CN109174191A - A kind of catalyst of ethylene selectivity oligomerisation reaction - Google Patents
A kind of catalyst of ethylene selectivity oligomerisation reaction Download PDFInfo
- Publication number
- CN109174191A CN109174191A CN201811081332.1A CN201811081332A CN109174191A CN 109174191 A CN109174191 A CN 109174191A CN 201811081332 A CN201811081332 A CN 201811081332A CN 109174191 A CN109174191 A CN 109174191A
- Authority
- CN
- China
- Prior art keywords
- diphenyl
- catalyst
- phosphorus
- ethylene selectivity
- compound
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
- B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
- B01J31/188—Amide derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/42—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons homo- or co-oligomerisation with ring formation, not being a Diels-Alder conversion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
Abstract
The present invention relates to a kind of catalyst of ethylene selectivity oligomerisation reaction, contain heteroatomic ligand a, a kind of transistion metal compound b and a kind of organo-metallic compound activator c comprising a kind of.Described is to meet general formula I compound represented containing heteroatomic ligand a:Wherein, R1、R2Alkyl selected from linear chain or branched chain.This catalyst activity is greater than 1.0 × 106G ethylene mol‑1Cr·h‑1, C in product6~C8Mass percentage > 80%, C of linear alpha-alkene8The features such as mass percentage > 60% of linear alpha-alkene, catalyst synthesis is simple, at low cost, catalyst life is long.
Description
Technical field
The invention belongs to catalytic fields, are related to ethylene selectivity oligomerisation reaction, and especially a kind of ethylene selectivity oligomerisation is anti-
The catalyst answered.
Technical background
It is well known that octene-1, the linear alpha-alkenes such as alkene -1 have been important chemical products and intermediate, it is widely used in
The fields such as ethylene comonomer, plasticizer alcohol, flavors and fragrances, synthetic lubricant fluid and oil dope.Octene-1, alkene -1 are used
The density that comonomer can be obviously improved polyethylene is done, the mechanical performances such as its tearing toughness and tensile strength are improved.It is used as
When plasticizer alcohol, low-temperature pliability, processability, the outdoor weather resistance of polyethylene products can be made more preferable, be particularly suitable for manufacturing
Cable and wire, automobile parts or decoration etc..
At present industrial production octene-1, the method for the linear alpha-alkenes such as alkene -1 mainly have wax cracking, dehydrating alkanes,
The methods of dehydration of alcohols and ethylene oligomerization, ethylene oligomerization is the main method of current production of linear alpha-olefins according to statistics.Traditional second
The carbon number distribution for the product that alkene oligomerisation technology obtains meets Schulz-Flory distribution, and this distribution makes octene-in oligomerization product
1, the content of hexene -1 can not be too high.Such as US6184428 discloses a kind of Raney nickel, uses boron compound for co-catalysis
Agent can be catalyzed ethylene oligomerization and obtain the mixture of linear alpha-alkene, and wherein the content of octene-1 accounts for 19%.SHOP technique
(US3676523, US3635937) uses similar catalyst system, and the content of octene-1 accounts for 11% in oligomerization product.Other typical cases
Ethylene oligomerization technique, as the Chevron technique (DE1443927) of Gulf Oil Corporation, ethyl corporation (BP/Amoco,
US3906053 in ethylene oligomerization technique), the content of octene-1 is generally 13~25%.Chromium-based catalysts system is used for ethylene
Trimerization prepares hexene -1, also has been carried out industrialized production (US5550305), but the content of its principal product hexene -1 is generally all big
In 90%, the content of octene-1 is seldom (< 3%).The reports such as Brookhart Fe-series catalyst (J.Am.Chem.Soc.,
1998,120:7143；Chem.Commun.1998,849；WO 99/02472) it is used for ethylene oligomerization, obtained oligomerization product
It is distributed in width, the content of octene-1 is relatively low (< 20%).The ethylene tetramerization ternary catalyst systems reported recently can Gao Xuan
Selecting property synthesizing octene -1 (WO2004/056478A1, US2006/0229480, US 2006/0173226, CN107282132A,
CN107282123A, CN107282127A, CN107282131A, CN107282130A etc.), octene-1 contains in purpose product
Amount reaches 60%.
In conclusion the structure in activated centre and central metal are control ethylene oligomerization products in ethylene oligomerization catalysis system
The key of selectivity, and the hot spot of the area research of ethylene selectivity oligomerisation in recent years exploitation.Ethylene selectivity oligomerisation is urged
For agent, related central metal mainly has chromium, titanium etc..The structure of metal complex ligand is to influence catalyst performance
Key, therefore the innovative design for carrying out ligand structure is also the key of highly selective oligomerization catalysis system exploitation.
Summary of the invention
It is an object of the invention to make up the shortcomings of the prior art, provide a kind of comprising heteroatomic ligand
A, the preparation and use of the catalyst system, catalyst system of tri- components of transistion metal compound b and organo-metallic compound activator c
In ethylene oligomerization, especially highly selective oligomerisation prepares octene-1, hexene -1, and there is catalytic activity height, octene-1+hexene -1 to select
The advantages that selecting property is high, catalyst life is long, by-product polyethylene is few, it is ensured that the long-term operation of process units.
Realize the technical solution of the object of the invention are as follows:
A kind of catalyst of ethylene selectivity oligomerisation reaction contains heteroatomic ligand a, a kind of transition metal comprising a kind of
A kind of object b and organo-metallic compound activator c is closed, described containing heteroatomic ligand a is met shown in general formula (I)
Compound:
Wherein, R1、R2The alkyl of linear chain or branched chain can be selected.Such as: methyl, ethyl, isobutyl group, n-hexyl, n-octyl
Deng.Preferred R1、R2For methyl and ethyl, monocycle or polyaromatic and its derivative.
Preferably, described is (diphenyl) phosphorus nitrogen (dimethyl aluminium) phosphorus (diphenyl), (hexichol containing heteroatomic ligand a
Base) phosphorus nitrogen (diethyl aluminum) phosphorus (diphenyl), (diphenyl) phosphorus nitrogen (dipropyl aluminium) phosphorus (diphenyl), (diphenyl) phosphorus nitrogen (two
Octyl aluminium) phosphorus (diphenyl), (diphenyl) phosphorus nitrogen (diphenyl aluminium) phosphorus (diphenyl), (diphenyl) phosphorus nitrogen (dicyclohexyl aluminium) phosphorus
(diphenyl)
Synthesis containing heteroatomic ligand a can carry out by the following method: first by N, bis- (diphenyl phosphinylidyne) amine of N-
It is reacted, is obtained containing heteroatomic ligand a according to the molar ratio of 1:1 with corresponding alkyl aluminum.
R3Alkyl selected from linear chain or branched chain.
(I) the heteroatomic ligand described in is also possible to one or more units such as (I) formula structures, by group,
Chemical bond or intermolecular force etc. are combined together.Bridging, dendroid and star-shaped compound are such as obtained, is also possible to combine
In the polymer of the producing high-molecular formed on macromolecular chain.
The transistion metal compound b is the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium；Preferably
Chromium, zirconium, titanium compound, it is still further preferred that chromium compound.Selectable chromium compound includes general formula CrRn mThose of shown compound,
R in formulanFor organic negative ion or neutral molecule, RnIn usually contain 1~10 carbon atom, the integer that n is 0~6, the valence of chromium
State is 0~6 valence.Specific RnGroup for example organic matter or its group containing carboxyl, beta-diketon base and alkyl.From easy to dissolve and
From the point of view of easily operated, chromium compound preferably includes chromic acetate, isooctyl acid chromium, caprylic acid chromium, chromium acetylacetonate, two
Isoprene chromium, dibenzene-chromium, CrCl3(THF)3, (phenyl) tricarbonyl chromium, one kind of chromium carbonyl and or a variety of mixture.Most
Good chromium compound is CrCl3(THF)3, isooctyl acid chromium, chromium acetylacetonate.
The organo-metallic compound activator c be alkyl aluminum compound, aluminium alkoxide compound, organoboron compound,
Organic salt, inorganic acid and inorganic salts are also possible to the mixture of one or more of they；Specifically it is selected from various three alkane
Base aluminium and aluminium alkoxide compound, such as triethyl aluminum, triisobutyl aluminium, three n-butylaluminums, three just base aluminium, tri-n-octylaluminium, first
Base aikyiaiurnirsoxan beta, ethylaluminoxane, isobutyl aluminium alkoxide and aikyiaiurnirsoxan beta of modification etc..Also aluminum alkyl halide, alkyl can be used
Alanate or alkylaluminium sesquichloride, such as AlEt2Cl and A12Et3C13, be also possible to it is above-mentioned refer to it is one or more
The mixture of alkyl aluminum or aikyiaiurnirsoxan beta.Organic salt activator such as lithium methide, methyl-magnesium-bromide etc.；Inorganic acid and inorganic salts are living
Agent such as tetrafluoro boric acid etherate, tetrafluoroborate, hexafluoro antimonate etc..Organoboron compound includes boroxin, hydroboration
Sodium, boron triethyl, three (pentafluorophenyl group) boron, tri butyl boron hydrochlorate etc..
In the catalyst, the molar ratio of component a, b and c for including are a:b:c=1:0.5~100:0.1~5000；
Molar ratio containing heteroatomic ligand a and transistion metal compound b can be from 1:0.5~100.Containing heteroatomic ligand a with have
Molar ratio 1:0.1~1:5000 of machine metallic compound activator c, preferably from 1:1~1000:1, more preferably from 1:1~
200:1.
(I) reactive mode of heteroatomic ligand, transistion metal compound, metal organic activator described in, can be with
By liquid phase reactor, such as tri- components of a, b and c are pre-mixed, are reacted under the action of the solvent, selectable solvent is such as
Hexane, hexamethylene and its derivative etc.；Toluene, benzene and its derivative etc.；It can also be former by being carried out during oligomerisation reaction
Position reaction generates catalyst.Reaction described here, which can be above-mentioned heteroatomic ligand, transistion metal compound and metal, to be had
One kind of machine activator, two kinds, the reaction between three kinds of compounds.The process of this reaction is also ageing (the pre- network of catalyst
Close) process.
The catalytic component is used for ethylene selectivity oligomerisation, and reaction carries out in inert solvent, 0 DEG C of the temperature of reaction
~200 DEG C, preferably 50 DEG C~150 DEG C.Reaction pressure 0.1MPa~20MPa, preferably 1.0MPa~10MPa.It is urged in reaction system
The concentration of agent can from 0.01 μm of ol metal/L~1000 μm ol metal/L, preferably 0.1 μm of ol metal/L~10 μm ol metal/
L。
Selectable solvent includes alkane, aromatic hydrocarbons, halogenated hydrocarbons, alkene etc..Typical solvent includes, but are not limited to benzene, first
Benzene, dimethylbenzene, isopropylbenzene, normal heptane, n-hexane, hexahydrotoluene, hexamethylene, 1- hexene, 1- octene, ionic liquid etc..
The advantages of the present invention:
Catalyst of the invention is used for ethylene oligomerization, and especially ethylene selectivity oligomerisation has such as compared with prior art
Lower advantage: catalyst activity is high, purpose product octene-1 selectivity is high, catalyst synthesis is simple, at low cost, catalyst life is long
The features such as, C in product6~C8Mass percentage > 90%, C of linear alpha-alkene8The mass percentage of linear alpha-alkene >
60%.
Specific embodiment
The following examples and comparative example are set forth below, the present invention is further illustrated, rather than are used to limit this
The range of invention.
Embodiment 1
1, (diphenyl) phosphorus nitrogen (dimethyl aluminium) phosphorus (diphenyl) ligand (C is prepared26H26AlNP2)
Through N2N-hexane (20mL) of the addition through dehydration in the 100mL reactor with stirring being sufficiently displaced from, N,
Bis- (diphenyl phosphinylidyne) amine (1.387g, 3.6mmol) of N-, are cooled to 0 DEG C, be slowly added dropwise into trimethyl aluminium (0.345mL,
3.6mmol).It is stirred to react after 30min and is warmed to room temperature that the reaction was continued 12 hours.It is dried to obtain product.
2, the preparation (belonging to a, tri- kinds of catalyst components of b, c) of catalyst
Through N2The toluene (10mL) through dehydration is added in the 100mL reactor with stirring being sufficiently displaced from,
MAO (methylaluminoxane) toluene solution (7.0mL, 9.9mmol) of 1.4mol/L, (diphenyl) phosphorus nitrogen (dimethyl aluminium) phosphorus (two
Phenyl) (29.13mg) (66 μm of ol), CrCl3·(THF)3(12mg, 33 μm of ol), react at room temperature 5min after it is spare.
3, ethylene oligomerization
The autoclave of 500mL is heated to vacuumize 2 hours, is filled with ethylene after nitrogen displacement for several times, cools to predetermined temperature
Toluene (200mL) and above-mentioned catalyst through dehydration is added in degree.Oligomerisation reaction is carried out under 40 DEG C, the pressure of 5.0MPa,
With ice bath cooling, release after reaction 30min, reaction is terminated with the acidic ethanol that mass fraction is 10%.Obtain oligomerization product
37.78g catalyst activity is 2.29 × 106G oligomer/molCr.h.The distribution of oligomerization product is shown in Table 1.
Embodiment 2
1, (diphenyl) phosphorus nitrogen (diethyl aluminum) phosphorus (diphenyl) ligand (C is prepared28H30AlNP2)
Through N2N-hexane (20mL) of the addition through dehydration in the 100mL reactor with stirring being sufficiently displaced from, N,
Bis- (diphenyl phosphinylidyne) amine (1.387g, 3.6mmol) of N-, are cooled to 0 DEG C, be slowly added dropwise into triethyl aluminum (0.494mL,
3.6mmol).It is stirred to react after 30min and is warmed to room temperature that the reaction was continued 12 hours.It is dried to obtain product.
2, the preparation (belonging to a, tri- kinds of catalyst components of b, c) of catalyst
Through N2The toluene (10mL) through dehydration is added in the 100mL reactor with stirring being sufficiently displaced from,
MAO (methylaluminoxane) toluene solution (7.0mL, 9.9mmol) of 1.4mol/L, (diphenyl) phosphorus nitrogen (diethyl aluminum) phosphorus (two
Phenyl) (30.985mg) (66 μm of ol), CrCl3·(THF)3(12mg, 33 μm of ol), react at room temperature 5min after it is spare.
3, ethylene oligomerization
The autoclave of 500mL is heated to vacuumize 2 hours, is filled with ethylene after nitrogen displacement for several times, cools to predetermined temperature
Toluene (200mL) and above-mentioned catalyst through dehydration is added in degree.Oligomerisation reaction is carried out under 40 DEG C, the pressure of 5.0MPa,
With ice bath cooling, release after reaction 30min, reaction is terminated with the acidic ethanol that mass fraction is 10%.Obtain oligomerization product
41.74g, catalyst activity are 2.53 × 106G oligomer/molCr.h.The distribution of oligomerization product is shown in Table 1.
Embodiment 3
1, (diphenyl) phosphorus nitrogen (dipropyl aluminium) phosphorus (diphenyl) ligand (C is prepared30H34AlNP2)
Through N2N-hexane (20mL) of the addition through dehydration in the 100mL reactor with stirring being sufficiently displaced from, N,
Bis- (diphenyl phosphinylidyne) amine (1.387g, 3.6mmol) of N-, are cooled to 0 DEG C, be slowly added dropwise into triethyl aluminum (0.685mL,
3.6mmol).It is stirred to react after 30min and is warmed to room temperature that the reaction was continued 12 hours.It is dried to obtain product.
2, the preparation (belonging to a, tri- kinds of catalyst components of b, c) of catalyst
Through N2The toluene (10mL) through dehydration is added in the 100mL reactor with stirring being sufficiently displaced from,
MAO (methylaluminoxane) toluene solution (7.0mL, 9.9mmol) of 1.4mol/L, (diphenyl) phosphorus nitrogen (diethyl aluminum) phosphorus (two
Phenyl) (32.836mg) (66 μm of ol), CrCl3·(THF)3(12mg, 33 μm of ol), react at room temperature 5min after it is spare.
3, ethylene oligomerization
The autoclave of 500mL is heated to vacuumize 2 hours, is filled with ethylene after nitrogen displacement for several times, cools to predetermined temperature
Toluene (200mL) and above-mentioned catalyst through dehydration is added in degree.Oligomerisation reaction is carried out under 40 DEG C, the pressure of 5.0MPa,
With ice bath cooling, release after reaction 30min, reaction is terminated with the acidic ethanol that mass fraction is 10%.Obtain oligomerization product
36.47g, catalyst activity are 2.21 × 106G oligomer/molCr.h.The distribution of oligomerization product is shown in Table 1.
Embodiment 4
1, (diphenyl) phosphorus nitrogen (dioctyl aluminium) phosphorus (diphenyl) ligand (C is prepared30H34AlNP2)
Through N2N-hexane (20mL) of the addition through dehydration in the 100mL reactor with stirring being sufficiently displaced from, N,
Bis- (diphenyl phosphinylidyne) amine (1.387g, 3.6mmol) of N-, are cooled to 0 DEG C, be slowly added dropwise into trioctylaluminum (1.583mL,
3.6mmol).It is stirred to react after 30min and is warmed to room temperature that the reaction was continued 12 hours.It is dried to obtain product.
2, the preparation (belonging to a, tri- kinds of catalyst components of b, c) of catalyst
Through N2The toluene (10mL) through dehydration is added in the 100mL reactor with stirring being sufficiently displaced from,
MAO (methylaluminoxane) toluene solution (7.0mL, 9.9mmol) of 1.4mol/L, (diphenyl) phosphorus nitrogen (dioctyl aluminium) phosphorus (two
Phenyl) (42.094mg) (66 μm of ol), CrCl3·(THF)3(12mg, 33 μm of ol), react at room temperature 5min after it is spare.
3, ethylene oligomerization
The autoclave of 500mL is heated to vacuumize 2 hours, is filled with ethylene after nitrogen displacement for several times, cools to predetermined temperature
Toluene (200mL) and above-mentioned catalyst through dehydration is added in degree.Oligomerisation reaction is carried out under 40 DEG C, the pressure of 5.0MPa,
With ice bath cooling, release after reaction 30min, reaction is terminated with the acidic ethanol that mass fraction is 10%.Obtain oligomerization product
43.89g, catalyst activity are 2.66 × 106G oligomer/molCr.h.The distribution of oligomerization product is shown in Table 1.
Embodiment 5
With embodiment 1.The difference is that tri- kinds of catalyst components of a, b, c fabricated in situ in the course of the polymerization process.Obtain oligomerisation
Product 39.32g, catalyst activity are 2.38 × 106G oligomer/mol Cr.h.The distribution of oligomerization product is shown in Table 1.
Embodiment 6
With embodiment 1.The difference is that reaction pressure is 6.0MPa.Obtain oligomerization product 45.33g, catalyst activity
It is 2.75 × 106G oligomer/mol Cr.h.The distribution of oligomerization product is shown in Table 1.The distribution of oligomerization product is shown in Table 1.
Embodiment 7
With embodiment 1.The difference is that reaction temperature is 80 DEG C.Oligomerization product 36.7g is obtained, catalyst activity is
2.22×106G oligomer/mol Cr.h.The distribution of oligomerization product is shown in Table 1.
The comparison of 1 oligomerization product carbon number distribution of table
aRefer to C6Middle 1-C6 =Percentage composition.bRefer to C8Middle 1-C8 =Percentage composition.
Claims (9)
1. a kind of catalyst of ethylene selectivity oligomerisation reaction contains heteroatomic ligand a, a kind of transition metal compound comprising a kind of
Object b and a kind of organo-metallic compound activator c, it is characterised in that: described is to meet general formula containing heteroatomic ligand a
Chemical structure shown in I:
Wherein, R1、R2Alkyl selected from linear chain or branched chain, monocycle or polyaromatic and its derivative.
2. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1, it is characterised in that: described contains hetero atom
Ligand a be (diphenyl) phosphorus nitrogen (dimethyl aluminium) phosphorus (diphenyl), (diphenyl) phosphorus nitrogen (diethyl aluminum) phosphorus (diphenyl),
(diphenyl) phosphorus nitrogen (dipropyl aluminium) phosphorus (diphenyl), (diphenyl) phosphorus nitrogen (dioctyl aluminium) phosphorus (diphenyl), (diphenyl) phosphorus
Nitrogen (diphenyl aluminium) phosphorus (diphenyl), (diphenyl) phosphorus nitrogen (dicyclohexyl aluminium) phosphorus (diphenyl).
3. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1 or 2, it is characterised in that: described containing is miscellaneous
The ligand a of atom is by N, and bis- (diphenyl phosphinylidyne) amine of N- react to obtain with corresponding trialkylaluminium, and specific reaction equation is as follows:
R3Alkyl selected from linear chain or branched chain.
4. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1 or 2, it is characterised in that: described containing is miscellaneous
The ligand a of atom is to connect newization to be formed by group or chemical bond containing structural unit shown in two or more general formula I
Close object.
5. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1 or 2, it is characterised in that: the transition
Metallic compound b is the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium.
6. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1 or 2, it is characterised in that: described is organic
Metallic compound activator c is alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid, inorganic
One or more of mixtures of salt.
7. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1 or 2, it is characterised in that: the catalysis
Molar ratio containing heteroatomic ligand a, transistion metal compound b, organo-metallic compound activator c in agent is a:b:c=1:
0.5~100:0.1~5000.
8. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1 or 2, it is characterised in that: preparation method is
Tri- component of a, b, c is pre-mixed synthesis, or is added directly into reaction system and carries out fabricated in situ.
9. the catalyst of ethylene selectivity oligomerisation reaction according to claim 1 or 2, it is characterised in that: ethylene selectivity
Oligomerisation reaction carries out in inert solvent, 0 DEG C~200 DEG C of the temperature of reaction, reaction pressure 0.1MPa~20MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811081332.1A CN109174191B (en) | 2018-09-17 | 2018-09-17 | Catalyst for ethylene selective oligomerization reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811081332.1A CN109174191B (en) | 2018-09-17 | 2018-09-17 | Catalyst for ethylene selective oligomerization reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109174191A true CN109174191A (en) | 2019-01-11 |
| CN109174191B CN109174191B (en) | 2022-01-25 |
Family
ID=64911521
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811081332.1A Active CN109174191B (en) | 2018-09-17 | 2018-09-17 | Catalyst for ethylene selective oligomerization reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109174191B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449186A (en) * | 2019-06-28 | 2019-11-15 | 天津科技大学 | A kind of reaction method, catalyst system and its application of ethylene selectivity oligomerisation |
| CN111905832A (en) * | 2020-07-23 | 2020-11-10 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene, reaction method and application thereof |
| CN112517080A (en) * | 2020-12-25 | 2021-03-19 | 中化泉州石化有限公司 | Ethylene selective tetramerization catalyst composition and application thereof |
| CN114471718A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Catalytic system for ethylene selective oligomerization and ethylene selective oligomerization method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3865457B2 (en) * | 1997-04-23 | 2007-01-10 | 三井化学株式会社 | Process for producing branched polyene compounds |
| CN101646684A (en) * | 2007-03-29 | 2010-02-10 | 诺瓦化学品(国际)股份有限公司 | Amino phosphine |
| CN102040624A (en) * | 2009-10-19 | 2011-05-04 | 中国石油化工股份有限公司 | Method for synthesizing ligand for ethylene trimerization or tetramerization catalyst and ligand synthesized thereby and application thereof |
| CN102164935A (en) * | 2008-09-29 | 2011-08-24 | 诺瓦化学品(国际)股份有限公司 | Ethylene trimerization catalysts comprising P-N-P ligands and their use |
| CN102725251A (en) * | 2009-10-19 | 2012-10-10 | 沙索技术有限公司 | Oligomerisation of olefinic compounds with reduced polymer formation |
| CN103100421A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization |
| CN106582851A (en) * | 2016-10-17 | 2017-04-26 | 天津科技大学 | Catalyst component for selective oligomerization of ethylene and catalyst thereof |
-
2018
- 2018-09-17 CN CN201811081332.1A patent/CN109174191B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3865457B2 (en) * | 1997-04-23 | 2007-01-10 | 三井化学株式会社 | Process for producing branched polyene compounds |
| CN101646684A (en) * | 2007-03-29 | 2010-02-10 | 诺瓦化学品(国际)股份有限公司 | Amino phosphine |
| CN102164935A (en) * | 2008-09-29 | 2011-08-24 | 诺瓦化学品(国际)股份有限公司 | Ethylene trimerization catalysts comprising P-N-P ligands and their use |
| CN102040624A (en) * | 2009-10-19 | 2011-05-04 | 中国石油化工股份有限公司 | Method for synthesizing ligand for ethylene trimerization or tetramerization catalyst and ligand synthesized thereby and application thereof |
| CN102725251A (en) * | 2009-10-19 | 2012-10-10 | 沙索技术有限公司 | Oligomerisation of olefinic compounds with reduced polymer formation |
| CN103100421A (en) * | 2011-11-09 | 2013-05-15 | 中国石油化工股份有限公司 | Catalyst composition for ethylene tetramerization |
| CN106582851A (en) * | 2016-10-17 | 2017-04-26 | 天津科技大学 | Catalyst component for selective oligomerization of ethylene and catalyst thereof |
Non-Patent Citations (1)
| Title |
|---|
| HUBERT SCHMIDBAUR等: ""Synthese und Struktur von dimerem Dimethylaluminium-[bis(diphenylphosphino)amid], {(CH&AlN[P(CsH&12}2,und verwandten Verbindungen"", 《CHEM. BER.》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449186A (en) * | 2019-06-28 | 2019-11-15 | 天津科技大学 | A kind of reaction method, catalyst system and its application of ethylene selectivity oligomerisation |
| CN110449186B (en) * | 2019-06-28 | 2022-08-09 | 天津科技大学 | Reaction method for selective oligomerization of ethylene, catalyst system and application thereof |
| CN111905832A (en) * | 2020-07-23 | 2020-11-10 | 天津科技大学 | Catalyst system for selective oligomerization of ethylene, reaction method and application thereof |
| CN114471718A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Catalytic system for ethylene selective oligomerization and ethylene selective oligomerization method |
| CN112517080A (en) * | 2020-12-25 | 2021-03-19 | 中化泉州石化有限公司 | Ethylene selective tetramerization catalyst composition and application thereof |
| CN112517080B (en) * | 2020-12-25 | 2023-06-23 | 中化泉州石化有限公司 | Ethylene selective tetramerization catalyst composition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109174191B (en) | 2022-01-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105289742B (en) | For the catalyst of ethylene selectivity oligomerisation, ligand and preparation method thereof | |
| CN109174191A (en) | A kind of catalyst of ethylene selectivity oligomerisation reaction | |
| EP2396112B1 (en) | Oligomerisation of olefinic compounds in the presence of an activated oligomerisation catalyst | |
| CN100443178C (en) | Catalyst composition of ethylene oligomerization and the application | |
| CN108686706B (en) | Ethylene selective oligomerization method and catalyst | |
| JP4273257B2 (en) | Catalyst composition for dimerization, codimerization, oligomerization and polymerization of olefins | |
| CN108097322A (en) | It is a kind of for the catalyst system of ethylene selectivity oligomerisation and ethylene oligomerization reaction method | |
| CN106582851B (en) | Catalytic component and its catalyst for ethylene selectivity oligomerisation | |
| JP6468539B2 (en) | Method for producing olefin oligomer | |
| CN105562099A (en) | Ethylene tetrapolymerization catalyst composition and ethylene tetrapolymerization method | |
| CN107282129A (en) | A kind of ethylene trimer, four poly- carbon monoxide-olefin polymerics and its application | |
| CN105562095A (en) | Ethylene tetrapolymerization catalyst composition and ethylene tetrapolymerization method | |
| CN103100420A (en) | Catalyst composition for ethylene tetramerization and preparation method of ligand thereof | |
| CN111282596B (en) | Ethylene oligomerization high-selectivity catalyst system and application thereof | |
| CN105268480B (en) | A kind of method of the hexene of ethylene oligomerization coproduction 1 and 1 octene of corrdination type catalyst and the use catalyst | |
| CN103100421B (en) | Catalyst composition for ethylene tetramerization | |
| CN104415790A (en) | Ethylene tetramerization catalyst composition and application thereof | |
| CN106925353B (en) | Catalyst and its application | |
| CN109476779A (en) | Ethylene it is oligomeric | |
| CN110449186B (en) | Reaction method for selective oligomerization of ethylene, catalyst system and application thereof | |
| CN109174190A (en) | Catalyst system for ethylene selectivity oligomerisation | |
| CN105562098A (en) | Ethylene oligomerization catalyst composition and applications thereof | |
| CN114160199B (en) | Catalytic system for selectively trimerizing and tetramerizing ethylene and application thereof | |
| CN104624235A (en) | Preparation and application of ethylene oligomerization catalyst composition | |
| CN107233919B (en) | Oligomerization catalyst composition and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |