CN102260133B - Complete hydrogenation method for synthesizing saturated alkane by catalyzing poly alpha olefin - Google Patents
Complete hydrogenation method for synthesizing saturated alkane by catalyzing poly alpha olefin Download PDFInfo
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- CN102260133B CN102260133B CN 201110156970 CN201110156970A CN102260133B CN 102260133 B CN102260133 B CN 102260133B CN 201110156970 CN201110156970 CN 201110156970 CN 201110156970 A CN201110156970 A CN 201110156970A CN 102260133 B CN102260133 B CN 102260133B
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- polyalphaolefin
- poly alpha
- alpha olefin
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Abstract
The invention belongs to the technical field of fine chemical engineering, in particular a complete hydrogenation method for synthesizing saturated alkane by catalyzing poly alpha olefin. A co-precipitation method is adopted to synthesize an Ni/SiO2-Al2O3 type catalyst. Under the existence of the Ni/SiO2-Al2O3 catalyst, the poly alpha olefin can be catalyzed and reduced to the saturated alkane under the conditions that the reaction temperature is 60-200 DEG C, the pressure ranges from 1.0-6.0 MPa, the liquid hourly space velocity is 0.4-0.8 per hour, and a molar ratio of the hydrogen to the poly alpha olefin is 5-20. The complete hydrogenation reduction of the poly alpha olefin to the alkane is realized through the simple and feasible method, so that the olefin double bonds in the molecules are saturated so as to ensure the chemical stability and thermal stability of a product; and the conversion rate of the poly alpha olefin can reach 100 percent. The catalyst preparation process is simple, and the cost is low. The method has good application prospect.
Description
Technical field
The invention belongs to the fine chemical technology field, be specifically related to the method for the synthetic saturated alkane of a kind of catalysis polyalphaolefin complete hydrogenation.
Background technology
After 20 century 70s, along with the technical progress of various engines and other mechanical means and day by day urgent " energy-conservation " " environmental protection " requirement, the salient featuress such as the sticking warm nature of lubricating oil, volatility, thermal oxidation stability have also been proposed day by day harsh requirement, the capability and performance of natural mineral matter base oil is near the limit, is difficult to modulating performance, product with a higher standard again.This has just directly promoted the development of synthetic base oil.Because lubricating oil specification, particularly Internal Combustion Engine Oil is stricter in recent years, and many indexs only depend on mineral oil to be difficult to satisfy the requirement of new spec, impels people that the interest of synthetic oil is increased, and has also promoted the demand growth of ucon oil.
The long-chain saturated alkane has been compared many advantages as the engine oil of base oil modulation with the mineral oil engine oil.The thermostability and the oxidation stability that at first are this alkene obviously are better than mineral oil, can prolong the oil draining period, have reduced maintenance cost and have reduced shutdown period.In addition, when using this ucon oil, the additive compatibility commonly used with the mineral substance base oil is good, and can reduce the consumption of additive, or with more cheap additive, this can dwindle the price variance of this ucon oil and mineral oil origin auto engine oil.
Ucon oil has also that operating temperature range is wide, viscosity-temperature characteristics can be good, pour point is low, viscosity index is high, vaporization losses is little, low volatility, and lightning, point of ignition, spontaneous ignition temperature are high, non-hygroscopic under the high temperature, hydrolysis stability is good, and shear stability is good, to the equipment non-corrosiveness.In addition, little to engine wear under low temperature and hot conditions, carbon distribution is few, and is biodegradable, and long service life, and efficient is high, and coking is few, nontoxic and skin had characteristics such as immersional wetting.
In the process of producing ucon oil, wish polyalphaolefin is carried out hydrogenation, make olefinic double bonds remaining in the molecule saturated, to guarantee chemical stability and the thermostability of product.The quality of this step for product plays vital effect.If do not carry out this step hydrogenation reaction, the life-span can be very short in the engine of rapidly running or in the steam turbine of high temperature for alkene.Even if not in such environment, airborne oxygen also can with destroy two keys, thereby the capability and performance of product is reduced greatly, lost its original meaning.
The catalyzer that is used at present the polyalphaolefin hydrogenation mainly contains Raney's nickel and pickling process loaded catalyst.Although adopt Raney's nickel can reach certain hydrogenation effect, Raney's nickel is unstable in air, meets oxygen and burn easily, to preserving and using and bring very large inconvenience.Although pickling process technique is simple, can save metal, metal component active relatively poor, and short easy inactivation of the life-span of catalyzer, add precious metal after cost rise, be not suitable for present industrialization yet.
By comparison, it is very thin to adopt coprecipitation method to produce granules of catalyst, can reach Nano grade, and simultaneously activity component metal nickel dispersion is all better than the above two, and the characteristics that surface-area is large, stability is superior are arranged.Therefore, the invention provides a kind of with active component nickel and SiO
2, Al
2O
3Be precipitated out simultaneously the method that obtains the large outside surface nickel catalyzator of high dispersive, and be applied to the polyalphaolefin hydrogenation.
Summary of the invention
The method that the purpose of this invention is to provide the synthetic saturated alkane of catalysis polyalphaolefin complete hydrogenation that a kind of technique is simple, efficient is high, with low cost.
The method of the synthetic saturated alkane of catalysis polyalphaolefin complete hydrogenation provided by the invention the steps include: that the fixed bed that polyalphaolefin and hydrogen together enter loading catalyst carries out catalyzed reaction, and polyalphaolefin is hydrogenated to alkane fully; Described catalyzer is by SiO
2, Al
2O
3Prepare through co-precipitation with metallic nickel, be designated as Ni/SiO
2-Al
2O
3Its reaction formula is:
C
nH
2n + H
2 → C
nH
2n+2 (n=20—100)；
Wherein, the catalyzed reaction actual conditions is:
(1) temperature range of catalyzed reaction is 60-200
oC;
(2) pressure range of catalyzed reaction is 1.0-6.0 MPa;
(3) the liquid hourly space velocity scope is 0.4-0.8 h
-1
(4) hydrogen and polyalphaolefin mol ratio are 5-20.
Described polyalphaolefin, molecular formula are C
nH
2n, wherein n is that carbonatoms is 20-100.
The used catalyzer of the present invention is the Ni/SiO of co-precipitation preparation
2-Al
2O
3Catalyzer, its concrete preparation method is as follows:
With aluminum nitrate (Al (NO
3)
3 .9H
2O) with nickelous nitrate (Ni (NO
3)
2 .6H
2O) mixing solutions is added drop-wise to water glass (Na
2SiO
3 .9H
2O) in the solution, it is precipitated fully, then washing and filtering oven dry.Generate NiO/SiO by the high temperature air roasting again
2-Al
2O
3Catalyzer reduces with reducing gas before using, and obtains Ni/SiO
2-Al
2O
3Catalyzer.Large, active high, the good stability of this catalyst surface area.
Among the present invention, the Ni/SiO of co-precipitation preparation
2-Al
2O
3In the catalyzer, SiO
2-Al
2O
3Be the carrier of catalyzer, metallic nickel is catalytic active component, disperses wherein.The charge capacity of metallic nickel is 30-60wt%, SiO
2With Al
2O
3Mol ratio be 8:1-16:1.
Among the present invention, the temperature of described high temperature air roasting is 600-750 ℃, roasting time 4-10h.
Among the present invention, described reducing gas is the mixed gas of hydrogen and nitrogen, and the content of hydrogen is 1%-100% in the reducing gas, and reduction temperature is 200-500 ℃.
Coprecipitation method prepares Ni/SiO
2-Al
2O
3The concrete operation step of catalyzer is:
With a certain amount of Na
2SiO
3 .9H
2O puts into 500ml beaker 1, adds the about 100ml of water, is stirred well to it and dissolves fully.In beaker 2, put into a certain amount of Al (NO
3)
3 .9H
2O and Ni (NO
3)
2 .6H
2O adds the about 100ml of water, is stirred well to it and dissolves fully.Under churned mechanically condition the solution in the beaker 2 dropwise is added drop-wise in the beaker 1, dropwises rear use NaOH solution and transfer change pH values, the pH value that makes precipitated liquid is 7.8-8.2, then stirs 2-10h.Stir and pour precipitated liquid in sand core funnel suction filtration after complete, and with distilled water wash number time, use again washing with alcohol, ambient temperature overnight.Put into baking oven until its complete drying places 600-750 ℃ of roasting 4-10h under the air atmosphere again.When being used for active testing, the equal compressing tablet granulation of catalyzer obtains Ni/SiO to 20-40 order size
2-Al
2O
3Catalyzer.
The present invention uses simple method, has realized that the complete hydrogenation of polyalphaolefin is reduced into alkane, makes the olefinic double bonds in the molecule saturated, and to guarantee chemical stability and the thermostability of product, the transformation efficiency of polyalphaolefin can reach 100%.The catalyst preparation process that the present invention uses is simple, with low cost.Therefore, the present invention has a good application prospect.
Embodiment
Further describe the present invention below by example.
Embodiment 1
Ni (40wt.%)/SiO
2: Al
2O
3=8:1 catalyzer prepares as follows:
Na with a 56.80g
2SiO
3 .9H
2O puts into 500ml beaker 1, adds the about 100ml of water and is stirred well to it and dissolves fully.In beaker 2, put into the Al (NO of 18.75g
3)
3 .9H
2O and 48.05gNi (NO
3)
2 .6H
2O adds the about 100ml of water and is stirred well to it and dissolves fully.Under churned mechanically condition, the solution in the beaker 2 dropwise is added drop-wise in the beaker 1, dropwises rear use NaOH solution and transfer change pH values to make the pH value of precipitated liquid to be about 8, then to stir 10h.Stir and pour precipitated liquid in sand core funnel suction filtration after complete, and with distilled water wash 3 times, washing with alcohol 2 times is in ambient temperature overnight.Put into 70 ℃ of baking ovens until its complete drying places lower 600 ℃ of air atmosphere to be burnt 10h again.When being used for active testing, the equal compressing tablet granulation of catalyzer obtains Ni (40wt.%)/SiO to 20-40 order size
2: Al
2O
3=8:1 catalyzer.
Restrain the Ni (40wt.%) get ready/SiO with 10
2: Al
2O
3=8:1 catalyzer the diameter of packing into is in 8 millimeters the stainless steel reaction pipe, with polyalphaolefin (C
100H
200) pass in the reaction tubes after mixing with hydrogen, entering the catalytic bed reaction, temperature of reaction is 200 ℃, and reaction system pressure is 1.0Mpa, and liquid hourly space velocity is 0.8, and hydrogen and polyalphaolefin mol ratio are 5, polyalphaolefin (C
100H
200) transformation efficiency is 100%.
Embodiment 2
Ni (40wt.%)/SiO
2: Al
2O
3=10:1 catalyzer prepares as follows:
Na with a 56.80g
2SiO
3 .9H
2O puts into 500ml beaker 1, and about 100ml that is dissolved in water is stirred well to it and dissolves fully.In beaker 2, put into the Al (NO of 15.00g
3)
3 .9H
2O and 46.37gNi (NO
3)
2 .6H
2O, about 100ml that is dissolved in water is stirred well to it and dissolves fully.Under churned mechanically condition, the solution in the beaker 2 dropwise is added drop-wise in the beaker 1, dropwises rear use NaOH solution and transfer change pH values to make the pH value of precipitated liquid to be about 8, then to stir 8h.Stir and pour precipitated liquid in sand core funnel suction filtration after complete, and with distilled water wash 3 times, washing with alcohol 2 times is in ambient temperature overnight.Put into 70 ℃ of baking ovens until its complete drying places lower 640 ℃ of air atmosphere to be burnt 8h again.When being used for active testing, the equal compressing tablet granulation of catalyzer obtains Ni (40wt.%)/SiO to 20-40 order size
2: Al
2O
3=10:1 catalyzer.
Restrain the Ni (40wt.%) get ready/SiO with 10
2: Al
2O
3=10:1 catalyzer the diameter of packing into is in 8 millimeters the stainless steel reaction pipe, with polyalphaolefin (C
80H
160) pass in the reaction tubes after mixing with hydrogen, entering the catalytic bed reaction, temperature of reaction is 160 ℃, and reaction system pressure is 5.0Mpa, and liquid hourly space velocity is 0.8, and hydrogen and polyalphaolefin mol ratio are 15, polyalphaolefin (C
80H
160) transformation efficiency is 100%.
Embodiment 3
Ni (40wt.%)/SiO
2: Al
2O
3=12:1 catalyzer prepares as follows:
Na with a 56.80g
2SiO
3 .9H
2O puts into 500ml beaker 1, and about 100ml that is dissolved in water is stirred well to it and dissolves fully.In beaker 2, put into the Al (NO of 12.75g
3)
3 .9H
2O and 45.25gNi (NO
3)
2 .6H
2O, about 100ml that is dissolved in water is stirred well to it and dissolves fully.Under churned mechanically condition, the solution in the beaker 2 dropwise is added drop-wise in the beaker 1, dropwises rear use NaOH solution and transfer change pH values to make the pH value of precipitated liquid to be about 8, then to stir 6h.Stir and pour precipitated liquid in sand core funnel suction filtration after complete, and with distilled water wash 3 times, washing with alcohol 2 times is in ambient temperature overnight.Put into 70 ℃ of baking ovens until its complete drying places lower 675 ℃ of air atmosphere to be burnt 6h again.When being used for active testing, the equal compressing tablet granulation of catalyzer obtains Ni (40wt.%)/SiO to 20-40 order size
2: Al
2O
3=12:1 catalyzer.
Restrain the Ni (40wt.%) get ready/SiO with 10
2: Al
2O
3=12:1 catalyzer the diameter of packing into is in 8 millimeters the stainless steel reaction pipe, with polyalphaolefin (C
60H
120) pass in the reaction tubes after mixing with hydrogen, entering the catalytic bed reaction, temperature of reaction is 140 ℃, and reaction system pressure is 4.0Mpa, and liquid hourly space velocity is 0.7, and hydrogen and polyalphaolefin mol ratio are 13, polyalphaolefin (C
60H
120) transformation efficiency is 100%.
Embodiment 4
Ni (40wt.%)/SiO
2: Al
2O
3=14:1 catalyzer prepares as follows:
Na with a 56.80g
2SiO
3 .9H
2O puts into 500ml beaker 1, and about 100ml that is dissolved in water is stirred well to it and dissolves fully.In beaker 2, put into the Al (NO of 10.70g
3)
3 .9H
2O and 44.35gNi (NO
3)
2 .6H
2O, about 100ml that is dissolved in water is stirred well to it and dissolves fully.Under churned mechanically condition, the solution in the beaker 2 dropwise is added drop-wise in the beaker 1, dropwises rear use NaOH solution and transfer change pH values to make the pH value of precipitated liquid to be about 8, then to stir 4h.Stir and pour precipitated liquid in sand core funnel suction filtration after complete, and with distilled water wash 3 times, washing with alcohol 2 times is in ambient temperature overnight.Put into 70 ℃ of baking ovens until its complete drying places lower 710 ℃ of air atmosphere to be burnt 5h again.When being used for active testing, the equal compressing tablet granulation of catalyzer obtains Ni (40wt.%)/SiO to 20-40 order size
2: Al
2O
3=14:1 catalyzer.
Restrain the Ni (40wt.%) get ready/SiO with 10
2: Al
2O
3=14:1 catalyzer the diameter of packing into is in 8 millimeters the stainless steel reaction pipe, with polyalphaolefin (C
40H
80) pass in the reaction tubes after mixing with hydrogen, entering the catalytic bed reaction, temperature of reaction is 100 ℃, and reaction system pressure is 3.0Mpa, and liquid hourly space velocity is 0.6, and hydrogen and polyalphaolefin mol ratio are 10, polyalphaolefin (C
40H
80) transformation efficiency is 100%.
Embodiment 5
Ni (40wt.%)/SiO
2: Al
2O
3=16:1 catalyzer prepares as follows:
Na with a 56.80g
2SiO
3 .9H
2O puts into 500ml beaker 1, and about 100ml that is dissolved in water is stirred well to it and dissolves fully.In beaker 2, put into the Al (NO of 9.38g
3)
3 .9H
2O and 43.84gNi (NO
3)
2 .6H
2O, about 100ml that is dissolved in water is stirred well to it and dissolves fully.Under churned mechanically condition, the solution in the beaker 2 dropwise is added drop-wise in the beaker 1, dropwises rear use NaOH solution and transfer change pH values to make the pH value of precipitated liquid to be about 8, then to stir 2h.Stir and pour precipitated liquid in sand core funnel suction filtration after complete, and with distilled water wash 3 times, washing with alcohol 2 times is in ambient temperature overnight.Put into 70 ℃ of baking ovens until its complete drying places lower 750 ℃ of air atmosphere to be burnt 4h again.When being used for active testing, the equal compressing tablet granulation of catalyzer obtains Ni (40wt.%)/SiO to 20-40 order size
2: Al
2O
3=16:1 catalyzer.
Restrain the Ni (40wt.%) get ready/SiO with 10
2: Al
2O
3=16:1 catalyzer the diameter of packing into is in 8 millimeters the stainless steel reaction pipe, with polyalphaolefin (C
20H
40) pass in the reaction tubes after mixing with hydrogen, entering the catalytic bed reaction, temperature of reaction is 60 ℃, and reaction system pressure is 6.0Mpa, and liquid hourly space velocity is 0.4, and hydrogen and polyalphaolefin mol ratio are 20, polyalphaolefin (C
20H
40) transformation efficiency is 100%.
Claims (3)
1. the method for the synthetic saturated alkane of a catalysis polyalphaolefin complete hydrogenation is characterized in that the fixed bed that polyalphaolefin and hydrogen together enter loading catalyst carries out catalyzed reaction, and polyalphaolefin is hydrogenated to alkane fully; Described catalyzer is by SiO
2, Al
2O
3Prepare through co-precipitation with metallic nickel, be designated as Ni/SiO
2-Al
2O
3Wherein, described catalytic reaction condition is:
(1) temperature is 60-200
oC;
(2) pressure is 1.0-6.0 MPa;
(3) the liquid hourly space velocity scope is 0.4-0.8 h
-1
(4) hydrogen and polyalphaolefin mol ratio are 5-20;
Wherein, described co-precipitation prepares Ni/SiO
2-Al
2O
3The step of catalyzer is: the mixing solutions of aluminum nitrate and nickelous nitrate is added drop-wise in the sodium silicate solution, it is precipitated fully, then washing and filtering oven dry; Generate NiO/SiO by the high temperature air roasting again
2-Al
2O
3Before using, catalyzer with the reducing gas reduction, obtains Ni/SiO
2-Al
2O
3Catalyzer;
Described Ni/SiO
2-Al
2O
3In the catalyzer, SiO
2-Al
2O
3Be the carrier of catalyzer, metallic nickel is catalytic active component, disperses wherein; The charge capacity of metallic nickel is 30-60wt%, SiO
2With Al
2O
3Mol ratio be 8:1-16:1.
2. method according to claim 1, the temperature that it is characterized in that described high temperature air roasting is 600-750 ℃, roasting time 4-10h.
3. method according to claim 1 is characterized in that described reducing gas is the mixed gas of hydrogen and nitrogen, and the content of hydrogen is 1%-100% in the reducing gas, and reduction temperature is 200-500 ℃.
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|---|---|---|---|
| CN 201110156970 CN102260133B (en) | 2011-06-13 | 2011-06-13 | Complete hydrogenation method for synthesizing saturated alkane by catalyzing poly alpha olefin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110156970 CN102260133B (en) | 2011-06-13 | 2011-06-13 | Complete hydrogenation method for synthesizing saturated alkane by catalyzing poly alpha olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102260133A CN102260133A (en) | 2011-11-30 |
| CN102260133B true CN102260133B (en) | 2013-10-16 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378767A (en) * | 1993-06-18 | 1995-01-03 | Shell Oil Company | Fixed bed hydrogenation of low molecular weight polydiene polymers |
| EP1101530A1 (en) * | 1999-11-19 | 2001-05-23 | Engelhard Corporation | Nickel-iron containing hydrogenation catalyst |
| CN1699309A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
| CN102079684A (en) * | 2010-12-06 | 2011-06-01 | 复旦大学 | Method for catalyzing complete hydrogenation of polyalphaolefin into saturated alkane |
-
2011
- 2011-06-13 CN CN 201110156970 patent/CN102260133B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378767A (en) * | 1993-06-18 | 1995-01-03 | Shell Oil Company | Fixed bed hydrogenation of low molecular weight polydiene polymers |
| EP1101530A1 (en) * | 1999-11-19 | 2001-05-23 | Engelhard Corporation | Nickel-iron containing hydrogenation catalyst |
| CN1699309A (en) * | 2004-05-20 | 2005-11-23 | 中国石化上海石油化工股份有限公司 | Process for preparing pentane from light C5 distillate |
| CN102079684A (en) * | 2010-12-06 | 2011-06-01 | 复旦大学 | Method for catalyzing complete hydrogenation of polyalphaolefin into saturated alkane |
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