CN100365103C - Cellulose material possessing dethiol action and its preparation method - Google Patents
Cellulose material possessing dethiol action and its preparation method Download PDFInfo
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- CN100365103C CN100365103C CNB2005100954699A CN200510095469A CN100365103C CN 100365103 C CN100365103 C CN 100365103C CN B2005100954699 A CNB2005100954699 A CN B2005100954699A CN 200510095469 A CN200510095469 A CN 200510095469A CN 100365103 C CN100365103 C CN 100365103C
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- copper
- mercaptan
- thiol
- sodium
- water
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Abstract
The present invention relates to a composition and a preparing method thereof, particularly to a cellulosic material with a thiol removing function, which can be used for removing the thiol in gas or liquid organic substances. The composition is prepared by the reaction of a method of using sodium carboxymethyl cellulose and sodium hydroxyethlcellulose for sufficiently mixing with copper salt composed of positive divalent copper ions and anions under a solid condition. That is to say, the sodium carboxymethyl cellulose, the sodium hydroxyethlcellulose and the copper salt are sufficiently mixed and reacted under the solid condition according to the molar ratio of 0.5 to 2.5 of copper ions and sodium ions, and the water whose weight accounts for 0% to 10% of that of the total material is added; after the reaction, water soluble substances are removed by water washing, corresponding carboxymethyl cellulose copper and carboxyethyl cellulose copper which are the thiol removing material are obtained after natural drying. The present invention can be used for removing the thiol of gas or liquid organic substances, and can greatly decrease and even entirely remove the thiol content in the material. Strong alkali, other catalysts, air and oxygen are not required in the thiol removing process. The use is convenient, and the applicability is wide.
Description
Technical field
The present invention relates to composition and method of making the same, refer in particular to a kind of cellulose materials with dethiol action and preparation method thereof, 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 material with dethiol action and preparation method thereof, 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.
The technical scheme that realizes above-mentioned purpose is as follows:
Cellulose materials with dethiol action of the present invention be carboxymethyl cellulose copper (A) and carboxyethyl cellulose copper (B) both one of, or this two mixture.
A：-[CH
2COO
-]
n[Cu
2+]
n/2
B：-[CH(CH
3)COO
-]
n[Cu
2+]
n/2
-expression Mierocrystalline cellulose
This mercaptan removal material is by making the well-mixed method reaction under solid conditions of Xylo-Mucine, sodium hydroxyethlcellulose and mantoquita, promptly the mol ratio according to cupric ion and sodium ion is 0.5-2.5, with the thorough mixing reaction under solid conditions of Xylo-Mucine, sodium hydroxyethlcellulose and mantoquita, and interpolation accounts for the water of total weight of material 0-10%, reaction finishes after washing and removes the water solubles, and seasoning obtains corresponding mercaptan removal material carboxymethyl cellulose copper, carboxyethyl cellulose copper.
The mantoquita that uses when preparing this mercaptan removal material is the compound that positive bivalent cupric ion and negatively charged ion constitute, and contains crystal water and does not contain crystal water and all can.
Its using method is to separate after making the gas that contains mercaptan or liquid state organics and mercaptan removal 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.
Beneficial effect of the present invention is as follows:
(1) mercaptan removal material 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 35%, the decreasing ratio of most of mercaptan reaches 70～100%.
When (2) utilizing mercaptan removal material 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) mercaptan removal material of the present invention is by making the well-mixed method reaction under solid conditions of Xylo-Mucine, sodium hydroxyethlcellulose and mantoquita.Be reflected under the dry or wetting condition and carry out, do not need the reaction raw materials dissolving, easy and simple to handle, avoided the generation of a large amount of waste water.
Embodiment
1. material with dethiol action of the present invention and preparation method thereof
Cellulose materials with dethiol action of the present invention is one of carboxymethyl cellulose copper and carboxyethyl cellulose copper, or this two mixture.
The preparation method of carboxymethyl cellulose copper, carboxyethyl cellulose copper is: the mol ratio according to cupric ion and sodium ion is 0.5-2.5, with the thorough mixing reaction under solid conditions of Xylo-Mucine, sodium hydroxyethlcellulose and mantoquita, and interpolation accounts for the water of total weight of material 0-10%, reaction finishes after washing and removes the water solubles, and seasoning obtains corresponding mercaptan removal material carboxymethyl cellulose copper, carboxyethyl cellulose copper.
Carboxymethyl cellulose copper and carboxyethyl cellulose copper mixing material obtain by following two kinds of methods:
Method one: carboxymethyl cellulose copper that will prepare and carboxyethyl cellulose copper are directly mixed to be got;
Method two: the mol ratio according to cupric ion and sodium ion is 0.5-2.5, mixture and mantoquita thorough mixing reaction under solid conditions with Xylo-Mucine and sodium hydroxyethlcellulose, and interpolation accounts for the water of total weight of material 0-10%, reaction finishes after washing and removes the water solubles, and seasoning obtains.
The mantoquita that uses when preparing the cellulose materials with dethiol action of the present invention is the compound that positive bivalent cupric ion and negatively charged ion constitute, and contains crystal water and does not contain crystal water and all can.
2, the form of mercaptan removal material of the present invention
Mercaptan removal material appearance form of the present invention is particulate state or pulverulent solids.
3, the using method of mercaptan removal material of the present invention
Using method with 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.
Use temperature scope with mercaptan removal material of the present invention is-10～120 ℃.
4, the range of application of mercaptan removal material of the present invention
Mercaptan removal material 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.
Embodiment 1
Get Xylo-Mucine 10.0 grams, cupric chloride 26.2 grams, thorough mixing is 10 minutes under stirring, spray into the water smoke wet mix in the mixing process, water spray total amount 1.5 grams continue to stir 5 minutes, with 200 ml water washed twice, seasoning obtains mercaptan removal material M1 with mixture.
Embodiment 2
Get Xylo-Mucine 10.0 gram, cupric sulfate pentahydrate 48.9 grams, thorough mixing is 10 minutes under the high-speed stirring, and with 200 ml water washed twice, seasoning obtains mercaptan removal material M2 with mixture.
Embodiment 3
Get sodium hydroxyethlcellulose 10.0 gram, cupric nitrate 31.6 grams, thorough mixing under the high-speed stirring drips 1.5 gram water-wets while stirring, after 10 minutes with mixture with 200 ml water washed twice, seasoning obtains mercaptan removal material M3.
Embodiment 4
Get sodium hydroxyethlcellulose 5.3 gram, carboxymethyl cellulose 4.7 grams, neutralized verdigris 33.0 grams, thorough mixing under the high-speed stirring drips 1.5 gram water-wets while stirring, after 10 minutes with mixture with 200 ml water washed twice, seasoning obtains mercaptan removal material M4.
Embodiment 5
With mercaptan removal material (M2) 7.9 grams that embodiment 2 makes, the mercaptan removal material (M3) that embodiment 3 makes
8.1 the gram uniform mixing obtains mercaptan removal material M5.
The application example of mercaptan removal material such as following table:
| Sequence number | Material type | Material is formed | Temperature ℃ | Mercaptan decreasing ratio (%) | ||||
| Thiomethyl alcohol | Sulfur alcohol | Isopropyl mercaptan | Cyclopentyl mercaptan | Hexylmercaptan | ||||
| Embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 embodiment 13 | M1 M2 M3 M4 M5 M2 M3 M4 | H1 H2 H3 H4 H5 H6 H7 H8 | -5 -10 25 25 65 65 105 120 | - - 95 100 85 - - - | 82 - - 100 35 - 100 80 | 75 70 - - - 82 95 - | 76 74 - - - 85 - - | 80 - - - - - 100 - |
Illustrate:
A, working method:
The mercaptan removal material is filled in the tubular vessel of 12 millimeters of internal diameters, about 15 centimetres of length, makes 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 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 cellulose materials that has dethiol action, it is characterized in that for carboxymethyl cellulose copper (A) and carboxyethyl cellulose copper (B) both one of, or this two mixture;
A：-[CH
2COO-]
n[Cu
2+]
n/2
B：-[CH(CH
3)COO
-]
n[Cu
2+]
n/2
-expression Mierocrystalline cellulose.
2. prepare the described method of claim 1 with cellulose materials of dethiol action, it is characterized in that the mol ratio according to cupric ion and sodium ion is 0.5-2.5, with Xylo-Mucine, sodium hydroxyethlcellulose and mantoquita be the thorough mixing reaction under solid conditions, and interpolation accounts for the water of total weight of material 0-10%, reaction finishes after washing and removes the water solubles, seasoning obtains corresponding mercaptan removal material carboxymethyl cellulose copper, carboxyethyl cellulose copper, wherein said mantoquita is the compound that positive bivalent cupric ion and negatively charged ion constitute, and contains crystal water or does not contain crystal water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100954699A CN100365103C (en) | 2005-11-17 | 2005-11-17 | Cellulose material possessing dethiol action and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100954699A CN100365103C (en) | 2005-11-17 | 2005-11-17 | Cellulose material possessing dethiol action and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1786122A CN1786122A (en) | 2006-06-14 |
| CN100365103C true CN100365103C (en) | 2008-01-30 |
Family
ID=36783736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100954699A Expired - Fee Related CN100365103C (en) | 2005-11-17 | 2005-11-17 | Cellulose material possessing dethiol action and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100365103C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106422814B (en) * | 2016-10-28 | 2019-07-09 | 西北大学 | A kind of sodium carboxymethylcellulose infiltration evaporation desulfurizing film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1033230A (en) * | 1987-11-24 | 1989-06-07 | 山西省临猗县精细化工厂 | Anti-wither chemical and preparation method thereof |
| CN1012085B (en) * | 1986-11-24 | 1991-03-20 | 国营长岭机器厂 | Design system of cleaning yarn monitoring device |
| US5948564A (en) * | 1992-11-12 | 1999-09-07 | Energy Conversion Devices, Inc. | Compositionally and structurally disordered multiphase nickel hydroxide positive electrode containing modifiers |
-
2005
- 2005-11-17 CN CNB2005100954699A patent/CN100365103C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1012085B (en) * | 1986-11-24 | 1991-03-20 | 国营长岭机器厂 | Design system of cleaning yarn monitoring device |
| CN1033230A (en) * | 1987-11-24 | 1989-06-07 | 山西省临猗县精细化工厂 | Anti-wither chemical and preparation method thereof |
| US5948564A (en) * | 1992-11-12 | 1999-09-07 | Energy Conversion Devices, Inc. | Compositionally and structurally disordered multiphase nickel hydroxide positive electrode containing modifiers |
Non-Patent Citations (1)
| Title |
|---|
| CMC与方铅矿和闪锌矿作用机理的探讨. 孟青书，刘金华，廖平婴，黄炎珠.矿冶工程，第3期. 1982 * |
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| Publication number | Publication date |
|---|---|
| CN1786122A (en) | 2006-06-14 |
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Assignee: Jiangsu Leading Material Science Co., Ltd. Assignor: Jiangsu Polytechnic University Contract fulfillment period: 2009.5.4 to 2014.5.4 contract change Contract record no.: 2009320000829 Denomination of invention: Cellulose material possessing dethiol action and its preparation method Granted publication date: 20080130 License type: Exclusive license Record date: 2009.5.11 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.5.4 TO 2014.5.4; CHANGE OF CONTRACT Name of requester: JIANGSU LINGHANG MATERIAL SCIENCE CO., LTD. Effective date: 20090511 |
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Granted publication date: 20080130 Termination date: 20131117 |