CN102794156A - Preparation of adsorbing-oxidizing coupling desulfurizing agent - Google Patents
Preparation of adsorbing-oxidizing coupling desulfurizing agent Download PDFInfo
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- CN102794156A CN102794156A CN2012103283234A CN201210328323A CN102794156A CN 102794156 A CN102794156 A CN 102794156A CN 2012103283234 A CN2012103283234 A CN 2012103283234A CN 201210328323 A CN201210328323 A CN 201210328323A CN 102794156 A CN102794156 A CN 102794156A
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- desulfurizing agent
- active carbon
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- iron oxide
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Abstract
The invention provides a preparation method of an adsorbing-oxidizing coupling desulfurizing agent by introducing a catalyst structure design idea in a desulfurizing agent preparation process. The method comprises the following steps of: taking ferric nitrate and active carbon as main raw materials and utilizing a plurality of times of immersing methods to prepare a dry-method desulfurizing agent which has a great mass transfer rate and a high sulfur capacity and can be used for removing sulfur-containing gas. The desulfurizing agent prepared by using the method can show a relatively high desulfurizing performance at a low temperature, a high pressure and a high speed, wherein the disposable sulfur penetration capacity of the desulfurizing agent which is prepared by taking self-made active carbon as a carrier can be up to 56.3%; and the disposable sulfur penetration capacity of the desulfurizing agent which is prepared by taking commercial active carbon as the carrier can be up to 23.9%. Furthermore, the preparation method disclosed by the invention has a simple preparation process and does not generate waste liquid or waste dregs and the like.
Description
Technical field:
The present invention relates to the preparation method of a kind of adsorption and oxidation coupled desulfurization agent, this technology belongs to the oil gas field of purification, and prepared desulfurizing agent is exclusively used in removing of sulfur-containing compound.
Background technology:
Because the heaviness day by day of crude oil and poor qualityization, make in the liquefied gas sulfur content particularly the total sulfur content in the delayed coking liquefied gas obviously increase.Research shows that the sulfide in the delayed coking liquefied gas removes has acid cure beyond the region of objective existences such as a certain amount of hydrogen sulfide and low-molecular-weight mercaptan, also contains the neutral sulfide such as thiophene, thioether and cos of a great deal of.And these neutral sulfide can not remove with the hydramine method of routine, alkali wash, solid alkaline process etc.This just makes and can not satisfy instructions for use from the liquefied gas of delayed coking and the total sulfur content from isolated low-carbon alkene wherein.And the comprehensive utilization of liquefied gas, matter of utmost importance is exactly the desulfurizing and purifying of unstripped gas, and it is to guarantee that liquefied gas carries out the key that deep processing utilizes.Therefore seeking a kind of effective ways that remove neutral sulfide is to solve the key that liquefied gas efficiently utilizes bottleneck.
The sulfurous gas purification can roughly be divided into dry method, wet method and other are such as novel sulfur methods such as biological desulphurizations.In recent years; Since wet desulphurization exist desulfurization precision not high, shortcomings such as discharging of waste liquid, solvent reclamation energy consumption are high, complex process is tediously long are arranged; People then paid attention to progressively that technological process is simple, desulfurization precision is high, and do not have the dry desulfurization of advantages such as waste liquid, waste sludge discharge.Common dry-desulphurizer comprises metal oxide (metal oxide desulfurizers such as iron-based, zinc-base, manganese base), molecular sieve, active carbon etc.The active carbon raw material sources are extensive; Have highly developed pore structure and reach lower input cost etc. with great specific area, good heat endurance, higher adsorption capacity, these all make its advantage that will have metal oxide and molecular sieve to be difficult to compare as adsorption desulfurizing agent.But existing activated carbon desulphurization agent desulphurizing activated low, Sulfur capacity is low.Although the desulphurizing activated height of traditional oxidation desulfurizing agent because the active component particle size is big, has only the active component on top layer and sulfide to have an effect; The utilization rate of active component is low, thereby the Sulfur capacity of desulfurizing agent is low, the palpus frequent regeneration; Recovery time is long, and is very high like the gas sulfur content, and inactivation is too fast; Be difficult to carry out large-scale continuous production, limited its range of application, often only be used for removing of low sulfur content gas.
This research adopts multiple maceration to prepare the agent of adsorption and oxidation coupled desulfurization, through the coupling of absorption and oxidation desulfurizing agent, two kinds of traditional desulfurizing agents is had complementary advantages, and gained coupled desulfurization agent Sulfur capacity is high, reaction rate is fast, regenerability good, and preparation technology is simple.
Summary of the invention:
The present invention is intended to avoid the weak point of above-mentioned prior art and preparation method that the agent of a kind of adsorption and oxidation coupled desulfurization is provided, obtains to have the desulfurizing agent of high Sulfur capacity, high mass transfer rate, high desulfurization precision.
It is to adopt multiple maceration that the present invention solves its technical problem, is carrier with the active carbon, Fe (NO
3)
39H2O is active phase predecessor, the agent of preparation absorption-oxidation coupled desulfurization.Concrete steps are following:
(1) mass ratio by iron oxide and active carbon takes by weighing active carbon and Fe (NO
3)
39H
2O, and with Fe (NO
3)
39H
2O is dissolved in certain water gaging fully, and iron oxide and quality of activated carbon ratio are controlled at 1～13%;
(2) slowly pour the active carbon that takes by weighing into Fe (NO
3)
39H
2In the O aqueous solution, leave standstill about 10h, carry out single-steeping;
(3) with products therefrom at 80-100 ℃ down behind the dry 12h, then at 300-500 ℃ of following roasting 2h;
(4) repeat (1), slowly pour (3) products therefrom into Fe (NO
3)
39H
2In the O aqueous solution, leave standstill about 10h, carry out double-steeping, iron oxide and quality of activated carbon ratio are controlled at 1～13%;
(5) repeating step (3) promptly gets the agent of adsorption and oxidation coupled desulfurization.
The present invention is a theory of in the preparation process of dry-desulphurizer, introducing Catalyst Design, with the advantage performance complement of adsorption desulfurizing agent and oxidation desulfurizing agent, changes the application defects that traditional desulfurizing agent Sulfur capacity is low, mass transfer rate is slow and the regeneration period is short.With the active carbon is carrier, is active phase with iron oxide, prepares the agent of adsorption and oxidation coupled desulfurization through multiple maceration.This method gained desulfurizing agent is through the cooperative effect of two kinds of traditional desulfurizing agents; On basis, realized oxide of high activity iron desulfurizing agent high degree of dispersion by the flourishing hole series structure of active carbon; Make it show higher desulfurization performance; It once penetrates Sulfur capacity can be up to 56.3%, and this desulfurized effect is far above current domestic and international report data.In addition, not only desulfurization performance is good for this method gained desulfurizing agent, and preparation technology is simple.
The specific embodiment:
To combine specific embodiment that technical characterstic of the present invention is detailed below.
Embodiment 1:
This instance is the agent of immersion process for preparing adsorption and oxidation coupled desulfurization.
(1) be 1%, 5%, 7%, 9%, 11%, 13 to take by weighing self-control super-activated carbon and Fe (NO by the mass ratio of iron oxide and active carbon respectively
3)
39H
2O, and it is dissolved in certain water gaging fully;
What (2) will take by weighing slowly pours Fe (NO into from preparing active carbon
3)
39H
2In the O aqueous solution, leave standstill about 10h, carry out incipient impregnation one time;
(3) with products therefrom at 80-100 ℃ down behind the dry 12h, then at 300 ℃ of following roasting 2h;
(4) repeat (1), slowly pour (3) gained into Fe (NO
3)
39H
2In the O aqueous solution, leave standstill about 10h, carry out double-steeping;
(5) repeat (3), promptly get the agent of adsorption and oxidation coupled desulfurization.
The desulfurization performance appreciation condition of desulfurizing agent is specially: unstripped gas is the gaseous mixture of nitrogen and hydrogen sulfide, H
2The concentration of S is about 2900ppm.Measure the adsorption and oxidation coupled desulfurization agent of about 3ml, adding internal diameter is in the fixed bed reactors of φ 11mm, and reaction tube two ends filling glass is cotton, and bed loads quartz sand up and down.Reaction temperature is 25-90 ℃, and reaction pressure is a normal pressure, and air speed is 8400h
-1Adopt PFPD-GC to detect H in the desulfidation tail gas
2The content of S is the breakthrough point of desulfurizing agent when choosing sulfide content for 343ppm, and once penetrates Sulfur capacity with what this calculated desulfurizing agent.
Adopt multiple maceration, the structural parameters and the Sulfur capacity of the agent of the different prepared adsorption and oxidation coupled desulfurization with the mass ratio of active carbon of iron oxide are seen table 1.
Table 1 iron oxide load capacity is to desulfurizing agent structure and Effect on Performance
Embodiment 2
This instance adopts single-steeping to prepare the adsorption and oxidation coupled desulfurization agent that load capacity is 11% iron oxide.The practical implementation step is following:
(1) be 11% to take by weighing self-control super-activated carbon and Fe (NO by the mass ratio of iron oxide and active carbon
3)
39H
2O, and it is dissolved in certain water gaging fully;
What (2) will take by weighing slowly pours Fe (NO into from preparing active carbon
3)
39H
2In the O aqueous solution, leave standstill about 10h, flood;
(3) with products therefrom at 80-100 ℃ down behind the dry 12h, then at 300 ℃ of following roasting 2h; Promptly get the agent of adsorption and oxidation coupled desulfurization.
The desulfurization appreciation condition is with instance 1, and the physical arrangement and the Sulfur capacity of single-steeping 11% and twice dipping 11 gained desulfurizing agent are shown in table 2.
The different dipping methods of table 2 prepare desulfurizing agent relatively
Embodiment 3:
This instance is an immersion process for preparing adsoption catalysis oxidation desulfurizing agent.Identical with the preparation method of instance 1, be carrier just with commercial active carbon, the mass ratio of iron oxide and active carbon is respectively 4%, 6%, 8%, 10%, 12% in addition.The desulfurization appreciation condition is with instance 1.Different Fe/C mass ratio prepared adsoption catalysis oxidation desulfurizing agent pore structure parameters and Sulfur capacity are shown in table 3.
Table 3 is the structure and the Sulfur capacity of the adsorption and oxidation coupled desulfurization agent of preparing carriers with commercial active carbon
The adsorption and oxidation coupled desulfurization agent of the present invention preparation demonstrate the characteristic of high Sulfur capacity, high mass transfer rate, and preparation technology is simple, has remedied problems such as the Sulfur capacity that present industrial activited carbon occurs is little, mass transfer rate is slow, the regeneration period is short greatly.In addition, because the present invention adopts multiple maceration, so need the low amounts of water except the raw material Activated Carbon Pretreatment, this preparation process can not produce extra waste liquid or waste residue etc.
Claims (1)
1. the preparation method of adsorption and oxidation coupled desulfurization agent, this method is to be that carrier, iron oxide are active phase with the active carbon, adopts multiple maceration to prepare the highly effective dry-desulphurizer that is used for the oil gas desulfurization, its concrete preparation process is following:
⑴ take by weighing active carbon and Fe (NO by iron oxide and quality of activated carbon ratio
3)
39H
2O, and with Fe (NO
3)
39H
2O is dissolved in certain water gaging fully, and iron oxide and quality of activated carbon ratio are controlled at 1～13%;
⑵ slowly pour the active carbon that takes by weighing into Fe (NO
3)
39H
2In the O aqueous solution, leave standstill about 10h, carry out single-steeping;
With products therefrom at 80-100 ℃ down behind the dry 12h, then at 300-500 ℃ of following roasting 2h;
⑷ repeat (1), slowly pours (3) products therefrom into Fe (NO
3)
39H
2In the O aqueous solution, leave standstill about 10h, carry out double-steeping, iron oxide and quality of activated carbon ratio are controlled at 1～13%;
⑸ repeating step (3) promptly gets the agent of adsorption and oxidation coupled desulfurization.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103283234A CN102794156A (en) | 2012-09-07 | 2012-09-07 | Preparation of adsorbing-oxidizing coupling desulfurizing agent |
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|---|---|---|---|
| CN2012103283234A CN102794156A (en) | 2012-09-07 | 2012-09-07 | Preparation of adsorbing-oxidizing coupling desulfurizing agent |
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| Publication Number | Publication Date |
|---|---|
| CN102794156A true CN102794156A (en) | 2012-11-28 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109576003A (en) * | 2018-12-18 | 2019-04-05 | 内蒙古大学 | A method of removing sulfide and Recovered sulphur from coal gas |
| CN117563556A (en) * | 2024-01-16 | 2024-02-20 | 北京北大先锋科技股份有限公司 | Renewable load-type desulfurizing agent and preparation method thereof |
-
2012
- 2012-09-07 CN CN2012103283234A patent/CN102794156A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109576003A (en) * | 2018-12-18 | 2019-04-05 | 内蒙古大学 | A method of removing sulfide and Recovered sulphur from coal gas |
| CN117563556A (en) * | 2024-01-16 | 2024-02-20 | 北京北大先锋科技股份有限公司 | Renewable load-type desulfurizing agent and preparation method thereof |
| CN117563556B (en) * | 2024-01-16 | 2024-04-02 | 北京北大先锋科技股份有限公司 | Renewable load-type desulfurizing agent and preparation method thereof |
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Application publication date: 20121128 |