CN1175920C - Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed - Google Patents
Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed Download PDFInfo
- Publication number
- CN1175920C CN1175920C CNB02113667XA CN02113667A CN1175920C CN 1175920 C CN1175920 C CN 1175920C CN B02113667X A CNB02113667X A CN B02113667XA CN 02113667 A CN02113667 A CN 02113667A CN 1175920 C CN1175920 C CN 1175920C
- Authority
- CN
- China
- Prior art keywords
- tail gas
- fixed bed
- catalytic oxidation
- catalyst
- phosphorus
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a method for purifying the exhaust gas of yellow phosphorus in a fixed bed by catalytic oxidation, which comprises the steps of alkali washing, the catalyzed oxidation, etc. The simple substance of the phosphorus, the oxide of the phosphorus, fluoride, hydrogen sulfide, dust, etc. are removed by the step of alkali washing, and heated exhaust gas enters the static bed for the catalytic oxidation; after the impurities of the phosphorus, sulfur, fluorine, etc. are removed by the catalyzed oxidation, the contents of the impurities of the phosphorus, the sulfur and the fluorine are all smaller than 10 mg/m<3>, and the requirement for preparing the qualified material gas of C1 chemical industry is achieved. With the utilization of a catalyst prepared with the method, the removal efficiency of the exhaust gas of the yellow phosphorus can be enhanced considerably; the catalyst is easy to regenerate and has high utilization rate, and the method has the advantages of simple technological process and low purification cost.
Description
(1) technical field: purifying exhausting gas of yellow phosphorus
(2) background technology:
Yellow phosphorus is a kind of important chemical product, and China is main in the world product phosphorus state and exported country, and present national phosphorus production device capability reaches more than 70 ten thousand tons, and yellow phosphorus annual production in 2000 reaches 50.59 ten thousand tons.
Since the eighties, along with carbonizer's technical development, especially in the achievement that is obtained aspect the carbon monoxide carbonyl synthetic technology, the synthetic various utmost points such as methyl formate, dimethyl ether, acetic acid, methyl alcohol, dimethyl carbonate of making of CO carbonyl have the organic compound of economic worth to become possibility, if can utilize the yellow phosphoric tail gas that contains carbon monoxide nearly 90%, by purifying the synthetic carbonizer's product in back, both avoided environmental pollution, can reduce the production cost of yellow phosphorus again, it is too high because of cost to change present phosphorus production, the unable situation of competition on market.But resemble the precious resources that yellow phosphoric tail gas is rich in carbon monoxide like this, so far it is used and only is confined to products such as the lower sodium phosphate trimer of production added value, sodium hexametaphosphate, the emptying and most of yellow phosphoric tail gas all directly burns, its limiting factor just is that yellow phosphoric tail gas contains the synthetic three kinds of impurity of sulphur, phosphorus, fluorine of influential its carbonyl, be that the purifying exhausting gas of yellow phosphorus problem is not resolved, especially the removal of phosphorus in the yellow phosphoric tail gas directly has a strong impact on the synthetic catalyst of carbon monoxide carbonylation.
During producing yellow Phosphorus by electric oven, because reaction is a reduction reaction at high temperature, so the impurity in the tail gas mainly exists to go back ortho states.Phosphorus mainly is elemental phosphorous (P
4) and hydrogen phosphide (PH
3), sulphur mainly is hydrogen sulfide (H
2S) and organic sulfur, fluorine mainly is hydrogen fluoride (HF), silicon fluoride (SiF
4) etc.At the existence form of impurity in the tail gas, present industrial purification yellow phosphoric tail gas mainly adopts washing and two kinds of methods of alkali cleaning:
1. washing: to tail gas lower the temperature, dedusting, can remove simultaneously that a fluoride and a part are elemental phosphorous, hydrogen phosphide, hydrogen fluoride and hydrogen sulfide.Because the vapour pressure of phosphorus reduces rapidly with the reduction of temperature, so some phosphorus are removed because of condensation in the tail gas of washing cooling back, and hydrogen sulfide can be removed a part because of being dissolved in the water.
2. alkali cleaning: the NaOH with 5～10% (NaOH) solution is removed a large amount of carbon dioxide (CO by chemical reaction
2), sour gas such as hydrogen sulfide, hydrogen fluoride.
The subject matter that said method exists is: the removal efficient to phosphorus is lower, and removing not exclusively of phosphorus can cause catalyst to poison to the occasion of using various catalyst, can't satisfy the requirement of a carbonizer to unstripped gas.
How to solve the purification preliminary treatment difficult problem of yellow phosphoric tail gas, make in the yellow phosphoric tail gas after the purification phosphorus, sulphur, fluorine impurity concentration less than 10mg/m
3, reach the requirement of carbonizer's products material gas of producing high added value, impelled formation of the present invention.
(3) summary of the invention:
1. the objective of the invention is to have proposed fixed bed catalytic oxidation new technology, solved the purification preliminary treatment difficult problem of yellow phosphoric tail gas, make sulphur, phosphorus, fluorine impurity concentration＜10mg/m in the yellow phosphoric tail gas after the purification at purifying exhausting gas of yellow phosphorus
3, make it to meet the requirement of carbonizer's technology to unstripped gas.
2. Fig. 1 is a process chart of the present invention, and Fig. 2 is equipment connection figure.
1) technological process: common yellow phosphoric tail gas composition is as shown in table 1, and yellow phosphoric tail gas is tentatively removed oxide and hyrate, hydrogen sulfide and the dust of elemental phosphorous, the phosphorus in the yellow phosphoric tail gas with the solution washing (alkali cleaning) of alkali.The key reaction process is as follows:
Tail gas after the alkali cleaning is by the preheater preheating, and supplemental oxygen (air) makes that oxygen content increases in the tail gas, and passes through reactor from bottom to top, in the reactor filling fixed bed (catalytic oxidation fixed bed) made of catalyst.At this, elemental phosphorous, hydrogen phosphide, hydrogen sulfide, hydrogen fluoride impurity are specifically reacted as follows by catalytic oxidation:
Me in the formula
nO
mThe metal oxide that adds in-the catalyst.
The tail gas that is cleaned that comes out from reactor obtains qualified carbonizer's unstripped gas through cooling.
2) step of this method comprises: (1) tail gas washs with aqueous alkali; (2) tail gas after the washing is preheating to 50-110 ℃; (3) oxygen content is 0.5-2.5% in the adjusting tail gas; (4) tail gas is by the catalyst fixed bed catalytic oxidation that carries out, and described catalyst is the carried catalyst of dipping alkali metal or transition metal or rare earth metal; (5) the tail gas speed by fixed bed is 300～600 meters
3(gas volume)/rice
3(catalyst volume) hour; (6) reduce to 25～35 ℃ through cooling tower tail gas discharged temperature.
3) processing method of catalyst
The catalyst that uses in the technology is the effective catalyst through modification, processing technology is as follows: on the basis of having determined catalyst carrier (activated alumina, zeolite, active carbon, diatomite), and the NaOH with 0.1～2% (NaOH), potassium hydroxide (KOH), ferrous sulfate (FeSO
4), cobalt acetate [Co (AC)
2], copper nitrate [Cu (NO
3)
2], lead chloride [PdCl
2], aluminum nitrate [Al (NO)
3], manganese sulfate [Mn (SO
4)
2] or the aqueous solution lanthanum nitrate [La (NO of rare earth metal
3)
3] it is flooded 10～24h, ageing 18～24 hours, at 350～650 ℃ of roasting 6～12h, 110 ℃ of down dry 2～8h make.
4) method of catalyst regeneration
Catalyst after the inefficacy activates 4～8 hours with hot-air, make and be adsorbed but the material of complete oxidation not, as elemental phosphorous, hydrogen phosphide, diphosphorus trioxide, hydrogen sulfide exhaustive oxidation, used steam activation again 2～4 hours, to remove the impurity of catalyst surface, the water flushing was used Steam Heating 4～8 hours again to neutral then, can use after 24～48 hours with the dry activation of hot-air down at 95～110 ℃ at last again.The whole catalyst regeneration cycle is 34～68 hours.
This technology catalyzing, oxidizing and purifying adopts two fixed bed parallel systems, and one of them fixed bed changed regeneration over to after losing efficacy, and the catalyst regeneration time is 1/3～1/2 of the yellow phosphoric tail gas catalyzing, oxidizing and purifying time, can guarantee that whole system moves continuously.
5) technical indicator that reaches
Under the process conditions that the present invention proposes, catalyst is to PH
3Adsorption capacity is 12～28%, is 24～56% to elemental phosphorous adsorption capacity, is 11～25% to the hydrogen sulfide adsorption capacity, is 10～22% to the hydrogen fluoride adsorption capacity.Purify the content＜10mg/m of hydrogen sulfide in the yellow phosphoric tail gas of back
3, total phosphorus content＜10mg/m
3, hydrogen fluoride content＜5mg/m
3, reach and produce the requirement of carbonizer's product unstripped gas.
The principal element that influences purification efficiency is a reaction temperature, oxygen content and flow rate of carrier gas degree in the tail gas, and it is as follows that it influences rule:
(1) in the presence of catalyst, oxidation reaction can be carried out under 50～100 ℃ of lower temperatures.Reaction temperature raises and to help the raising of purification efficiency, when reaction temperature greater than 100 ℃, the temperature that raises again, the raising of purification efficiency is not obvious;
(2) in the tail gas oxygen content in 0.5～2.5% scope, along with the increase purification efficiency of oxygen content improves;
(3) flow rate of carrier gas is at 300～600 meters
3(gas volume)/rice
3In (catalyst volume) hour scope, reduce flow rate of carrier gas and can improve clean-up effect, but flow velocity is reduced to 300 meters
3(gas volume)/rice
3After (catalyst volume) hour, clean-up effect endlessly significantly improves.
3 compare advantage and the good effect that the present invention has with known technology
1) purification efficiency height, the yellow phosphoric tail gas after purifying reach and produce the requirement of a carbonizer to unstripped gas;
2) technological process is simple, and catalyst is inexpensive, be easy to get;
3) catalyst after poisoning or the inefficacy is easy to regeneration, and catalyst catalytic performance after repeatedly regenerating is constant substantially, has reduced the purification cost;
4) measure by oxygen content and raising exhaust temperature in the extra oxygenating increase tail gas has improved purification efficiency greatly;
5) whole system is operated under positive pressure, can guarantee the security of operating.
(4) description of drawings:
Fig. 1 is a process chart of the present invention.Fig. 2 is equipment connection figure, and 1 is Safety water seal, the 2nd among the figure, water ring vacuum pump, the 3rd, caustic wash tower, the 4th, cyclone demister, the 5th, Na Shi pump, the 6th, preheater, the 7th, reactor, the 8th, air exhauster, the 9th, washing cooling tower.Table 1 is the yellow phosphoric tail gas component list.Table 2,3,4,5 is respectively the exhaust gas component table after embodiment one, two, three, four purifies.
(5) specific embodiment:
Embodiment one
(1) Preparation of catalysts
It is 0.2% lanthanum nitrate hexahydrate dipping 20 hours that active aluminum oxide carrier is placed concentration, through ageing in 24 hours, evaporate to dryness on electric-heated thermostatic water bath, put into the Muffle furnace roasting at last, during roasting earlier 110 ℃ of constant temperature 4 hours, then 500 ℃ of roastings 6 hours, 110 ℃ dry 4 hours down, make the catalyst finished product, and be loaded into and make the catalytic oxidation fixed bed in the reactor.
(2) tail gas clean-up condition
Yellow phosphoric tail gas by air exhauster with 500 meters
3(gas volume)/rice
3The flow velocity of (catalyst volume) hour is removed carbon dioxide and part phosphorus, sulphur, fluorine impurity through caustic wash tower, then is heated to 80 ℃ by preheater, mends oxygen simultaneously, and passes through the reactor fixed bed from bottom to top.At this, phosphorus, sulphur impurity are by catalytic oxidation, and the product phosphorus pentoxide after the oxidation, diphosphorus trioxide, sulphur etc. are attracted to catalyst surface.Tail gas after the purification send a carbonizer workshop section to use after the cooling tower cooling.
Exhaust gas component after the purification sees Table 2.
Embodiment two
(1) Preparation of catalysts
It is 0.3% copperas solution dipping 24 hours that Zeolite support is placed concentration, after ageing in 24 hours, evaporate to dryness on electric-heated thermostatic water bath, put into the Muffle furnace roasting at last, during roasting earlier 110 ℃ of constant temperature 2 hours, 550 ℃ of roastings 5 hours, 110 ℃ were descended dry 4 hours, and made the catalyst finished product then.
(2) tail gas clean-up condition
Yellow phosphoric tail gas by air exhauster with 550 meters
3(gas volume)/rice
3The flow velocity of (catalyst volume) hour is removed carbon dioxide and part phosphorus, sulphur, fluorine impurity through caustic wash tower, then is heated to 70 ℃ by preheater, the gas of oxygenating simultaneously, and pass through the reactor fixed bed from bottom to top.At this, phosphorus, sulphur impurity are by catalytic oxidation, and the product phosphorus pentoxide after the oxidation, diphosphorus trioxide, sulphur etc. are attracted to catalyst surface.Tail gas after the purification send a carbonizer workshop section to use after the cooling tower cooling.
Exhaust gas component after the purification sees Table 3.
Embodiment three
(1) Preparation of catalysts
Absorbent charcoal carrier was placed 0.5% potassium hydroxide solution dipping 18 hours, after ageing in 24 hours, evaporate to dryness on electric-heated thermostatic water bath, 110 ℃ dry 6 hours down, make the catalyst finished product.
(2) tail gas clean-up condition
Yellow phosphoric tail gas by air exhauster with 600 meters
3(gas volume)/rice
3The flow velocity of (catalyst volume) hour is removed carbon dioxide and part phosphorus, sulphur, fluorine impurity through caustic wash tower, then is heated to 110 ℃ by preheater, mends oxygen simultaneously, and passes through the reactor fixed bed from bottom to top.At this, phosphorus, sulphur impurity are by catalytic oxidation, and the product phosphorus pentoxide after the oxidation, diphosphorus trioxide, sulphur etc. are attracted to catalyst surface.Tail gas after the purification send a carbonizer workshop section to use after the cooling tower cooling.
Exhaust gas component after the purification sees Table 4.
Embodiment four
(1) Preparation of catalysts
It is 0.4% aluminum nitrate solution dipping 20 hours that diatomite support is placed concentration, after ageing in 18 hours, evaporate to dryness on electric-heated thermostatic water bath, put into the Muffle furnace roasting at last, during roasting earlier 110 ℃ of constant temperature 2 hours, then 200,300,400 ℃ of each constant temperature 0.5 hour,, flood concentration again and be 0.1% PdCl in 600 ℃ of roastings 4 hours
224 hours, 110 ℃ were descended dry 2 hours, and made the catalyst finished product.
(2) tail gas clean-up condition
Yellow phosphoric tail gas by air exhauster with 400 meters
3(gas volume)/rice
3The flow velocity of (catalyst volume) hour is removed carbon dioxide and part phosphorus, sulphur, fluorine impurity through caustic wash tower, then is heated to 100 ℃ by preheater, mends oxygen simultaneously, and passes through the reactor fixed bed from bottom to top.At this, phosphorus, sulphur impurity are by catalytic oxidation, and the product phosphorus pentoxide after the oxidation, diphosphorus trioxide, sulphur etc. are attracted to catalyst surface.Tail gas after the purification send a carbonizer workshop section to use after the cooling tower cooling.
Exhaust gas component after the purification sees Table 5.
| Tail gas is formed | CO | CO 2 | H 2、N 2 | O 2 | Other | Total phosphorus | H 2S | HF |
| Composition | 85～95％ | 3～7％ | 5～12％ | 0.2～1％ | ～5 | 1000～5000 mg/m 3 | 1000～5000 mg/m 3 | 300～4000 mg/m 3 |
Table 1
| The yellow phosphoric tail gas composition | CO | CO 2 | H 2、N 2 | O 2 | Total phosphorus | H 2S | HF | Other |
| Content before purifying | 87％ | 5％ | 6％ | 0.5％ | 1200 mg/m 3 | 1500 mg/m 3 | 1300 mg/m 3 | 1.5％ |
| Purify back content | 91％ | 0.8％ | 6％ | 0.2％ | 4 mg/m 3 | 5 mg/m 3 | 5 mg/m 3 | 2.0％ |
Table 2
| The yellow phosphoric tail gas composition | CO | CO 2 | H 2、N 2 | O 2 | Total phosphorus | H 2S | HF | Other |
| Content before purifying | 90％ | 4％ | 5％ | 0.4％ | 1200 mg/m 3 | 1500 mg/m 3 | 1300 mg/m 3 | 0.6 |
| Purify back content | 93％ | 1％ | 5％ | 0.1％ | 6 mg/m 3 | 4 mg/m 3 | 3 mg/m 3 | 0.9 |
Table 3
| The yellow phosphoric tail gas composition | CO | CO 2 | H 2 | N 2 | O 2 | Total phosphorus | H 2S | HF | Other |
| Content before purifying | 85.4％ | 2.4％ | 6.47％ | 4.29％ | 0.95 ％ | 1170 mg/m 3 | 1500 mg/m 3 | 317 mg/m 3 | 0.49％ |
| Purify back content | 87.6％ | 0.4％ | 6.47％ | 4.29％ | 0.4％ | 6 mg/m 3 | 4 mg/m 3 | 3 mg/m 3 | 0.84％ |
Table 4
| The yellow phosphoric tail gas composition | CO | CO 2 | H 2、N 2 | O 2 | Total phosphorus | H 2S | HF | Other |
| Content before purifying | 88％ | 4％ | 5％ | 0.5％ | 1500 mg/m 3 | 1000 mg/m 3 | 700 mg/m 3 | 2.5％ |
| Purify back content | 91.4％ | 0.6％ | 5％ | 0.3％ | 7 mg/m 3 | 7 mg/m 3 | 3 mg/m 3 | 2.7％ |
Table 5
Claims (7)
1. the method that purifies of a yellow phosphoric tail gas fixed bed catalytic oxidation, yellow phosphoric tail gas is through the solution washing of alkali, tentatively remove oxide and hyrate, hydrogen fluoride, hydrogen sulfide and the dust of elemental phosphorous, the phosphorus in the yellow phosphoric tail gas, tail gas after the alkali cleaning is through intensification preheating, supplemental oxygen, and from bottom to top with the flow rate of carrier gas of regulation and temperature by the catalytic oxidation fixed bed in the reactor, at this, impurity is by further catalytic oxidation and be adsorbed on the catalyst and be removed, and obtains carbonizer's acceptable material gas from the reactor tail gas discharged through the water cooling tower cooling; It is characterized in that: the step of this method comprises: (1) tail gas washs with aqueous alkali; (2) tail gas after the washing is preheating to 50-110 ℃; (3) oxygen content is 0.5-2.5% in the adjusting tail gas; (4) tail gas is by the catalyst fixed bed catalytic oxidation that carries out, and described catalyst is the carried catalyst of dipping alkali metal or transition metal or rare earth metal.
2. the method that yellow phosphoric tail gas fixed bed catalytic oxidation according to claim 1 purifies, it is characterized in that: the air velocity by the catalytic oxidation fixed bed is a per hour 300-600 cubic meter of gas volume of every cubic metre of catalyst volume.
3. the method that yellow phosphoric tail gas fixed bed catalytic oxidation according to claim 1 purifies is characterized in that: reduce to 25～35 ℃ through cooling tower tail gas discharged temperature.
4. the method that yellow phosphoric tail gas fixed bed catalytic oxidation according to claim 1 purifies, it is characterized in that: catalyst carrier is that active alundum (Al, maceration extract are that concentration is 0.2% lanthanum nitrate aqueous solution.
5. the method that yellow phosphoric tail gas fixed bed catalytic oxidation according to claim 1 purifies, it is characterized in that: catalyst carrier is a zeolite, maceration extract is that concentration is 0.3% ferrous sulfate aqueous solution.
6. the method that yellow phosphoric tail gas fixed bed catalytic oxidation according to claim 1 purifies, it is characterized in that: catalyst carrier is an active carbon, maceration extract is that concentration is 0.5% potassium hydroxide aqueous solution.
7. the method that yellow phosphoric tail gas fixed bed catalytic oxidation according to claim 1 purifies, it is characterized in that: catalyst carrier is a diatomite, maceration extract is that concentration is 0.4% aluminum nitrate aqueous solution for the first time, is that concentration is 0.1% the lead chloride aqueous solution for the second time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02113667XA CN1175920C (en) | 2002-04-26 | 2002-04-26 | Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02113667XA CN1175920C (en) | 2002-04-26 | 2002-04-26 | Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1398658A CN1398658A (en) | 2003-02-26 |
| CN1175920C true CN1175920C (en) | 2004-11-17 |
Family
ID=4742744
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB02113667XA Expired - Fee Related CN1175920C (en) | 2002-04-26 | 2002-04-26 | Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1175920C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013134910A1 (en) * | 2012-03-12 | 2013-09-19 | 昆明理工大学 | Process for purifying tail gas from ore-smelting electrical furnace by catalytic oxidization |
| CN105194996A (en) * | 2015-09-15 | 2015-12-30 | 华烁科技股份有限公司 | Method for comprehensively utilizing yellow phosphorus tail gas |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427390C (en) * | 2006-02-24 | 2008-10-22 | 昆明理工大学 | Method of purifying furnace gas of closed calcium carbide furnace |
| CN101024140B (en) * | 2007-01-15 | 2010-06-02 | 左建国 | Method for purifying phosphor tail-gas |
| CN101507897B (en) * | 2009-02-24 | 2012-01-25 | 昆明理工大学 | Method for catalytically oxidizing and purifying hot-process phosphoric acid tail-gas using load type active carbon |
| CN101972604B (en) * | 2010-11-08 | 2013-06-12 | 昆明理工大学 | Method and device for removing phosphorus hydride in warehouse waste gas |
| CN102019141A (en) * | 2010-12-20 | 2011-04-20 | 昆明理工大学 | Process for purifying tail gas containing hydrothion by using liquid phase catalytic oxidation method |
| CN102773013B (en) * | 2012-07-23 | 2014-11-05 | 昆明理工大学 | Method for purifying silicon tetrafluoride in industrial tail gas |
| CN103316624B (en) * | 2013-06-08 | 2015-03-04 | 华烁科技股份有限公司 | Dephosphorization agent and preparation method thereof |
| CN104190250B (en) * | 2014-09-04 | 2016-03-30 | 昆明理工大学 | A kind of purification method of methine phosphorus |
| CN104610087B (en) * | 2014-11-28 | 2017-01-18 | 西南化工研究设计院有限公司 | Device and method for purifying yellow phosphorus tail gas and continuously synthesizing oxamide |
| CN107626195A (en) * | 2017-10-19 | 2018-01-26 | 云南江磷集团股份有限公司 | The tail gas treatment process of red phosphorus purification |
| CN111228980B (en) * | 2020-03-10 | 2020-11-24 | 昆明理工大学 | Method for combined removal of phosphorus, sulfur, cyanogen and nitrogen oxide in waste gas |
| CN111617631A (en) * | 2020-04-28 | 2020-09-04 | 江苏易行环保新能源有限公司 | Yellow phosphorus tail gas dephosphorization purification method |
| CN113457438A (en) * | 2021-06-27 | 2021-10-01 | 昆明理工大学 | Method for removing hydrogen sulfide, phosphine and arsine by low-temperature plasma modified alumina-based catalyst |
-
2002
- 2002-04-26 CN CNB02113667XA patent/CN1175920C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013134910A1 (en) * | 2012-03-12 | 2013-09-19 | 昆明理工大学 | Process for purifying tail gas from ore-smelting electrical furnace by catalytic oxidization |
| CN105194996A (en) * | 2015-09-15 | 2015-12-30 | 华烁科技股份有限公司 | Method for comprehensively utilizing yellow phosphorus tail gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1398658A (en) | 2003-02-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1175920C (en) | Catalytic yellow phosphorus tail gas oxidizing and purifying method in fixed bed | |
| CN1830526A (en) | Purification technology and equipment of waste gas containing high concentration nitrogen oxide | |
| CN1843575A (en) | Method and apparatus for optic catalytic oxidizing, desulfurizing and denitrifying flue gas simultaneously | |
| CN101337157B (en) | Purification method of low concentration phosphine waste gas | |
| CN108786859A (en) | A kind of preparation method of carbon doping iodine oxygen bismuth acid iodide oxygen bismuth heterojunction structure | |
| CN102500323B (en) | Modified active carbon desulfurizer and preparation method thereof and treatment method of hydrogen sulfide waste gas | |
| CN101804344A (en) | Manganese/carbon nanotube denitrification catalytic reduction catalyst and preparation method thereof | |
| CN105536886A (en) | Regeneration method of arsenic poisoning denitration catalyst | |
| CN109675436A (en) | A kind of system and method for flue gas pollutant combined desulfurization and denitration | |
| CN107519940B (en) | Catalyst for removing arsenic and mercury in yellow phosphorus tail gas and preparation method thereof | |
| CN102614775A (en) | Method for removing and recovering low concentration sulfur dioxide in industrial exhaust gas | |
| CN101507897B (en) | Method for catalytically oxidizing and purifying hot-process phosphoric acid tail-gas using load type active carbon | |
| CN101318124A (en) | Method for preparing molecular sieve adsorption agent for low-concentration hydrogen phosphide purification | |
| CN110813232A (en) | Sulfur-resistant adsorbent for purifying yellow phosphorus tail gas and preparation method thereof | |
| CN1237472A (en) | Method for recovering sulfur dioxide from gas and its equipment | |
| CN101564683A (en) | Method for preparing transitional metal ion copper modified adsorbent for purifying low-concentration phosphine | |
| CN1128001C (en) | Method for removing phosphorus, phosphide, surfide and recovering phosphorus from yellow phosphorus tail gas | |
| CN107159230B (en) | Catalyst for normal-temperature catalytic removal of low-concentration nitrogen oxides and preparation method thereof | |
| CN1087180C (en) | Process for purifying and recovering waste SOx gas from coal boiler | |
| CN101695653A (en) | Modified activated carbon adsorbent for low-concentration phosphine, preparation method and application thereof | |
| CN101564684A (en) | Method for preparing transitional metal ion Co modified adsorbent for purifying low-concentration phosphine | |
| WO2013134910A1 (en) | Process for purifying tail gas from ore-smelting electrical furnace by catalytic oxidization | |
| CN1314783C (en) | Catalyst of inverting thiol in liquefied gas and producing process thereof | |
| CN103447002A (en) | Active carbon modification method for removing hydrocyanic acid | |
| CN1295875A (en) | Detergent and washing method for harmful gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |