CN1321736C - Resin adsorbent for desulfurizing hydrocarbon and its prepn - Google Patents
Resin adsorbent for desulfurizing hydrocarbon and its prepn Download PDFInfo
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- CN1321736C CN1321736C CNB031323278A CN03132327A CN1321736C CN 1321736 C CN1321736 C CN 1321736C CN B031323278 A CNB031323278 A CN B031323278A CN 03132327 A CN03132327 A CN 03132327A CN 1321736 C CN1321736 C CN 1321736C
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Abstract
The present invention can be used for adsorbing and eliminating organic sulfur compounds in gasoline, diesel oil and other liquid hydrocarbons. The present invention comprises a resin frame and a functional group which are connected by methylene (-CH2-), wherein the resin frame is divinylbenzene crosslinked styrene resin, and is connected with the functional group which contains an organic group with halogen, hydroxy groups or amide structures via the methylene (-CH2-). The present invention uses chlorosulfonated styrene-divinylbenzene copolymerization bead bodies as raw materials, and is prepared by the methylene amidation reaction of the raw materials and the organic substances which conform to functional group structural requirements in a solvent. The adsorption agent has good water resistance and has obvious adsorption effect on organic sulfide in liquid hydrocarbons. The adsorption agent has good physical stability and chemical stability in use, can be repeatedly used conveniently, and the phenomenon of product pollution because metallic ions or metal compounds enter treated hydrocarbons can be avoided.
Description
Affiliated technical field
The present invention relates to composition, refer in particular to a kind of resin sorbent that is used for hydrocarbon desulfurization and preparation method thereof, it can be used for the adsorbing and removing of organosulfur compound in gasoline, diesel oil and other liquid hydrocarbons.
Background technology
Hydrocarbon products is carried out desulfurization be not only the needs that guarantee product quality, also be the protection environment, improve one of effective measures of air quality, this is particularly important for fuel hydrocarbons such as gasoline, diesel oil.Sulfide in the hydrocarbon product such as gasoline, diesel oil mainly comprises three classes: i.e. mercaptan, thioether and thiophene and derivative thereof, this three classes sulfide all is the processing object of hydrocarbon desulfurization.
From prior art, remove that the main method of sulfide comprises hydrodesulfurization, oxidation sweetening, abstraction desulfurization, adsorption desulfurize and biological desulphurization etc. in the hydro carbons.Wherein adsorption desulfurize progressively is subjected to paying close attention to widely with features such as its low cost, low-loss and non-destructives, embodies special advantages.
In adsorption desulfurize, the selection of adsorbent and preparation are core technologies.At the various sulfide in the hydrocarbon products, the adsorbent of existing report mainly comprises adsorbent of molecular sieve and oxide adsorbent two classes, enumerates the partial monopoly document of relevant these a few class adsorbents at this, as a reference:
Adsorbent of molecular sieve: CN 00109630.3; CN 00808906.X; CN 00136870.2; CN 01118444.2; CN 01119820.6; US 5146039; US 5057473
Oxide adsorbent: CN 93111222.2; CN 02109088.2; CN 02112509.0; CN00808908.6; CN 00814793.0; US 4163708; US 4336130; US 4419224
In addition, Raney Ni (US 6221280), (CN 02126018.4 for amorphous nickel; CN 02126020.6) and load have the zinc titanate (CN 00814798.1) of reduction valence state metal to wait the patent report that also has as desulfurization usefulness adsorbent.
From existing report, existing hydrocarbon desulfurization adsorbent generally with inorganic material as base material, by adjusting ratio of component and adsorbent specific area, perhaps introduce different metals, slaine as the adsorption activity composition, play suction-operated to sulfide.This type of sorbing material goes to toward needing to add the adhesives moulding in application, and there is the possibility of metal ion loss in some adsorbent to water sensitive.
Summary of the invention
The present invention proposes a kind of resinae adsorbent that is used for hydrocarbon desulfurization and preparation method thereof, adsorbent is used for the adsorption desulfurize of liquefied hydrocarbon, have good physical stability and chemical stability in the use, and have tangible suction-operated.
The technical scheme that realizes above-mentioned purpose is as follows:
Adsorbent composition of the present invention comprises " resin matrix " and " functional group " two parts, it is characterized in that " resin matrix " is the styrene resin (with " " expression) of divinyl benzene crosslinked, by methylene (CH
2-) link to each other with functional group." functional group " is for containing the organic group of halogen, hydroxyl or amide structure.
For the structure of adsorbent of the present invention clearly is described, " functional group " represented with M-Q that M is two atomic groups that link to each other with covalent bond with Q at this.The structure of adsorbent of the present invention can be expressed as follows:
-CH
2-M-Q
is the styrene resin of divinyl benzene crosslinked in the said structure, and M-Q is the functional group in the adsorbent, two atomic groups of M and Q or exist simultaneously in the functional group, or do not have M, Q directly with-CH
2-link to each other.
The structure of M and Q can be expressed as follows particularly:
M be in two kinds of structures any:
a.-NHR-
R=-CH wherein
2-;-C
2H
4-;
" N " termination-CH in two kinds of structures of above-mentioned a and b
2-, " R-" termination-QQ can be in the following groups any:
Cl，OH，-NHCOCH
3，-N(COCH
3)
2，-N(CH
3)CHO，M-Cl，M-OH，
When Q is
Or
During Deng group, Q can be directly and methylene (CH in the functional group
2-) link to each other.
Preparation of adsorbent method of the present invention is:
Macroporous type styrene-divinylbenzene copolymerization pearl body (also claiming the chlorine ball) with chloromethylation is a raw material, by carrying out the aminating reaction preparation with the organic matter that meets the functional group structural requirement (being expressed as H-M-Q) in solvent.
The macroporous type styrene of chloromethylation-divinylbenzene copolymerization pearl body and organic matter H-M-Q can make by conventional method.
Specifically can be:
Place the solvent of 2～10 times of volumes to soak a few hours the styrene-divinylbenzene copolymerization pearl body (chlorine ball) of the chloromethylation of drying, add the organic matter H-M-Q of 2～5 times of amounts (with the mol ratio of chlorine in the chlorine ball), add hot reflux.Isolate the resin bead body and, remove adsorbate, be dried to constant weight, promptly get adsorbent of the present invention with 75～90 ℃ of hot-airs with ethanol extracting repeatedly.
The process that adsorbent of the present invention is used for adsorption desulfurize is that the liquefied hydrocarbon that contains organic sulfur compound is contacted with adsorbent of the present invention, and the hydrocarbon with the gained low sulfur content separates with the adsorbent that has adsorbed sulfide then.The adsorbent that has adsorbed sulfide is reused through regeneration.
The present invention does not have the sulfur-bearing liquid hydrocarbon and explicitly calls for, and the sulfide content in the hydrocarbon (in the sulphur atom quality) is 50～2000ppm.Temperature when the liquefied hydrocarbon that contains organic sulfur compound contacts with adsorbent of the present invention is-5～90 ℃, and pressure is normal pressure to 1 MPa.
Beneficial effect of the present invention is as follows:
(1) adsorbent composition of the present invention has tangible suction-operated for the organic sulfur compound that contains in the liquid hydrocarbon (comprising mercaptan, thioether and thiophene and derivative thereof).Under the experiment condition removal efficiency (in sulphur atom weight) of various sulfide in the simulation sample is reached 70～100% all above 12.7% to partial vulcanization thing removal efficiency.
(2) adsorbent composition of the present invention is the polymer that links to each other with covalent bond, must not add the adhesives moulding, has good physical stability and chemical stability in the use, can reuse easily.
(3) adsorbent of the present invention has excellent water tolerance, can be because of not containing the destruction that moisture causes adsorbent physical arrangement and chemical constitution in the object being treated under the normal temperature.
(4) do not contain the metal ion and the metallic compound of any valence state in the adsorbent composition of the present invention, can not enter the pollution that causes product in the processed hydrocarbon in the use because of metal ion or metallic compound.
The specific embodiment
1. the structure of the described adsorbent of the embodiment of the invention
The structure of adsorbent of the present invention can be expressed as follows:
-CH
2-M-Q
is the styrene copolymer of 0～35% divinyl benzene crosslinked in the above structural formula; M-Q is the functional group in the adsorbent, and two atomic groups of M in the functional group and Q can exist simultaneously, and (this moment, the structure of adsorbent of the present invention can be reduced to -CH also can only Q
2-Q).
Adsorbent outward appearance of the present invention is the spherical particle thing, particle diameter 0.2～1.2mm; The ratio of functional group quality in the adsorbent gross mass is not less than 4.5%.
2. the described preparation of adsorbent method of the embodiment of the invention
Place the solvent of 2～10 times of volumes to soak a few hours the styrene-divinylbenzene copolymerization pearl body (chlorine ball) of the chloromethylation of drying, the organic matter H-M-Q that adds 2～5 times of amounts (with the mol ratio of chlorine in the chlorine ball), optionally add an amount of KOH, added hot reflux 6～20 hours.Isolate the resin bead body and, remove adsorbate, be dried to constant weight, promptly get adsorbent of the present invention with 75～90 ℃ of hot-airs with ethanol extracting repeatedly.
3. embodiment
The following examples will further specify the present invention, but therefore not limit the present invention.
Embodiment 1
Place 30ml toluene to soak 2 hours the styrene-divinylbenzene copolymerization pearl body (chlorinity 18.6%) of the chloromethylation of 5g drying, add 11.0g HN (CH
2CH
2Cl)
2, added hot reflux 8 hours under stirring.Isolate the resin bead body and, remove adsorbate, be dried to constant weight, make adsorbent 1, gross weight 7.4g, functional group content 32.2% with 75～105 ℃ of hot-airs with ethanol extracting repeatedly.Its structure is:
Adsorbent 1: -CH
2-N (CH
2CH
2Cl)
2
Embodiment 2
Place 40ml toluene to soak 3 hours in the chlorine ball (chlorinity 18.6%) of 5g drying, add 12.6gH
2NCH
2CH
2N (COCH
3)
2, added hot reflux 10 hours under stirring.Isolate the resin bead body and, remove adsorbate, be dried to constant weight, make adsorbent 2, gross weight 7.0g, functional group content 28.4% with 75～105 ℃ of hot-airs with ethanol extracting repeatedly.Its structure is:
Adsorbent 2: -CH
2-NHCH
2CH
2N (COCH
3)
2
Embodiment 3
Place 40ml THF to soak 2 hours in the chlorine ball (chlorinity 18.6%) of 5g drying, be added dropwise to the methanol solution of 3.4g alpha-pyrrolidone and 1.5g KOH, added hot reflux 10 hours under stirring.Isolate the resin bead body and, remove adsorbate, be dried to constant weight, make adsorbent 3, gross weight 6.1g, functional group content 18.0% with 75～105 ℃ of hot-airs with ethanol extracting repeatedly.Its structure is:
Adsorbent 3:
Embodiment 4
Place the 40ml cyclohexane to soak 4 hours in the chlorine ball (chlorinity 9.6%) of 5g drying, add 9.0gH
2NCH
2CH (CH
3) NHCH
2CH (CH
3) OH, added hot reflux 12 hours under stirring.Isolate the resin bead body and, remove adsorbate, be dried to constant weight, make adsorbent 4, gross weight 6.0g, functional group content 16.7% with 75～105 ℃ of hot-airs with ethanol extracting repeatedly.Its structure is:
Adsorbent 4: -CH
2-NHCH
2CH (CH
3) NHCH
2CH (CH
3) OH
Embodiment 5
Place 40ml toluene to soak 5 hours in the chlorine ball (chlorinity 9.6%) of 5g drying, add 2.9gH
2NCH
2N (CH
3) CHO, added hot reflux 8 hours under stirring.Isolate the resin bead body and, remove adsorbate, be dried to constant weight, make adsorbent 5, gross weight 5.6g, functional group content 10.7% with 75～105 ℃ of hot-airs with ethanol extracting repeatedly.Its structure is:
Adsorbent 5: -CH
2-NHCH
2N (CH
3) CHO
4. the desulfurized effect of the described adsorbent of the embodiment of the invention
The embodiment of this test desulfurized effect uses liquid hydrocarbon with the benzinum of 60～90 ℃ of boiling ranges as test, adds different organic sulfur compound S1～S6 respectively and makes sulfur-bearing simulation sample, and simulation sample sulfur content (in sulphur atom) is between 50～600ppm.To simulate sample and fully contact by a certain percentage with adsorbent, the contact temperature is 28～35 ℃.Hydrocarbon with the gained low sulfur content separates with the adsorbent that has adsorbed sulfide then, with the simulation sample after separating, measures sulfur content, calculates desulfurization degree.The result is as shown in the table:
| Sequence number | Adsorbent | Pressure (Mpa) | The material ratio | Desulfurization degree | |||||
| S1 | S2 | S3 | S4 | S5 | S6 | ||||
| 1 2 3 4 5 | 1 2 3 4 5 | 0.36 0.36 0.15 0.15 0.10 | 10∶1 10∶1 7.5∶1 7.5∶1 5∶1 | 100 92.8 - - - | - - 61.7 83.0 57.7 | 57.5 65.3 - - - | - - 62.5 52.7 34.6 | 36.6 32.5 - - - | - - 12.7 22.2 26.1 |
Material ratio=simulation volume of sample (m1): adsorbent weight (g)
S1: propanethiol; S2: cyclopentanethiol; S3: thiophene; S4: benzothiophene
S5: ethyl sulfide: S6: dipropyl sulfide
Claims (3)
1. the resin sorbent that is used for hydrocarbon desulfurization, it is made up of " resin matrix " and " functional group " two parts, it is characterized in that " resin matrix " is the styrene resin of divinyl benzene crosslinked, with " " expression, by methylene (CH
2-) link to each other with " functional group ", " functional group " is expressed as the organic group that contains halogen, hydroxyl or amide structure with M-Q, and the structure of adsorbent is expressed as follows: -CH
2-M-Q, wherein M be in following two kinds of structures any:
Wherein R is-CH
2-;-C
2H
4-;
" N " termination-CH in two kinds of structures of above-mentioned a and b
2-, " R-" termination-Q,
Wherein
Q is a kind of in the following groups:
Cl，OH，-NHCOCH
3，-N(COCH
3)
2，-N(CH
3)CHO，M-Cl，M-OH，
And when Q is
Or
During group, the direct and methylene of Q in the functional group
(CH
2-) link to each other.
2. obtain the described preparation method who is used for the resin sorbent of hydrocarbon desulfurization of claim 1, it is characterized by: the styrene-divinylbenzene copolymerization pearl body with chloromethylation is a raw material, by with the organic matter that meets the functional group structural requirement, be expressed as H-M-Q, in solvent, carry out the aminating reaction preparation.
3. the preparation method who is used for the resin sorbent of hydrocarbon desulfurization according to claim 3, it is characterized in that: with the styrene-divinylbenzene copolymerization pearl body of the chloromethylation of drying is that the chlorine ball places the solvent of 2～10 times of volumes to soak a few hours, the mol ratio of chlorine is the organic matter H-M-Q of 2～5 times of amounts in adding and the chlorine ball, add hot reflux, isolate the resin bead body and with ethanol extracting repeatedly, remove adsorbate, be dried to constant weight with 75～90 ℃ of hot-airs and get final product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031323278A CN1321736C (en) | 2003-08-14 | 2003-08-14 | Resin adsorbent for desulfurizing hydrocarbon and its prepn |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031323278A CN1321736C (en) | 2003-08-14 | 2003-08-14 | Resin adsorbent for desulfurizing hydrocarbon and its prepn |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1487058A CN1487058A (en) | 2004-04-07 |
| CN1321736C true CN1321736C (en) | 2007-06-20 |
Family
ID=34154109
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031323278A Expired - Fee Related CN1321736C (en) | 2003-08-14 | 2003-08-14 | Resin adsorbent for desulfurizing hydrocarbon and its prepn |
Country Status (1)
| Country | Link |
|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103614157A (en) * | 2013-12-02 | 2014-03-05 | 济南开发区星火科学技术研究院 | Method for adsorption desulfurization of fuel oil |
| CN108250380A (en) * | 2016-12-28 | 2018-07-06 | 中国科学院宁波材料技术与工程研究所 | Desulphurization and denitrification functions high-molecular compound, preparation method and application |
| CN114736382B (en) * | 2022-04-28 | 2023-08-01 | 常州大学 | Linear polyamine polystyrene adsorption resin and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04202203A (en) * | 1990-11-29 | 1992-07-23 | Mitsui Toatsu Chem Inc | Production of ion exchange resin |
| RU1838332C (en) * | 1991-12-06 | 1993-08-30 | Научно-исследовательский институт строительных материалов при Томском инженерно-строительном институте | Method of preparing of polymeric sorbent for chromatography |
| RU2061705C1 (en) * | 1990-02-27 | 1996-06-10 | Научно-исследовательский институт строительных материалов при Томской государственной архитектурно-строительной академии | Method for production of polymer sorbent for chromatography |
-
2003
- 2003-08-14 CN CNB031323278A patent/CN1321736C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2061705C1 (en) * | 1990-02-27 | 1996-06-10 | Научно-исследовательский институт строительных материалов при Томской государственной архитектурно-строительной академии | Method for production of polymer sorbent for chromatography |
| JPH04202203A (en) * | 1990-11-29 | 1992-07-23 | Mitsui Toatsu Chem Inc | Production of ion exchange resin |
| RU1838332C (en) * | 1991-12-06 | 1993-08-30 | Научно-исследовательский институт строительных материалов при Томском инженерно-строительном институте | Method of preparing of polymeric sorbent for chromatography |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1487058A (en) | 2004-04-07 |
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| 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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Changzhou Yuxing Insulation Material Co., Ltd. Assignor: Jiangsu Polytechnic University Contract fulfillment period: 2008.12.20 to 2013.12.20 contract change Contract record no.: 2009320000029 Denomination of invention: Resin adsorbent for desulfurizing hydrocarbon and its prepn Granted publication date: 20070620 License type: Exclusive license Record date: 2009.1.22 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.12.20 TO 2013.12.20; CHANGE OF CONTRACT Name of requester: CHANGZHOU YUXING INSULATED MATERIALS CO., LTD. Effective date: 20090122 |
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Granted publication date: 20070620 Termination date: 20130814 |