CN1164592C - Preparation method of oxidative desulfurization catalyst phthalocyanine cobalt sulfonate - Google Patents
Preparation method of oxidative desulfurization catalyst phthalocyanine cobalt sulfonate Download PDFInfo
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- CN1164592C CN1164592C CNB011307692A CN01130769A CN1164592C CN 1164592 C CN1164592 C CN 1164592C CN B011307692 A CNB011307692 A CN B011307692A CN 01130769 A CN01130769 A CN 01130769A CN 1164592 C CN1164592 C CN 1164592C
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- Prior art keywords
- phthalocyanine cobalt
- ammonium salt
- phthalic anhydride
- sulfonate
- preparation
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- 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 title claims abstract description 29
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 14
- 230000001590 oxidative effect Effects 0.000 title claims description 5
- 238000006477 desulfuration reaction Methods 0.000 title abstract description 6
- 230000023556 desulfurization Effects 0.000 title abstract description 5
- 239000013067 intermediate product Substances 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 9
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims abstract description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 7
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 12
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- -1 Tetra hydro Phthalic anhydride sulfonic acid ammonium salt Chemical class 0.000 claims description 5
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 230000003009 desulfurizing effect Effects 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 230000008719 thickening Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 11
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 4
- 230000005494 condensation Effects 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 3
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract 2
- 229910052945 inorganic sulfide Inorganic materials 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000012255 calcium oxide Nutrition 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Catalysts (AREA)
Abstract
A method for preparing phthalocyanine cobalt sulfonate comprises the steps of carrying out sulfonation reaction on phthalic anhydride under the action of fuming sulfuric acid, neutralizing and concentrating to obtain a solid intermediate product phthalic anhydride sulfonate, adding cobalt chloride and urea, and carrying out condensation reaction to obtain the phthalocyanine cobalt sulfonate, and is characterized in that: the solvent used for condensation is sulfolane and the catalyst is titanium tetrachloride. The condensation reaction process is simple and high in safety. The product is used as an oxidation desulfurization catalyst for removing organic sulfide and inorganic sulfide in sulfur-containing wastewater, and the desulfurization rate can reach more than 95%.
Description
Technical field
The present invention relates to a kind of preparation method's of oxidation-desulfurizing catalyst, particularly phthalocyanine cobalt sulfonate preparation.
Background technology
For the sulfur-containing waste water that produces in the petrochemical production process, the general most forms with sodium salt of sulfide in the waste water exist, also have a spot of mercaptan, thioether class material, when with after pressurized air fully contacts, carry out the oxidizing reaction of gas-liquid two-phase, but the reaction times is longer, if add a certain amount of phthalocyanine cobalt compounds as catalyzer when oxidation in waste water, then the reaction times can shorten greatly.
Phthalocyanine cobalt compounds is that to the principle that oxidation desulfur reaction has katalysis phthalocyanine cobalt class has very high oxygen absorption rate, phthalocyanine cobalt compounds and reducing substances after the oxygen uptake meet, will discharge the oxygen of activated state, thereby make the material of reductibility obtain oxidation.Phthalocyanine cobalt compounds has multiple, and as poly-phthalocyanine cobalt, PDS (binuclear phthalocyanine cobalt sulfonate), phthalocyanine cobalt sulfonate etc., wherein poly-phthalocyanine cobalt is to form with condensations such as pyromellitic acid anhydride, urea and cobalt chloride, and is water insoluble because of not being with hydrophilic radical.And phthalocyanine cobalt sulfonate is to become phthalic anhydride sulfonate to form with condensations such as urea and cobalt chloride the Tetra hydro Phthalic anhydride sulfonation earlier again, because have hydrophilic radical on the molecule, so it is water-soluble fine, its activity can recovered in the oxygen supply regeneration again repeatedly, and this just provides reliable assurance for its industrial application.
CN1045414A discloses with all this tetracarboxylic acid dianhydride, 4 water ammonium sulphonates, industrial urea, CoCL2 and ammonium molybdate are that raw material mixes by a certain percentage, it is even to be put in the iron pan fusion, foaming and Cheng Lanse, moved in 250 ℃ High Temperature Furnaces Heating Apparatus dry 2 hours, crisp, the poly-phthalocyanine cobalt of porous.This processing unit requires harsh, complicated operation.This product is used to remove sulfide, and it is little to exist solubleness, the shortcoming that desulfuration efficiency is low.
The condensation reaction of phthalocyanine cobalt compounds requires to carry out under anhydrous condition, and solid material is joined in the organic solvent, and solid materials is reacted in liquid phase environment, can improve reaction efficiency.Usually solvent for use is noxious solvents such as oil of mirbane, chlorobenzene, makes condensation reaction exist reaction mass viscosity big, processing condition complexity, shortcoming such as production security is low.Unexposed condensation reaction solvent for use of CN 1042636C and catalyzer.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of oxidizing and desulfurizing catalyst phthalocyanine cobalt sulfonate, it is characterized in that adopting specific solvent and catalyzer, make condensation reaction technology simple, safe.
This preparation method comprises: Tetra hydro Phthalic anhydride and oleum carry out sulfonation reaction under 180 ℃ of-190 ℃ of temperature, reaction times is 2～8 hours, remove free acid with the neutralization of solid alkaline materials such as lime earlier then, neutralize with ammoniacal liquor again, through thickening filtration, obtain Tetra hydro Phthalic anhydride sulfonic acid ammonium salt intermediate product; Again with intermediate product Tetra hydro Phthalic anhydride sulfonic acid ammonium salt, cobalt chloride, urea, ammonium chloride in the presence of organic solvent tetramethylene sulfone and catalyzer titanium tetrachloride, under 180 ℃ of-200 ℃ of temperature, carry out condensation reaction, reaction times is 3.5-4.5 hour, obtain phthalocyanine cobalt tetrasulfonic acid ammonium salt, obtain the dark blue-green powder-product after drying.
The solid alkaline material can be unslaked lime or white lime, or the two mixture.Because adopted tetramethylene sulfone to substitute common used solvent oil of mirbane as reaction solvent, reaction mass viscosity is reduced, reduce the wall built-up scale forming matter, can improve productive rate.The product material very easily filters simultaneously, and is time saving and energy saving.Therefore this preparation method is characterised in that: the condensation solvent for use is a tetramethylene sulfone, and catalyzer is a titanium tetrachloride.
The desulfurization oxide catalyst molecular formula of the present invention's preparation is: C
32H
12N
8Co (SO
3NH
4)
4, molecular weight is 959.18, and proterties is the mazarine powder, and is nonpoisonous and tasteless, is insoluble to ethanol, very easily water-soluble, and structural formula is:
Adopt non-harmful organic solvent to substitute deleterious organic solvent and prepare phthalocyanine cobalt sulfonate, can reduce to operator's harm and to the pollution of environment.And make reaction solvent with tetramethylene sulfone as can be seen from Comparative Examples and can make simplified control, reduce labour intensity greatly.As seen to have condensation reaction technology simple, safe for this preparation method, the advantage of non-environmental-pollution.No matter its product to inorganic sulphide or organic sulfide, all is as lively as a cricket oxide catalyst.Its major advantage is: (1) working concentration is low, and oxygen absorption rate is fast; (2) can remove inorganic sulphide and organic sulfide simultaneously; (3) higher chemical stability and thermostability are arranged.Use this product to handle sulfur-containing waste water, have preparation conveniently as oxidation-desulfurizing catalyst, simple to operate, nontoxic nothing corrosion, catalytic activity height, the characteristics that desulphurization cost is low.By evaluation test, prove that desulfurization degree can reach more than 95% to this product catalytic activity.
Embodiment
Further narrate the present invention below in conjunction with embodiment:
Embodiment 1:
Get Tetra hydro Phthalic anhydride 1080 grams, 25% oleum, 3210 grams reacted 6 hours down at 180 ~ 190 ℃, added the calcium oxide neutralization then and removed free sulfuric acid, added ammoniacal liquor again and made it generate phthalic acid tetrasulfonic acid ammonium salt.Obtain intermediate product through separation again, get intermediate product 98 grams again, urea 80 grams, cobalt chloride 17 grams, join in 150 milliliters of tetramethylene sulfone, add 1 milliliter of titanium tetrachloride, reacted 3.5 hours down at 190 ℃ as catalyzer, filtration obtains phthalocyanine cobalt tetrasulfonic acid ammonium salt, and dry back product is the dark blue-green powder.Solvent reclaiming.
Embodiment 2:
The preparation of intermediate product ammonium salt is with embodiment 1, get intermediate product ammonium salt 98 grams, urea 90 grams, (adding at twice), cobalt chloride 17 grams, ammonium chloride 5 grams, thick phthalocyanine cobalt tetrasulfonic acid ammonium salt 5 grams join in 200 milliliters of tetramethylene sulfone, add 0.5 milliliter of titanium tetrachloride as catalyzer, react 3.5 hours down at 190 ℃, filtration obtains phthalocyanine cobalt tetrasulfonic acid ammonium salt, and dry back product is the dark blue-green powder.Solvent reclaiming.
The comparative example:
The preparation of intermediate product ammonium salt is got intermediate product ammonium salt 98 grams with embodiment 1, urea 90 grams, (adding at twice), cobalt chloride 17 grams, ammonium chloride 5 grams, thick phthalocyanine cobalt tetrasulfonic acid ammonium salt 5 grams join in 200 milliliters of oil of mirbane, add ammonium molybdate as catalyzer, reacted 6 hours down at 190 ℃, reaction finishes, and product caking wall built-up is serious in the flask, can't pour out filtration, need add dehydrated alcohol and wash out and refilter.Filtration obtains phthalocyanine cobalt tetrasulfonic acid ammonium salt, and dry back product is the mazarine solid, has lump to need to pulverize with ball mill.Solvent can't reuse.
Embodiment 3:
The preparation of intermediate product ammonium salt is with embodiment 1, get intermediate product ammonium salt 98 grams, urea 74 grams, (adding at twice), cobalt chloride 17 grams, ammonium chloride 2 grams, thick phthalocyanine cobalt tetrasulfonic acid ammonium salt 17 grams join in 150 milliliters of tetramethylene sulfone, add 2 milliliters of titanium tetrachlorides as catalyzer, react 4.5 hours down at 190 ℃, filtration obtains phthalocyanine cobalt tetrasulfonic acid ammonium salt, and dry back product is the dark blue-green powder.Solvent reclaiming.
Embodiment 4:
The test of oxidation sweetening catalytically active assessment:
In 1000 milliliters of there-necked flasks, add 500 milliliters of sulfur-containing waste lyes, add concentration and be 5 milliliters of the catalyzer water solvents of 1 grams per liter.At room temperature, blowing air carries out oxidation, reacts 12 hours, and the clearance of sodium sulphite is 95%.
Claims (1)
1. the preparation method of an oxidizing and desulfurizing catalyst phthalocyanine cobalt sulfonate, it is characterized in that: Tetra hydro Phthalic anhydride and oleum carry out sulfonation reaction under 180 ℃～190 ℃ temperature, reaction times is 2～8 hours, remove free acid with the alkaline matter neutralization earlier then, neutralize with ammoniacal liquor again, through thickening filtration, obtain Tetra hydro Phthalic anhydride sulfonic acid ammonium salt intermediate product; Again intermediate product Tetra hydro Phthalic anhydride sulfonic acid ammonium salt, cobalt chloride, urea and ammonium chloride are being organic solvent with the tetramethylene sulfone and are being the existing under the prerequisite of catalyzer with the titanium tetrachloride, under 180 ℃～200 ℃ temperature, carry out condensation reaction, reaction times is 3.5-4.5 hour, obtain phthalocyanine cobalt tetrasulfonic acid ammonium salt, obtain the dark blue-green powder-product after drying, its molecular formula is C
32H
12N
8Co (SO
3NH
4)
4, structural formula is:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011307692A CN1164592C (en) | 2001-08-24 | 2001-08-24 | Preparation method of oxidative desulfurization catalyst phthalocyanine cobalt sulfonate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011307692A CN1164592C (en) | 2001-08-24 | 2001-08-24 | Preparation method of oxidative desulfurization catalyst phthalocyanine cobalt sulfonate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403459A CN1403459A (en) | 2003-03-19 |
| CN1164592C true CN1164592C (en) | 2004-09-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011307692A Expired - Lifetime CN1164592C (en) | 2001-08-24 | 2001-08-24 | Preparation method of oxidative desulfurization catalyst phthalocyanine cobalt sulfonate |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101717588B (en) * | 2009-11-18 | 2012-09-05 | 淄博福颜化工集团有限公司 | Method for preparing metal cobalt phthalocyanine |
| CN102689976A (en) * | 2012-06-20 | 2012-09-26 | 中钢集团鞍山热能研究院有限公司 | Application of water-soluble phthalocyanine catalyst in treating semi-coke wastewater |
| CN105032487B (en) * | 2015-06-11 | 2017-08-15 | 吉林市环喜科技有限公司 | A kind of preparation method of PDS desulphurization catalysts |
| CN105013465A (en) * | 2015-08-10 | 2015-11-04 | 浙江工业大学 | Heterogeneous sulfide oxidation reaction catalyst and preparation method and application thereof |
| CN112958155B (en) * | 2021-02-03 | 2022-06-14 | 中国科学院兰州化学物理研究所 | Phthalocyanine polymer catalyst and preparation method and application thereof |
| CN113443753A (en) * | 2021-08-20 | 2021-09-28 | 宁波大地化工环保有限公司 | Treatment process of high-sulfur wastewater in metallurgical industry |
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2001
- 2001-08-24 CN CNB011307692A patent/CN1164592C/en not_active Expired - Lifetime
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