CN1974651A - Regenerable resin material with mercaptan eliminating effect - Google Patents
Regenerable resin material with mercaptan eliminating effect Download PDFInfo
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- CN1974651A CN1974651A CNA2005100954701A CN200510095470A CN1974651A CN 1974651 A CN1974651 A CN 1974651A CN A2005100954701 A CNA2005100954701 A CN A2005100954701A CN 200510095470 A CN200510095470 A CN 200510095470A CN 1974651 A CN1974651 A CN 1974651A
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- mercaptan
- resin material
- eliminating
- ion exchange
- ion
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Abstract
The present invention relates to composition, and is especially one kind of regenerable resin material with mercaptan eliminating effect and capacity of eliminating mercaptan from gaseous one liquid organic matter. The structure of the regenerable resin material includes two parts: the first part of sulfonic acid type styrene line ion exchange resin and the second part of bivalent copper ion. The sulfonate radical in the first part and the copper ion are connected through ion bond, so that after the mercaptan eliminating resin material is made to contact with mercaptan containing gas or liquid organic matter or some time, the mercaptan content in the gas or liquid organic matter may be reduced greatly. The mercaptan eliminating resin material has convenient mercaptan eliminating process, and the used mercaptan eliminating resin material may be regenerated through conventional ion exchange process for reuse.
Description
Affiliated technical field
The present invention relates to composition, refer in particular to a kind of renewable resin material with dethiol action, it can be used in the gas or the removing of mercaptan in the liquid state organics.
Background technology
Mercaptan has stench, as long as contain few low-carbon (LC) mercaptan in gas or the liquid state organics, will have undesirable stink.Mercaptan is again to have highly active organism, and the existence of mercaptan can have a strong impact on the use properties of organic chemical industry's product, and the stability of gasoline, diesel etc. and storage stability are descended, also can corroding metal, shorten the work-ing life of equipment.Remove mercaptan and be not only the needs that guarantee quality product; also be the protection environment, improve one of effective measure of Air quality; this is particularly important for the great gasoline of daily consumption, diesel oil, Sweet natural gas etc., and is also significant for many industries such as chemical industry, material, pharmacy and thermoelectricity.
The traditional method that removes mercaptan is alkali cleaning, promptly allows the material that contains mercaptan fully contact with certain density alkali lye, removes mercaptan.But owing to there are problems such as waste lye pollution and corrodibility, alkali wash is not an ideal mercaptan removal method.Other method that removes mercaptan mainly is a catalytic oxidation, promptly under certain catalytic condition, remove mercaptan by oxidizing reaction, concrete technology comprises liquid-liquid method, liquid-solid method, and carried by active carbon phthalocyanine cobalt is the no caustic alkali fixed bed process of catalyzer, the improvement fixed bed process (CN1067709C) that activated carbon fiber is carried cobalt, copper or zinc salt, the main drawback of these technologies is on the one hand need be with highly basic or comparatively expensive material as catalyzer, need aerating oxygen or air as oxygenant on the other hand, cost is higher, and technology is also complicated.
Summary of the invention
The present invention proposes a kind of resin material with dethiol action, this material is used for gas or liquid state organics mercaptan removal, mercaptans content is significantly reduced even all removes.Do not need highly basic or other catalyzer in the mercaptan removal process, also need not use air or oxygen, easy to use, suitability is wide.This mercaptan removal resin material can be reused with conventional ion-exchange techniques regeneration back.
The technical scheme that realizes above-mentioned purpose is as follows:
Resin material with dethiol action of the present invention, be characterised in that and comprise two parts in its structure: a part is the sulfonic acid type styrene ion exchange resin, another part is positive bivalent cupric ion, be connected with ionic linkage between sulfonate radical in the sulfonic acid type styrene ion exchange resin and the cupric ion, form following structure:
Wherein
Expression sulfonic acid type styrene ion exchange resin.
Resin material with dethiol action of the present invention adopts copper salt solution and sulfonic acid type styrene ion exchange resin to carry out the method preparation of ion-exchange.Used mantoquita is the compound that positive bivalent cupric ion and negatively charged ion constitute.
Its using method is to separate after making the gas that contains mercaptan or liquid state organics and mercaptan removal resin material contact certain hour of the present invention, and original mercaptan can significantly reduce or all disappears in isolated gas or the liquid state organics.
Resin material with dethiol action of the present invention adopts the method regeneration of carrying out ion-exchange with regenerated liquid after use is saturated, reuse.Regenerated liquid is that the aqueous solution of mantoquita carries out, and used mantoquita is the compound that positive bivalent cupric ion and negatively charged ion constitute, and regenerated liquid concentration is 3-15%.
Beneficial effect of the present invention is as follows:
(1) resin material with dethiol action of the present invention has the effect that significantly removes for the mercaptan that contains in gas or the liquid state organics.Under the experiment condition to the decreasing ratio of mercaptan all above 30%, wherein the decreasing ratio of most of mercaptan reaches more than 60%.
When (2) utilizing the resin material with dethiol action of the present invention to remove mercaptan in the material, do not need aerating oxygen or air, do not need the highly basic condition yet, easy to operate, safe.
(3) resin material with dethiol action of the present invention can be regenerated with ion exchange method after use is saturated, reuses.
Embodiment
1. the described structure of the embodiment of the invention with material of dethiol action
The described resin material of the embodiment of the invention with dethiol action, comprise two parts in its structure: a part is the sulfonic acid type styrene ion exchange resin, another part is positive bivalent cupric ion, be connected with ionic linkage between sulfonate radical in the sulfonic acid type styrene ion exchange resin and the cupric ion, form following structure:
Wherein
Expression sulfonic acid type styrene ion exchange resin comprises gel type resin and macroporous ion-exchange resin.
Resin material with dethiol action of the present invention adopts the aqueous solution of mantoquita and the method that the sulfonic acid type styrene ion exchange resin carries out ion-exchange to prepare.Used mantoquita is the compound that positive bivalent cupric ion and negatively charged ion constitute.
2, the form with resin material of dethiol action of the present invention
Resin material mode of appearance with dethiol action of the present invention is a solid, comprises that particle, film, fiber and fiber constitute thing.
3, the using method of mercaptan removal material of the present invention
Using method with resin material of dethiol action of the present invention is to separate after making the material that contains mercaptan and mercaptan removal material contact certain hour, and mercaptan reduces or disappears in the isolated material.
Resin material use temperature scope with dethiol action of the present invention is-10～140 ℃.
Resin material with dethiol action of the present invention adopts the method regeneration of carrying out ion-exchange with regenerated liquid after use is saturated, reuse.Regenerated liquid is that the aqueous solution of mantoquita carries out, and used mantoquita is the compound that positive bivalent cupric ion and negatively charged ion constitute, and regenerated liquid concentration is 3-15%.
4, the range of application with resin material of dethiol action of the present invention
Resin material with dethiol action of the present invention be applied in the gas and liquid state organics in the removing of mercaptan, comprise being used to remove single mercaptan and being used for removing simultaneously multiple mercaptan.
5, embodiment
The following examples will further specify the present invention, but therefore not limit the present invention.
| Sequence number | Material | Material | Temperature | Mercaptan decreasing ratio (%) |
| Type | Form | ℃ | Thiomethyl alcohol | Sulfur alcohol | Isopropyl mercaptan | Cyclopentyl mercaptan | Hexylmercaptan | |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 | M1 M2 M3 M4 M5 M6 M7 M8 | H1 H2 H3 H4 H5 H6 H7 H8 | -5 -10 25 25 65 65 105 140 | - - 35 50 65 - - - | 75 - - 60 40 - 100 50 | 65 50 - - - 90 85 - | 65 80 - - - 85 - - | 80 - - - - - 75 - |
Illustrate:
A, working method:
The mercaptan removal material is riddled in the tubular vessel of 20 millimeters of internal diameters, about 15 centimetres of length, make the material that contains mercaptan by this tubular vessel at a certain temperature, the take-off rate of control material is measured the mercaptans content in the effluent, calculates the decreasing ratio of mercaptan.
B, material type
| M1 | The sulfonic acid type styrene ion exchange resin of 1% divinylbenzene crosslink; The macroporous type particulate state, copper content 12.5% |
| M2 | No crosslinked sulfonic acid type styrene ion exchange resin; The gel-type fine particulate, copper content 10.6% |
| M3 | The sulfonic acid type styrene ion exchange resin of 14.6% divinylbenzene crosslink; Film, copper content 7.2% |
| M4 | The sulfonic acid type styrene ion exchange resin of 5.5% divinylbenzene crosslink; Fiber, copper content 8.9% |
| M5 | The sulfonic acid type styrene ion exchange resin of 5.5% divinylbenzene crosslink; Fibrous braid, copper content 8.9% |
| M6 | Be the M1 through ion exchange regenerant, regenerated liquid is 10% copper sulfate solution |
| M7 | Be the M2 through ion exchange regenerant, regenerated liquid is 7.5% copper nitrate aqueous solution |
| M8 | Be the M4 through ion exchange regenerant, regenerated liquid is the 5% neutralized verdigris aqueous solution |
C, material is formed
| H1 | Gasoline; Sulfur alcohol 10ppm, isopropyl mercaptan 10ppm, cyclopentyl mercaptan 10ppm, hexylmercaptan 5ppm |
| H2 | Ethanol; Isopropyl mercaptan 2ppm, cyclopentyl mercaptan 5ppm |
| H3 | Hydrogen; Thiomethyl alcohol 5ppm |
| H4 | Sweet natural gas; Thiomethyl alcohol 1ppm, sulfur alcohol 1ppm |
| H5 | Propylene; Thiomethyl alcohol 0.5ppm, sulfur alcohol 0.1ppm |
| H6 | Virahol and acetone mixture; Isopropyl mercaptan 10ppm, cyclopentyl mercaptan 10ppm |
| H7 | Benzene; Sulfur alcohol 10ppm, isopropyl mercaptan 10ppm, hexylmercaptan 5ppm |
| H8 | Air; Sulfur alcohol 0.1ppm |
Claims (1)
1. renewable resin material with dethiol action, it is characterized in that comprising in the structure two parts: a part is the sulfonic acid type styrene ion exchange resin, another part is positive bivalent cupric ion, be connected with ionic linkage between sulfonate radical in the sulfonic acid type styrene ion exchange resin and the cupric ion, form following structure:
Wherein
Expression sulfonic acid type styrene ion exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100954701A CN1974651A (en) | 2005-11-17 | 2005-11-17 | Regenerable resin material with mercaptan eliminating effect |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2005100954701A CN1974651A (en) | 2005-11-17 | 2005-11-17 | Regenerable resin material with mercaptan eliminating effect |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1974651A true CN1974651A (en) | 2007-06-06 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2005100954701A Pending CN1974651A (en) | 2005-11-17 | 2005-11-17 | Regenerable resin material with mercaptan eliminating effect |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1974651A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780421A (en) * | 2010-03-12 | 2010-07-21 | 中南大学 | Ammonia nitrogen adsorbent and preparation method and application method thereof |
-
2005
- 2005-11-17 CN CNA2005100954701A patent/CN1974651A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101780421A (en) * | 2010-03-12 | 2010-07-21 | 中南大学 | Ammonia nitrogen adsorbent and preparation method and application method thereof |
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