CN103182236B - A kind of high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof - Google Patents
A kind of high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof Download PDFInfo
- Publication number
- CN103182236B CN103182236B CN201110446769.2A CN201110446769A CN103182236B CN 103182236 B CN103182236 B CN 103182236B CN 201110446769 A CN201110446769 A CN 201110446769A CN 103182236 B CN103182236 B CN 103182236B
- Authority
- CN
- China
- Prior art keywords
- feooh
- sulfur capacity
- water
- preparation
- desulfurizer
- 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.)
- Active
Links
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of high-strength water-resistance high-sulfur capacity desulfurizer, described desulfurizing agent is prepared from by the raw material of following weight portion: FeOOH, 90-98 part; Sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium, 2-4 part; Starch, 0.2-2 part.The present invention also further discloses the preparation method of above-mentioned desulfurizing agent on the basis of the above.The FeOOH desulfurizer utilizing this preparation method to prepare not only has higher Sulfur capacity, but also has higher mechanical strength and resistance to water, and applicable desulfurization scope is more extensive.
Description
Technical field
The present invention relates to one and there is high strength, enhanced water resistance, high-sulfur capacity desulfurizer, belong to technical field of desulfuration purification.
Background technology
Fe-series desulfurizing agent uses one of comparatively general desulfurizing agent, Fe-series desulfurizing agent is mainly using ferriferous oxide as the active component of desulfurizing agent, described ferriferous oxide comprise in tri-iron tetroxide, di-iron trioxide and FeOOH one or more, in above-mentioned ferriferous oxide, FeOOH is again because have higher desulphurizing activated and be widely used.
In prior art, a kind of thinking preparing amorphous FeOOH in laboratory is disclosed in Chinese science and technology document " a kind of sign of high sulfur capacity ferric oxide desulfurizer active component " (see " national gas purification information station technical conferences collection of thesis in 2006 " 107-111 page), and the Sulfur capacity of described amorphous FeOOH is measured, realize result to show, the Sulfur capacity of described amorphous FeOOH is 56.5%.
But the preparation of above-mentioned amorphous FeOOH is only limited to laboratory stage, the above-mentioned amorphous FeOOH prepared is powdery, although Sulfur capacity is higher, the amorphous FeOOH of powdery is not suitable for industrial applications.And in actual applications, desulfurizing agent is except possessing higher Sulfur capacity, also should there be enough mechanical strengths and water resistance, because the desulfurizing agent of intensity and water resistance difference in use easily occurs broken or runs into the phenomenon that steam produces caking, thus have a strong impact on its desulfurized effect.Good mechanical strength and water resistance is possessed in order to reach; prior art is the preparation method to amorphous FeOOH be optimized; usually a certain amount of binding agent can be added in the preparation; as Chinese patent literature CN101898110A discloses a kind of high sulfur capacity dry-desulphurizer; described desulfurizing agent is made up of the amorphous FeOOH material of 88-93wt% and the organic binder bond of 7-12wt%; wherein; described organic binder bond is sodium carboxymethylcellulose; sesbania powder, one or more in cellulose powder.This technology improves the mechanical strength of described amorphous FeOOH desulfurizer to a certain extent by adding methylcellulose sodium salt, sesbania powder or cellulose powder, but the water resistance of described desulfurizing agent is still poor, still there will be the problem of fragmentation or caking when being used in the occasion of the high water contents such as such as desulfurization of water gas.
Summary of the invention
In order to solve the binding agent not yet occurred by adding suitable proportion, while not reducing described desulfurizing agent Sulfur capacity, the problem of the technology of desulfurizing agent mechanical strength and water resistance can also be improved, in the present invention, the additive of described desulfurizing agent is optimized, a kind of FeOOH desulfurizer with high strength, enhanced water resistance, high sulfur capacity is provided, meanwhile, present invention also offers its preparation method of described desulfurizing agent.
The technical scheme of high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof described in the present invention is:
Described desulfurizing agent is prepared from by the raw material of following weight portion:
FeOOH, 90-98 part;
Sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium, 2-4 part;
Starch, 0.2-2 part.
Described raw material also comprises the active carbon of 2-3 weight portion.
Described FeOOH is 94-96 weight portion.
Described sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium are 2-3 weight portion, and described starch is 0.5-1 weight portion.
Described FeOOH is a kind of in nano-spun capitate alpha-feooh or amorphous FeOOH or two kinds.
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer, comprising:
(1) wiring solution-forming that the sodium carboxymethylcellulose of specified quantitative or hydroxypropyl methylcellulose sodium is added to the water is stand-by;
(2) in step (1) gained solution, add the FeOOH of specified quantitative and the FeOOH of starch or specified quantitative and active carbon and starch mix;
(3) mixture obtained in step (2) is after kneading, extrusion, drying.
In described step (1), the consumption of water is the 35-50% of FeOOH weight.
Kneading time in described step (3) is at least 15-30 minute.
Baking temperature in described step (3) is 60 DEG C ~ 90 DEG C.
The advantage of desulfurizing agent of the present invention is:
(1) desulfurizing agent of the present invention, by adding the starch of Sq and sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium, these two kinds of materials and FeOOH active component mutually act synergistically and fully disperse and combine closely in pore passage structure, and appropriate filling has been carried out to inside, duct, improve mechanical strength and the resistance to water of desulfurizing agent on the whole, desulfurizing agent poach in the present invention 4 hours is not cracked, and long-term water logging is not fallen apart.Desulfurizing agent of the prior art is difficult to take into account high mechanical properties, resistance to water and high sulfur capacity simultaneously, and the present inventor is by long-term research, select suitable additive and consumption thereof, make described desulfurizing agent can also reach higher Sulfur capacity while guarantee high mechanical properties, water resistance.
(2) the present invention also arranges the active carbon that described raw material comprises 2-3 weight portion, and the interpolation of described active carbon can optimize the pore passage structure of described desulfurizing agent further.
In addition, FeOOH desulfurizer of the present invention, further preferred described additive is hydroxypropyl methylcellulose sodium, 2-4 part; Starch, 0.5-1 part; Active carbon, 2-3 weight portion.The present inventor is found by research, by using appropriate hydroxypropyl methylcellulose sodium, starch and active carbon, can reach more excellent result of use.The another one advantage that desulfurizing agent of the present invention has is, the additive added can by burning removing, after desulfurization after used, useless agent does not remain, and the agent of giving up of the FeOOH desulfurizer therefore in the present invention can be used for remanufacture sulphur and iron oxide red, adds economic benefit.
(3) FeOOH desulfurizer of the present invention, described FeOOH is a kind of in nano-spun capitate alpha-feooh or amorphous FeOOH or two kinds, and reason is that described nano-spun capitate alpha-feooh or amorphous FeOOH have better desulphurizing activated compared to the FeOOH of other crystal formation.
Detailed description of the invention
embodiment 1
High-strength water-resistant high-sulfur capacity desulfurizer in the present embodiment is prepared from by the raw material of following weight portion:
Nano-spun capitate alpha-feooh, 90g;
Sodium carboxymethylcellulose, 4g;
Starch, 0.2.
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof, comprising:
(1) 4g sodium carboxymethylcellulose is joined wiring solution-forming in 31.5 grams of water stand-by;
(2) in step (1) gained solution, add 90g FeOOH, 0.2g starch mix, and the granularity of described nano-spun capitate Alpha-hydroxy iron oxide is 80-100 order;
(3) mixture obtained in step (2) is dried in 80 DEG C after kneading, extrusion, and drying time is 3h, obtains high-sulfur capacity desulfurizer A of the present invention.
embodiment 2
High-strength water-resistant high-sulfur capacity desulfurizer in the present embodiment is prepared from by the raw material of following weight portion:
Amorphous FeOOH, 98g;
Sodium carboxymethylcellulose, 4g;
Starch, 2g.
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof, comprising:
(1) 4g sodium carboxymethylcellulose is joined wiring solution-forming in 40 grams of water stand-by;
(2) in step (1) gained solution, add 98g FeOOH, 2g starch mix, and the granularity of described amorphous FeOOH is 80-100 order;
(3) mixture obtained in step (2) is dried in 90 DEG C after kneading, extrusion, and drying time is 3h, obtains high-sulfur capacity desulfurizer B of the present invention.
embodiment 3
High-strength water-resistant high-sulfur capacity desulfurizer in the present embodiment is prepared from by the raw material of following weight portion:
Amorphous FeOOH, 94g;
Sodium carboxymethylcellulose, 2g;
Starch, 0.5g;
Active carbon, 2g.
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof, comprising:
(1) 2g sodium carboxymethylcellulose is joined wiring solution-forming in 47 grams of water stand-by;
(2) in step (1) gained solution, add the FeOOH of 94g, 0.5g starch and 2g active carbon mix, the granularity of described amorphous FeOOH is 80-100 order;
(3) mixture obtained in step (2) is dried in 90 DEG C after kneading, extrusion, and drying time is 3h, obtains high-sulfur capacity desulfurizer C of the present invention.
embodiment 4
High-strength water-resistant high-sulfur capacity desulfurizer in the present embodiment is prepared from by the raw material of following weight portion:
Nano-spun capitate Alpha-hydroxy iron oxide, 95g;
Hydroxypropyl methylcellulose sodium, 2.5g;
Starch, 1g;
Active carbon, 2.5g.
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof, comprising:
(1) 2.5g hydroxypropyl methylcellulose sodium is joined wiring solution-forming in 40 grams of water stand-by;
(2) in step (1) gained solution, add the FeOOH of 95g, 1g starch and 2.5g active carbon mix, the granularity of described nano-spun capitate Alpha-hydroxy iron oxide is 80-100 order;
(3) mixture obtained in step (2) is dried in 90 DEG C after kneading, extrusion, and drying time is 3h, obtains high-sulfur capacity desulfurizer D of the present invention.
embodiment 5
High-strength water-resistant high-sulfur capacity desulfurizer in the present embodiment is prepared from by the raw material of following weight portion:
Nano-spun capitate Alpha-hydroxy iron oxide, 96g;
Sodium carboxymethylcellulose, 3g;
Starch, 1;
Active carbon, 3g.
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof, comprising:
(1) 3g sodium carboxymethylcellulose is joined wiring solution-forming in 40 grams of water stand-by;
(2) in step (1) gained solution, add the FeOOH of 96g, 1g starch and 3g active carbon mix, the granularity of described nano-spun capitate Alpha-hydroxy iron oxide is 80-100 order;
(3) mixture obtained in step (2) is dried in 90 DEG C after kneading, extrusion, and drying time is 3h, obtains high-sulfur capacity desulfurizer E of the present invention.
embodiment 6
High-strength water-resistant high-sulfur capacity desulfurizer in the present embodiment is prepared from by the raw material of following weight portion:
Nano-spun capitate Alpha-hydroxy iron oxide, 95g;
Sodium carboxymethylcellulose, 3g;
Starch, 0.5;
Active carbon, 2g.
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof, comprising:
(1) 3g sodium carboxymethylcellulose is joined wiring solution-forming in 39 grams of water stand-by;
(2) in step (1) gained solution, add the FeOOH of 95g, 0.5g starch and 2g active carbon mix, the granularity of described nano-spun capitate Alpha-hydroxy iron oxide is 80-100 order;
(3) mixture obtained in step (2) is dried in 90 DEG C after kneading, extrusion, and drying time is 3h, obtains high-sulfur capacity desulfurizer F of the present invention.
comparative example
1. take 9.8g cellulose powder to be dissolved in suitable quantity of water and to stir into paste, add the amorphous FeOOH of 98g and mix, said mixture material is put into kneader, kneading carried out extruded moulding after 20 minutes, dry in 80 DEG C above-mentioned article shaped, drying time is 5h, obtains desulfurizing agent H.
2. take 5g sodium carboxymethylcellulose to be dissolved in suitable quantity of water and to stir into paste, add the amorphous FeOOH of 95g to mix, said mixture material is put into kneader, kneading carried out extruded moulding after 20 minutes, above-mentioned article shaped is dried in 80 DEG C, drying time is 5h, obtains desulfurizing agent G.
Desulfurizing agent G, H in above-mentioned comparative example, in process gas band water more (in as coal gas a large amount of saturation water) situation, can cause desulfurizing agent efflorescence, produce caking phenomenon, increase bed pressure drop, so that desulfuration efficiency declines, and even cause stopping work.
activity rating example
Get each 5g of desulfurizing agent A ~ H that above-described embodiment 1 to embodiment 6 and comparative example prepare, under normal temperature (refer to environment temperature, be generally-5 DEG C to 45 DEG C) normal pressure (environmental pressure is generally 1 atmospheric pressure), with containing H
2s is that the Standard Gases of 40000ppm carries out evaluation test.Wherein, qualitative detection, can detect outlet sulphur by autogamy 1% liquor argenti nitratis ophthalmicus; Quantitative detection, the comprehensive Microcoulomb instrument of domestic WK-2C (Jiangsu Electrical Analysis Instrument Factory's production) can be adopted to detect, and the detection limit of this instrument is 0.2ppm.Detection for the desulfurizing agent mechanical strength prepared in above-described embodiment measures by evaluating its pressure measurement intensity, and wherein the radial anti-crushing power mean value of particle is pressed HG/T2782 standard and performed mensuration.Testing result is as follows:
As can be seen from above-mentioned test result, FeOOH desulfurizer of the present invention, uses at normal temperatures and pressures, and its Sulfur capacity can up to more than 50%, and its pressure measurement intensity can up to more than 119N/cm.And although desulfurizing agent G Sulfur capacity in comparative example is higher, mechanical strength obviously declines, and poor water resistance; Although another comparative example H mechanical strength is higher, Sulfur capacity is very low again, and resistance to water is very poor equally, and the CMC excess added is described; Therefore desulfurizing agent of the present invention to possess skills effect compared to the desulfurizing agent in comparative example.
Although the present invention is elaborated it by above-mentioned specific embodiment; but; those skilled in the art should be understood that and made on this basis not exceed any form of claims and the change of details, all belong to invention which is intended to be protected.
Claims (8)
1. a high-strength water-resistant high-sulfur capacity desulfurizer, is characterized in that, described desulfurizing agent is prepared from by the raw material of following weight portion:
FeOOH, 90-98 part;
Sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium, 2-4 part;
Starch, 0.2-2 part;
Active carbon, 2-3 weight portion;
The preparation method of described high-strength water-resistant high-sulfur capacity desulfurizer, comprising:
(1) wiring solution-forming that sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium is added to the water is stand-by;
(2) in step (1) gained solution, FeOOH is added and active carbon, starch mix;
(3) mixture obtained in step (2) is after kneading, extrusion, drying.
2. high-strength water-resistant high-sulfur capacity desulfurizer according to claim 1, is characterized in that, described FeOOH is 94-96 weight portion.
3. high-strength water-resistant high-sulfur capacity desulfurizer according to claim 1 and 2, is characterized in that, described sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium are 2-3 weight portion, and described starch is 0.5-1 weight portion.
4. high-strength water-resistant high-sulfur capacity desulfurizer according to claim 1, is characterized in that: described FeOOH is a kind of in nano-spun capitate alpha-feooh or amorphous FeOOH or two kinds.
5., according to the preparation method of the arbitrary described high-strength water-resistant high-sulfur capacity desulfurizer of claim 1-4, comprising:
(1) wiring solution-forming that sodium carboxymethylcellulose or hydroxypropyl methylcellulose sodium is added to the water is stand-by;
(2) in step (1) gained solution, FeOOH is added and active carbon, starch mix;
(3) mixture obtained in step (2) is after kneading, extrusion, drying.
6. according to preparation method according to claim 5, it is characterized in that, in described step (1), the consumption of water is the 35-50% of FeOOH weight.
7. according to preparation method according to claim 6, it is characterized in that, the kneading time in described step (3) is at least 15-30 minute.
8. preparation method according to claim 7, is characterized in that, the baking temperature in described step (3) is 60 DEG C ~ 90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110446769.2A CN103182236B (en) | 2011-12-28 | 2011-12-28 | A kind of high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110446769.2A CN103182236B (en) | 2011-12-28 | 2011-12-28 | A kind of high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103182236A CN103182236A (en) | 2013-07-03 |
| CN103182236B true CN103182236B (en) | 2016-03-30 |
Family
ID=48673833
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110446769.2A Active CN103182236B (en) | 2011-12-28 | 2011-12-28 | A kind of high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103182236B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706227B (en) * | 2013-12-23 | 2017-07-21 | 北京三聚环保新材料股份有限公司 | A kind of preparation method of normal temperature compound desulfurizer |
| CN110115921A (en) * | 2019-05-27 | 2019-08-13 | 沈阳三聚凯特催化剂有限公司 | A kind of Fe-series desulfurizing agent and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6664210B1 (en) * | 1999-08-24 | 2003-12-16 | M-I Llc | Compressed metal oxide product |
| CN101584962A (en) * | 2008-05-23 | 2009-11-25 | 北京三聚环保新材料股份有限公司 | High-strength FeOOH desulfurizer and preparation method thereof |
| CN101898108A (en) * | 2009-05-31 | 2010-12-01 | 北京三聚环保新材料股份有限公司 | Recyclable desulfurizer and preparation method thereof and regeneration method |
-
2011
- 2011-12-28 CN CN201110446769.2A patent/CN103182236B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6664210B1 (en) * | 1999-08-24 | 2003-12-16 | M-I Llc | Compressed metal oxide product |
| CN101584962A (en) * | 2008-05-23 | 2009-11-25 | 北京三聚环保新材料股份有限公司 | High-strength FeOOH desulfurizer and preparation method thereof |
| CN101898108A (en) * | 2009-05-31 | 2010-12-01 | 北京三聚环保新材料股份有限公司 | Recyclable desulfurizer and preparation method thereof and regeneration method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103182236A (en) | 2013-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2438986B1 (en) | Renewable and reusable desulfurizer and preparation method and regeneration method thereof | |
| CN106672967B (en) | The preparation method and desulphurization denitration active carbon and purposes of desulphurization denitration active carbon | |
| CN104927958A (en) | Dry powder briquette adhesive, briquette including adhesive and preparation method of briquette | |
| CN102491664A (en) | Modified steel slag composite admixture and preparation method thereof | |
| CN104248961A (en) | Sulfur-tolerant shift catalyst and preparation method thereof | |
| CN103933994A (en) | Preparation method of high-temperature methanation catalyst applicable to preparation of methane by reacting CO and CO2 with hydrogen | |
| CN113244752A (en) | Carbon-based iron oxide composite desulfurizer and preparation method thereof | |
| CN103182236B (en) | A kind of high-strength water-resistant high-sulfur capacity desulfurizer and preparation method thereof | |
| CN106311280A (en) | Copper sulfide containing mercury removal agent and preparation method thereof | |
| CN103172064A (en) | Low-ash coal-based activated carbon quick activation production technology | |
| CN108300531B (en) | Composite briquette adhesive and preparation method thereof | |
| CN110872120A (en) | Preparation method of activated carbon | |
| CN104399472A (en) | Calcium-based compound catalyst and loading method thereof | |
| CN103212369A (en) | High-strength ferric hydroxide desulfurizer for normal temperature desulfurization, and preparation method thereof | |
| CN105779076A (en) | Efficient fire coal desulfurizer and preparing method thereof | |
| CN103418230A (en) | Supported amorphous ferric hydroxide desulfurizer and preparation method thereof | |
| CN101768458B (en) | Coke property modifying agent and method for mixing coal and coking | |
| CN102049236A (en) | Copper zinc normal temperature desulfurizing agent and preparation method thereof | |
| CN105797686A (en) | Adsorption material for desulfuration of liquefied petroleum gas and preparation method | |
| CN101590359A (en) | Room temperature marsh gas desulfurizer and preparation method thereof | |
| CN104785278A (en) | Mercury-removing catalyst and preparation method thereof | |
| CN104549324A (en) | Magnesium-aluminum-carbon composite support sulfur-tolerant shift catalyst and preparation method thereof | |
| CN101844074B (en) | Method for preparing activated carbon used for flue gas demercuration | |
| CN103897764B (en) | A kind of Coal sulfur-fixation flame accelerator and preparation method thereof | |
| CN101768457A (en) | Non-coal-series composite additive and applications thereof in blending coal coking |
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 | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: 100080 9th floor, Dahang Jiye building, No.1 building, 33 Renmin North Road, Haidian District, Beijing Patentee after: Beijing Haixin Energy Technology Co.,Ltd. Address before: 100080, Beijing, Haidian District people's Congress Road 33, the big line foundation building 17 floor Patentee before: BEIJING SANJU ENVIRONMENTAL PROTECTION & NEW MATERIALS Co.,Ltd. |