CN109399578A - Utilize the method for coke-stove gas production sulfur dioxide - Google Patents
Utilize the method for coke-stove gas production sulfur dioxide Download PDFInfo
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- CN109399578A CN109399578A CN201811545694.1A CN201811545694A CN109399578A CN 109399578 A CN109399578 A CN 109399578A CN 201811545694 A CN201811545694 A CN 201811545694A CN 109399578 A CN109399578 A CN 109399578A
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- sulphur
- sulfur dioxide
- coke
- gas
- stove gas
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- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 238000000034 method Methods 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 131
- 239000005864 Sulphur Substances 0.000 claims abstract description 112
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 36
- 230000023556 desulfurization Effects 0.000 claims abstract description 35
- 150000003839 salts Chemical group 0.000 claims abstract description 32
- 239000003034 coal gas Substances 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 18
- 239000010808 liquid waste Substances 0.000 claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 17
- 239000011593 sulfur Substances 0.000 claims abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 27
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 20
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 16
- 230000008025 crystallization Effects 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 15
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 12
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 12
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 11
- 238000011069 regeneration method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 10
- XHHZBVWPCLTQQQ-UHFFFAOYSA-L S(=O)=O.C([O-])([O-])=O.[Na+].[Na+] Chemical compound S(=O)=O.C([O-])([O-])=O.[Na+].[Na+] XHHZBVWPCLTQQQ-UHFFFAOYSA-L 0.000 claims description 8
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 8
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 8
- 230000003009 desulfurizing effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 230000004927 fusion Effects 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000009279 wet oxidation reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims 1
- 239000004744 fabric Substances 0.000 claims 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000571 coke Substances 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 12
- 238000004939 coking Methods 0.000 abstract description 6
- 239000013067 intermediate product Substances 0.000 abstract description 6
- 239000011833 salt mixture Substances 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 70
- 239000000945 filler Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002802 bituminous coal Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/48—Sulfur dioxide; Sulfurous acid
- C01B17/50—Preparation of sulfur dioxide
- C01B17/56—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
- C01D5/14—Preparation of sulfites
- C01D5/145—Pyrosulfites or metabisulfites
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Industrial Gases (AREA)
Abstract
The present invention provides a kind of methods using coke-stove gas production sulfur dioxide, it is related to coke-stove gas technical field of resource utilization, coke-stove gas is passed through in coal gas desulfurizer carries out desulfurization process first by the method, obtain the doctor solution and salt bearing liquid wastes rich in sulphur simple substance, it then carries out the doctor solution to regenerate molten sulphur and obtains sulphur, and salt bearing liquid wastes progress salt extraction is obtained into ammonium thiocyanate, it then will be burned after obtained sulphur and ammonium thiocyanate co-grinding, obtain sulfur dioxide gas.The above method will burn after intermediate products sulphur and ammonium thiocyanate co-grinding that coke-stove gas generates in sweetening process and the higher sulfur dioxide product of market added value be prepared, existing coke oven gas desulfurization low efficiency has been effectively relieved, the low-quality sulfur that desulfurization generates, the market capacitys such as salt-mixture and ammonium thiocyanate are small, it is not easy the problem of dissolving, product structure is improved, the economic benefit of coking enterprise is improved.
Description
Technical field
The present invention relates to coke-stove gas technical field of resource utilization, produce dioxy using coke-stove gas more particularly, to a kind of
Change the method for sulphur.
Background technique
Coke-stove gas, also known as oven gas refer to and are configured to coal for coking with several bituminous coal, dry by high temperature in coke oven
After evaporating, generated a kind of imflammable gas while output coke and tar product, is the byproduct of coking industry.Coke oven
Coal gas belongs to high heating value gas since combustible component, but contains a large amount of hydrogen sulfide, the coal without desulfurization in coke-stove gas
Gas can not only reduce the quality of steel for steel-making and civil time, but also it is dirty that a large amount of pernicious gas can be also generated in combustion process
Contaminate environment.Therefore, to reach corresponding environmental requirement, China's coking enterprise is both needed to before coke-stove gas application to coke-oven coal
Gas carries out desulfurization process.
But desulfurization link is more in existing coke oven gas desulfurization treatment process, leads to coke oven gas desulfurization cost always
It is high, the pressure of very big cost is brought to coking manufacturing enterprise, while the sulphur quality that coal gas desulfurization generates is low, desulfurization
Also a large amount of by-products can be generated, the by-product of these low-quality sulphur cream and complicated component can disappear without market at all
It receives.
Therefore, the method that the coke-stove gas that a kind of pair of coking industry generates carries out desulfurization is researched and developed, coke oven is being improved
While the desulfuration efficiency of coal gas, the higher titanium dioxide of added value is further prepared using the intermediate product generated in sweetening process
Sulphur product becomes very necessary and urgent to improve the economic benefit of coke oven gas desulfurization.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of method using coke-stove gas production sulfur dioxide, above method general
It is attached that market is prepared in burning after intermediate products sulphur and ammonium thiocyanate co-grinding that coke-stove gas generates in sweetening process
Value added higher sulfur dioxide product, has been effectively relieved existing coke oven gas desulfurization low efficiency, the low-quality sulfur that desulfurization generates,
The market capacitys such as salt-mixture and ammonium thiocyanate are small, are not easy the problem of dissolving, and effectively improve product structure, improve economic effect
Benefit.
A kind of method using coke-stove gas production sulfur dioxide provided by the invention, the described method comprises the following steps:
Coke-stove gas is passed through in coal gas desulfurizer first and carries out desulfurization process, obtain the doctor solution rich in sulphur simple substance and is contained
Doctor solution then regenerate molten sulphur and obtains sulphur, and salt bearing liquid wastes progress salt extraction is obtained ammonium thiocyanate crystallization by bisulfate waste liquor,
Then it will be burned after obtained sulphur and ammonium thiocyanate co-grinding, obtain sulfur dioxide gas.
Further, the desulfurization process is to be handled using HPF wet desulfurizing process；
Preferably, the coal gas desulfurizer is material filling type devulcanizer.
Further, the doctor solution melts the process of sulfur regeneration are as follows: the doctor solution that will be enriched in sulphur simple substance first enters regeneration
Oxidation regeneration is carried out in device, sulphur simple substance is precipitated in the form of sulphur foam, and then sulphur foam is added in molten sulphur device and carries out molten sulphur, cold
But sulphur is generated afterwards.
Further, the molten sulphur device is continuous molten sulphur device；
Preferably, the continuous molten sulphur device is continuous fusion formula molten sulfur separator.
Further, the salt bearing liquid wastes are the mixing salt solution containing ammonium thiocyanate, ATS (Ammonium thiosulphate) and ammonium sulfate.
Further, the method that the salt bearing liquid wastes carry out salt extraction are as follows: first will be thio using the method for wet oxidation
Ammonium sulfate is converted into ammonium sulfate, is then separated ammonium sulfate using the method for distribution crystallization, obtains ammonium thiocyanate crystallization.
Further, the partial size after the sulphur and ammonium thiocyanate co-grinding is 3~30mm.
Further, the incineration temperature burned after the sulphur and ammonium thiocyanate co-grinding is 350~850 DEG C.
Further, the method also includes sulfur dioxide gas is further prepared as to liquid or solid sulfur dioxide
Step.
Further, described the step of sulfur dioxide gas is further prepared as to liquid or solid sulfur dioxide are as follows:
Using sodium hydroxide or sodium carbonate sulfur dioxide absorption gas, sodium hydrogensulfite or sodium metabisulfite solution are obtained,
Sulfuric acid decomposition then is added in sodium hydrogensulfite or sodium metabisulfite solution, obtains the sulfur dioxide that purity is 95~99.5%
Then the sulfur dioxide gas that purity is 95~99.5% is successively compressed, is condensed, obtains sulfur dioxide liquid by gas；
Or, sodium metabisulfite solution is obtained using sodium carbonate sulfur dioxide absorption gas, then by sodium metabisulfite solution
Condensing crystallizing obtains sodium pyrosulfite crystallization, i.e. solid sulfur dioxide.
Compared with prior art, the invention has the benefit that
Coke-stove gas is passed through by the method provided by the invention using coke-stove gas production sulfur dioxide, the method first
Desulfurization process is carried out in coal gas desulfurizer, obtains the doctor solution and salt bearing liquid wastes rich in sulphur simple substance, then carries out doctor solution again
Raw molten sulphur obtains sulphur, and salt bearing liquid wastes progress salt extraction is obtained ammonium thiocyanate, then mixes obtained sulphur and ammonium thiocyanate
It closes and is burned after crushing, obtain sulfur dioxide gas.The intermediate products sulphur that the above method generates coke-stove gas in sweetening process
It is burned after sulphur and ammonium thiocyanate co-grinding and the higher sulfur dioxide product of market added value is prepared, be effectively relieved existing
Coke oven gas desulfurization low efficiency, the low-quality sulfur that desulfurization generates, the market capacitys such as salt-mixture and ammonium thiocyanate are small, are not easy to dissolve
The problem of, product structure is effectively improved, economic benefit is improved.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is that the process for the production system that the present invention that embodiment 1 provides produces sulfur dioxide using coke-stove gas is illustrated
Figure；
Fig. 2 is that the existing coke-stove gas that embodiment 1 provides recycles production system schematic diagram.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation
Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill
Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.
In order to facilitate the clearer understanding present invention, now the present invention is described in detail by specific embodiment.
In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical",
The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to
Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation,
It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.In addition, term " first ", " second ",
" third " is used for descriptive purposes only and cannot be understood as indicating or suggesting relative importance.
In the description of the present invention, it should be noted that unless otherwise clearly defined and limited, term " installation ", " phase
Even ", " connection " shall be understood in a broad sense, for example, it may be being fixedly connected, may be a detachable connection, or be integrally connected；It can
To be mechanical connection, it is also possible to be electrically connected；It can be directly connected, can also can be indirectly connected through an intermediary
Connection inside two elements.For the ordinary skill in the art, above-mentioned term can be understood at this with concrete condition
Concrete meaning in invention.
According to an aspect of the present invention, a method of sulfur dioxide being produced using coke-stove gas, the method includes
Following steps:
Coke-stove gas is passed through in coal gas desulfurizer first and carries out desulfurization process, obtain the doctor solution rich in sulphur simple substance and is contained
Doctor solution then regenerate molten sulphur and obtains sulphur, and salt bearing liquid wastes progress salt extraction is obtained ammonium thiocyanate crystallization by bisulfate waste liquor,
Then it will be burned after obtained sulphur and ammonium thiocyanate co-grinding, obtain sulfur dioxide gas.
Coke-stove gas is passed through by the method provided by the invention using coke-stove gas production sulfur dioxide, the method first
Desulfurization process is carried out in coal gas desulfurizer, obtains the doctor solution and salt bearing liquid wastes rich in sulphur simple substance, then carries out doctor solution again
Raw molten sulphur obtains sulphur, and salt bearing liquid wastes progress salt extraction is obtained ammonium thiocyanate, then mixes obtained sulphur and ammonium thiocyanate
It closes and is burned after crushing, obtain sulfur dioxide gas.The intermediate products sulphur that the above method generates coke-stove gas in sweetening process
It is burned after sulphur and ammonium thiocyanate co-grinding and the higher sulfur dioxide product of market added value is prepared, be effectively relieved existing
Coke oven gas desulfurization low efficiency, the low-quality sulfur that desulfurization generates, the market capacitys such as salt-mixture and ammonium thiocyanate are small, are not easy to dissolve
The problem of, product structure is effectively improved, economic benefit is improved.
In the preferred embodiment of the present invention, the desulfurization process be using HPF wet desulfurizing process at
Reason；
Preferably, the coal gas desulfurizer is material filling type devulcanizer, and the filler that specific filler desulfurizing tower uses is that Tsing-Hua University is big
Learn the QH-5 flat plum blossom formula filler of exploitation.Above-mentioned material filling type devulcanizer can effectively improve coke oven gas desulfurization efficiency, will take off
Coke-stove gas H2S content is down to 5-10mg/m3 after sulphur, and SO2 is down in the flue gas after making coke-stove gas combustion heating coke oven
30mg/m3 once, meets national emission standard, carries out desulfurizing and purifying processing without to flue gas；
Meanwhile the present invention PDS (binuclear phthalocyanine cobalt sulfonate) catalyst formulation in material filling type devulcanizer has been carried out it is excellent
Change, increases mixing polyphenol (substances such as benzenediol and benzenetriol compounding), and mixing ferrous salt (ferrous sulfate, protochloride
The substances such as iron and ferrous carbonate compounding), it is suppressed that the growth of secondary salt improves the yield of sulphur.
In the preferred embodiment of the present invention, the doctor solution melts the process of sulfur regeneration are as follows: will be enriched in sulphur first
The doctor solution of simple substance, which enters, carries out oxidation regeneration in regenerator, sulphur simple substance is precipitated in the form of sulphur foam, then adds sulphur foam
Enter and carry out molten sulphur in molten sulphur device, generates sulphur after cooling.
In above-mentioned preferred embodiment, the molten sulphur device is continuous molten sulphur device；
Preferably, the continuous molten sulphur device is continuous fusion formula molten sulfur separator.Above-mentioned continuous fusion formula molten sulfur separator
It consists of three parts, first part is brokenly bubble section, and the sulphur foam for carrying out bin cure foam pump is heated to 70 DEG C~80 DEG C in this section, makes sulphur
Bubble collapse, sulfur granules gradually sink.The liquid of brokenly bubble section outflow enters upright de- clear (liquid) section, in this pars infrasegmentalis by sulphur
Grain is heated to 150 DEG C~160 DEG C, and sulphur is made to be fused into liquid, and the clear liquid that sulphur foam is brought into floats up to de- clear since density is smaller
(liquid) section top continuously produces, and the clear liquid of extraction returns to coal gas desulfurization workshop section supplement doctor solution and uses.It is formed after sulphur lather collapse
Air release at the top of section since then, release rate view ullage gaseous pressure and determine, exhaust is then opened usually above 5kg/cm2
Valve；De- clear (liquid) section is thermally formed the Temperature Distribution gradually reduced from bottom to top, the liquefied sulphur stream in lower part due to lower part coil pipe
Enter smart sulphur slot, the sulphur improved for purity.Sulphur slag then flows into slag chute from side line, returns to coal yard coal blending.
As a preferred embodiment of the present invention, by above-mentioned continuous sulfur melting device to the obtained elemental sulfur of regeneration into
Row continuous purification obtains the high-quality sulphur that purity is not less than 98%；
In the preferred embodiment of the present invention, the salt bearing liquid wastes be containing ammonium thiocyanate, ATS (Ammonium thiosulphate) and
The mixing salt solution of ammonium sulfate.
In above-mentioned preferred embodiment, the method for the salt bearing liquid wastes progress salt extraction are as follows: first using wet oxidation
ATS (Ammonium thiosulphate) is converted ammonium sulfate by method, then separates ammonium sulfate using the method for distribution crystallization, obtains ammonium thiocyanate
Crystallization.
In the preferred embodiment of the present invention, the partial size after the sulphur and ammonium thiocyanate co-grinding be 3~
30mm。
In the preferred embodiment of the present invention, the burning temperature burned after the sulphur and ammonium thiocyanate co-grinding
Degree is 350~850 DEG C.
In the preferred embodiment of the present invention, the method also includes being further prepared as sulfur dioxide gas
The step of liquid or solid sulfur dioxide.
As a preferred embodiment, sulfur dioxide gas can be further prepared as to meet the needs in market
Liquid or solid sulfur dioxide.
It is described that sulfur dioxide gas is further prepared as to liquid or solid sulfur dioxide in above-mentioned preferred embodiment
The step of are as follows:
Using sodium hydroxide or sodium carbonate sulfur dioxide absorption gas, sodium hydrogensulfite or sodium metabisulfite solution are obtained,
Sulfuric acid then is added in sodium hydrogensulfite or sodium metabisulfite solution, the sulfur dioxide gas after being purified, after purification
Sulfur dioxide gas successively compressed, condensed, obtain sulfur dioxide liquid；
Or, sodium metabisulfite solution is obtained using sodium carbonate sulfur dioxide absorption gas, then by sodium metabisulfite solution
Condensing crystallizing obtains sodium pyrosulfite crystallization, i.e. solid sulfur dioxide.
Below in conjunction with drawings and examples, detailed description of the preferred embodiments.It should be understood that
The specific embodiments described herein are merely illustrative of the invention, is not intended to restrict the invention.
Embodiment 1
As shown in Figure 1, a kind of production system for preparing sulfur dioxide using coke-stove gas provided by the invention, the production
System includes coal gas desulfurizer, regenerator, molten sulphur device, waste liquid salt extraction device, pulverizer, incinerator and purification absorption plant；
The doctor solution outlet of the coal gas desulfurizer is connected with regenerator, and the regenerator connects molten sulphur device to prepare sulphur
Acid；
The salt bearing liquid wastes outlet of the coal gas desulfurizer is connect with waste liquid salt extraction device to prepare ammonium thiocyanate；
The pulverizer is used for the crushing of sulfuric acid and ammonium thiocyanate, and the pulverizer is sequentially connected incinerator, purification is inhaled
Receiving apparatus.
Above-mentioned coal gas desulfurizer is material filling type devulcanizer, and the filler that specific filler desulfurizing tower uses is Tsinghua University's exploitation
QH-5 flat plum blossom formula filler.Above-mentioned material filling type devulcanizer can effectively improve coke oven gas desulfurization efficiency, by coke oven after desulfurization
Coal gas H2S content is down to 5-10mg/m3, SO in the flue gas after making coke-stove gas combustion heating coke oven2It is down to 30mg/m3Once,
Meet national emission standard, carries out desulfurizing and purifying processing without to flue gas.
Above-mentioned molten sulphur device is continuous molten sulphur device, and the continuous molten sulphur device is continuous fusion formula molten sulfur separator.The desulfurization
Liquid melt sulfur regeneration process are as follows: the doctor solution that will be enriched in sulphur simple substance first, which enters, carries out oxidation regeneration in regenerator, sulphur simple substance with
The form of sulphur foam is precipitated, and then sulphur foam is added in molten sulphur device and carries out molten sulphur, generates sulphur after cooling.
Continuous purification carried out to the obtained elemental sulfur of regeneration by above-mentioned continuous sulfur melting device, made from the continuous molten sulphur device
Purity >=98% of sulphur.
The production method of the above-mentioned production system using coke-stove gas production sulfur dioxide are as follows: be first passed through coke-stove gas
Desulfurization process is carried out in material filling type devulcanizer, obtains the doctor solution and salt bearing liquid wastes rich in sulphur simple substance, then successively by doctor solution
Regenerate molten sulphur by regenerator and continuous sulfur melting device and obtain the sulphur of purity >=98%, and salt bearing liquid wastes progress salt extraction is obtained
It is crystallized to ammonium thiocyanate, then will be burned after obtained sulphur and ammonium thiocyanate co-grinding, obtain sulfur dioxide gas.
Sodium hydroxide or sodium carbonate sulfur dioxide absorption gas are then used, sodium hydrogensulfite is obtained or sodium pyrosulfite is molten
Then sulfuric acid decomposition is added in sodium hydrogensulfite or sodium metabisulfite solution in liquid, obtains the dioxy that purity is 95~99.5%
Change sulphur gas, then the sulfur dioxide gas that purity is 95~99.5% is successively compressed, is condensed, liquid titanium dioxide is obtained
Sulphur；
Or, sodium metabisulfite solution is obtained using sodium carbonate sulfur dioxide absorption gas, then by sodium metabisulfite solution
Condensing crystallizing obtains sodium pyrosulfite crystallization, i.e. solid sulfur dioxide.
The method of above-mentioned waste liquid salt extraction is to convert ammonium sulfate for ATS (Ammonium thiosulphate) using the method for wet oxidation first, with
Ammonium sulfate is separated using the method for distribution crystallization afterwards, obtains ammonium thiocyanate crystallization.
Partial size after above-mentioned sulphur and ammonium thiocyanate co-grinding is 20mm.
The incineration temperature burned after above-mentioned sulphur and ammonium thiocyanate co-grinding is 500 DEG C.
Absorbent in above-mentioned purification absorption plant is sodium hydroxide or sodium carbonate.
Fig. 1 is the flow diagram for the production system that the present invention produces sulfur dioxide using coke-stove gas.As shown in Figure 1,
Coke-stove gas is passed through in coal gas desulfurizer carries out desulfurization process first by the present invention, obtains the doctor solution and saliferous rich in sulphur simple substance
Doctor solution then regenerate molten sulphur and obtains sulphur, and salt bearing liquid wastes progress salt extraction is obtained ammonium thiocyanate by waste liquid, then will
It is burned after obtained sulphur and ammonium thiocyanate co-grinding, obtains sulfur dioxide gas.
Fig. 2 is that existing coke-stove gas recycles production system schematic diagram.The above method of the present invention utilizes coke-stove gas
The production system for producing sulfur dioxide recycles production system schematic diagram relative to existing coke-stove gas shown in Fig. 2, can
City is prepared to burn after the intermediate products sulphur and ammonium thiocyanate co-grinding that generate coke-stove gas in sweetening process
The field higher sulfur dioxide product of added value, has been effectively relieved existing coke oven gas desulfurization low efficiency, and desulfurization generates low-quality
The market capacitys such as sulphur, salt-mixture and ammonium thiocyanate are small, are not easy the problem of dissolving, and effectively improve product structure, improve through
Ji benefit.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method using coke-stove gas production sulfur dioxide, which is characterized in that the described method comprises the following steps:
Coke-stove gas is passed through in coal gas desulfurizer first and carries out desulfurization process, doctor solution and saliferous rich in sulphur simple substance is obtained and gives up
Doctor solution then regenerate molten sulphur and obtains sulphur, and salt bearing liquid wastes progress salt extraction is obtained ammonium thiocyanate crystallization by liquid, then
It will be burned after obtained sulphur and ammonium thiocyanate co-grinding, obtain sulfur dioxide gas.
2. the method according to claim 1 using coke-stove gas production sulfur dioxide, which is characterized in that at the desulfurization
Reason is to be handled using HPF wet desulfurizing process；
Preferably, the coal gas desulfurizer is material filling type devulcanizer.
3. the method according to claim 1 using coke-stove gas production sulfur dioxide, which is characterized in that the doctor solution
The process of molten sulfur regeneration are as follows: the doctor solution that will be enriched in sulphur simple substance first, which enters, carries out oxidation regeneration in regenerator, sulphur simple substance is with sulphur
The form of foam is precipitated, and then sulphur foam is added in molten sulphur device and carries out molten sulphur, generates sulphur after cooling.
4. the method according to claim 3 using coke-stove gas production sulfur dioxide, which is characterized in that the molten sulphur device
For continuous molten sulphur device；
Preferably, the continuous molten sulphur device is continuous fusion formula molten sulfur separator.
5. the method according to claim 1 using coke-stove gas production sulfur dioxide, which is characterized in that the saliferous is useless
Liquid is the mixing salt solution containing ammonium thiocyanate, ATS (Ammonium thiosulphate) and ammonium sulfate.
6. the method according to claim 5 using coke-stove gas production sulfur dioxide, which is characterized in that the saliferous is useless
The method of liquid progress salt extraction are as follows: ammonium sulfate is converted for ATS (Ammonium thiosulphate) using the method for wet oxidation first, then uses and divides
The method of cloth crystallization separates ammonium sulfate, obtains ammonium thiocyanate crystallization.
7. it is according to claim 1 using coke-stove gas production sulfur dioxide method, which is characterized in that the sulphur and
Partial size after ammonium thiocyanate co-grinding is 3~30mm.
8. it is according to claim 1 using coke-stove gas production sulfur dioxide method, which is characterized in that the sulphur and
The incineration temperature burned after ammonium thiocyanate co-grinding is 350~850 DEG C.
9. the method according to claim 1 using coke-stove gas production sulfur dioxide, which is characterized in that the method is also
Include the steps that further for sulfur dioxide gas being prepared as liquid or solid sulfur dioxide.
10. the method according to claim 9 using coke-stove gas production sulfur dioxide, which is characterized in that described by two
Sulfur oxide gas is further prepared as the step of liquid or solid sulfur dioxide are as follows:
Using sodium hydroxide or sodium carbonate sulfur dioxide absorption gas, sodium hydrogensulfite or sodium metabisulfite solution are obtained, then
Sulfuric acid decomposition is added in sodium hydrogensulfite or sodium metabisulfite solution, obtains the sulfur dioxide gas that purity is 95~99.5%
Then the sulfur dioxide gas that purity is 95~99.5% is successively compressed, is condensed, obtains sulfur dioxide liquid by body；
Or, obtaining sodium metabisulfite solution using sodium carbonate sulfur dioxide absorption gas, then sodium metabisulfite solution being concentrated
Crystallization obtains sodium pyrosulfite crystallization, i.e. solid sulfur dioxide.
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| CN110028086A (en) * | 2019-04-12 | 2019-07-19 | 南京汇仁化工设备有限公司 | A kind of method of sulphur gas production anhydrous sodium sulfite |
| CN114590946A (en) * | 2022-03-24 | 2022-06-07 | 安徽益硫环境科技有限公司 | Drying method of sulfur foam and desulfurization waste liquid |
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