CN1163456C - Ethylene oligomerizing catalyst coated with solid hydrocarbon compound and its prepn - Google Patents
Ethylene oligomerizing catalyst coated with solid hydrocarbon compound and its prepn Download PDFInfo
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- CN1163456C CN1163456C CNB001358995A CN00135899A CN1163456C CN 1163456 C CN1163456 C CN 1163456C CN B001358995 A CNB001358995 A CN B001358995A CN 00135899 A CN00135899 A CN 00135899A CN 1163456 C CN1163456 C CN 1163456C
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- hydrocarbon compound
- solid hydrocarbon
- catalyst
- ethylene
- ethylene oligomerization
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Abstract
The present invention provides an ethylene oligomerizing catalyst which is composed of an ethylene oligomerizing catalyst and a solid hydrocarbon compound coated on the catalyst, wherein the melting range of the solid hydrocarbon compound is from 30 to 300 DEG C. The present invention also provides a preparation method of the ethylene oligomerizing catalyst which has the advantages of stability in air, little possibility of affection from water and oxygen and no possibility of fire ignition and combustion due to triethyl aluminium.
Description
Technical field
The present invention relates to ethylene oligomerization catalyst of a kind of solid hydrocarbon compound parcel and preparation method thereof.
Background technology
The reaction and the technical study thereof of at present relevant chromium-based catalysts catalyzed ethylene oligomerisation have had many reports, and US 5,331, and transistion metal compound is a pyridine chromium in 104 the catalyst for oligomerization system, and JP 08,239,328th, diethyl caproic acid chromium (Cr (EH)
3), they are with 2, and the 5-dimethyl pyrrole (2,5-DMP), germanium tetrachloride (GeCl
4), triethyl aluminum (TEA) and Cr (EH)
3, pre-mixing does not directly add in the oligomerisation reaction device, and US 5,523,507th, and above-mentioned each component is carried out pre-mixing earlier, and then join and carry out ethylene oligomerization reaction in the oligomerisation reaction device.But these reaction systems are liquid phase at normal temperatures, very easily be subjected to the influence of airborne water and oxygen and lost efficacy, and can be because of triethyl aluminum (TEA) catching fire is arranged in air.
Summary of the invention
The objective of the invention is to overcome the shortcoming that catalyst system in the background technology is subject to the influence of water in air and oxygen, by adopting a kind of method of inert substance parcel catalyst system, make catalyzer more stable in air, be subjected to the influence of water and oxygen less, can be because of not containing the triethyl aluminum catching fire yet.
Related natural instincts wrap is solid-state hydrocarbon compound among the present invention, and melting range is at 30-300 ℃, and alkane can be single hydro carbons, also can be hydrocarbon mixture, and commonly used is fusing point is at 50-150 ℃ hydrocarbon compound, the most frequently used is 50-80 ℃ paraffin.
The embedding method of related inertia wrap goes for any olefin oligomerization or polymeric catalyzer among the present invention, vinyl polymerization or oligomerisation, and propylene polymerization or oligomerisation are usually used in ethylene oligomerization.These Preparation of catalysts are well known in the prior art, and are as described below.
The compound of chromium metal is according to US 5,523, and report in 507 can be the compound of organic or inorganic chromium.The oxidation state of chromium is 0-6, and common form is CrX
nX can be identical, also can be different, n is the integer of 1-6, and the carbonatoms of each organic group is 1-20, can be from alkyl, alkoxyl group, ester group, ketone group or amino, organically group can be a straight chain, also can be side chain, can be aromatic base, fatty group or cyclic group, also can be mixed group.The divalence and the trivalent iron compound of chromium commonly used, trivalent chromium compound more usually, Dichloroethyl caproic acid chromium, dioxoethyl caproic acid chromium, lauric acid chromium, beta-diketon chromium, pyridine chromium, diethyl caproic acid chromium, the most frequently used diethyl caproic acid chromium (Cr (EH)
3).
The general formula of the compound of aluminium has AlR
3, AlR
2X, AlRX
2, AlR
2OR, AlRXOR, Al
2R
3X
3, R is an alkyl group, X is a halogen atom.Usually with triethyl aluminum, triisobutyl aluminium, diethyl aluminum chloride, ethyl oxyethyl group aluminum chloride, use trialkylaluminium, the most frequently used triethyl aluminum in the oligomerisation always.
Nitrogenous compound has pyrroles and derivative, pyridine and derivative thereof, azole compounds commonly used, and the diethyl pyrroles, Pyrrolidine, 2, the 5-dimethyl pyrrole, 2,4-dimethyl-3-N-ethyl pyrrole N-, the most frequently used 2, the 5-dimethyl pyrrole.
Halogen compounds can increase the activity and the selectivity of catalyst system, also can increase product selectivity.Halogen has fluorine, chlorine, bromine, iodine.Chlorine normally, the form of halogen compounds is R
mX
n, R can be the organic or inorganic base, X is a halogen.M+n is greater than 0.When R is inorganic group, often be aluminium, silicon, germanium, tin, lead etc., the most frequently used germanium tetrachloride.
This catalyst system is easy to carry out in unsaturated hydrocarbon, can be gas phase, liquid phase, solid phase with aromatic hydrocarbon or aliphatic hydrocarbon, alkene such as aromatic hydrocarbon such as toluene commonly used, benzene, vinylbenzene or ethene, 1-hexene, 1,3-butadiene, the most frequently used toluene.
The invention provides a kind of ethylene oligomerization catalyst, this catalyzer is made up of ethylene oligomerization catalyst and the solid-state hydrocarbon compound that is wrapped on this catalyzer, and the melting range of this solid hydrocarbon compound is at 30-300 ℃.
In catalyzer of the present invention, described solid hydrocarbon compound is paraffin preferably.
Related catalyzer parcel temperature can be at 40-300 ℃ among the present invention, usually at 50-150 ℃, and preferably 50-80 ℃.
Method for preparing catalyst order of the present invention is as follows:
1. preparation ethylene oligomerization catalyst;
2. ethylene oligomerization catalyst and the solid hydrocarbon compound of preparing carried out embedding treatment, wherein the weight ratio of solid hydrocarbon compound and ethylene oligomerization catalyst is 100: 1-1: 200, preferred 75 :-1: 20.Temperature of reaction is 60-150 ℃, and preferably 75-100 ℃, the reaction times is 15 minutes-2 hours, preferably 30 minutes-1 hour.
Above-mentioned solid hydrocarbon compound preferably carries out processed earlier, can with vacuumize, heating, chemical process or additive method.The method that heating commonly used vacuumizes, temperature 50-150 ℃, preferably 70-100 ℃.Can there be very big variation range in treatment time, is generally 4-48 hour, is preferably 20-30 hour.
In the method for the invention, described solid hydrocarbon compound paraffin preferably.
The prepared catalyzer of the present invention has following characteristics:
1, the present invention can manipulate in air with the catalyzer of solid hydrocarbon compound parcel, is not subject to the influence of water, and can be placed in the air and preserve;
2, catalyst activity of the present invention is higher, and selectivity is good, and 1-hexene selectivity is up to 97.9%;
3, the 1-hexene productive rate of catalyzer of the present invention can reach 94.41%;
4, promotor of the present invention is the cheap aluminum alkyls of relative price.
Prepare catalyzer and institute's controlling catalyst is used for the ethylene oligomerization gained by method of the present invention and the results are shown in table one.
Table one: Preparation of Catalyst and oligomerization catalysis result
| Embodiment | Mg chromium (atom) | Active 10 5G product/mol chromium/hr | The weight percent liquid phase | The weight percent solid phase | Liquid product distributed weight per-cent | |||
| C 6， | 1-C 6 | C 8 | C 10+ | |||||
| 1 | 5.63 | 2.76 | 99.33 | 0.66 | 97.08 | 97.91 | 1.39 | 1.53 |
| 2 | 5.63 | 1.80 | 98.24 | 1.76 | 95.14 | 92.70 | 1.54 | 3.32 |
| 3 | 4.11 | 2.42 | 99.38 | 0.62 | 94.58 | 95.70 | 3.41 | 2.01 |
| 4 | 4.11 | 2.35 | 99.55 | 0.45 | 96.87 | 97.91 | 2.39 | 0.74 |
| 5 | 5.88 | 1.22 | 98.17 | 1.83 | 94.76 | 89.62 | 2.21 | 3.03 |
| 6 | 5.35 | 1.39 | 94.92 | 5.08 | 98.60 | 95.25 | 0.69 | 0.71 |
| 7 | 5.35 | 1.12 | 94.33 | 5.67 | 93.65 | 91.22 | 2.88 | 3.47 |
| 8 | 2.85 | 6.82 | 99.76 | 0.24 | 98.13 | 96.90 | 1.01 | 0.86 |
| 9 | 2.85 | 5.96 | 99.88 | 0.12 | 36.56 | 88.93 | 1.30 | 62.14 |
| 10 | 5.43 | 1.85 | 99.69 | 0.31 | 85.20 | 87.40 | 6.58 | 8.22 |
Annotate: catalyst system is Cr (EH)
3+ TEA+2,5-DMP+GeCl
4Mol ratio is: 1/3/15/2
Embodiment
Embodiment one:
Vehicle treated: paraffin 80 ℃ vacuumize 24 hours standby under drying nitrogen.
Preparation of Catalyst: get above-mentioned paraffin carrier 40 grams and put into two mouthfuls of flasks of 100ml round bottom, vacuumize the dry N of displacement
2Protection.Get 0.22g Cr (EH)
32 of (being dissolved in the toluene solution) and 0.13ml, 5-DMP, the GeCl of adding 0.1ml
4, the TEA of 1.9M (being dissolved in the toluene solution) 3.4ml, product vacuumizes removes toluene solvant.Prepared catalyzer is added in the paraffin at 60 ℃, stir and be cooled to room temperature, 42.234g weighs.Cr (g)/paraffin (g) is 2.2 * 10
-4G/g.
Ethylene oligomerization: get above-mentioned carried catalyst 10g and add in 0.2 liter of reactor, vacuumized 5 hours, at normal temperatures and pressures 40ml nonane solvent is added reactor, be warming up to 80 ℃, inject ethene and carry out polyreaction.Ethylene pressure is 2.68MPa, lowers the temperature behind the reaction 30min.Altogether liquid product 14.896g, solid product 0.034g.
Embodiment two:
Ethylene oligomerization: the carried catalyst 10g placement of getting among the embodiment one added in 0.2 liter of reactor after 24 hours, vacuumized 5 hours, at normal temperatures and pressures 40ml nonane solvent was added reactor, was warming up to 80 ℃, injected ethene and carried out polyreaction.Ethylene pressure is 2.68MPa, lowers the temperature behind the reaction 30min.Altogether liquid product 9.57g, solid product 0.17g.
Embodiment three:
Preparation of Catalyst: get above-mentioned paraffin carrier 100 grams and put into two mouthfuls of flasks of 100ml round bottom, vacuumize the dry N of displacement
2Protection.Add in the paraffin as the reinforced order among the embodiment one, 102.234g weighs.Cr (g)/paraffin (g) is 8.8 * 10
-5G/g.
Ethylene oligomerization: get above-mentioned carried catalyst 20g and add in 0.2 liter of reactor, vacuumized 5 hours, at normal temperatures and pressures 40ml nonane solvent is added reactor, be warming up to 80 ℃, inject ethene and carry out polyreaction.Ethylene pressure is 2.68MPa, lowers the temperature behind the reaction 30min.Altogether liquid product 9.56g, solid product 0.06g.
Embodiment four:
Ethylene oligomerization: the carried catalyst 20g placement of getting among the embodiment three added in 0.2 liter of reactor after 24 hours, vacuumized 5 hours, at normal temperatures and pressures 20ml nonane solvent was added reactor, was warming up to 80 ℃, injected ethene and carried out polyreaction.Ethylene pressure is 2.68MPa, and reaction is lowered the temperature behind the 80min, altogether liquid product 24.65g, solid product 0.11g.
Embodiment five:
Preparation of Catalyst: get above-mentioned paraffin carrier 100 grams and put into two mouthfuls of flasks of 100ml round bottom, vacuumize the dry N of displacement
2Protection.As the reinforced order among the embodiment one prepared catalyzer is got 0.11g and add in the paraffin at 60 ℃, stir and be cooled to room temperature, 101.167g weighs.Cr (g)/paraffin (g) is 4.4 * 10
-5G/g.
Ethylene oligomerization: get above-mentioned carried catalyst 50g and add in 0.2 liter of reactor, vacuumized 5 hours, be warming up to 80 ℃, inject ethene and carry out polyreaction.Ethylene pressure is 2.68MPa, lowers the temperature behind the reaction 30min.Altogether liquid product 6.77g, solid product 0.13g.
Embodiment six:
Preparation of Catalyst: get above-mentioned paraffin carrier 20 grams and put into two mouthfuls of flasks of 100ml round bottom, vacuumize the dry N of displacement
2Protection.Add in the paraffin at 60 ℃ as the prepared catalyzer of reinforced order among the embodiment one, stir and be cooled to room temperature, 22.34g weighs.Cr (g)/paraffin (g) is 4.4 * 10
-4G/g.
Ethylene oligomerization: get above-mentioned carried catalyst 5g and add in 0.2 liter of reactor, vacuumized 5 hours, at normal temperatures and pressures 40ml nonane solvent is added reactor, be warming up to 80 ℃, inject ethene and carry out polyreaction.Ethylene pressure is 2.68MPa, lowers the temperature behind the reaction 30min.Altogether liquid product 6.79g, solid product 0/36g.
Embodiment seven:
Ethylene oligomerization: the carried catalyst 5g placement of getting among the embodiment six added in 0.2 liter of reactor after 24 hours, vacuumized 5 hours, at normal temperatures and pressures 40ml nonane solvent was added reactor, was warming up to 80 ℃, injected ethene and carried out polyreaction.Ethylene pressure is 2.68MPa, lowers the temperature behind the reaction 30min.Altogether liquid product 5.43g, solid product 0.33g.
Comparative example one:
Preparation of Catalyst: get 0.22gCr (EH)
32 of (being dissolved in the toluene solution) and 0.13ml, 5-DMP, the GeCl of adding 0.1ml
4, brown, brown solution and solid appear in the TEA of 1.9M (being dissolved in the toluene solution) 3.4ml, and vacuum is removed solvent, and the 15ml nonane extracts, and filters.Be diluted to 25ml with nonane.
Olefinic polymerization: 0.2 liter of reactor was vacuumized 4 hours 40 ℃ of heating, add 40ml nonane, the above-mentioned catalyzer of 3ml at normal temperatures and pressures successively, be warming up to 80 ℃, inject ethene and carry out polyreaction.Ethylene pressure is 2.68Mpa, lowers the temperature behind the reaction 30min.Altogether liquid product 18.65g, solid product 0.04g.
Comparative example two:
Preparation of Catalyst such as comparative example one.
Olefinic polymerization: 0.2 liter of reactor was vacuumized 4 hours 40 ℃ of heating, add the catalyzer of placing 24h among 40ml nonane, the 3ml embodiment one at normal temperatures and pressures successively, be warming up to 80 ℃, inject ethene and carry out polyreaction.Ethylene pressure is 2.68Mpa, lowers the temperature behind the reaction 60min.Altogether liquid product 32.644g, solid product 0.04g.
Comparative example three:
Preparation of Catalyst such as comparative example one.
Olefinic polymerization: 0.2 liter of reactor was vacuumized 4 hours 40 ℃ of heating, add 40ml nonane, 6ml catalyzer at normal temperatures and pressures successively, be warming up to 80 ℃, inject ethene and carry out polyreaction.Ethylene pressure is 2.68MPa, lowers the temperature behind the reaction 30min.Altogether liquid product 6.48g, solid product 0.04g.
Claims (8)
1. the ethylene oligomerization catalyst of solid hydrocarbon compound parcel, this catalyzer is made up of ethylene oligomerization catalyst and the solid-state hydrocarbon compound that is wrapped on this catalyzer, and the melting range of this solid hydrocarbon compound is at 30-300 ℃.
2. according to the described catalyzer of claim 1, wherein, described solid hydrocarbon compound is a paraffin.
3. method for preparing the ethylene oligomerization catalyst of the described solid hydrocarbon compound of claim 1 parcel may further comprise the steps:
(1) preparation ethylene oligomerization catalyst;
(2) ethylene oligomerization catalyst and the solid hydrocarbon compound of preparing carried out embedding treatment, wherein the weight ratio of solid hydrocarbon compound and ethylene oligomerization catalyst is 100: 1-1: 200, and temperature of reaction is 60-150 ℃, the reaction times is 15 minutes-2 hours;
4. in accordance with the method for claim 3, wherein, the weight ratio of solid hydrocarbon compound and ethylene oligomerization catalyst is 75: 1-1: 20.
5. in accordance with the method for claim 3, wherein, the temperature of reaction during embedding is 75-100 ℃, and the reaction times is 30 minutes-1 hour.
6. in accordance with the method for claim 3, wherein, before carrying out embedding treatment, earlier solid hydrocarbon compound is carried out processed.
7. in accordance with the method for claim 6, wherein, described processed vacuumizes under 50-150 ℃ carries out, and the time is 4-48 hour.
8. in accordance with the method for claim 7, wherein, described processed vacuumizes under 70-100 ℃ carries out, and the time is 20-30 hour.
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050187418A1 (en) | 2004-02-19 | 2005-08-25 | Small Brooke L. | Olefin oligomerization |
| US20050187098A1 (en) | 2004-02-20 | 2005-08-25 | Knudsen Ronald D. | Methods of preparation of an olefin oligomerization catalyst |
| US9550841B2 (en) | 2004-02-20 | 2017-01-24 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US20070043181A1 (en) | 2005-08-19 | 2007-02-22 | Knudsen Ronald D | Methods of preparation of an olefin oligomerization catalyst |
| US7384886B2 (en) | 2004-02-20 | 2008-06-10 | Chevron Phillips Chemical Company Lp | Methods of preparation of an olefin oligomerization catalyst |
| US7902415B2 (en) | 2007-12-21 | 2011-03-08 | Chevron Phillips Chemical Company Lp | Processes for dimerizing or isomerizing olefins |
| CN103100419B (en) * | 2011-11-09 | 2015-04-15 | 中国石油化工股份有限公司 | Mixed decene oligomerization catalyst |
| US9586872B2 (en) | 2011-12-30 | 2017-03-07 | Chevron Phillips Chemical Company Lp | Olefin oligomerization methods |
| CN109675642B (en) * | 2017-10-18 | 2021-07-09 | 中国石油化工股份有限公司 | Micro-channel Fischer-Tropsch synthesis catalyst, preparation method thereof and Fischer-Tropsch synthesis reaction method |
| CN109675593B (en) * | 2017-10-18 | 2021-07-09 | 中国石油化工股份有限公司 | Iron-containing Fischer-Tropsch synthesis catalyst, preparation method thereof and Fischer-Tropsch synthesis reaction method |
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