CN100418628C - Preparation method of non-odor solvent oil - Google Patents
Preparation method of non-odor solvent oil Download PDFInfo
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- CN100418628C CN100418628C CNB2006100016912A CN200610001691A CN100418628C CN 100418628 C CN100418628 C CN 100418628C CN B2006100016912 A CNB2006100016912 A CN B2006100016912A CN 200610001691 A CN200610001691 A CN 200610001691A CN 100418628 C CN100418628 C CN 100418628C
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- solvent naphtha
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Abstract
A catalyst for preparing odorless solvent oil, its expression is: Qnn+Hm[ABXOY](m + n)-,and Q+ is quaternary ammonium salt cation and its component is R4N+, at least one group carbon chain length is more than or equal with eight carbon atoms; A refers to P and/or Si; B refers to metals element W; H refers to hydrogen atom; O refers to oxygen atom; m+n<=12; 1<=X<=12; 4<=y <=40. The method using catalyst for preparing odorless solvent oil, main steps are: adding 5-10 mg Qnn+Hm[ABXOY](m+n)- catalyst into 0.1-0.3 ml hydrogen dioxide solution and mixing, moistening catalyst; then adding 1 L solvent oil and stirring, stopping reaction until the odor of mercaptan and sulfide in oil, then stewing and separating the oil layer.
Description
Technical field
The present invention relates to a kind of preparation method of non-odor solvent oil.
Background technology
The deodorization of solvent naphtha is a requisite technical process in the petrochemical industry, its objective is the organic sulfur compound that has foul smell in the oil product is removed or be converted into tasteless material, produces needs and environmental requirement to satisfy.Along with the exploitation of oil, petroleum reserves is fewer and feweri on the earth.In recent years, the heaviness of crude oil, poor qualityization, and the raising of the level of crude oil processing, mercaptan, thioether content in the solvent oil product in the refinery are higher, and molecular structure is complicated more, make the deodorization of oil product difficult more.For this reason, each refinery tries to explore to improve the new technology of deodorising effect both at home and abroad.
The at present industrial deodorization technique that generally adopts is the alkali-free sweetening technology.Be characterized in raw material oil product and activator solution after blender fully mixes, with air during by beds reaction to remove mercaptan.The domestic patent No. is the preparation method of the described fixed bed catalyst impregnating solution of CN1248609A, is in the aqueous solution of compound with the phthalocyanine cobalt class alkali metal oxide that is dissolved in 0.5-2%.Because solution is strong basicity, the compound of phthalocyanine cobalt class can transform to inactive ingredients, makes that the compound concentration of active phthalocyanine cobalt class reduces in the maceration extract.The preparation method of U.S. Pat 4913802 disclosed maceration extracts is the compounds that add phthalocyanine cobalt class in the quaternary ammonium base mixed liquor of 2% ammoniacal liquor and 1%, although can slow down the compound of phthalocyanine cobalt class transforms to inactive ingredients, but the bed catalyst with this maceration extract preparation runs off in the process of deodorization easily, causes bed shorter service life.And these are unfriendly to environment, easily form and pollute.
Foul smell in the solvent naphtha mainly is owing to wherein contain the cause of mercaptan and thioether.Promptly be to make the content of wherein mercaptan and thioether extremely low, even reach the ppb level, oil product also can have foul smell.If want deodorizing, then must remove mercaptan and thioether in the oil product.
Summary of the invention
The object of the present invention is to provide a kind of catalyst that is used to prepare non-odor solvent oil.
Another purpose of the present invention is to provide a kind of method of using above-mentioned Preparation of Catalyst non-odor solvent oil.
For achieving the above object, catalyst provided by the invention, its expression formula is:
Q
n n+H
m[AB
XO
Y]
(m+n)-
In the formula:
Q is meant quaternary ammonium salt;
Q
+Be meant quaternary ammonium salt cationic, it consists of R
4N
+, the carbon chain lengths that wherein has a group at least is more than or equal to 8 carbon atoms;
A is meant P or/and Si, preferably P;
B is meant metal elements W;
H is meant hydrogen ion;
O is meant oxonium ion;
m+n≤12；1≤X≤12；4≤y≤40。
Described catalyst, the quaternary ammonium salt ion in the expression formula is: (C
8H
17)
4N
+, (C
12H
25)
4N
+, (C
16H
33)
4N
+, (π-C
5H
5N
+C
16H
33), [(C
18H
37) (75%)+(C
16H
33) (25%)]
2N
+(CH
3)
2Or/and (C
18H
37) 2N+ (CH
3)
2Preferred (C
18H
37) N
+(CH
3)
3
The present invention uses the method for above-mentioned Preparation of Catalyst non-odor solvent oil, mainly goes on foot to gather to be:
Press the Q of 5-milligram
n N+H
m[AB
XO
Y]
(m+n)-The hydrogen peroxide that catalyst adds the 0.1-0.3 milliliter mixes moistening catalyst; Add 1 liter of solvent naphtha again, stir, treat that the smell of mercaptan and thioether disappears in the oil product after, stop reaction, standing separation reclaims oil reservoir and catalyst respectively.Separate to refer to and filter or/and centrifugation, preferred separate mode is centrifugation.
Catalyst provided by the invention, both had catalytic activity, had interfacial activity again, adopted the method for catalytic oxidation, in emulsion system, the mercaptan in the solvent naphtha and thioether are oxidized to sulfonic acid and sulfone respectively and from oil product, remove, thereby reach the purpose of deodorization with 30% hydrogenperoxide steam generator.Simultaneously, because sulfonic acid is water miscible, most sulfone is water soluble also, so that the sulfur content in the solvent naphtha also can reduce, make the better quality of oil product.
The invention has the beneficial effects as follows:
1, this method is exceedingly fast to solvent naphtha deodorization speed, and efficient is high, and because of almost being the metering reaction, the amount of the hydrogen peroxide of consumption is few, so investment is few; And this method is environmentally friendly, and is free from environmental pollution.
2, Preparation of catalysts is easy, the yield height.
3, the catalyst of this law preparation is insoluble in oil, can contaminated product, be easy to come out so that reclaim use from separation of oil.
4, use this method oil product free of losses in deodorising process.
The specific embodiment
In order to further specify the present invention, enumerate following embodiment, but it does not limit the defined invention scope of each accessory claim.
Embodiment 1: Preparation of catalysts.
As an illustrative examples, catalyst [(C
18H
37) N
+(CH
3)
3] [PW
3O
q] can prepare as follows: take by weighing the 1.87g wolframic acid and be suspended in the 10.0ml hydrogen peroxide, 60 ℃ of oil bath vigorous stirring 30min, room temperature is reduced in dissolving; Take by weighing sodium dihydrogen phosphate 0.39g, be dissolved in 5ml water, stir 5min under the room temperature, it is joined in the hydrogen peroxide solution of wolframic acid, stir, regulate PH=2-3; Get doped quaternary ammonium salt OTAC 2.6g again and be dissolved in the 10ml absolute ethyl alcohol, splash in the above-mentioned mixed solution, vigorous stirring generates white precipitate immediately simultaneously, and the dropping time is 1-2h, continues to stir 3-4h; At last after filtration, get deionised water, vacuum drying gets the white solid catalyst.Be called catalyst A.
Embodiment 2
With embodiment 1, just phosphorus tungsten ratio is 1: 1, is called catalyst C.
Embodiment 3
With embodiment 1, just phosphorus tungsten ratio is 1: 6, is called catalyst D.
Embodiment 4
With embodiment 1, just phosphorus tungsten ratio is 1: 10, is called catalyst E.
Embodiment 5
With embodiment 1, just replace wolframic acid with silicic acid, be called catalyst F.
Embodiment 6
With embodiment 1, just replace OTAC with positive eight alkyl trimethyl ammonium chlorides, be called catalyst G.
Embodiment 7
With embodiment 1, just replace OTAC with hexadecyltrimethylammonium chloride, be called catalyst H.
Embodiment 8
The deodorization of the 110# solvent naphtha (70～110 ℃ cuts) that Ba Ling petrochemical industry group company is provided: take by weighing the 5.0mg catalyst A, join in the flask of 1000ml, 0.1ml30%H reinjects
2O
2Solution, shaking flasks makes H
2O
2The abundant moistening catalyst of solution adds 1000ml 110# solvent naphtha then, and vigorous stirring makes the rapid emulsification of solution, approximately reacts 1 hour down at 30 ℃, and solution can complete deodorization.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the 110# solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 6.4ng/ μ l and 2.4ng/ μ l.
Embodiment 9
Give and continue to add 0.1ml30%H among the embodiment 8 in the reacted flask
2O
2Solution and 1000ml110# solvent naphtha are to use the second time of carrying out catalyst.Vigorous stirring was approximately reacted 1 hour down at 30 ℃, and the stink of solution disappears.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the 110# solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 6.4ng/ μ l and 2.7ng/ μ l.
Embodiment 10
Give and continue to add 0.1ml30%H among the embodiment 9 in the reacted flask
2O
2Solution and 1000ml110# solvent naphtha are to carry out the use for the third time of catalyst.Vigorous stirring was approximately reacted 1 hour down at 30 ℃, and the stink of solution disappears.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the 110# solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 6.4ng/ μ l and 1.9ng/ μ l.
Embodiment 11
The deodorization of the 200# solvent naphtha (140～200 ℃ of cuts) that Ba Ling petrochemical industry group company is provided: take by weighing the 10mg catalyst A, join in the flask of 1000ml, 0.3ml30%H reinjects
2O
2Solution, shaking flasks makes H
2O
2The abundant moistening catalyst of solution adds 1000ml 200# solvent naphtha then, and vigorous stirring makes the rapid emulsification of solution, approximately reacts 1 hour down at 30 ℃, and solution can complete deodorization.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the 200# solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 48.0ng/ μ l and 33.2ng/ μ l.
Embodiment 12
Give and continue to add 0.3ml30%H among the embodiment 11 in the reacted flask
2O
2Solution and 1000ml200# solvent naphtha are to use the second time of carrying out catalyst.Vigorous stirring was approximately reacted 1 hour down at 30 ℃, and the stink of solution disappears.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the 200# solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 48.0ng/ μ l and 31.7ng/ μ l.
Embodiment 13
Give and continue to add 0.3ml 30%H among the embodiment 12 in the reacted flask
2O
2Solution and 1000ml 200# solvent naphtha are to carry out the use for the third time of catalyst.Vigorous stirring was approximately reacted 1 hour down at 30 ℃, and the stink of solution disappears.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the 200# solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 48.0ng/ μ l and 29.9ng/ μ l.
Embodiment 14
The deodorization of the high-sulfur solvent naphtha (70～110 ℃ cuts) that oil seven factories in Dalian are provided: take by weighing the 10mg catalyst A, join in the flask of 250ml, 0.2ml 30%H reinjects
2O
2Solution, shaking flasks makes H
2O
2The abundant moistening catalyst of solution adds 100ml high-sulfur solvent naphtha then, and vigorous stirring makes the rapid emulsification of solution, approximately reacts 1 hour down at 30 ℃, and solution can complete deodorization.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the high-sulfur solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 274.6ng/ μ l and 4.7ng/ μ l.
Embodiment 15
After reaction finishes and oil reservoir poured out among the embodiment 14, give and continue to add 0.2ml30%H in the flask
2O
2Solution, and then add 100ml high-sulfur solvent naphtha, vigorous stirring makes the rapid emulsification of solution, approximately reacts 1 hour down at 30 ℃, and solution can complete deodorization.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the high-sulfur solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 274.6ng/ μ l and 5.2ng/ μ l.
Embodiment 16
After reaction finishes and oil reservoir poured out among the embodiment 15, give and continue to add 0.2ml30%H in the flask
2O
2Solution, and then add 100ml high-sulfur solvent naphtha, vigorous stirring makes the rapid emulsification of solution, approximately reacts 1 hour down at 30 ℃, and solution can complete deodorization.Leave standstill afterwards and make emulsion breaking, oil reservoir is poured out promptly obtained deodorised oil.With the sulfur content in the high-sulfur solvent naphtha before and after the reaction of micro-coulometric titration instrument mensuration is respectively 274.6ng/ μ l and 4.8ng/ μ l.
Embodiment 17
With embodiment 8, just use catalyst C, the result is also similar, deodorization fully.
Embodiment 19
With embodiment 8, just use catalyst D, the result is also similar, deodorization fully.
Embodiment 20
With embodiment 8, just use catalyst E, the result is also similar, deodorization fully.
Embodiment 21
With embodiment 8, just use catalyst F, the result is also similar, deodorization fully.
Embodiment 22
With embodiment 11, just use catalyst G, the result is also similar, deodorization fully.
Embodiment 23
With embodiment 11, just use catalyst H, the result is also similar, deodorization fully.
Can find out that from above all examples all catalyst are reusable.
Can find out also that from above all examples this method not only can deodorizing to solvent naphtha, and the sulfur content of solvent naphtha is significantly reduced.
Claims (7)
1. catalyst that is used to prepare non-odor solvent oil, its expression formula is:
Q
n n+H
m[AB
XO
Y]
(m+n)-
In the formula:
Q
+Be meant quaternary ammonium salt cationic, it consists of R
4N
+, the carbon chain lengths that wherein has a group at least is more than or equal to 8 carbon atoms;
A is meant P or/and Si;
B is meant metal elements W;
H is meant hydrogen atom;
O is meant oxygen atom;
m+n≤12；1≤X≤12；4≤y≤40。
2. catalyst as claimed in claim 1 is characterized in that the A in the expression formula is meant P.
3. catalyst as claimed in claim 1 is characterized in that, the quaternary ammonium salt ion in the expression formula is: (C
8H
17)
4N
+, (C
12H
25)
4N
+, (C
16H
33)
4N
+, (π-C
5H
5N
+C
16H
33), [(C
18H
37) (75%)+(C
16H
33) (25%)]
2N
+(CH
3)
2Or (C
18H
37)
2N
+(CH
3)
2
4. as claim 1 or 3 described catalyst, it is characterized in that the quaternary ammonium salt ion in the expression formula is: (C
18H
37) N
+(CH
3)
3
5. the described catalyst of claim 1 is used to prepare the method for non-odor solvent oil, mainly goes on foot to gather to be:
Press the Q of 5-10 milligram
n N+H
m[AB
XO
Y]
(m+n)-The hydrogen peroxide that catalyst adds the 0.1-0.3 milliliter mixes moistening catalyst; Add 1 liter of solvent naphtha again, stir, treat that the smell of mercaptan and thioether disappears in the oil product after, stop reaction, static, separate and reclaim oil reservoir.
6. method as claimed in claim 5 is characterized in that, separates to refer to and filters or/and centrifugation.
7. as claim 5 or 6 described methods, it is characterized in that, separate referring to centrifugation.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100016912A CN100418628C (en) | 2006-01-24 | 2006-01-24 | Preparation method of non-odor solvent oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100016912A CN100418628C (en) | 2006-01-24 | 2006-01-24 | Preparation method of non-odor solvent oil |
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| CN100418628C true CN100418628C (en) | 2008-09-17 |
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|---|---|---|---|
| CNB2006100016912A Expired - Fee Related CN100418628C (en) | 2006-01-24 | 2006-01-24 | Preparation method of non-odor solvent oil |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173179B (en) * | 2007-10-24 | 2010-09-29 | 中国科学院大连化学物理研究所 | Catalyst for diesel oil oxidation distillation ultra-deepness desulfurization and desulfurization method |
| CN101543789A (en) * | 2008-03-28 | 2009-09-30 | 中国科学院大连化学物理研究所 | Gasoline desulfurizing-deodorizing catalysts and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143667A (en) * | 1995-08-21 | 1997-02-26 | 寿光市文家乡建筑安装公司 | Method and use for producing civil liquid fuel and leadless gasoline from C5 fraction oil |
| US6171478B1 (en) * | 1998-07-15 | 2001-01-09 | Uop Llc | Process for the desulfurization of a hydrocarbonaceous oil |
| US20030102252A1 (en) * | 1999-12-28 | 2003-06-05 | Alain Rabion | Method for desulphurizing thiopene derivatives contained in fuels |
| CN1554729A (en) * | 2003-12-26 | 2004-12-15 | 南化集团研究院 | Process for producing hydrogenation refining solvent oil |
-
2006
- 2006-01-24 CN CNB2006100016912A patent/CN100418628C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1143667A (en) * | 1995-08-21 | 1997-02-26 | 寿光市文家乡建筑安装公司 | Method and use for producing civil liquid fuel and leadless gasoline from C5 fraction oil |
| US6171478B1 (en) * | 1998-07-15 | 2001-01-09 | Uop Llc | Process for the desulfurization of a hydrocarbonaceous oil |
| US20030102252A1 (en) * | 1999-12-28 | 2003-06-05 | Alain Rabion | Method for desulphurizing thiopene derivatives contained in fuels |
| CN1554729A (en) * | 2003-12-26 | 2004-12-15 | 南化集团研究院 | Process for producing hydrogenation refining solvent oil |
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