CN1029482C - Process for deodorizing coal oil fraction - Google Patents
Process for deodorizing coal oil fraction Download PDFInfo
- Publication number
- CN1029482C CN1029482C CN 91109141 CN91109141A CN1029482C CN 1029482 C CN1029482 C CN 1029482C CN 91109141 CN91109141 CN 91109141 CN 91109141 A CN91109141 A CN 91109141A CN 1029482 C CN1029482 C CN 1029482C
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- China
- Prior art keywords
- oil
- alkali lye
- mercaptan
- phthalocyanine compound
- metal phthalocyanine
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- 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.)
- Expired - Fee Related
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Fats And Perfumes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention provides a technological method for deeply eliminating an abnormal flavor in coal oil (distillation range: 150 to 270DEG C) distillate, which is used for simultaneously enabling a product to obtain a fragrant flavor. The whole technological process comprises oxidation with a strong oxidizing agent, catalytic oxidation with an added auxiliary agent and adsorption with a solid adsorbing agent as three different chemical industry processes. The treated product meets the requirements of odorless mineral oil matched with fine chemicals, and the product yield reaches higher than 99%.
Description
The present invention relates to a kind of process for purification of hydrocarbon polymer, kerosene fraction peculiar smell deep removal technology.
Peculiar smell comprises the bad smell that stink that mercaptan causes and non-mercaptan material (comprising alkene, aromatic hydrocarbons etc.) cause in kerosene (boiling range: the 150-270 ℃) fraction.Through data at home and abroad investigation, conclusion is got up, and the method that is used for removing the mercaptan stink at present has following 4 kinds: (1) changes disulphide into airborne oxygen or the existing mercaptan of oxygenant direct oxidation stock oil.(2) with the mercaptan in the aqueous sodium hydroxide solution extracting stock oil, change sodium mercaptides into, the alkali lye water steam stripped after will using is then decomposed the method for sodium mercaptides or with the method recovery of air direct oxidation sodium mercaptides with recycle.(3) method of use molecular sieve adsorption, hydrogen sulfide and low molecule mercaptan are removed in absorption.(4) utilize metal phthalocyanine compound to make mercaptan in the oil product under aqueous alkali and oxidizing gas existence condition, be oxidized to disulphide as catalyzer.But the bad smell that above four kinds of methods all cause non-mercaptan material in the stock oil, removal effect is not remarkable.In order to satisfy the needs of the growing required supporting finish of fine chemicals, the technological process of peculiar smell in the sulfonated method deep removal light-end products has appearred adopting, sulfonation method mainly is by add the purpose that sulphonating agent generation sulfonation reaction reaches peculiar smell in the deep removal oil in oil product, along with the emergence of hydrogenation industry in the petroleum industry, the technological process of peculiar smell in the high-pressure hydrogenation method deep removal lightweight oil has also appearred utilizing.More than sulfonation method technology in two kinds of methods, equipment simpler, but the sulphonating agent consumption is big, it is many to produce waste residue, contaminate environment, yield is low etc.; Hydrogenation method has been used the modern technique of modern industry, is applicable to the large-scale commercial production of hi-tech, but exists the processing condition harshness, equipment requirements height, investment, the shortcoming that process cost is big.
In view of above situation, seek a kind of simple, efficient, low consumption, oligosaprobic light-end products peculiar smell removal methods, for researchers are paid attention to.At present, by literature search,, also there be not to find the report identical or similar with the present invention as hentriaconta-piece of writing patents such as US4581129, DE3828603 and seven pieces of domestic and international relevant documents.The objective of the invention is to be to provide a kind of simply, light-end products peculiar smell deep removal technology efficiently, produce the required supporting finish product of qualified fine chemicals.
The invention provides the processing method of peculiar smell in a kind of deep removal kerosene (boiling range: 150-270 ℃) cut.Four partial contents are arranged: (1) uses the oxygenizement of strong oxidizer to unsaturated organic compound in the oil and aromatic hydrocarbons, removes the peculiar smell of unsaturated hydrocarbons, aromatic hydrocarbons; (2) adopt most thio-alcohol sordes in the one-level adding assistant catalytic oxidative desulfurization oil, residual in the secondary adding assistant catalyzed oxidation deep removal oil on a small quantity than macromole mercaptan sordes, wherein auxiliary agent is used for increasing the solubleness of macromole mercaptan at alkali lye for containing pure analog assistant; (3) by solid adsorbent absorption, imperfect composition and excessive strong oxidizer improve oil quality in the deep removal oil; (4) utilize the organic acid of strong oxidizer oxidation unsaturated hydrocarbons and aromatic hydrocarbons generation and the alcohols material that catalyzed oxidation is partly added, under the katalysis of solid adsorbent, add the thermogenesis esterification, generation has the Ester of aromatising flavour, make the oil product after the adsorption treatment not only remove peculiar smell, and contain aromatising flavour, reach the requirement of the supporting finish of fine chemicals.Technical process of the present invention is: normal temperature, under the normal pressure, kerosene (boiling range: 150-270 ℃) fraction oil with enter the one-level catalytic oxidation unit after pure analog assistant mixes, contact with oxygen with containing metal phthalocyanine compound catalyzer alkali lye, remove the thio-alcohol material, oil plant after the processing is delivered to the strong oxidizer oxide treatment, in the strong oxidizer unit, oil plant and strong oxidizer reaction, oil plant enters the processing of secondary catalytic oxidation unit after the oxidation, processing condition are identical with the one-level catalytic oxidation unit, further remove in the oil residual than macromole mercaptan sordes, last oil plant is by extraordinary solid adsorbent absorption, and imperfect composition and excessive strong oxidizer produce esterification simultaneously in the deep removal oil, improve oil quality, make and finally obtain the required supporting finish product of fine chemicals.Solid adsorbent is reused by hot carrier gas desorption and regeneration, changes until losing efficacy, and spent sorbents can be done the fuel utilization.
The invention has the advantages that and adopted novel chemical unit combination, i.e. strong oxidizer oxidation-adding assistant catalyzed oxidation-solid adsorbent absorbing process.Peculiar smell in deep removal kerosene (boiling range: the 150-270 ℃) fraction, and make product produce pure and fresh aromatising flavour by esterification, produce the required supporting finish product of qualified fine chemicals.Whole technological process is all carried out under normal pressure, lesser temps, thereby processing condition relax, facility investment is few, and is easy to operate, has avoided processing condition harshness in the hydrogenation technique, shortcoming that facility investment is big.In addition, the big and residue contamination environmental problem of sulphonating agent consumption in the process for sulfonation has also been avoided in this invention.Oil plant is used as the required supporting finish of fine chemicals after treatment, and product price is appreciated bigger, and remarkable economic efficiency is arranged.
Description of drawings:
Accompanying drawing is kerosene of the present invention (boiling range: a 150-270 ℃) fraction peculiar smell deep removal technology quick-reading flow sheets synoptic diagram, wherein:
1-one-level catalytic oxidation unit;
2-strong oxidizer oxidation unit;
3-secondary catalytic oxidation unit;
4-solid adsorbent absorbing unit;
5-alkali liquid regeneration device;
A-kerosene (150-270 ℃) fraction;
B-contains catalyzer alkali lye;
Oil plant behind the c-first grade desulfurizing alcohol;
D-contains the mercaptan extraction liquid;
Oil plant after the oxidation of e-strong oxidizer;
The f-oxidized tail gas;
The g-strong oxidizer;
Oil plant behind the h-secondary mercaptan removal;
I-contains catalyzer alkali lye;
J-contains the mercaptan extraction liquid;
K-odorless mineral oil;
The l-solid adsorbent;
M-desorb tail gas;
The n-spent sorbents;
The hot carrier gas of o-;
Contain catalyzer alkali lye after the p-regeneration;
Contain catalyzer alkali lye after the q-regeneration;
R-tail gas;
The s-air;
The t-auxiliary agent.
Embodiments of the invention as shown in drawings, concrete steps are that pure analog assistant (t) and kerosene (boiling range: 150-270 ℃) fraction (a) are mixed the back with being pumped into one-level catalytic oxidation unit (1) and containing catalyzer alkali lye (b) and fully contact, wherein amount of auxiliary is 200-1000ppm in the oil, extraction process carries out at normal temperatures and pressures in the one-level catalytic oxidation unit, catalyzer is a metal phthalocyanine compound, content 50-150ppm, concentration of lye 5-15%(weight), oil plant behind the first grade desulfurizing alcohol (c) enters strong oxidizer oxidation unit (2), after strong oxidizer (g) oxide treatment, enter secondary catalytic oxidation unit (3), strong oxidizer (g) is an acid potassium permanganate, hydrogen peroxide, ozone etc., consumption 1-15mg/kg oil, the unit is at normal temperature, normal pressure is operation down, and emit oxidized tail gas (f), oil plant is identical with one-level catalytic oxidation unit (1) in the mechanism of secondary catalytic oxidation unit (3).Oil plant behind the secondary mercaptan removal (h) enters solid adsorbent absorbing unit (4) at last, 40-100 ℃ of temperature, normal pressure contacts 20-60 minute with solid adsorbent (1) gac down, by the charcoal absorption effect, imperfect composition and excessive strong oxidizer in the deep removal oil, simultaneously, under the katalysis and heating condition of gac, produce esterification, obtain the mineral oil (k) of the supporting odorless of fine chemicals at last, the saturated back of charcoal absorption 180-250 ℃ of hot carrier gas (o) desorption and regeneration, emit desorb tail gas (m), regeneration back gac is reused, make spent sorbents (n) until inefficacy and discharge, waste active carbon can be made fuel and use one, contain mercaptan extraction liquid (d) in the secondary catalytic oxidation process, (j) regeneration is at same alkali liquid regeneration device (5), regenerate with air (s) down at 40 ℃, remove the mercaptan that is dissolved in the alkali lye, tail gas (r) emptying contains catalyzer alkali lye (p) after the regeneration, (q) recycle.
Claims (1)
1, a kind of processing method of deep removal kerosene fraction peculiar smell is characterized in that the method includes the steps of:
A. fraction oil mixes with pure analog assistant, the alcohols auxiliary dosage is 200-1000ppm, contacts concentration of lye 5-15% (weight) with containing metal phthalocyanine compound catalyzer alkali lye again, the content of metal phthalocyanine compound in alkali lye is 50-150ppm, removes a part of mercaptan sordes in the oil;
B. the oil plant of handling through step a is sent into the strong oxidizer oxidation unit, feeds ozone, and consumption is a 1-15mg/kg oil, removes the peculiar smell of unsaturated hydrocarbons, aromatic hydrocarbons;
C. enter the secondary catalytic oxidation unit through the oil plant after the step b oxidation, contact with containing metal phthalocyanine compound catalyzer alkali lye, concentration of lye 5-15% (weight), the content of metal phthalocyanine compound in alkali lye is 50-150ppm, further removes in the oil residual on a small quantity than macromole mercaptan sordes;
D. the oil plant of handling through step c enters the solid adsorbent absorbing unit again, is adsorbed under 40-100 ℃, normal pressure to carry out, and oil plant contacts 20-60 minute with gac.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109141 CN1029482C (en) | 1991-09-17 | 1991-09-17 | Process for deodorizing coal oil fraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91109141 CN1029482C (en) | 1991-09-17 | 1991-09-17 | Process for deodorizing coal oil fraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1060305A CN1060305A (en) | 1992-04-15 |
| CN1029482C true CN1029482C (en) | 1995-08-09 |
Family
ID=4909665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91109141 Expired - Fee Related CN1029482C (en) | 1991-09-17 | 1991-09-17 | Process for deodorizing coal oil fraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1029482C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1062295C (en) * | 1996-08-16 | 2001-02-21 | 中国科学院动物研究所 | Technological process of deodorization of kersene |
| CN1063776C (en) * | 1996-08-23 | 2001-03-28 | 中国石化兰州炼油化工总厂 | Method for separating color material from color kerosene used in lamp |
-
1991
- 1991-09-17 CN CN 91109141 patent/CN1029482C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1060305A (en) | 1992-04-15 |
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| C14 | Grant of patent or utility model | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |