CN1786038A - Polymer material possessing thiol removal action - Google Patents
Polymer material possessing thiol removal action Download PDFInfo
- Publication number
- CN1786038A CN1786038A CN 200510095468 CN200510095468A CN1786038A CN 1786038 A CN1786038 A CN 1786038A CN 200510095468 CN200510095468 CN 200510095468 CN 200510095468 A CN200510095468 A CN 200510095468A CN 1786038 A CN1786038 A CN 1786038A
- Authority
- CN
- China
- Prior art keywords
- polymer materials
- mercaptan
- cupric ion
- polymer
- acid
- 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
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a polymer material with action of removing thioalcohol. It can be used for removing thioalcohol in gas or liquid organic material. It is characterized by that said polymer material contains positive dibasic copper ions, said copper ions can be connected on the polymer skeleton by means of chelation group.
Description
Technical field
The present invention relates to composition, refer in particular to the polymer materials 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 polymer materials that removes the mercaptan effect that has, this material is used for gas or liquid state organics material mercaptan removal, can make that mercaptans content obviously reduces in the material.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 polymer materials is the chelating type polymkeric substance that combines positive bivalent cupric ion, and outward appearance is fibrous or particulate solid, makes according to the ordinary method reaction with polymkeric substance that has chelation group and cupric salt.
The technical scheme that realizes above-mentioned purpose is as follows:
It is of the present invention that to have the polymer materials that removes the mercaptan effect be the chelating type polymkeric substance that combines bivalent cupric ion, it is characterized in that polymer materials contains the cupric ion of positive divalence, cupric ion is connected on the polymer backbone by chelate group, and the structural table of this polymer materials is shown:
In the following formula
Be the chelating type polymkeric substance, wherein
The expression polymer backbone,
ChExpression is used for and cupric ion bonded chelate group.
Skeleton in this polymer materials
Comprise polystyrene, resol, polypropylene, polyacrylonitrile, Mierocrystalline cellulose.
In this polymer materials with cupric ion bonded chelate group
ChComprise phosphonic acids, aminophosphonic acid, aminocarboxylic acid, amido thiocarboxylic acid, together with hydroxamamide, thiocarbamide and amido thiocarbamide.
Of the present invention have the polymer materials that removes the mercaptan effect and obtained by corresponding chelating polymer and copper salt solution reaction, and used mantoquita is positive bivalent cupric ion and the compound of negatively charged ion formation.Content of copper ion is between 0.5-10mmol/g in the polymer materials that makes.
Its using method is to separate after making the gas that contains mercaptan or liquid state organics and polymer materials contact certain hour of the present invention, and original mercaptan can significantly reduce or all disappears in isolated gas or the liquid state organics.
Beneficial effect of the present invention is as follows:
(1) polymer materials of the present invention has the effect that significantly removes for the mercaptan that contains in gas or the liquid state organics.Decreasing ratio to mercaptan under the experiment condition reaches 25-90%.
When (2) polymer materials of the present invention is used for removing the mercaptan of material, do not need aerating oxygen or air, do not need the highly basic condition yet, safe.
(3) this polymer materials can be regenerated according to ordinary method, reuses.
Embodiment
1. the described structure of embodiment with polymer materials of dethiol action:
Embodiments of the invention are described, and to have the polymer materials that removes the mercaptan effect be the chelating type polymkeric substance that combines bivalent cupric ion, obtain by corresponding chelating type polymkeric substance and cupric salt reaction, its constitutional features is to contain in the polymer materials cupric ion of positive divalence, cupric ion is connected on the polymer backbone by chelate group, and the structural table of this polymer materials is shown:
In the following formula
Be the chelating type polymkeric substance, wherein
The expression polymer backbone,
ChExpression is used for and cupric ion bonded chelate group.
Skeleton in this polymer materials
Comprise polystyrene, resol, polypropylene, polyacrylonitrile, Mierocrystalline cellulose.
In this polymer materials with cupric ion bonded chelate group
ChComprise phosphonic acids, aminophosphonic acid, aminocarboxylic acid, amido thiocarboxylic acid, together with hydroxamamide, thiocarbamide and amido thiocarbamide.
The physical aspect of described polymer materials is the solid of gel-type or multi-hole type, and outward appearance is particle, fiber or fibrous braid.
Of the present invention have the polymer materials that removes the mercaptan effect and obtained by corresponding chelating polymer and copper salt solution reaction, and used mantoquita is positive bivalent cupric ion and the compound of negatively charged ion formation.Content of copper ion is between 0.5-10mmol/g in the polymer materials that makes.
2, the using method of polymer materials of the present invention
The using method of material of the present invention is to separate after making the material that contains mercaptan and polymer materials contact certain hour, and mercaptan reduces or disappears in the isolated material.
The use temperature scope of polymer materials of the present invention is-5～140 ℃.
This polymer materials can carry out wash-out and regeneration to cupric ion according to the conventional treatment method of chelating type polymkeric substance, reuses.
3, the range of application of mercaptan removal polymer materials of the present invention
Polymer materials of the present invention is applied to the removing of mercaptan in gas and the liquid state organics, and comprises being used to remove single mercaptan and being used for removing simultaneously multiple mercaptan.
4, embodiment
The following examples will further specify the present invention, but therefore not limit the present invention.
| Sequence number | Material type | Material is formed | Temperature ℃ | Mercaptan decreasing ratio (%) | ||||
| 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 embodiment 9 embodiment 10 embodiment 11 embodiment 12 | M1 M2 M3 M4 M5 M6 M7 M8 M9 M10 M11 M12 | H1 H2 H3 H4 H5 H6 H7 H8 H5 H6 H7 H8 | -5 -5 25 25 65 65 105 80 80 80 140 140 | - - 47 68 50 - - - 80 - - - | 62 - - 75 40 - 82 50 50 - 85 90 | 45 26 - - - 72 55 - - 80 72 - | 51 39 - - - 75 - - - 85 - - | 56 - - - - - 76 - - - 90 - |
Illustrate:
A, working method:
Polymer materials is riddled in the tubular vessel of 12 millimeters of internal diameters, about 20 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
| Material | Framework types | Chelate group | Material shape | Copper content (mmol/g) |
| M1 | Polystyrene | Phosphonic acids | The gel-type spherical particle | 3.1 |
| M2 | Polystyrene | Aminophosphonic acid | The gel-type fine particle | 1.4 |
| M3 | Polystyrene | Amino oxalic acid | The macroporous type spherical particle | 1.9 |
| M4 | Polyacrylonitrile | The amido thiocarbamide | Fibrous | 1.3 |
| M5 | Polyacrylonitrile | Together with hydroxamamide | Fibrous | 1.7 |
| M6 | Mierocrystalline cellulose | Aminophosphonic acid | Fibrous braid | 2.7 |
| M7 | Polyacrylonitrile | Amido dithio formic acid, | Fibrous braid | 2.9 |
| M8 | Polystyrene | The amido thiocarbamide | The macroporous type spherical particle | 0.65 |
| M9 | Mierocrystalline cellulose | Amino oxalic acid | Random particulate state | 1.2 |
| M10 | Polypropylene | The amido bamic acid | The gel-type fine particle | 0.95 |
| M11 | Resol | Amino oxalic acid | The macroporous type spherical particle | 2.8 |
| M12 | Resol | Thiocarbamide | The macroporous type spherical particle | 1.1 |
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 (2)
1. the polymer materials that has dethiol action is characterized in that polymer materials contains the cupric ion of positive divalence, and cupric ion is connected on the polymer backbone by chelate group, and the structural table of this polymer materials is shown:
In the following formula
Be the chelating type polymkeric substance, wherein
The expression polymer backbone,
ChExpression is used for and cupric ion bonded chelate group; Skeleton in this polymer materials
Comprise polystyrene, resol, polypropylene, polyacrylonitrile, Mierocrystalline cellulose; In this polymer materials with cupric ion bonded chelate group
ChComprise phosphonic acids, aminophosphonic acid, aminocarboxylic acid, amido thiocarboxylic acid, together with hydroxamamide, thiocarbamide and amido thiocarbamide.
2. the polymer materials with dethiol action according to claim 1 is characterized in that content of copper ion is between 0.5-10mmol/g in the polymer materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510095468 CN1786038A (en) | 2005-11-17 | 2005-11-17 | Polymer material possessing thiol removal action |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510095468 CN1786038A (en) | 2005-11-17 | 2005-11-17 | Polymer material possessing thiol removal action |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1786038A true CN1786038A (en) | 2006-06-14 |
Family
ID=36783655
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510095468 Pending CN1786038A (en) | 2005-11-17 | 2005-11-17 | Polymer material possessing thiol removal action |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1786038A (en) |
-
2005
- 2005-11-17 CN CN 200510095468 patent/CN1786038A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Depositing Cu2O of different morphology on chitosan nanoparticles by an electrochemical method | |
| CN113398889A (en) | Multi-adsorption-site type biomass-based hyperbranched multi-metal ion adsorption material and preparation method and application thereof | |
| CN1061633C (en) | Multi-function iron oxide fine sweetening agent and preparation thereof | |
| CN1108885C (en) | Technological process using electroplating sludge as resource to make harmless treatment | |
| CN1786038A (en) | Polymer material possessing thiol removal action | |
| CN109759135B (en) | Preparation method of composite material for removing heavy metal/hydrophobic ppcps in reclaimed water | |
| CN1775924A (en) | Liquefied gas desulfurizing and refining method | |
| CN1974651A (en) | Regenerable resin material with mercaptan eliminating effect | |
| CN109722271B (en) | Method for reducing mercaptan content of light oil product | |
| CN1786058A (en) | Copper carboxylate type resin material possessing thioalcohol removing action | |
| CN1837077A (en) | Process for treating coking waste water containing phenol and cyanogen by physical chemistry method and special device therefor | |
| CN101063044A (en) | Diesel oxidation desulfurizing method | |
| CN85104661A (en) | A kind of solid acid catalyst that can be used for producing gylcol ether | |
| CN107603728B (en) | Auxiliary agent for improving quality of regenerated finished product of waste lubricating oil and preparation method thereof | |
| CN1259251C (en) | Method for biochemical treatment of discharged water | |
| CN114988534A (en) | Cresol wastewater treatment method and composite catalytic electrode used in method | |
| CN1310129A (en) | Zns photocatalyst, its producing method and method for producing hydrogen using with the same catalyst | |
| CN104399433A (en) | Composite material of phenolic pollutants in refinery waste water | |
| CN1786122A (en) | Cellulose material possessing dethiol action and its preparation method | |
| CN111620389A (en) | Application of amorphous alloy in catalytic degradation of antibiotic pollutants | |
| CN1872958A (en) | Catalyst in use for oxidation and deodoration of light oil, and preparation method | |
| CN100362074C (en) | Decomposition agent for extracting fuel oil from dirty oil mud | |
| CN111167453A (en) | Preparation method and application method of catalyst for removing ammonia nitrogen in water | |
| CN212025022U (en) | Integrated system for continuously removing mercury from high-acidity mercury-containing waste liquid | |
| CN112760146B (en) | Auxiliary agent for improving regeneration performance of liquefied gas sweetening extractant and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |