CN102773116B - Method for preparing catalyst capable of promoting ammonia nitrogen conversion in chemical wastewater - Google Patents
Method for preparing catalyst capable of promoting ammonia nitrogen conversion in chemical wastewater Download PDFInfo
- Publication number
- CN102773116B CN102773116B CN201210253193.2A CN201210253193A CN102773116B CN 102773116 B CN102773116 B CN 102773116B CN 201210253193 A CN201210253193 A CN 201210253193A CN 102773116 B CN102773116 B CN 102773116B
- Authority
- CN
- China
- Prior art keywords
- ammonia
- hours
- under
- parts
- catalyst
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing catalyst capable of promoting ammonia nitrogen conversion in chemical wastewater. The method includes the following steps of proportionally weighing argil, zeolite, silica gel and graphite as adsorbent carriers after drying and smashing, proportionally weighing and mixing lead oxide, vanadium oxide, chromic oxide, copper oxide and the like to obtain maceration extract, macerating the same volume of adsorbent carriers in the maceration extract for 11 to 17 hours, drying, roasting, and reducing by hydrogen to obtain the catalyst, and the obtained catalyst is filled into an ammonia distillation tower as filler. The filler 3cm to 5cm in thickness for each layer is filled in the ammonia distillation tower for every 50cm till a tower top. By the aid of the catalyst, the temperature of steam in a normal pressure condition can be utilized to directly convert ammonia in the chemical wastewater into nitrogen to be exhausted to the atmosphere, so that secondary pollution is avoided, high temperature pressurization is needless, cost is low, and ammonia nitrogen removing rate is high.
Description
Technical field
The present invention relates to a kind of method for preparing catalyst that promotes mineralized nitrogen in wastewater from chemical industry, belong to sewage treatment area.
Background technology
In recent years, along with expanding economy, the heavy industry such as oil, chemical industry development rapidly, various places chemical enterprise like rain after pound as bamboo shoot and gush out, thing followed air, water pollution problems are also day by day by people are paid attention to, and the high ammonia-nitrogen wastewater producing therefrom also becomes one of industry development restraining factors.And in order to keep the sustainable development of enterprise, reduce the waste of water resource and environmental pollution, raising Business Economic Benefit and society's effect, wastewater from chemical industry is carried out to advanced treating imperative.
And it is at present varied to the processing of ammonia nitrogen waste water, in " ammonia nitrogen in the Co/Bi catalyst wet oxidation degraded rubbish infiltration filtrate " literary composition being proposed by Jilin University's environment and Resource Institute, it adopts CWCO technology, take Co/Bi as catalyst, ammonia nitrogen is degraded, under high pressure 0.5～2.0MPa condition, along with the rising of temperature, CWCO is to NH
3the degradation capability of-N strengthens gradually, in temperature-rise period (20～300 ℃), and NH
3-N is oxidized degraded gradually, has reached CWCO technology degradation of organic substances and NH simultaneously
3the object of-N.In addition, the technology of utilizing ammonia still process method to remove wastewater from chemical industry middle and high concentration ammonia nitrogen neither not have, such as publication number is CN102351265A, name is called in a kind of " coking production remained ammonia negative pressure ammonia distillation process and device " disclosed method and in desulfurizing tower ammonia vapour porch, a Venturi tube is set in advance, and distilled ammonia wastewater/cyclic ammonia water heat exchanger and distilled ammonia wastewater circulating pump are set at the bottom of ammonia still; Then open heat exchanger and circulating pump, the heat of cyclic ammonia water is brought in ammonia still by distilled ammonia wastewater, when ammonia still process tower top temperature reaches 60～80 ℃, open into Venturi tube doctor solution pipeline valve, ammonia vapour is sucked to desulfurizing tower, open afterwards remained ammonia pump and distilled ammonia wastewater pump, remaining ammoniacal liquor is entered to ammonia still through heat exchanger and process.
But, in the method for more than enumerating, the former needs the condition of HTHP, and operating cost is high, although the latter is under steam condition, just ammonia can be transformed to nitrogen, but still Shortcomings part: 1,, because the discharge meeting of ammonia causes secondary pollution 2, adopts the processing method that absorbs the ammonia emitting environment, because containing multiple other materials, cause product impure, and concentration is not high, can not meet produce market demand.
Summary of the invention
For above prior art, need the condition of HTHP ammonia could be changed into the expensive problem of nitrogen and with catalyst, in conjunction with ammonia still process blow-off method, can cause to air the problem of secondary pollution when the catalysis, a kind of catalyst preparation and application process thereof that just can promote that in ammonia still process process wastewater from chemical industry middle and high concentration mineralized nitrogen becomes nitrogen is provided, the present invention utilizes the temperature of steam that the ammonia in waste water is directly changed into nitrogen discharge in atmosphere, avoided the problem of secondary pollution, and without pressurization, cost is low, and ammonia nitrogen removal frank is high.
In order to achieve the above object, the technical scheme of taking is:
A method for preparing catalyst that promotes mineralized nitrogen in wastewater from chemical industry, is characterized in that:
(1) carrier pretreatment: meter by ratio of weight and the number of copies, get 30 parts of potter's clay, 20 parts of zeolites, 25 parts of silica gel, 25 parts of graphite dryings, pulverizing, grind into powder, as adsorbing agent carrier;
(2) maceration extract preparation: be made into mass concentration and be respectively 10～30g/L plumbi nitras, 5～8g/L vanadic sulfide, 5～7g/L chromium sulfate, 1～2g/L copper nitrate, 5～6g/L mercuric nitrate, 4～5g/L caddy, 5～9g/L nickel chloride, 3～5g/L titanium chloride, 2～4g/L thorium nitrate, 2～4g/L cobalt chloride, 25～30g/L malic acid, 8～11g/L tolysulfonyl hydrazine solution;
(3) dipping: flood 11～17 hours according to carrier and maceration extract equal-volume (V);
(4) dry, roasting: under vacuum normal temperature condition dry 11～17 hours, then in baking oven 110 ℃ dry 6 hours; In negative pressure, being that 0.3MPa, temperature are roasting 3 hours under 700 ℃ of conditions, is then cool drying rapidly under 0.5MPa, normal temperature condition in negative pressure, can obtain the cellular catalyst containing various heavy;
(5) activation: under nitrogen protection condition, pass into hydrogen reducing under 900 ℃ of conditions.
The invention has the beneficial effects as follows:
(1) can directly the ammonia nitrogen in wastewater from chemical industry be reduced into nitrogen discharge, can not cause secondary pollution to environment;
(2) solve catalyst not needing to be reduced into nitrogen under ultra-high temperature and pressure condition, saved cost;
(3) for the water quality situation of wastewater from chemical industry, selected take plumbi nitras as main catalyst, with strong points.
The specific embodiment:
First, take 30 parts of potter's clay, 20 parts of zeolites, after 25 parts of silica gel and 25 parts of graphite mix through drying, pulverize grind into powder as adsorbing agent carrier, then get 10～30g/L plumbi nitras, 5～8g/L vanadic sulfide, 5～7g/L chromium sulfate, 1～2g/L copper nitrate, 5～6g/L mercuric nitrate, 4～5g/L caddy, 5～9g/L nickel chloride, 3～5g/L titanium chloride, 2～4g/L thorium nitrate, 2～4g/L cobalt chloride, 25～30g/L malic acid, 8～11g/L tolysulfonyl hydrazine solution is made into maceration extract, then according to carrier and maceration extract incipient impregnation 11～17 hours, again under condition of normal pressure, be dried after 11～17 hours and under 110 ℃ of conditions, be dried 6 hours in baking oven, in negative pressure, be then that 0.3MPa, temperature are roasting 3 hours under the condition of 700 ℃, in negative pressure, be rapid cool drying under 0.5MPa, normal temperature condition again, can obtain the cellular catalyst containing various heavy, under nitrogen protection condition, in the temperature of 900 ℃, pass into hydrogen reducing afterwards.Finally using the catalyst making in filler is placed in ammonia still, depth of packing is 3～5cm, every 50cm, lays one deck, until tower top.
Example 1:
First, take 30 parts of potter's clay, 20 parts of zeolites, after 25 parts of silica gel and 25 parts of graphite mix through drying, pulverize grind into powder as adsorbing agent carrier, then get 30g/L plumbi nitras, 5g/L vanadic sulfide, 7g/L chromium sulfate, 1g/L copper nitrate, 5g/L mercuric nitrate, 5g/L caddy, 5g/L nickel chloride, 3g/L titanium chloride, 2g/L thorium nitrate, 2g/L cobalt chloride, 25g/L malic acid, 10g/L tolysulfonyl hydrazine solution is made into maceration extract, then according to carrier and maceration extract incipient impregnation 11 hours, again under condition of normal pressure, be dried after 11 hours and under 110 ℃ of conditions, be dried 6 hours in baking oven, in negative pressure, be then that 0.3MPa, temperature are roasting 3 hours under the condition of 700 ℃, in negative pressure, be rapid cool drying under 0.5MPa, normal temperature condition again, can obtain the cellular catalyst containing various heavy, under nitrogen protection condition, in the temperature of 900 ℃, pass into hydrogen reducing afterwards.Finally using the catalyst making in filler is placed in ammonia still, depth of packing is 3cm, every 50cm, lays one deck, until tower top.
Gather the waste water sample of Changzhou drugmaker, then utilize the catalyst of being made by said method to process the ammonia nitrogen in waste water, the ammonia nitrogen concentration after processing in this waste water is reduced to 0.2mg/L from 10000mg/L, and ammonia nitrogen removal frank is 99.98%, meanwhile, record airborne NH
3content is 1.1mg/m
3, reach national ammonia secondary discharge standard.
Example 2:
First, take 30 parts of potter's clay, 20 parts of zeolites, after 25 parts of silica gel and 25 parts of graphite mix through drying, pulverize grind into powder as adsorbing agent carrier, then get 30g/L plumbi nitras, 8g/L vanadic sulfide, 7g/L chromium sulfate, 2g/L copper nitrate, 6g/L mercuric nitrate, 5g/L caddy, 9g/L nickel chloride, 5g/L titanium chloride, 4g/L thorium nitrate, 4g/L cobalt chloride, 30g/L malic acid, 10g/L tolysulfonyl hydrazine solution is made into maceration extract, then according to carrier and maceration extract incipient impregnation 17 hours, again under condition of normal pressure, be dried after 17 hours and under 110 ℃ of conditions, be dried 6 hours in baking oven, in negative pressure, be then that 0.3MPa, temperature are roasting 3 hours under the condition of 700 ℃, in negative pressure, be rapid cool drying under 0.5MPa, normal temperature condition again, can obtain the cellular catalyst containing various heavy, under nitrogen protection condition, in the temperature of 900 ℃, pass into hydrogen reducing afterwards.Finally using the catalyst making in filler is placed in ammonia still, depth of packing is 5cm, every 50cm, lays one deck, until tower top.
Gather the waste water sample of Wuxi pharmaceutical factory, then utilize the catalyst of being made by said method to process the ammonia nitrogen in waste water, the ammonia nitrogen concentration after processing in this waste water is reduced to 0.2mg/L from 15000mg/L, and ammonia nitrogen removal frank is 99.99%, meanwhile, record airborne NH
3content is 1.0mg/m
3, reach national ammonia first discharge standard.
Example 3:
First, take 30 parts of potter's clay, 20 parts of zeolites, after 25 parts of silica gel and 25 parts of graphite mix through drying, pulverize grind into powder as adsorbing agent carrier, then get 20g/L plumbi nitras, 6g/L vanadic sulfide, 6g/L chromium sulfate, 1g/L copper nitrate 6g/L mercuric nitrate, 4g/L caddy, 8g/L nickel chloride, 4g/L titanium chloride, 3g/L thorium nitrate, 3g/L cobalt chloride, 27g/L malic acid, 9g/L tolysulfonyl hydrazine solution is made into maceration extract, then according to carrier and maceration extract incipient impregnation 14 hours, again under condition of normal pressure, be dried after 15 hours and under 110 ℃ of conditions, be dried 6 hours in baking oven, in negative pressure, be then that 0.3MPa, temperature are roasting 3 hours under the condition of 700 ℃, in negative pressure, be rapid cool drying under 0.5MPa, normal temperature condition again, can obtain the cellular catalyst containing various heavy, under nitrogen protection condition, in the temperature of 900 ℃, pass into hydrogen reducing afterwards.Finally using the catalyst making in filler is placed in ammonia still, depth of packing is 4cm, every 50cm, lays one deck, until tower top.
Gather the waste water sample of Shanghai pharmaceutical factory, then utilize the catalyst of being made by said method to process the ammonia nitrogen in waste water, the ammonia nitrogen concentration after processing in this waste water is reduced to 0.2mg/L from 18000mg/L, and ammonia nitrogen removal frank is 99.99%, meanwhile, record airborne NH
3content is 1.0mg/m
3, reach national ammonia first discharge standard.
Claims (1)
1. a method for preparing catalyst that promotes mineralized nitrogen in wastewater from chemical industry, is characterized in that:
(1) carrier pretreatment: meter by ratio of weight and the number of copies, get 30 parts of potter's clay, 20 parts of zeolites, 25 parts of silica gel, 25 parts of graphite dryings, pulverizing, grind into powder, as adsorbing agent carrier;
(2) maceration extract preparation: be made into mass concentration and be respectively 10～30g/L plumbi nitras, 5～8g/L vanadic sulfide, 5～7g/L chromium sulfate, 1～2g/L copper nitrate, 5～6g/L mercuric nitrate, 4～5g/L caddy, 5～9g/L nickel chloride, 3～5g/L titanium chloride, 2～4g/L thorium nitrate, 2～4g/L cobalt chloride, 25～30g/L malic acid, 8～11g/L tolysulfonyl hydrazine solution;
(3) dipping: flood 11～17 hours according to carrier and maceration extract equal-volume (V);
(4) dry, roasting: under vacuum normal temperature condition dry 11～17 hours, then in baking oven 110 ℃ dry 6 hours; In negative pressure, being that 0.3MPa, temperature are roasting 3 hours under 700 ℃ of conditions, is then cool drying rapidly under 0.5MPa, normal temperature condition in negative pressure, can obtain the cellular catalyst containing various heavy;
(5) activation: under nitrogen protection condition, pass into hydrogen reducing under 900 ℃ of conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210253193.2A CN102773116B (en) | 2012-07-18 | 2012-07-18 | Method for preparing catalyst capable of promoting ammonia nitrogen conversion in chemical wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210253193.2A CN102773116B (en) | 2012-07-18 | 2012-07-18 | Method for preparing catalyst capable of promoting ammonia nitrogen conversion in chemical wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102773116A CN102773116A (en) | 2012-11-14 |
| CN102773116B true CN102773116B (en) | 2014-05-07 |
Family
ID=47118357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210253193.2A Expired - Fee Related CN102773116B (en) | 2012-07-18 | 2012-07-18 | Method for preparing catalyst capable of promoting ammonia nitrogen conversion in chemical wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102773116B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104148089B (en) * | 2014-07-18 | 2016-02-10 | 常州大学 | A kind of preparations and applicatio method of Processing Paper Wastewater middle and high concentration ammonia nitrogen catalyst |
| CN104229970A (en) * | 2014-08-26 | 2014-12-24 | 常州大学 | Device for treating high-concentration ammonia nitrogen in refinery wastewater by using surface activity catalyst |
| CN106669735A (en) * | 2016-12-27 | 2017-05-17 | 常州大学 | Catalyst for enhancing ammonia conversion in domestic wastewater, and application method thereof |
| CN107096498B (en) * | 2017-05-02 | 2019-09-10 | 杭州师范大学 | A kind of modified zeolite ball preparation method and application |
| CN109647466B (en) * | 2017-10-12 | 2020-10-16 | 中国石油化工股份有限公司 | Catalyst for synthesis reaction of partial anhydride |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5460290A (en) * | 1977-10-21 | 1979-05-15 | Nippon Steel Corp | Production of catalyst for removing nitrogen oxide from exhaustion gas producted in ammonia contact reducing system |
| KR100549778B1 (en) * | 2003-09-27 | 2006-02-08 | 한국전력기술 주식회사 | Vanadium/titania-based catalyst for the removal of nitrogen oxide at low temperature, its uses and method of removing nitrogen oxide using the same |
-
2012
- 2012-07-18 CN CN201210253193.2A patent/CN102773116B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102773116A (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102773116B (en) | Method for preparing catalyst capable of promoting ammonia nitrogen conversion in chemical wastewater | |
| CN107008326B (en) | A kind of preparation method of the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material | |
| CN104009242B (en) | The porous carbon network structure material preparation method of the N doping of a kind of fuel battery cathod catalyst metal/metal oxide load | |
| US11235305B2 (en) | Malic acid and KMnO4-based combined and modified cow dung biogas residue hydrochar preparation method | |
| CN108380214B (en) | A kind of preparation of modified meerschaum and method applied to wastewater treatment | |
| CN108993475B (en) | Ternary composite material heterogeneous light Fenton catalyst and preparation and application thereof | |
| CN108671960B (en) | High hydrothermal stability MOFs catalyst, preparation method thereof and method for preparing chemicals by using MOFs catalyst for cellulose conversion | |
| CN104399500B (en) | Sludge iron-supported multiphase photo-Fenton catalytic material and preparation method thereof | |
| CN104084126A (en) | Preparation method of biomass-based ferroaluminium complex spherical carbon | |
| CN105195092A (en) | Sludge-based charcoal and preparation method thereof | |
| CN104001538A (en) | Nickel-loaded SBA-15 catalyst modified by cerium dioxide and preparation method and application of nickel-loaded SBA-15 catalyst modified by cerium dioxide | |
| CN113120900B (en) | Preparation process of petroleum coke-based activated carbon with high specific surface area | |
| CN106076301B (en) | Preparation method of succinic anhydride modified shaddock peel oil absorption material | |
| CN111644149B (en) | Preparation method of composite modified functional pig manure charcoal | |
| CN103849414B (en) | The method of comprehensive utilization of vinasse | |
| CN102516322B (en) | Method for preparing levoglucosenone with magnetic solid phosphoric acid catalyst | |
| CN114749154B (en) | Preparation method of nitrogen-rich porous carbon-based composite functional material | |
| CN102921432B (en) | Method for preparing catalyst used in promotion of conversion of ammonia nitrogen in oil refining waste water | |
| CN102836748A (en) | Method for preparing ozone oxidation catalyst by utilizing waste beer yeast | |
| CN105170090A (en) | Method for preparing residual active sludge-based active carbon water treatment agent | |
| CN105032475A (en) | Modified ZSM-5 molecular sieve catalyst for preparing light aromatic hydrocarbon through biomass pyrolysis and application | |
| CN102773089B (en) | Preparation method of catalyst for promoting transformation of ammonia nitrogen in garbage leachate wastewater | |
| CN103755717A (en) | Method for preparing LAC through catalytic pyrolysis of cellulose/biomass | |
| CN105170088A (en) | Method for preparing oil-containing sludge-based active carbon water treatment agent | |
| CN109231739B (en) | Biomass phosphorus-locking agent and method for removing phosphorus from bottom mud of polluted water body in situ |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140507 Termination date: 20150718 |
|
| EXPY | Termination of patent right or utility model |