CN1011203B - Complex catalyst for hydrocarbon oxidation - Google Patents
Complex catalyst for hydrocarbon oxidationInfo
- Publication number
- CN1011203B CN1011203B CN 88105772 CN88105772A CN1011203B CN 1011203 B CN1011203 B CN 1011203B CN 88105772 CN88105772 CN 88105772 CN 88105772 A CN88105772 A CN 88105772A CN 1011203 B CN1011203 B CN 1011203B
- Authority
- CN
- China
- Prior art keywords
- oxidation
- hedp
- catalyzer
- lightweight
- hydrocarbon oxidation
- Prior art date
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a complex catalyst for hydrocarbon oxidation, which comprises diphosphonate ester and transitional metal salt, improves the condition of hydrocarbon oxidation, has no need of changes of the existing equipment to a cyclohexane liquid phase oxidation technology, prevents slag formation from blocking equipment and pipelines, extends the period of continuous production and improves the selectivity and the yield of useful products.
Description
The present invention relates to a kind of catalyzer of hydrocarbon oxidation.
The hydro carbons liquid-phase oxidation, at present in industrial main employing organic carboxylate liquid phase catalytic oxidation and non-catalyst oxidation method, as hexanaphthene, annual in the world have nearly 3,000,000 tons to become hexalin and pimelinketone and their derivative by molecular oxygen oxidation.Present topmost commercial run is cobalt salt liquid phase catalytic oxidation and non-catalyst oxidation method.
The emerging product of japanese character portion (UBE), West Germany's BASF (BASF) adopt cobalt octoate catalysis; Holland mining company (DSM) is with no catalysis technique, and the reaction product major part maintains peroxide stage, further under the katalysis of Cobaltous diacetate, is decomposed into hexalin and pimelinketone again; Production cycle all near or surpass half a year.
The domestic cobalt naphthenate catalytic oxidation that all adopts, molecular yield be lower than 80% and slagging scorification serious, adopt pyrophosphate salt to be coated with after the wall technology production cycle and be about two months and will stop scarfing cinder.Liaoyang petro-chemical fiber company introduces Long Boli technical equipment of the patent non-catalyst oxidation device from France, trisodium phosphate is coated with wall passivation reaction wall and prevents slagging scorification, but temperature of reaction and working pressure will be higher than catalysis of cobalt salt, chromatize catalytic decomposition again, the misery ester that phosphorates is simultaneously done precipitating inhibitor, the slagging scorification phenomenon is also arranged, and the production cycle is half a year.
The objective of the invention is under the prerequisite of processing parameter that does not change the cobalt salt catalyzed oxidation and equipment, propose with 1-hydroxyl alkane-1, the catalyzer that 1-bisphosphonates and transition metal salt are formed, improve the catalytic oxidation activity of cobalt ion to hydro carbons, reduce deep oxidation, prevent to generate slagging scorification occluding device and pipeline, prolong the quantity-produced cycle, improve alcohol, ketone yield.
The catalyzer of the hydrocarbon oxidation that the present invention proposes is characterized in that comprising 1-hydroxyl alkane-1,1-bisphosphonates and transition metal salt.
1-hydroxyl alkane-1 in the catalyzer of the hydrocarbon oxidation that the present invention proposes, the chemical structure of general formula of 1-bisphosphonates is
" be alkyl, X is OH, and condition is (OH) and (OR ') or (OH) and (sum of OR ") equals 2 for wherein R, R ', R.1-hydroxy ethylidene-1 wherein, 1-di 2 ethylhexyl phosphonic acid (HEDP) is a 1-hydroxyl alkane-1, first representative that is synthesized in the 1-diphosphonic acids, its chemical formula is
By HEDP with contain C
1～C
18Various alcohol reactions obtain the HEDP esters.Byproduct when the lightweight oil of the lightweight grease of HEDP is cyclohexane oxidation process production hexalin, pimelinketone, wherein effective constituent has Pentyl alcohol, propyl carbinol etc., generates HEDP pentyl ester, HEDP butyl ester.
Transition metal salt in the catalyzer of the hydrocarbon oxidation that the present invention proposes can be a cobalt salt.
The catalyst concentration of the hydrocarbon oxidation that the present invention proposes is 0.1～100PPm, promptly one to ten thousand/(weight)/10000000th of the raw material hydro carbons.
The hydro carbons liquid-phase oxidation is at present at industrial main employing organic carboxyl acid transition metal salt liquid phase catalytic oxidation, as cobalt octoate, cobalt naphthenate catalyzed oxidation; The non-catalyst oxidation method be after the oxidation again through catalytic decomposition, the acid sludge that two kinds of methods all exist side reaction to generate blocks pipeline and equipment, makes to produce to interrupt, produce again after cleaning slag, adopt trisodium phosphate to be coated with wall, though prolonged the production cycle, but desired reaction temperature and pressure all will improve, and is unfavorable to safety.
1-hydroxyl alkane-1, the complex compound that 1-bisphosphonates and transition metal ion generate is used for hydrocarbon oxidation and can improves catalytic oxidation activity, reduce deep oxidation, improve the ability of directional catalyzing oxidation, and prevented slagging scorification precipitation, occluding device, prolong the quantity-produced cycle, improve the productive rate of oxidation, and reduce the tail gas oxygen level, the production cycle can prolong.
Below in conjunction with the embodiment explanation, the oxidation of hexanaphthene is one of most important industry of petroleum chemistry, the present invention utilizes existing domestic hexanaphthene cobalt salt catalytic oxidizing equipment, keep original temperature of reaction, pressure, feeding quantity, air feeding amount is constant, with 1-hydroxyl alkane-, the representative 1-hydroxy ethylidene-1 of 1-bisphosphonates, 1-di 2 ethylhexyl phosphonic acid (HEDP) is produced hexalin with cyclohexane oxidation process, byproduct main ingredient during pimelinketone is that the lightweight oil of Pentyl alcohol reacts the HEDP lightweight grease of production and the catalyzer that cobalt salt is formed, and carries out hexanaphthene and becomes hexalin and pimelinketone by molecular oxygen oxidation.
Embodiment 1: take by weighing the HEDP200 gram, lightweight oil 2000 grams, add in the flask, ebuillition of heated refluxes under the normal pressure, in time tell moisture, reacted 3～4 hours, generate the HEDP ester,, slowly be added dropwise to the cyclohexane oxidation system that produces 5000～8000 tons of pimelinketone per year above-mentioned product, catalyst levels is in cobalt in the oxidation liquid, still be 0.3～1PPM, the weight ratio of HEDP ester consumption and cobalt salt is 0.3～2: 1, promptly adds cobalt naphthenate 2kg every day, then add HEDP lightweight grease 1～4kg, (mol ratio of HEDP lightweight grease and cobalt salt is 1: 2.3～9.3).Reaction result, slagging scorification obviously reduces, the production cycle extended to half a year from 2 months more than (half a year, the afterreaction wall still was stainless steel gloss), yield also has raising (improve 10%).
Example 2: in the chemical general factory cyclohexane oxidation full scale plant of Jinxi, adopt trisodium phosphate to be coated with wall, all processing parameters are constant, and cobalt naphthenate 2kg and HEDP lightweight grease 1kg are dissolved in 2m
3Hexanaphthene, be mixed with catalyst solution, per hour in oxidation reactor, inject 83 liters of this catalyst solutions, add HEDP lightweight grease with ram pump again to oxidation reactor in addition with proportioning pump, its add-on per hour is 100g, with the weight ratio of cobalt salt be 1.2: 1.Every day, total consumption of catalyzer was: cobalt naphthenate 2kg, and HEDP lightweight grease 3.4kg, the mol ratio of HEDP lightweight grease and cobalt salt is 1: 3(HEDP lightweight grease is with wherein main component HEDP diamyl ester calculating), cobalt concentration is 0.3～1ppm in the oxidation system.Reaction result, it is clear that oxidation liquid color becomes, side reaction reduces, yield improves (10%), slagging scorification obviously reduces, production cycle extends to (the afterreaction wall still was stainless steel gloss in 6 months, and originally the production cycle is 2 months, and producing had the thick slagging scorification of 10～100mm in 2 months on the afterreaction wall) more than 6 months.
Claims (4)
1, a kind of hydrocarbon oxidation catalyzer is characterized in that this catalyzer by following formula 1-hydroxyl alkane-1, and 1-bisphosphonates and transition metal salt are formed,
" be alkyl, X is a hydroxyl, and condition is (OH) and (OR ') or (OH) and (sum of OR ") equals 2 for wherein R, R ' and R.
2, according to the catalyzer of claim 1, wherein general formula compound is a 1-hydroxy ethylidene-1, and 1-di 2 ethylhexyl phosphonic acid (HEDP) reacts the HEDP lightweight grease of being produced with cyclohexane oxidation byproduct lightweight oil (main component Pentyl alcohol, propyl carbinol).
3, according to the catalyzer of claim 1, transition metal salt wherein is a cobalt salt.
4, according to the catalyzer of claim 1～3, diphosphonate derivatives wherein such as 1-hydroxy ethylidene-1, the mol ratio of 1-di 2 ethylhexyl phosphonic acid lightweight grease and cobalt salt is that 1: 2.3～9.3(HEDP lightweight grease calculates with wherein main effective ingredient HEDP diamyl ester).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105772 CN1011203B (en) | 1988-09-16 | 1988-09-16 | Complex catalyst for hydrocarbon oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105772 CN1011203B (en) | 1988-09-16 | 1988-09-16 | Complex catalyst for hydrocarbon oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1035960A CN1035960A (en) | 1989-10-04 |
| CN1011203B true CN1011203B (en) | 1991-01-16 |
Family
ID=4833917
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105772 Expired CN1011203B (en) | 1988-09-16 | 1988-09-16 | Complex catalyst for hydrocarbon oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1011203B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5233092A (en) * | 1989-11-06 | 1993-08-03 | Xiao Zaosheng | Diphosphonate compounds, their preparation and application |
| CN100363317C (en) * | 2003-11-25 | 2008-01-23 | 肖藻生 | Method for preparing cyclohexanone and cyclohexanol by cyclohexane oxidation |
| US7828203B2 (en) | 2004-02-23 | 2010-11-09 | Nec Corporation | Data writing apparatus, method, and program for portable terminal memory |
| CN102627542B (en) * | 2012-03-28 | 2014-05-21 | 肖藻生 | Process for preparing hexanaphthene and cyclohexanone with cyclohexane serving as raw material |
| CN106831521B (en) * | 2017-03-07 | 2018-08-21 | 湖北科林博伦新材料有限公司 | A kind of method that toluene liquid-phase air oxidation process prepares benzyl peroxide |
-
1988
- 1988-09-16 CN CN 88105772 patent/CN1011203B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1035960A (en) | 1989-10-04 |
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