CN109758902A - A kind of defluorinating agent and preparation method thereof - Google Patents
A kind of defluorinating agent and preparation method thereof Download PDFInfo
- Publication number
- CN109758902A CN109758902A CN201910200988.9A CN201910200988A CN109758902A CN 109758902 A CN109758902 A CN 109758902A CN 201910200988 A CN201910200988 A CN 201910200988A CN 109758902 A CN109758902 A CN 109758902A
- Authority
- CN
- China
- Prior art keywords
- defluorinating agent
- earth metal
- defluorinating
- acid
- preparation
- 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.)
- Pending
Links
Abstract
The present invention provides a kind of defluorinating agent and preparation method thereof, the defluorinating agent, on the basis of defluorinating agent gross mass, the defluorinating agent is made of the component of following mass percent: alkaline earth metal compound MO is 3~45%, surplus is aluminium oxide, wherein M is alkali earth metal.Unique structure: since the extracting of diluted acid acts on, after the alkaline earth metal carbonate or hydroxide in alumina base body are dissolved out by diluted acid, various hollow holes can be left, and form macropore, the intracorporal duct of base is effectively connected to；Make defluorinating agent obtained that there is unique Multihollow macroporous structure, reactive material facilitated to pass in and out, at the same provide it is bigger can reaction surface, defluorinating agent hole obtained by this method, which holds, is greater than 1.0ml/g；It is active high: alkaline earth metal compound can be obtained due to the decomposition of alkali salt in duct due to unique Multihollow macroporous structure, and during after baking, the high activity defluorinating agent high to fluoride purification efficiency is thus made.
Description
Technical field
The invention belongs to technical field of waste gas treatment, and in particular to a kind of defluorinating agent and preparation method thereof.
Background technique
Waste gas containing fluoride typically refers to the industrial waste gas containing hydrogen fluoride, ocratation etc. containing fluorine element.In recent years, with
The fast development of the industries such as chemical industry, metallurgy, building materials, thermoelectricity is also significantly increased the consumption of various raw ores, contains fluorine ingredient
Ore raw materials calcine at high temperature, melt or chemically react, a large amount of fluorine-containing industrial waste gases can be released.It is fluorine-containing useless
Diffusion, the transfer of gas, including the sedimentation being mixed in acid rain, can form the pollution to atmosphere, water body, soil, and to building
Object, the corrosion of equipment and destruction of ozone layer etc..It is all these, other than causing various harm to crowd, also animals and plants are made
Object death, plant necrosis may be actuated at harm, when fluoride pollution is serious.Therefore, waste gas containing fluoride caused by industrial production must be net
Chemical combination lattice could discharge.
China possesses the most abundant phosphate rock resource in the world, and reserves, yield and the occupation rate of market of yellow phosphorus occupy the world
First.Phosphorus smelting process can generate a large amount of tail gas, these tail gas CO is up to 85%, have high utility value.Yellow phosphorus
After tail gas is purified, it can be used as the valable starting materials of one chemical industry of carbon, for producing the higher chemical products of added value.But yellow phosphorus tail
Gas impurity is numerous, and main component is CO in tail gas, and other impurities have inorganic sulfur (H2S, S, SO2), organic sulfur (CH4SH, COS), phosphorus
Compound (PH3、P4), fluoride (HF, SiF4)、As H3、CH4、CO2、O2、N2, cyanide and raw material dust etc..Therefore, yellow phosphorus
The premise and technical bottleneck of tail gas comprehensive utilization are the deep purifyings of yellow phosphoric tail gas, at present about about the fluoride in unstripped gas
Removing research seldom, almost without applicable product.
Fluorine belongs to halogen family, HF, SiF for being predominantly in the form of volatile in unstripped gas4, there is lone electron
It is right, it is the serious poisonous substance of catalyst, therefore must be removed in depth before comprehensive utilization synthesizes chemical products.
The defluorinating agent studied extensively at present mainly has three classes: the first kind is in phosphoric acid by wet process industry removing phosphoric acid solution
Small-scale inorganic fluorine impurity, it is therefore an objective to improve the grade of phosphoric acid；Second class is for micro- in animal feed industries removing solid
Measure inorganic fluorine impurity, it is therefore an objective to reduce fluorine content, reduce the harm to raised animal；Third class is for micro- in drinking water
Measure the removing of inorganic fluorine impurity, it is therefore an objective to reduce fluorine content, make up to national standard, avoid the harm to human body.
The defluorinating agent of these three types is helpless to the removing of fluoride in gas.Have in a small amount of removing flue gas and is fluorinated
The research of object, usually in such a way that the alkaline matters such as alkaline solution bubble absorption or sprinkling lime absorb, there are purification efficiencies
It is low, the subsequent secondary pollution problem for having waste water or waste sludge discharge etc..
It is added it can be seen that being suitable for unstripped gas not yet both at home and abroad and being particularly suitable for yellow phosphoric tail gas deep purifying height
The defluorinating agent of value chemical product；Therefore it develops and a kind of be suitable for unstripped gas to be particularly suitable for yellow phosphoric tail gas deep purifying height attached
The defluorinating agent of value added chemical products has important practical significance.
Summary of the invention
It is suitable for unstripped gas the purpose of the present invention is to provide one kind and is particularly suitable for yellow phosphoric tail gas deep purifying system height
The defluorinating agent and preparation method thereof of added value chemical products, the defluorinating agent have unique structure, purification efficiency are high, room temperature uses,
The features such as at low cost, can meet the removing requirement of unstripped gas especially yellow phosphorus tail fluoride.
To achieve the above object, a kind of defluorinating agent of the present invention, on the basis of defluorinating agent gross mass, the defluorinating agent by with
The component of lower mass percent is made: alkaline earth metal compound MO is 3~45%, and surplus is aluminium oxide, wherein M is alkaline earth gold
Belong to element.
On the basis of above scheme preferably, the alkali earth metal is at least one of magnesium, calcium, strontium and barium.
On the basis of above scheme preferably, the aluminium oxide is matrix, and described matrix is in the stereo structure of hollow shape, the base
Body is equipped with duct, and the alkaline earth metal compound is deposited in the duct, and the Kong Rong is greater than 1.0ml/g.
The present invention also provides a kind of preparation methods of defluorinating agent, include the following steps,
Step S1 presses the carbonate or hydroxide of the boehmite of powdery and alkaline-earth metal such as claim 1 institute
Ratio is stated, is sufficiently mixed, Aluminum sol is added and is sufficiently mixed, obtains plastic dough；
Step S2, to the plastic dough extruded moulding that the step S1 is obtained, and 100~150 DEG C dry 2 hours with
On, then roast 2~4 hours at 500~550 DEG C, it is cooling；
The cooling obtained plastic dough of the step 2 is immersed in dilute acid soln and carries out sour extracting by step S3, and acid is taken out
Mentioning the time is 1~4 hour；
Plastic dough after step S3 acid extracting is taken out, is drained, done at a temperature of 100~150 DEG C by step S4
It dry 2 hours or more, is carried out after baking 2~4 hours at a temperature of 600~700 DEG C.
On the basis of above scheme preferably, the concentration in terms of Al2O3 of the Aluminum sol in the step S1 is 5~20%.
On the basis of above scheme preferably, the dilute acid soln is at least one in dust technology, spirit of vinegar or dilute formic acid
Kind, the concentration of the dilute acid soln is 0.5~5.0mol/L；The liquid-solid ratio of the diluted acid and plastic dough be 2.0~
10.0ml/g。
On the basis of above scheme preferably, defluorinating agent use condition are as follows: normal pressure, 0~50 DEG C of reaction temperature, air speed 1000~
3000h-1。
Compared with prior art, the present invention the beneficial effect is that:
1, unique structure: since the extracting of diluted acid acts on, the alkaline earth metal carbonate or hydroxide in alumina base body
After being dissolved out by diluted acid, various hollow holes can be left, and form macropore, the intracorporal duct of base is effectively connected to；Make to make
Defluorinating agent there is unique Multihollow macroporous structure, facilitate reactive material to pass in and out, at the same provide it is bigger can reaction surface,
Defluorinating agent hole obtained by this method, which holds, is greater than 1.0ml/g.
2, activity is high: due to unique Multihollow macroporous structure, and due to alkaline earth in duct during after baking
The alkaline earth metal compound of high activity can be obtained in the decomposition of metal salt, and the height for being thus made high to fluoride purification efficiency is living
Property defluorinating agent.Under normal temperature conditions, it in inlet gas when HF content≤3000ppm, exports HF content in purified gas and is less than
0.1ppm, fluorine holds up to 12% at this time.
3, cheap and easy to get, it is low in cost.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of the preparation method of defluorinating agent of the invention.
Specific embodiment
By the technology contents that the present invention will be described in detail, construction feature, reached purpose and efficacy, hereby enumerates embodiment below
And attached drawing is cooperated to be explained in detail.
In order to illustrate the defluorination effect of defluorinating agent of the invention, following embodiment 1-19 shown in Fig. 1 are please referred to as the present invention
Defluorinating agent preparation example, and the institute=embodiment is merely to illustrate the present invention rather than for limiting the present invention.
Embodiment 1
1, it weighs containing 64.0 grams of Al2O3Boehmite powder and containing CaO30.0 grams of calcium carbonate powder, by two
Person is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 10%, and mixed grind is at plastic dough；
2, will be 8 hours dry in 100 DEG C after above-mentioned dough extruded moulding, then before roasting 2 hours at 550 DEG C up to defluorinating agent
Drive object；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute nitric acid solution that 500ml concentration is 2.0mol/L, acid extracting 2 is small
When；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 3 hours dry in 120, it is small in 600 DEG C of after bakings 2
When, it is cooling to obtain defluorinating agent A.
Embodiment 2
1, it weighs containing 77.0 grams of Al2O3Boehmite powder and containing CaO20.0 grams of calcium carbonate powder, by two
Person is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 5%, and mixed grind is at plastic dough；
2, will be 2 hours dry in 150 DEG C after above-mentioned dough extruded moulding, then before roasting 4 hours at 500 DEG C up to defluorinating agent
Drive object；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute nitric acid solution that 1000ml concentration is 0.7mol/L, acid extracting 4
Hour；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 2 hours dry in 150 DEG C, in 600 DEG C of after bakings 4
Hour, it is cooling to obtain defluorinating agent B.
Embodiment 3
1, it weighs containing 47.0 grams of Al2O3Boehmite powder and containing SrO50.0 grams of strontium carbonate powder, by two
Person is uniformly mixed, and Al is added2O3Content is 65 grams of Aluminum sol of 20%, and mixed grind is at plastic dough；
2, will be 3 hours dry in 120 DEG C after above-mentioned dough extruded moulding, then before roasting 3 hours at 520 DEG C up to defluorinating agent
Drive object；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute nitric acid solution that 200ml concentration is 0.85mol/L, acid extracting 1
Hour；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 3 hours dry in 120 DEG C, in 650 DEG C of after bakings 3
Hour, it is cooling to obtain defluorinating agent C.
Embodiment 4
1, it weighs containing 64.0 grams of Al2O3Boehmite powder and containing CaO30.0 grams of calcium hydroxide powder, will
The two is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 10%, and mixed grind is at plastic dough；
2, will be 6 hours dry in 120 DEG C after above-mentioned dough extruded moulding, then before roasting 2 hours at 500 DEG C up to defluorinating agent
Drive object；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute nitric acid solution that 800ml concentration is 1.0mol/L, acid extracting 3 is small
When；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 4 hours dry in 120 DEG C, in 620 DEG C of after bakings 3
Hour, it is cooling to obtain defluorinating agent D.
Embodiment 5
1, it weighs containing 54.0 grams of Al2O3Boehmite powder and containing MgO40.0 grams of magnesium carbonate powder, by two
Person is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 10%, and mixed grind is at plastic dough；
2, will be 6 hours dry in 120 DEG C after above-mentioned dough extruded moulding, then before roasting 2 hours at 500 DEG C up to defluorinating agent
Drive object；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute nitric acid solution that 300ml concentration is 1.5mol/L, acid extracting 4 is small
When；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 6 hours dry in 110 DEG C, in 600 DEG C of after bakings 4
Hour, it is cooling to obtain defluorinating agent E.
Embodiment 6
1, it weighs containing 54.0 grams of Al2O3Boehmite powder and containing MgO40.0 grams of magnesium hydrate powder, will
The two is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 10%, and mixed grind is at plastic dough；
2, will be 6 hours dry in 120 DEG C after above-mentioned dough extruded moulding, then before roasting 2 hours at 500 DEG C up to defluorinating agent
Drive object；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute acetic acid solution that 300ml concentration is 5.0mol/L, acid extracting 4 is small
When；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 6 hours dry in 110 DEG C, in 700 DEG C of after bakings 4
Hour, it is cooling to obtain defluorinating agent F.
Embodiment 7
1, it weighs containing 61.0 grams of Al2O3Boehmite powder and containing BaO40.0 grams of barium carbonate powder, by two
Person is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 15%, and mixed grind is at plastic dough；
2, will be 6 hours dry in 120 DEG C after above-mentioned dough extruded moulding, then before roasting 2 hours at 500 DEG C up to defluorinating agent
Drive object；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute nitric acid solution that 800ml concentration is 0.5mol/L, acid extracting 3 is small
When；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 6 hours dry in 110 DEG C, in 600 DEG C of after bakings 4
Hour, it is cooling to obtain defluorinating agent G.
Embodiment 8
1, it weighs containing 61.0 grams of Al2O3Boehmite powder and containing BaO40.0 grams of barium hydroxide powder, will
The two is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 15%, and mixed grind is at plastic dough；
2, will be 10 hours dry in 100 DEG C after above-mentioned dough extruded moulding, then 3 hours are roasted at 540 DEG C up to defluorinating agent
Predecessor；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute formic acid solution that 300ml concentration is 1.0mol/L, acid extracting 4 is small
When；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 4 hours dry in 150 DEG C, in 680 DEG C of after bakings 4
Hour, it is cooling to obtain defluorinating agent H.
Embodiment 9
1, it weighs containing 61.0 grams of Al2O3Boehmite powder and containing SrO40.0 grams of strontium hydroxide powder, will
The two is uniformly mixed, and Al is added2O3Content is 60 grams of Aluminum sol of 15%, and mixed grind is at plastic dough；
2, will be 10 hours dry in 125 DEG C after above-mentioned dough extruded moulding, then 3 hours are roasted at 550 DEG C up to defluorinating agent
Predecessor；
3, above-mentioned defluorinating agent predecessor is soaked in the dilute acetic acid solution that 300ml concentration is 0.8mol/L, acid extracting 4 is small
When；
4, the defluorinating agent predecessor after acid extracting taken out, drained, it is 3 hours dry in 140 DEG C, in 700 DEG C of after bakings 4
Hour, it is cooling to obtain defluorinating agent I.
Testing example
The present embodiment is the test effect for testing defluorinating agent A~I removing HF performance.Defluorinating agent strength test is in intelligent intensity
It is measured on instrument, in terms of side pressure strength.Defluorinate performance test carries out in Φ 28mm polytetrafluoro reaction tube, by defluorinating agent A~I with cutting
The ratio of height to diameter that knife is cut into is approximately equal to 1 particle, respectively 30ml is taken to be fitted into reactor, gas CO-N2Gaseous mixture, volume space velocity
1000~3000h-1, supplying HF content is 3000ppm, and 0~50 DEG C of reaction temperature, pressure is normal pressure, and fluorine capacity is with exit gas
Defluorinating agent adsorbance when middle HF content is greater than 0.1ppm, which penetrates fluorine, which to be held, indicates.The result is shown in tables 1:
Table 1, each embodiment defluorinating agent the performance test results
In conclusion only the preferred embodiments of the invention, is not limited the scope of protection of the present invention with this, it is all according to the present invention
Equivalent changes and modifications made by the scope of the patents and description are all within the scope of the invention patent covers.
Claims (7)
1. a kind of defluorinating agent, which is characterized in that on the basis of defluorinating agent gross mass, the defluorinating agent is by following mass percent
Component is made: alkaline earth metal compound MO is 3~45%, and surplus is aluminium oxide, wherein M is alkali earth metal.
2. a kind of defluorinating agent as described in claim 1, which is characterized in that the alkali earth metal is in magnesium, calcium, strontium and barium
At least one.
3. a kind of defluorinating agent as described in claim 1, which is characterized in that the aluminium oxide is matrix, and described matrix is in hollow
The stereo structure of shape, described matrix are equipped with duct, and the alkaline earth metal compound is deposited in the duct, and the Kong Rong great
In 1.0ml/g.
4. a kind of preparation method of defluorinating agent, which is characterized in that include the following steps,
Step S1, by the carbonate or hydroxide of the boehmite of powdery and alkaline-earth metal by ratio as described in claim 1
Example, is sufficiently mixed, and Aluminum sol is added and is sufficiently mixed, obtains plastic dough；
Step S2, to the plastic dough extruded moulding that the step S1 is obtained, and 100~150 DEG C dry 2 hours or more,
It is roasted 2~4 hours at 500~550 DEG C again, it is cooling；
The cooling obtained plastic dough of the step 2 is immersed in dilute acid soln and carries out sour extracting, when acid extracts by step S3
Between be 1~4 hour；
Plastic dough after step S3 acid extracting is taken out, is drained by step S4, dry 2 at a temperature of 100~150 DEG C
Hour or more, it is carried out after baking 2~4 hours at a temperature of 600~700 DEG C.
5. a kind of preparation method of defluorinating agent as claimed in claim 4, which is characterized in that Aluminum sol in the step S1 with
It is 5~20% that Al2O3, which counts concentration,.
6. a kind of preparation method of defluorinating agent as claimed in claim 4, which is characterized in that the dilute acid soln is dilute nitre
At least one of acid, spirit of vinegar or dilute formic acid, the concentration of the dilute acid soln are 0.5~5.0mol/L；The diluted acid with
The liquid-solid ratio of plastic dough is 2.0~10.0ml/g.
7. a kind of preparation method of defluorinating agent as claimed in claim 4, which is characterized in that defluorinating agent use condition are as follows: normal pressure,
0~50 DEG C of reaction temperature, 1000~3000h of air speed-1。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910200988.9A CN109758902A (en) | 2019-03-16 | 2019-03-16 | A kind of defluorinating agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910200988.9A CN109758902A (en) | 2019-03-16 | 2019-03-16 | A kind of defluorinating agent and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109758902A true CN109758902A (en) | 2019-05-17 |
Family
ID=66459263
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910200988.9A Pending CN109758902A (en) | 2019-03-16 | 2019-03-16 | A kind of defluorinating agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109758902A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632368B2 (en) * | 2000-02-23 | 2003-10-14 | Marc Blachman | Process for removing fluorides from fluids |
| CN1569311A (en) * | 2003-07-24 | 2005-01-26 | 中国疾病预防控制中心环境与健康相关产品安全所 | Highly effective defluorination agent for combustion coal smoke and preparation method thereof |
| CN101422690A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Gas dechlorination agent and preparation method thereof |
| CN104128162A (en) * | 2014-07-02 | 2014-11-05 | 浙江巨化股份有限公司 | Load-type fluorine remover used for removing hydrogen fluoride in hydrogen chloride gas and preparation method thereof |
| CN104841365A (en) * | 2015-04-29 | 2015-08-19 | 长沙清能环保科技有限公司 | Composite fluorine removal agent and preparation method |
| CN108380170A (en) * | 2018-03-19 | 2018-08-10 | 中南大学 | A kind of aluminium oxide of doped metallic oxide and its preparation and application |
-
2019
- 2019-03-16 CN CN201910200988.9A patent/CN109758902A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6632368B2 (en) * | 2000-02-23 | 2003-10-14 | Marc Blachman | Process for removing fluorides from fluids |
| CN1569311A (en) * | 2003-07-24 | 2005-01-26 | 中国疾病预防控制中心环境与健康相关产品安全所 | Highly effective defluorination agent for combustion coal smoke and preparation method thereof |
| CN101422690A (en) * | 2007-10-31 | 2009-05-06 | 中国石油化工股份有限公司 | Gas dechlorination agent and preparation method thereof |
| CN104128162A (en) * | 2014-07-02 | 2014-11-05 | 浙江巨化股份有限公司 | Load-type fluorine remover used for removing hydrogen fluoride in hydrogen chloride gas and preparation method thereof |
| CN104841365A (en) * | 2015-04-29 | 2015-08-19 | 长沙清能环保科技有限公司 | Composite fluorine removal agent and preparation method |
| CN108380170A (en) * | 2018-03-19 | 2018-08-10 | 中南大学 | A kind of aluminium oxide of doped metallic oxide and its preparation and application |
Non-Patent Citations (1)
| Title |
|---|
| 陈大明: "《先进陶瓷材料的注凝技术与应用》", 30 November 2011, 国防工业出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105238927B (en) | A kind of titanium based lithium-ion sieve adsorbant, its presoma, preparation method and application | |
| CN105289493B (en) | The straw-stem active charcoal adsorbent and its application that the ferrimanganic that one kind is used for As (III) absorption is modified | |
| CN103521174B (en) | Indoor air purification material and preparation method thereof | |
| CN109173976A (en) | It is a kind of to efficiently separate the synthetic method for extracting the metatitanic acid type lithium adsorbent of lithium in brine | |
| CN103864123B (en) | A kind of water column forming method of ball-aluminium oxide | |
| CN111204732B (en) | Transition metal doped porous carbon material and preparation method and application thereof | |
| CN104923150A (en) | Lanthanum-loaded activated aluminium oxide defluorinating adsorbent and preparation method thereof | |
| CN108238832B (en) | Method for preparing soluble potassium and calcium silicate soil conditioner by alkali-activated potassium feldspar | |
| CN106799205A (en) | A kind of preparation method of drinking water fluorine removal arsenic adsorbent | |
| CN107583606A (en) | The volcanic rock base porous ceramic grain and preparation method and application of high-effective defluorination | |
| CN103316624B (en) | Dephosphorization agent and preparation method thereof | |
| CN112723493B (en) | Cobaltosic oxide/magnesium oxide-titanium composite electrode, preparation method and application thereof, and treatment method of ammonia nitrogen-containing wastewater | |
| CN112591782B (en) | Conversion and purification method of low-consumption dihydrate phosphogypsum | |
| CN113820187A (en) | Passivation experiment method for applying attapulgite-rice straw composite material to heavy metal contaminated soil | |
| CN106629757A (en) | Method for removing nitrogen and phosphorus from water by using calcium silicate prepared from silicon recycled from red mud | |
| CN109758902A (en) | A kind of defluorinating agent and preparation method thereof | |
| CN104192902A (en) | Preparation method of modified mesoporous TiO2 for removing fluorinion in lead and zinc smelting waste water | |
| CN106390930A (en) | Method for preparing silver-loaded activated carbon through glycine and silver nitrate complexation | |
| CN105819564B (en) | A kind of processing method of paraformaldehyde waste water | |
| EP3838847B1 (en) | Composite material and method of removing fluorine in waste liquid | |
| CN107416845A (en) | A kind of method that potassium feldspar produces white silica gel | |
| CN109289784B (en) | Defluorination compound adsorption material prepared from garlic straw waste and application method thereof | |
| CN107308930A (en) | A kind of denitrating catalyst and preparation method thereof | |
| CN108993382B (en) | Defluorination material based on mushroom dregs and regeneration method thereof | |
| CN111974349A (en) | Porous lignin hydrothermal carbon-based phosphate adsorbent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190517 |