CN101760351B - High efficiency molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof - Google Patents
High efficiency molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof Download PDFInfo
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- CN101760351B CN101760351B CN2008100516556A CN200810051655A CN101760351B CN 101760351 B CN101760351 B CN 101760351B CN 2008100516556 A CN2008100516556 A CN 2008100516556A CN 200810051655 A CN200810051655 A CN 200810051655A CN 101760351 B CN101760351 B CN 101760351B
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- tower
- cobalt complex
- cleaning agent
- molybdate
- ammonium
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 25
- SXFQDYORBVIULR-UHFFFAOYSA-N azane;cobalt(2+) Chemical compound N.[Co+2] SXFQDYORBVIULR-UHFFFAOYSA-N 0.000 title claims abstract description 20
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 3
- 235000013495 cobalt Nutrition 0.000 claims description 11
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 9
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 9
- 241001330002 Bambuseae Species 0.000 claims description 9
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 9
- 239000011425 bamboo Substances 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000013067 intermediate product Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000010298 pulverizing process Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 239000003337 fertilizer Substances 0.000 abstract description 6
- 238000004140 cleaning Methods 0.000 abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004939 coking Methods 0.000 abstract description 4
- 230000003009 desulfurizing effect Effects 0.000 abstract description 3
- 238000012856 packing Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012847 fine chemical Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009279 wet oxidation reaction Methods 0.000 description 2
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000003708 ampul Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
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- Fertilizers (AREA)
Abstract
The invention belongs to the technical field of the preparation of the fine chemical materials and particularly discloses a high efficiency molybdate ammonium cobalt complex tower-cleaning agent and a preparation method thereof. The high efficiency molybdate ammonium cobalt complex tower-cleaning agent is prepared from the raw materials of ammonium tetramolybdate, CoPc and oxalic acid (analysis alcohol) through the process steps of mixing, heating reaction, drying, grinding and the like, and can be widely used for washing a desulfurizing tower and a packed tower of a coking and fertilizer enterprise desulfurization system. The high efficiency molybdate ammonium cobalt complex tower-cleaning agent has high tower-cleaning efficiency, can wash the packing of the desulfurizing tower under thecondition of no influence on the normal production and without parking and reduce the resistance of the desulfurization system, and improves the economic and social benefits of the enterprise.
Description
Technical field
The present invention relates to a kind of new and effective tower-cleaning agent, a kind of specifically molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof, it can be widely used in the thionizer of coking and fertilizer enterprises desulphurization system and the cleaning of packing tower, belongs to the fine chemistry industry technical field of material.
Background technology
The wet oxidation process desulfurization is a kind of desulfurization technology that present domestic coking and fertilizer industry generally use, and has been widely used in the desulfurizing and purifying of various sulfurous gass such as syngas for synthetic ammonia, coke(oven)gas, coal gas.Because contain various impurity in the unstripped gas, the wet oxidation process desulfurization is subjected to the restriction of each enterprise's processing condition, and sulphur recovery is insufficient, cause that impurity is accumulated in the thionizer filler in a part of sulphur and the unstripped gas, increase the thionizer resistance, increase consumption, influence enterprise's ordinary production.Original purging method is to stop to take off tower cleaning washing filler, and the cycle is long, and the pollution surrounding enviroment had not only caused secondary pollution but also influenced economic benefit of enterprises to environment, had now become each chemical fertilizer and coal chemical enterprise a great problem.
Summary of the invention
The objective of the invention is to take off tower cleaning washing filler for what exist in the thionizer that solves coking and fertilizer enterprises desulphurization system and the packing tower cleaning process, cycle is long, pollute surrounding enviroment, influence problems such as economic benefit of enterprises, a kind of molybdate ammonium cobalt complex tower-cleaning agent is provided, and the present invention also discloses the preparation method of above-mentioned molybdate ammonium cobalt complex tower-cleaning agent.
Raw material of the present invention is formed and proportioning following (following ratio is a ratio of weight and number):
5～6 parts of ammonium molybdates, 10～14 parts of phthalein mountain valley with clumps of trees and bamboo cobalts, 28～36 parts of oxalic acid;
The preparation method is as follows:
At first in having the reactor of whipping appts, oxalic acid (analytical pure) and ammonium tetramolybdate added and mix and stir, even heating to 55～60 ℃, adding phthalein mountain valley with clumps of trees and bamboo cobalt then mixes, keep temperature to react, time length is 3～4 hours, obtain the thick intermediate product of molybdate ammonium cobalt complex, taking-up is put into the electrically heated case and is heated, heating and temperature control is at 100～300 ℃, maintain the temperature at 100～150 ℃, 1.5～2 hours hold-times obtained purpose product molybdate ammonium cobalt complex, and obtaining granularity after pulverizing grinding is 20 purpose pale powders.
Have the molybdenum cobalt complex in the structure of above-mentioned tower-cleaning agent, used molybdenum is an ammonium tetramolybdate; Cobalt is a phthalein mountain valley with clumps of trees and bamboo cobalt.The mass ratio of molybdenum and cobalt is 1: (2.5～3).
Molybdate ammonium cobalt complex tower-cleaning agent of the present invention has following characteristics:
1, efficient height reduces thionizer resistance time weak point, and effect is obvious;
2, consumption is few, and at the fertilizer enterprises of 600 tons of daily output synthetic ammonia abilities, clear ampoule only needs about 200 kilograms of tower-cleaning agents;
3, easy and simple to handle, on the existing equipment basis, directly add;
4, do not stop, do not influence ordinary production;
5, do not increase consumption, additionally do not increase the consumption of catalyzer and soda ash;
6, pollution-free, pollution-free to surrounding enviroment, not etching apparatus and pipeline;
7, it has column efficiency height clearly, can clean the thionizer filler under the situation of ordinary production and reduce the desulphurization system resistance not stopping not influence simultaneously, has improved economic benefit of enterprises and social benefit.
Positively effect of the present invention is: as main raw material(s), adopt solid-phase synthesis with ammonium molybdate, phthalein mountain valley with clumps of trees and bamboo cobalt simultaneously, avoided in reaction process pollution on the environment with an organic solvent, the preparation process of tower-cleaning agent is not polluted environment.This product has that tower is effective clearly, and it is fast to reduce thionizer resistance speed, advantages such as stable processing technique.
Embodiment
Further set forth the present invention below in conjunction with embodiment, and do not limit the present invention in any way, under the prerequisite that does not deviate from technical solution of the present invention, any change or change that those of ordinary skills that the present invention did are realized easily all will fall within the claim scope of the present invention.
Embodiment 1:
Getting oxalic acid (analytical pure) 1500g, ammonium tetramolybdate 280g puts into reactor and constantly stirs, and during heat temperature raising to 60 ℃, stop heating, adding phthalein mountain valley with clumps of trees and bamboo cobalt 580g then mixes, keep temperature to react, keep 3-4 hour laggard line sampling of reaction to detect, if its solubleness in water is very big, then reaction finishes.Obtain the thick intermediate product of molybdate ammonium cobalt complex, taking-up is put into the electrically heated case and is heated, heating and temperature control is at 100～300 ℃, maintain the temperature at 100～150 ℃, 1.5～2 hours hold-times, obtain purpose product molybdate ammonium cobalt complex, obtaining granularity after pulverizing grinding is 20 purpose pale powders (tower-cleaning agent A).
Embodiment 2:
Getting oxalic acid (analytical pure) 1200g, ammonium tetramolybdate 280g puts into reactor and constantly stirs, and during heat temperature raising to 60 ℃, stop heating, adding phthalein mountain valley with clumps of trees and bamboo cobalt 600g then mixes, keep temperature to react, keep 3-4 hour laggard line sampling of reaction to detect, if its solubleness in water is very big, then reaction finishes.Obtain the thick intermediate product of molybdate ammonium cobalt complex, taking-up is put into the electrically heated case and is heated, heating and temperature control is at 100～300 ℃, maintain the temperature at 100～150 ℃, 1.5～2 hours hold-times, obtain purpose product molybdate ammonium cobalt complex, obtaining granularity after pulverizing grinding is 20 purpose pale powders (tower-cleaning agent B).
Embodiment 3:
Getting oxalic acid (analytical pure) 1200g, ammonium tetramolybdate 280g puts into reactor and constantly stirs, and during heat temperature raising to 60 ℃, stop heating, adding phthalein mountain valley with clumps of trees and bamboo cobalt 620g then mixes, keep temperature to react, keep 3-4 hour laggard line sampling of reaction to detect, if its solubleness in water is very big, then reaction finishes.Obtain the thick intermediate product of molybdate ammonium cobalt complex, taking-up is put into the electrically heated case and is heated, heating and temperature control is at 100～300 ℃, maintain the temperature at 100～150 ℃, 1.5～2 hours hold-times, obtain purpose product molybdate ammonium cobalt complex, obtaining granularity after pulverizing grinding is 20 purpose pale powders (tower-cleaning agent C).
The present invention will adopt the ammoniacal liquor of PH 〉=8.2 or buck to prepare tower-cleaning agent solution in use, and (being example under the normal temperature, with ammoniacal liquor) concrete process for preparation is as follows in the experiment:
(1) gets the volumetric flask (three bottles of A, B, C) that tower-cleaning agent A, tower-cleaning agent B, each 100g of tower-cleaning agent C place 1000ml respectively.
(2) ammoniacal liquor of measuring 800ml, PH 〉=8.2 adds respectively in each volumetric flask and dissolves tower-cleaning agent.
(3) ammoniacal liquor that slowly drips PH 〉=8.2 is demarcated to 1000ml in each volumetric flask.
(4) make the tower-cleaning agent solution that concentration is 0.1g/ml (A, B, C).
Under 40 ℃ of conditions of tower-cleaning agent solution temperature, the solubleness of elemental sulfur in solution and the comparison of dissolution rate.
Concrete data see the following form:
By above-mentioned data as can be seen, the clear tower effect of tower-cleaning agent A of the present invention is obvious, can reduce the tower resistance under the situation that does not influence ordinary production fast, prolongs the turnaround of equipment, reduces kinetic equation loss, brings tangible economic benefit and social benefit to enterprise.
Claims (1)
1. molybdate ammonium cobalt complex tower-cleaning agent, it is characterized in that: it is prepared from by following materials of weight proportions,
5～6 parts of ammonium tetramolybdates, 10～14 parts of phthalein mountain valley with clumps of trees and bamboo cobalts, 28～36 parts of analytical pure oxalic acid;
The preparation method is as follows:
At first will mix in oxalic acid and the ammonium tetramolybdate adding reactor and stir, be heated to 55～60 ℃, adding phthalein mountain valley with clumps of trees and bamboo cobalt then mixes, keep temperature to react, time length is 3～4 hours, obtain the thick intermediate product of molybdate ammonium cobalt complex, the taking-up intermediate product is put into the electrically heated case and is heated, heating and temperature control is at 100～300 ℃, maintain the temperature at 100～150 ℃, 1.5～2 hours hold-times obtained purpose product molybdate ammonium cobalt complex, and obtaining granularity after pulverizing grinding is 20 purpose pale powders.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100516556A CN101760351B (en) | 2008-12-23 | 2008-12-23 | High efficiency molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008100516556A CN101760351B (en) | 2008-12-23 | 2008-12-23 | High efficiency molybdate ammonium cobalt complex tower-cleaning agent and preparation method thereof |
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| Publication Number | Publication Date |
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| CN101760351A CN101760351A (en) | 2010-06-30 |
| CN101760351B true CN101760351B (en) | 2010-12-15 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104043623A (en) * | 2014-06-30 | 2014-09-17 | 赖禄波 | Method for cleaning desulfurizing tower |
| CN104998685B (en) * | 2015-07-15 | 2018-03-30 | 陕西省石油化工研究设计院 | The preparation method of ATS (Ammonium thiosulphate) desulphurization catalyst in a kind of coking waste liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045414A (en) * | 1985-12-05 | 1990-09-19 | 东北师范大学 | Process for synthesizing cobalt phthalocyanine desulfating catalyst |
| CN1242260A (en) * | 1999-07-23 | 2000-01-26 | 湖北省化学研究所 | Method for preparing cobalt olybdenum catalyst with resistance of changed sulfur content and anti low sulfur content |
| CN101058078A (en) * | 2006-04-18 | 2007-10-24 | 向松 | Addend preparation method and process for wet oxidation-desulfurizing catalyst |
-
2008
- 2008-12-23 CN CN2008100516556A patent/CN101760351B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1045414A (en) * | 1985-12-05 | 1990-09-19 | 东北师范大学 | Process for synthesizing cobalt phthalocyanine desulfating catalyst |
| CN1242260A (en) * | 1999-07-23 | 2000-01-26 | 湖北省化学研究所 | Method for preparing cobalt olybdenum catalyst with resistance of changed sulfur content and anti low sulfur content |
| CN101058078A (en) * | 2006-04-18 | 2007-10-24 | 向松 | Addend preparation method and process for wet oxidation-desulfurizing catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 郑民纲."我国湿法脱硫技术介绍".《煤气与热力》.1982,(第02期),11－15. |
| 郑民纲."我国湿法脱硫技术介绍".《煤气与热力》.1982,(第02期),11-15. * |
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| CN101760351A (en) | 2010-06-30 |
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