CN104593073B - A kind of preparation method of oxidized microcrystalline wax - Google Patents
A kind of preparation method of oxidized microcrystalline wax Download PDFInfo
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- CN104593073B CN104593073B CN201310532442.6A CN201310532442A CN104593073B CN 104593073 B CN104593073 B CN 104593073B CN 201310532442 A CN201310532442 A CN 201310532442A CN 104593073 B CN104593073 B CN 104593073B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
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Abstract
The invention provides a kind of preparation method of oxidized microcrystalline wax, comprise following content: using rotary drill reactor as conversion unit, described rotating bed is made up of corrosion-resistant framework and bed, bed is made up of catalyst filling, take Microcrystalline Wax as raw material, under air existent condition, carry out oxidizing reaction, described catalyzer is load potassium permanganate on the activated carbon, the HCl aqueous solution containing 50 ~ 150mL/L in described air.The present invention can realize continuous seepage, and temperature of reaction is low, and reactive behavior is high, and object product yield is high.
Description
Technical field
The present invention relates to a kind of preparation method of oxidized microcrystalline wax, belong to wax oxidizing process technical field.
Background technology
In recent years, along with all trades and professions are to the demand of special wax, with method for oxidation, chemical modification carried out to Microcrystalline Wax and receive most attention to obtain the modified waxes with more high added value.Because there is many excellent performances such as good emulsifying, pigment-dispersing, oilness, oil soluble, upper photosensitiveness after Microcrystalline Wax oxidation, also improve the snappiness of paraffin, therefore oxidized microcrystalline wax is obtained for and applies widely in synthesising biological degradable material, weaving, intermetallic composite coating, thermoplastic resin, pottery, lubricating oil, ink, metal finishing, ore floatation, vehicle glazing, coating, explosive, molding, leather etc. simultaneously.
Before the eighties in 20th century, Microcrystalline Wax is oxidized the catalyzer used and mainly utilizes the transition metal soap mixture of high price to coordinate air to produce lipid acid, but catalyst regeneration effect is undesirable, and, these catalyzer can form some by products and metallic residue, and are not easy to remove from product.At present, the technological process of industrial production oxidized microcrystalline wax is by KMnO
4the aqueous solution directly joins in the wax liquid of heat fused, passes into air, and be oxidized under certain temperature condition, preparation process belongs to periodical operation.The title complex of transition metal specifically reacts some and has good catalysed oxidn.In order to it is immobilized, people once attempted to be carried on zeolite molecular sieve, but were subject to the restriction of the latter's channel diameter, and these supported title complexs do not play its due catalytic activity well.Thus from this view point, the carrier that selection one is suitable just seems most important.
It is carrier with SPA-15 that CN102921447A proposes a kind of, and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES is the preparation method of the paraffin catalyst of active ingredient, although SPA-15 has very high pore radius, because its chemical reactivity is not high, and greatly limit its practical ranges; In addition, in Microcrystalline Wax composition, isomeric hydrocarbon content is up to more than 90%, and molecular weight ratio paraffin is large many, and isomeric hydrocarbon is more than the oxidation of straight chain hydrocarbon difficulty, and therefore, above-mentioned proprietary catalysts is also unsuitable for the oxidation of Microcrystalline Wax.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of oxidized microcrystalline wax, the inventive method reaction efficiency is high, and products obtained therefrom quality is good.
The invention provides a kind of preparation method of oxidized microcrystalline wax, comprise following content: using rotary drill reactor as conversion unit, described rotating bed is made up of corrosion-resistant framework and bed, bed is made up of catalyst filling, take Microcrystalline Wax as raw material, under air existent condition, carry out oxidizing reaction, described catalyzer is the potassium permanganate of load on modified activated carbon, the HCl aqueous solution containing 50 ~ 150mL/L in described air.
In the inventive method, oxidizing reaction effluent obtains oxidized microcrystalline wax, tail gas after being separated respectively, containing materials such as low mass molecule alcohol, aldehyde, carboxylic acids in described tail gas, wherein tail gas is separated by condenser, and isolated air can loop back oxidation reaction zone and reuse.
In the inventive method, oxidizing reaction use air in containing 60 ~ 100mL/L the HCl aqueous solution.
In the inventive method, described Microcrystalline Wax oleaginousness is not more than 5wt%, is preferably not more than 3.5wt%; Micro-crystal wax feed can be one or more of 75#, 80#, 85#, 90# Microcrystalline Wax.
In the inventive method, oxidation reaction condition is: reaction pressure is 1 ~ 10MPa, preferably 5 ~ 10MPa; Temperature of reaction is 140 ~ 190 DEG C, preferably 150 ~ 190 DEG C; Volume space velocity 0.3 ~ 1.0h
-1, preferably 0.4 ~ 0.7h
-1; Air and liquid phase volume ratio is in normal conditions 100:1 ~ 1200:1, preferred 600:1 ~ 1000:1.
In the inventive method, the rotating speed of rotating bed is 0 ~ 5000 rev/min, is preferably 150 ~ 2000 revs/min.
In the inventive method, reaction mass residence time in reactor is 60 ~ 6000 seconds, is preferably 120 ~ 600 seconds.
In the inventive method, catalyzer take modified activated carbon as carrier, in catalyst quality containing active ingredient potassium permanganate 10% ~ 25%, and preferably 15% ~ 25%.Described modified activated carbon obtains after gac is carried out ultrasonication.
The preparation method of used catalyst of the present invention is as follows: be first dissolved in water by potassium permanganate, make the aqueous solution of different concns, then modified activated carbon is joined in potassium permanganate solution, 2 ~ 8h is soaked under room temperature, dephlegmate, solid dry 4h at 120 DEG C of gained, obtained described catalyzer.
Compared with prior art, the preparation method of oxidized microcrystalline wax of the present invention adopts fixed bed oxidizing process, continuous seepage can be realized, oxidizing reaction can be realized under lower temperature of reaction, the cracking of Microcrystalline Wax carbochain can not be caused, very high catalytic activity and object selectivity of product is had to Microcrystalline Wax oxidation, technological process energy consumption is low, flexibly simple to operate, owing to containing a small amount of hydrochloric acid in air, can catalyst selectivity be improved, improve the transformation efficiency of object product carboxylic acid, suppress the generation of side reaction alcohol, aldehyde simultaneously to greatest extent.In the inventive method, adopt rotary drill reactor as the equipment of Microcrystalline Wax oxidizing reaction, and catalyzer is packed into the bed of rotating bed with the form of filler, significantly improve the contact efficiency of Microcrystalline Wax and catalyzer, substantially reduce the reaction times, and improve object product yield.
Embodiment
Below in conjunction with specific embodiment, the inventive method is described in detail.After Microcrystalline Wax dissolves and air mixed enter reactor, carry out oxidizing reaction, reaction product is separated, and obtains oxidized microcrystalline wax, tail gas, air respectively, and wherein isolated air can be introduced oxidation reaction zone and recycles.
In the present invention, raw materials used character is in table 1, and reaction conditions is in table 2, and products obtained therefrom character is in table 2.
Particular content and the effect of the inventive method are described below by specific embodiment.
The preparation of catalyzer: first gac is put into ultrasonic equipment and process 30min, then modified activated carbon 500g being joined 1000mL massfraction is in the potassium permanganate solution of 55%, 2 ~ 8h is soaked under room temperature, dephlegmate, solid dry 4h at 120 DEG C of gained, obtained described catalyzer.Catalyst body is potassium permanganate/gac, and its character is as follows: potassium permanganate content 40%, specific surface 2500m
2/ g, average pore radius 40nm.
Embodiment 1
The present embodiment adopt raw material 1, in air used containing 70mL/L the HCl aqueous solution, concrete reaction conditions and product property are in table 2.
Embodiment 2
Adopt raw material 2, in air used containing 90mL/L the HCl aqueous solution, concrete reaction conditions and product property are in table 2.
Embodiment 3
Identical with embodiment 1, in air used containing 70mL/L the HCl aqueous solution, difference is that reaction conditions is different, and concrete reaction conditions is in table 2.
Comparative example 1
Identical with embodiment 1, difference is not containing the HCl aqueous solution in air.
Comparative example 2
Adopt traditional paraffin oxidation technique, used catalyst is potassium permanganate solution, adopts traditional conversion unit, and all the other are identical with embodiment 1.Comparative example 2 reaction conditions is temperature of reaction 175 DEG C, reaction times 4h, air flow quantity 6.0L/h, containing catalyst residue in reaction product.
Table 1 feedstock property
Table 2 processing condition and product property
Claims (15)
1. the preparation method of an oxidized microcrystalline wax, it is characterized in that comprising following content: using rotary drill reactor as conversion unit, described rotating bed is made up of corrosion-resistant framework and bed, bed is made up of catalyst filling, take Microcrystalline Wax as raw material, under air existent condition, carry out oxidizing reaction, described catalyzer is the potassium permanganate of load on modified activated carbon, the HCl aqueous solution containing 50 ~ 150mL/L in described air.
2. in accordance with the method for claim 1, it is characterized in that: described Microcrystalline Wax oleaginousness is not more than 5%.
3. according to the method described in claim 1 or 2, it is characterized in that: described Microcrystalline Wax oleaginousness is not more than 3.5%.
4. in accordance with the method for claim 1, it is characterized in that: described Microcrystalline Wax is one or more of 75#, 80#, 85#, 90# Microcrystalline Wax.
5. in accordance with the method for claim 1, it is characterized in that: oxidation reaction condition is: reaction pressure is 1 ~ 10MPa, temperature of reaction is 140 ~ 190 DEG C, volume space velocity 0.3 ~ 1.0h
-1, air and liquid phase volume ratio is in normal conditions 100:1 ~ 1200:1.
6. according to the method described in claim 1 or 5, it is characterized in that: oxidation reaction condition is: reaction pressure is 5 ~ 10MPa; Temperature of reaction is 150 ~ 190 DEG C; Volume space velocity 0.4 ~ 0.7h
-1; Air and liquid phase volume ratio is in normal conditions 600:1 ~ 1000:1.
7. in accordance with the method for claim 1, it is characterized in that: catalyzer take gac as carrier, in catalyst quality containing active ingredient potassium permanganate 10% ~ 25%.
8. in accordance with the method for claim 7, it is characterized in that: catalyzer take gac as carrier, in catalyst quality containing active ingredient potassium permanganate 15% ~ 25%.
9. in accordance with the method for claim 1, it is characterized in that: the HCl aqueous solution containing 60 ~ 100mL/L in described air.
10. in accordance with the method for claim 1, it is characterized in that: the rotating speed of rotating bed is 0 ~ 5000 rev/min.
11. in accordance with the method for claim 10, it is characterized in that: the rotating speed of rotating bed is 150 ~ 2000 revs/min.
12. in accordance with the method for claim 1, it is characterized in that: reaction mass residence time in reactor is 60 ~ 6000 seconds.
13. in accordance with the method for claim 12, it is characterized in that: reaction mass residence time in reactor is 120 ~ 600 seconds.
14. in accordance with the method for claim 1, it is characterized in that: the preparation method of catalyzer is as follows: first potassium permanganate is dissolved in water, make the aqueous solution of different concns, then modified activated carbon is joined in potassium permanganate solution, 2 ~ 8h is soaked under room temperature, dephlegmate, solid dry 4h at 120 DEG C of gained, obtained described catalyzer.
15., according to the method described in claim 1 or 11, is characterized in that: described modified activated carbon obtains after gac is carried out ultrasonication.
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| CN201310532442.6A CN104593073B (en) | 2013-11-04 | 2013-11-04 | A kind of preparation method of oxidized microcrystalline wax |
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| CN201310532442.6A CN104593073B (en) | 2013-11-04 | 2013-11-04 | A kind of preparation method of oxidized microcrystalline wax |
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| CN104593073B true CN104593073B (en) | 2016-03-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106987274B (en) * | 2017-05-02 | 2018-08-21 | 上海五伦化工科技有限公司 | De- fragrant paraffin of one kind and preparation method thereof |
| CN112852486B (en) * | 2021-01-12 | 2022-10-14 | 国家能源集团宁夏煤业有限责任公司 | Oxidized wax and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB787921A (en) * | 1954-06-11 | 1957-12-18 | South African Coal Oil Gas | Wax processing |
| GB911813A (en) * | 1960-08-26 | 1962-11-28 | Shell Int Research | Process for the catalytic hydrogenative refining of hydrocarbon wax |
| CN102615244A (en) * | 2012-03-31 | 2012-08-01 | 四川德力铁道科技有限公司 | Technology for recycling paraffin-resin mold material |
| CN102921447A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Preparation method and using method for paraffin catalyst |
-
2013
- 2013-11-04 CN CN201310532442.6A patent/CN104593073B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB787921A (en) * | 1954-06-11 | 1957-12-18 | South African Coal Oil Gas | Wax processing |
| GB911813A (en) * | 1960-08-26 | 1962-11-28 | Shell Int Research | Process for the catalytic hydrogenative refining of hydrocarbon wax |
| CN102615244A (en) * | 2012-03-31 | 2012-08-01 | 四川德力铁道科技有限公司 | Technology for recycling paraffin-resin mold material |
| CN102921447A (en) * | 2012-10-30 | 2013-02-13 | 陕西启源科技发展有限责任公司 | Preparation method and using method for paraffin catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 氧化微晶蜡的研究;张志银;《当代化工》;20040831;第33卷(第4期);第217-219页 * |
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