CN1248609A - Preparation method of light oil product deodorization fixed bed catalyst impregnation liquid - Google Patents
Preparation method of light oil product deodorization fixed bed catalyst impregnation liquid Download PDFInfo
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- CN1248609A CN1248609A CN 99115588 CN99115588A CN1248609A CN 1248609 A CN1248609 A CN 1248609A CN 99115588 CN99115588 CN 99115588 CN 99115588 A CN99115588 A CN 99115588A CN 1248609 A CN1248609 A CN 1248609A
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- China
- Prior art keywords
- phthalocyanine cobalt
- fixed bed
- preparation
- solution
- steeping fluid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000004332 deodorization Methods 0.000 title abstract description 7
- 238000005470 impregnation Methods 0.000 title abstract 3
- 239000007788 liquid Substances 0.000 title abstract 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical class [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000243 solution Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 239000012530 fluid Substances 0.000 claims description 30
- 230000001877 deodorizing effect Effects 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052728 basic metal Inorganic materials 0.000 claims description 2
- 150000003818 basic metals Chemical class 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 5
- -1 cobalt phthalocyanine compound Chemical class 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 34
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000003637 basic solution Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000005414 inactive ingredient Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical group N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000012088 reference solution Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000013405 beer Nutrition 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention relates to a preparation method of a light oil product fixed bed deodorization catalyst impregnation liquid. The preparation process comprises the step of adding a cobalt phthalocyanine compound into 0.5-2 m% of an alkali metal oxide aqueous solution while stirring, wherein the concentration of the cobalt phthalocyanine compound is controlled to be 0.5-1.2 m%. The dipping solution has good stability within 48 hours, and cobalt phthalocyanine compounds are dissolved uniformly. The impregnation liquid is used for preparing the fixed bed deodorization catalyst, and the catalyst has high activity and long service life. The method is simple and practical, and is economical and practical.
Description
The present invention relates to a kind of preparation method of light oil products deodorizing fixed bed catalyst impregnating solution, or rather, the present invention relates to the preparation method of a kind of refinery alkali free method of light oil deodorization technology fixed bed catalyst impregnating solution.
In recent years, heaviness, poor qualityization along with crude oil, and the raising of the level of crude oil processing, mercaptan contains in the light-end products in the refinery (comprising catalytic gasoline, coker gasoline, aviation kerosene etc.), measure higher, and the mercaptan complex structure, polymer mercaptan, side chain mercaptans content rise, and have caused certain difficulty for the light-end products mercaptan removal; On the other hand, people strengthen day by day to environmental protection and awareness of saving energy, and high-quality oil product demand rises year by year.Domestic and international for this reason each refinery tries to explore to improve the new technology of deodorising effect.
The alkali-free sweetening technology is the industrial in recent years deodorization technique that generally adopts.Be characterized in that raw material light-end products and activator solution behind the mixing tank thorough mixing, can remove mercaptan with air by beds, mercaptan decreasing ratio height, and also sodium hydroxide concentration reduces greatly.Domestic notification number is the preparation method of CN1194294A, the described fixed bed catalyst impregnating solution of CN1004674U, be sulfonated phthalocyanine cobalt is dissolved in the sodium hydroxide solution of 3～10m% and makes the required steeping fluid solution of fixed bed catalyst, at present industrial generally the employing is dissolved in the required steeping fluid solution of preparation fixed bed catalyst in the sodium hydroxide solution of 10m% with sulfonated phthalocyanine cobalt or poly-phthalocyanine cobalt.Because the naoh concentration height, phthalocyanine cobalt compounds can transform to inactive ingredients in the sodium hydroxide solution of 3～10m%, makes that to have active phthalocyanine cobalt compounds concentration in the steeping fluid on the low side.The preparation method of U.S. Pat 4913802 disclosed steeping fluids adds sulfonated phthalocyanine cobalt to prepare steeping fluid solution in the quaternary ammonium hydroxide mixing solutions of the ammoniacal liquor of 2m% and 1m%, although can slow down of the conversion of phthalocyanine cobalt compounds to inactive ingredients, but with the bed catalyzer of this steeping fluid preparation, phthalocyanine cobalt compounds is easy to run off in deodorising process.And for poly-phthalocyanine cobalt, in the ammonia soln of the sodium hydroxide of 3～10m% or 2m%, because poly-phthalocyanine cobalt solubleness is little, particularly preparation gathers the high steeping fluid of phthalocyanine cobalt concentration, owing to dissolving fully, poly-phthalocyanine cobalt is not in suspended state, so the concentration of poly-phthalocyanine cobalt is difficult to satisfy the requirement of measuring on the bed catalyzer in the steeping fluid that makes with this method, and poly-phthalocyanine cobalt skewness on the bed, and easily run off, cause bed shorter work-ing life.
The preparation method who the purpose of this invention is to provide a kind of light oil products deodorizing fixed bed catalyst impregnating solution.The steeping fluid that uses this method to make, phthalocyanine cobalt compounds dissolves evenly in the steeping fluid, good stability, fixed bed catalyst is active high, long service life.
The present invention seeks to realize like this: in the alkalimetal oxide aqueous solution of 0.5～2m%, add phthalocyanine cobalt compounds while stirring, stir constant until the absorbancy of steeping fluid.
The method according to this invention, basic metal generally have sodium, potassium.Because the alkalimetal oxide aqueous solution is alkalescence, the particularly poly-phthalocyanine cobalt solubleness in basic solution of phthalocyanine cobalt compounds is bigger on the one hand, can make the high steeping fluid solution of phthalocyanine cobalt kind compound content; Can satisfy the condition that Merox method deodorization needs are finished on the other hand again under alkaline environment.Therefore the bed catalyzer with this steeping fluid preparation had both had oxidative function, had alkaline functional again.
Phthalocyanine cobalt compounds concentration in steeping fluid is 0.5%～1.2m%.Generally speaking, phthalocyanine cobalt compounds concentration is too low in the steeping fluid, and then the content of phthalocyanine cobalt compounds is on the low side on the bed catalyzer, and the bed catalyst activity is not high; Phthalocyanine cobalt compounds concentration is too high in the opposite steeping fluid, then the dissolving of phthalocyanine cobalt compounds not exclusively is in suspended state in the steeping fluid, phthalocyanine cobalt compounds skewness on bed causes the bed catalyzer lower to the mercaptan decreasing ratio of macromole and branched structure.
The phthalocyanine cobalt compounds that present industrial light-end products mercaptan removal generally adopts is poly-phthalocyanine cobalt and sulfonated phthalocyanine cobalt.Phthalocyanine cobalt compounds is dissolved in and forms blue purple solution in the basic solution, this explanation phthalocyanine cobalt compounds has stronger light absorptive in the visible region, and this extinction feature causes owing to the complex state cobalt ion vibrates in the phthalocyanine ring, the content of the strong and weak directly reflection phthalocyanine cobalt compounds of this vibration.According to this principle, adopt 752C ultraviolet-visible photometer, at wavelength 610nm place, sodium hydroxide solution with 1～10% is blank reference solution, the absorbancy minimum of blank reference solution, and also minimum to the influence of steeping fluid absorbancy, when the concentration of phthalocyanine cobalt compounds is 10～150ppm scope, the concentration of phthalocyanine cobalt compounds and the absorbancy of steeping fluid are linear, meet Beer's law.The concentration that therefore can directly reflect phthalocyanine cobalt compounds by the absorbancy of surveying steeping fluid.
Phthalocyanine cobalt compounds is a dynamic process in basic solution, also exists the phthalocyanine cobalt compound to be converted into the phenomenon of inactive ingredients except that dissolving, and this conversion is the transfer of cobalt ion from phthalocyanine hoop steeping fluid system.Before reaching balance, phthalocyanine cobalt compounds dissolving is occupied an leading position, and phthalocyanine cobalt compounds concentration increases gradually in this stage solution, when dissolving and conversion reach balance, phthalocyanine cobalt compounds concentration reaches the highest, and after this concentration of phthalocyanine cobalt compounds reduces gradually in the solution.Experimental results show that solution alkalescence is strong more, the speed of this transfer is big more; Phthalocyanine cobalt compounds concentration is high more, and the speed of this transfer is also big more, but what have the greatest impact is the alkaline intensity of solution.
Advantage of the present invention and positively effect
1, adopt method of the present invention, it is fast that steeping fluid prepares speed, and in 48 hours the steeping fluid good stability.
2, utilize steeping fluid of the present invention to prepare fixed bed catalyst, phthalocyanine cobalt compounds is evenly distributed on the catalyzer, the catalyst activity height, and the life-span is long.
Below specific embodiments of the present invention is further described but does not limit the present invention:
Embodiment 1
The sodium hydroxide solution that in the there-necked flask that 500 milliliters bands stir, adds 200 milliliters of 0.5m%, start stirring, slowly add the poly-phthalocyanine cobalt component of 1.96 grams again, get 100 times of 1 milliliter of dilutions at set intervals, with the absorbancy of spectrophotometric instrumentation diluting soln.Test number is A-1, and the solution absorbency variation sees Table 1.
Embodiment 2
In the there-necked flask that 500 milliliters bands stir, add the sodium hydroxide solution of 200 milliliters of 1m%, start stirring, slowly add the poly-phthalocyanine cobalt component of 2.06 grams again, get 100 times of 1 milliliter of dilutions at set intervals, with the absorbancy of spectrophotometric instrumentation diluting soln.Test number is A-2, and solution absorbency changes as table 1.
Embodiment 3
In the there-necked flask that 500 milliliters bands stir, add the sodium hydroxide solution of 247 milliliters of 2m%, start stirring, slowly add the poly-phthalocyanine cobalt component of 3.0 grams again, get 100 times of 1 milliliter of dilutions at set intervals, with the absorbancy of spectrophotometric instrumentation diluting soln.Test number is A-3, and solution absorbency changes as table 1.
Table 1
| Numbering | ????A-1 | ????A-2 | ????A-3 |
| Phthalocyanine cobalt concentration ppm in the steeping fluid | ????102 | ????97 | ????1200 |
| Time (hour) | Absorbancy | ||
| ?2 | ????1.534 | ????1.545 | ????2.155 |
| ?4 | ????1.728 | ????1.758 | ????2.222 |
| ?6 | ????1.887 | ????1.886 | ????2.301 |
| ?8 | ????1.935 | ????1.959 | ????2.301 |
| ?24 | ????2.010 | ????2.000 | ????2.301 |
| ?32 | ????2.010 | ????2.000 | ????2.301 |
| ?48 | ????2.010 | ????2.000 | ????2.301 |
| ?54 | ????1.980 | ????1.916 | ????1.959 |
Embodiment 4
In the there-necked flask that 500 milliliters bands stir, add the sodium hydroxide solution of 200 milliliters of 1m%, start stirring, slowly add the poly-phthalocyanine cobalt component of 2.05 grams again, stirred 8 hours, make the steeping fluid solution A.
Adopt documents CN1194294A, the described method of CN1004674U, make the steeping fluid solution B that contains poly-phthalocyanine cobalt component 100ppm with 10m% sodium hydroxide.
Handle the allovitalism charcoal with above-mentioned steeping fluid A, B respectively, prepare the alkali-free sweetening catalyst A
1, B
1Activity of such catalysts and estimation of stability are estimated result such as table 2 according to evaluating catalyst method among documents CN1194294A, the CN1004674U.
Table 2
| Experiment numbers | ???A 1 | ???B 1 |
| RSH ppm in the stock oil | ???133 | ???88 |
| Reaction velocity Hr -1(w) | ???6.0 | ???2.8 |
| Activation dosage: ppm | ???100～200 | ???100～200 |
| Poly-phthalocyanine cobalt (gac): % (w) | ???1.00 | ???0.24 |
| The deodorization result: | Mercaptan ppm in the deodorised oil | |
| Time: hour | ||
| ?8 | ????7 | ???9 |
| ?56 | ????9 | ???4 |
| ?88 | ????9 | ???4 |
| ?136 | ????9 | ???4 |
| ?182 | ????9 | ???13 |
| ?296 | ????9 | ???13 |
| ?302 | ????9 | ???18 |
| ?434 | ????9 | ???25 |
| ?470 | ????9 | ???26 |
| ?700 | ????9 | |
| ?800 | ????9 | |
| ?900 | ????9 | |
Claims (4)
1, a kind of preparation method of light oil products deodorizing fixed bed catalyst impregnating solution is characterized in that adding phthalocyanine cobalt compounds while stirring in the alkalimetal oxide aqueous solution of 0.5～2m%, stirs constant until the absorbancy of steeping fluid.
2, method according to claim 1 is characterized in that said basic metal is sodium, potassium.
3, method according to claim 1 is characterized in that phthalocyanine cobalt compounds concentration is 0.5%～1.2m% in the said steeping fluid.
4, method according to claim 1 is characterized in that said absorbancy is that the employing spectrophotometer is the numerical value that the 610nm place records at wavelength.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115588A CN1102638C (en) | 1999-10-01 | 1999-10-01 | Preparation method of light oil product deodorization fixed bed catalyst impregnation liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99115588A CN1102638C (en) | 1999-10-01 | 1999-10-01 | Preparation method of light oil product deodorization fixed bed catalyst impregnation liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1248609A true CN1248609A (en) | 2000-03-29 |
| CN1102638C CN1102638C (en) | 2003-03-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99115588A Expired - Fee Related CN1102638C (en) | 1999-10-01 | 1999-10-01 | Preparation method of light oil product deodorization fixed bed catalyst impregnation liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1102638C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501657B2 (en) | 2008-03-28 | 2013-08-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Science | Catalyst for desulfurization and deodorization of gasoline and method for preparation of the same and use thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1004674B (en) * | 1985-04-01 | 1989-06-28 | 夏敬释 | Series resonance constant-current electric charging machine with overdamping |
| US4913802A (en) * | 1989-05-08 | 1990-04-03 | Uop | Process for sweetening a sour hydrocarbon fraction |
| CN1194294A (en) * | 1997-03-21 | 1998-09-30 | 中国石化茂名石油化工公司 | No-base deodorizing technology for aviation kerosene |
-
1999
- 1999-10-01 CN CN99115588A patent/CN1102638C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8501657B2 (en) | 2008-03-28 | 2013-08-06 | Dalian Institute Of Chemical Physics, Chinese Academy Of Science | Catalyst for desulfurization and deodorization of gasoline and method for preparation of the same and use thereof |
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| Publication number | Publication date |
|---|---|
| CN1102638C (en) | 2003-03-05 |
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