows: ammonium carbonate 7~18%, oxidant 5~8% are urged
Agent 25~41%, ammonium oxalate 8~17%, urea 6~15%, sodium carbonate 8~26%, calcium oxide 5~17%, total amount 100%；
The percentage is mass percent.
Preferably, a kind of cement kiln flue gas desulfurizing agent, it is characterised in that: the oxidant is permanganic acid
Potassium.
Preferably, a kind of cement kiln flue gas desulfurizing agent, it is characterised in that: the catalyst is carbonic acid
The mixing of one or more of lithium, vanadic anhydride, copper oxide, bismuth oxide and potassium carbonate.
More preferably, a kind of cement kiln flue gas desulfurizing agent, which is characterized in that its raw material composition are as follows: ammonium carbonate
10%, oxidant 5%, catalyst 25%, ammonium oxalate 13%, urea 15%, sodium carbonate 17%, calcium oxide 15%, total amount
100%.
More preferably, a kind of cement kiln flue gas desulfurizing agent, which is characterized in that ammonium carbonate 7%, oxidant 8%,
Catalyst 41%, ammonium oxalate 10%, urea 8%, sodium carbonate 13%, calcium oxide 13%, total amount 100%.
More preferably, a kind of cement kiln flue gas desulfurizing agent, which is characterized in that its raw material composition are as follows: ammonium carbonate
13%, oxidant 6%, catalyst 30%, ammonium oxalate 12%, urea 15%, sodium carbonate 18%, calcium oxide 6%, total amount 100%.
More preferably, a kind of cement kiln flue gas desulfurizing agent, which is characterized in that its raw material composition are as follows: ammonium carbonate
18%, oxidant 7%, catalyst 22%, ammonium oxalate 16%, urea 6%, sodium carbonate 26%, calcium oxide 5%, total amount 100%.
The present invention also provides the preparation method of the cement kiln flue gas desulfurizing agent, the steps include: according to formula rate, it will
Ammonium carbonate, oxidant, catalyst, ammonium oxalate, urea, sodium carbonate, calcium oxide compounding be uniformly mixed to get.
The present invention provides a kind of cement kiln flue gas desulfurizing agents and preparation method thereof, according to cement production process feature and divide
The introducing form and existence for analysing sulphur, it is produced during 5 aspects are to sinter leaching from the desulfurization principle present invention
Oxysulfide be fixed.First, it is good and more stable at high temperature with oxysulfide effect generation to have screened desulfurization effect
The monomer desulfurizing agent of sulfate.Second, the technique selection according to sinter leaching promotes CaCO under cryogenic3It decomposes to generate and live
The activating agent of property CaO, can promote the reaction of calcium oxide and oxysulfide in middle low temperature, to reach the mesh of solid sulphur in this way
's.Oxidant appropriate is added to promote SO in third2It is oxidized to SO3And sulfite oxidation is stable sulfate to reach
Reduce SO in flue gas2Discharge.4th, activating agent is added and plays fortifying catalytic, promotes CaO and oxysulfide fast reaction raw
At sulfate or sulphite.
The utility model has the advantages that cement kiln flue gas desulfurizing agent provided by the invention and preparation method thereof, chemical stability is good, adds
Measure it is low, it is nontoxic and pollution-free, under middle low-temperature condition, catalyst accelerate calcium carbonate fast decoupled generate CaO, promote SO2It is preheating
It is fully absorbed in device by CaO, reach solid sulphur and reduces SO2The purpose of discharge.It has the advantage that
1) actual amount is less than common desulfurizing agent.
2) chemical stability is preferable, and catalyst degradation Decomposition of Calcium Carbonate temperature is added, and promotes calcium carbonate fast decoupled.
3) price is low, non-corrosive, "dead", nontoxic, is not belonging to hazardous chemical.
Specific embodiment
Illustrate below with reference to example to the present invention: percentage is mass percent in the present invention.
Embodiment 1:
A kind of cement kiln flue gas desulfurizing agent and preparation method thereof, raw material composition are as follows: ammonium carbonate 10%, oxidant 5% are urged
Agent 25%, ammonium oxalate 13%, urea 15%, sodium carbonate 17%, calcium oxide 15%, total amount 100%；According to formula rate, press
According to formula rate, by ammonium carbonate, oxidant, catalyst, ammonium oxalate, urea, sodium carbonate, calcium oxide compounding be uniformly mixed to get
Product 1.
Embodiment 2
A kind of cement kiln flue gas desulfurizing agent and preparation method thereof, raw material composition are as follows: ammonium carbonate 7%, oxidant 8% are urged
Agent 41%, ammonium oxalate 10%, urea 8%, sodium carbonate 13%, calcium oxide 13%, total amount 100%；According to formula rate, according to
Ammonium carbonate, oxidant, catalyst, ammonium oxalate, urea, sodium carbonate, calcium oxide compounding are uniformly mixed to get production by formula rate
Product 2.
Embodiment 3
A kind of cement kiln flue gas desulfurizing agent and preparation method thereof, raw material composition are as follows: ammonium carbonate 13%, oxidant 6% are urged
Agent 30%, ammonium oxalate 12%, urea 15%, sodium carbonate 18%, calcium oxide 6%, total amount 100%；According to formula rate, according to
Ammonium carbonate, oxidant, catalyst, ammonium oxalate, urea, sodium carbonate, calcium oxide compounding are uniformly mixed to get production by formula rate
Product 3.
Embodiment 4
A kind of cement kiln flue gas desulfurizing agent and preparation method thereof, raw material composition are as follows: ammonium carbonate 18%, oxidant 7% are urged
Agent 22%, ammonium oxalate 16%, urea 6%, sodium carbonate 26%, calcium oxide 5%, total amount 100%；According to formula rate, according to
Ammonium carbonate, oxidant, catalyst, ammonium oxalate, urea, sodium carbonate, calcium oxide compounding are uniformly mixed to get production by formula rate
Product 4.
Application method of the invention, the sulfur dioxide discharged in Cement clinker buring flue gas is according to current standard GB/T
4915-2014 " cement industry air pollution emission standard " requires monitoring.
Using the existing desulfurizing agent in market as reference substance；
| Project | Desulfurization dosage (kg/min) | Flue gas sulfur content (mg/m3) |
| Blank 1 | 0 | 1038.2 |
| Blank 2 | 0 | 1165.7 |
| Control 1 | 3.5 | 583.2 |
| Embodiment 1 | 3.5 | 218.6 |
| Embodiment 2 | 3.5 | 104.5 |
| Embodiment 3 | 3.5 | 109.3 |
| Embodiment 4 | 3.5 | 145.1 |
From the above, it can be seen that the present embodiment product can significantly reach solid sulphur and reduce SO2The purpose of discharge, compared to
The existing desulfurizing agent in market, significant desulfurization effect improve.
The present invention is disclosed with preferred embodiment above, so it is not intended to limiting the invention, all to use equivalent replacement
Or equivalent transformation mode technical solution obtained, it is within the scope of the present invention.
Claims (8)
1. a kind of cement kiln flue gas desulfurizing agent, it is characterised in that: the desulfurizing agent is by ammonium carbonate, oxidant, catalyst, oxalic acid
Ammonium, urea, sodium carbonate, calcium oxide compounding mixing composition, raw material composition are as follows: ammonium carbonate 7~18%, oxidant 5 ~ 8%, catalyst
25~41%, ammonium oxalate 8~17%, urea 6~15%, sodium carbonate 8~26%, calcium oxide 5~17%, total amount 100%；The percentage
It is mass percent.
2. a kind of cement kiln flue gas desulfurizing agent according to claim 1, it is characterised in that: the oxidant is permanganic acid
Potassium.
3. a kind of cement kiln flue gas desulfurizing agent according to claim 1, it is characterised in that: the catalyst be lithium carbonate,
The mixing of one or more of vanadic anhydride, copper oxide, bismuth oxide and potassium carbonate.
4. a kind of cement kiln flue gas desulfurizing agent according to claim 1, which is characterized in that its raw material composition are as follows: ammonium carbonate
10%, oxidant 5%, catalyst 25%, ammonium oxalate 13%, urea 15%, sodium carbonate 17%, calcium oxide 15%, total amount 100%.
5. a kind of cement kiln flue gas desulfurizing agent according to claim 1, which is characterized in that ammonium carbonate 7%, oxidant 8% are urged
Agent 41%, ammonium oxalate 10%, urea 8%, sodium carbonate 13%, calcium oxide 13%, total amount 100%.
6. a kind of cement kiln flue gas desulfurizing agent according to claim 1, which is characterized in that its raw material composition are as follows: ammonium carbonate
13%, oxidant 6%, catalyst 30%, ammonium oxalate 12%, urea 15%, sodium carbonate 18%, calcium oxide 6%, total amount 100%.
7. a kind of cement kiln flue gas desulfurizing agent according to claim 1, which is characterized in that its raw material composition are as follows: ammonium carbonate
18%, oxidant 7%, catalyst 22%, ammonium oxalate 16%, urea 6%, sodium carbonate 26%, calcium oxide 5%, total amount 100%.
8. the preparation method of any one of -7 cement kiln flue gas desulfurizing agents according to claim 1, the steps include: according to formula
Ratio, by ammonium carbonate, oxidant, catalyst, ammonium oxalate, urea, sodium carbonate, calcium oxide compound, be uniformly mixed to get.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910524918.9A CN110152482A (en) | 2019-06-18 | 2019-06-18 | A kind of cement kiln flue gas desulfurizing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910524918.9A CN110152482A (en) | 2019-06-18 | 2019-06-18 | A kind of cement kiln flue gas desulfurizing agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110152482A true CN110152482A (en) | 2019-08-23 |
Family
ID=67625180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910524918.9A Pending CN110152482A (en) | 2019-06-18 | 2019-06-18 | A kind of cement kiln flue gas desulfurizing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110152482A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110605014A (en) * | 2019-10-23 | 2019-12-24 | 嘉华特种水泥股份有限公司 | Dry-method desulfurizer production process and system |
| CN110683777A (en) * | 2019-11-14 | 2020-01-14 | 天津水泥工业设计研究院有限公司 | Powder desulfurizing agent for cement kiln and preparation method and application thereof |
| CN110721571A (en) * | 2019-10-23 | 2020-01-24 | 嘉华特种水泥股份有限公司 | Dry desulfurizing agent for cement production and preparation method thereof |
| CN111359653A (en) * | 2020-04-07 | 2020-07-03 | 中海油天津化工研究设计院有限公司 | Catalyst for improving desulfurization performance of calcium oxide |
| CN112774705A (en) * | 2020-12-17 | 2021-05-11 | 南京永能新材料有限公司 | Desulfurization catalyst for cement kiln flue gas and preparation method and application thereof |
| CN113499674A (en) * | 2021-08-27 | 2021-10-15 | 中晶环境科技股份有限公司 | Absorbent for flue gas desulfurization, preparation method thereof and application of composition |
| CN114082288A (en) * | 2020-06-08 | 2022-02-25 | 广东赛珐生物科技有限公司 | New application of folic acid wastewater |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050163690A1 (en) * | 2004-01-28 | 2005-07-28 | Shane Elwart | System and method for removing hydrogen sulfide from an emissions stream |
| CN105779074A (en) * | 2016-03-08 | 2016-07-20 | 广东万引科技发展有限公司 | Calcium-based catalytic desulfurization agent for cement kiln |
| CN107164013A (en) * | 2017-06-01 | 2017-09-15 | 严生 | A kind of powder nanometer catalytically fixed sulphur agent and preparation method thereof of new type nonaqueous cement raw material |
| CN107261825A (en) * | 2017-07-31 | 2017-10-20 | 董小军 | A kind of cement kiln flue gas catalytic desulfurization aqua |
| CN107261826A (en) * | 2017-07-31 | 2017-10-20 | 董小军 | A kind of cement kiln flue gas catalytically fixed sulphur pulvis |
| CN107500697A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The manufacture method of fibre cement product based on ozone oxidation |
-
2019
- 2019-06-18 CN CN201910524918.9A patent/CN110152482A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050163690A1 (en) * | 2004-01-28 | 2005-07-28 | Shane Elwart | System and method for removing hydrogen sulfide from an emissions stream |
| CN105779074A (en) * | 2016-03-08 | 2016-07-20 | 广东万引科技发展有限公司 | Calcium-based catalytic desulfurization agent for cement kiln |
| CN107164013A (en) * | 2017-06-01 | 2017-09-15 | 严生 | A kind of powder nanometer catalytically fixed sulphur agent and preparation method thereof of new type nonaqueous cement raw material |
| CN107261825A (en) * | 2017-07-31 | 2017-10-20 | 董小军 | A kind of cement kiln flue gas catalytic desulfurization aqua |
| CN107261826A (en) * | 2017-07-31 | 2017-10-20 | 董小军 | A kind of cement kiln flue gas catalytically fixed sulphur pulvis |
| CN107500697A (en) * | 2017-09-30 | 2017-12-22 | 中晶蓝实业有限公司 | The manufacture method of fibre cement product based on ozone oxidation |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110605014A (en) * | 2019-10-23 | 2019-12-24 | 嘉华特种水泥股份有限公司 | Dry-method desulfurizer production process and system |
| CN110721571A (en) * | 2019-10-23 | 2020-01-24 | 嘉华特种水泥股份有限公司 | Dry desulfurizing agent for cement production and preparation method thereof |
| CN110683777A (en) * | 2019-11-14 | 2020-01-14 | 天津水泥工业设计研究院有限公司 | Powder desulfurizing agent for cement kiln and preparation method and application thereof |
| CN110683777B (en) * | 2019-11-14 | 2021-03-19 | 天津水泥工业设计研究院有限公司 | Powder desulfurizing agent for cement kiln and preparation method and application thereof |
| CN111359653A (en) * | 2020-04-07 | 2020-07-03 | 中海油天津化工研究设计院有限公司 | Catalyst for improving desulfurization performance of calcium oxide |
| CN114082288A (en) * | 2020-06-08 | 2022-02-25 | 广东赛珐生物科技有限公司 | New application of folic acid wastewater |
| CN114082288B (en) * | 2020-06-08 | 2024-05-10 | 广东赛珐生物科技有限公司 | New application of folic acid wastewater |
| CN112774705A (en) * | 2020-12-17 | 2021-05-11 | 南京永能新材料有限公司 | Desulfurization catalyst for cement kiln flue gas and preparation method and application thereof |
| CN113499674A (en) * | 2021-08-27 | 2021-10-15 | 中晶环境科技股份有限公司 | Absorbent for flue gas desulfurization, preparation method thereof and application of composition |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110152482A (en) | A kind of cement kiln flue gas desulfurizing agent and preparation method thereof | |
| CN107174934A (en) | A kind of new dry process rotary kiln liquid nano catalytic desulfurizing agent and preparation method thereof | |
| CN108187490A (en) | Macromolecule Dry denitration agent and preparation method thereof and denitrating technique and denitration device | |
| JP2020536031A (en) | Manufacturing method of cement material by ozonolysis | |
| CN107983119A (en) | The dry desulfurization method of denitration of oxidation is forced based on ozone | |
| CN107456865A (en) | The method of flue gas desulfurization and denitrification | |
| CN110721571A (en) | Dry desulfurizing agent for cement production and preparation method thereof | |
| CN109647176A (en) | A kind of desulfurizing agent and preparation method thereof | |
| CN107164013A (en) | A kind of powder nanometer catalytically fixed sulphur agent and preparation method thereof of new type nonaqueous cement raw material | |
| CN108793789A (en) | A kind of desulfurizing agent and preparation method thereof in cement production process | |
| CN108404651A (en) | A kind of desulfurizing agent for new dry process rotary kiln smoke catalytic desulfurization | |
| CN111111773A (en) | Desulfurization and denitrification catalyst for cement production | |
| CN102114384B (en) | Flue gas denitration addition agent | |
| CN110327764A (en) | A kind of composite water stall fume desulfurizing agent and preparation method thereof | |
| CN106268283B (en) | The method of cement kiln flue gas removing heavy metal and sulphur nitre pollutant and resource utilization | |
| CN109663499A (en) | Quadruple effect denitrfying agent composition and its method of denitration | |
| CN102827665A (en) | Coal saving and desulfurating combustion improver and preparation method thereof | |
| CN100447223C (en) | Energy saving desulfurizer for bunker coal, and preparation method | |
| CN107500697A (en) | The manufacture method of fibre cement product based on ozone oxidation | |
| CN1320945C (en) | Method for carrying out flue gas desulfurization by using mineral powder of magnesite | |
| CN116212631A (en) | High-temperature SO removal for waste incineration flue gas 2 Synergistic catalytic NOx removal method | |
| CN113546514B (en) | Low-temperature liquid desulfurizing agent in cement kiln | |
| CN109621713A (en) | A kind of sludge composite denitration agent and its preparation and application | |
| CN111715050B (en) | Method for improving urea denitration efficiency by adopting alkaline alcohol solution | |
| CN107628801A (en) | The manufacture method of fibre cement product based on carbide slag desulphurization denitration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190823 |