CN100522364C - Catalyst and preparation process of the catalyst and its ligand, acetic acid and acetic anhydride - Google Patents
Catalyst and preparation process of the catalyst and its ligand, acetic acid and acetic anhydride Download PDFInfo
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- CN100522364C CN100522364C CNB2004100322694A CN200410032269A CN100522364C CN 100522364 C CN100522364 C CN 100522364C CN B2004100322694 A CNB2004100322694 A CN B2004100322694A CN 200410032269 A CN200410032269 A CN 200410032269A CN 100522364 C CN100522364 C CN 100522364C
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- vinylpyridine
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000003446 ligand Substances 0.000 title claims abstract description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title abstract description 24
- 238000002360 preparation method Methods 0.000 title description 4
- 239000010948 rhodium Substances 0.000 claims abstract description 79
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 57
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 53
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- -1 sodium tetraphenylborate Chemical compound 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 69
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 31
- 229920001577 copolymer Polymers 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 20
- MJNOTFQFWSGKOH-UHFFFAOYSA-N C(CCCCCCCCCCC)(=O)OCCOCCOC(CCCCCCCCCCC)=O.C(C=C)(=O)O Chemical compound C(CCCCCCCCCCC)(=O)OCCOCCOC(CCCCCCCCCCC)=O.C(C=C)(=O)O MJNOTFQFWSGKOH-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000009833 condensation Methods 0.000 claims description 13
- 230000005494 condensation Effects 0.000 claims description 13
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000278 bentonite Inorganic materials 0.000 claims description 11
- 239000000440 bentonite Substances 0.000 claims description 11
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 11
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 208000035126 Facies Diseases 0.000 claims description 8
- 150000001450 anions Chemical group 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 8
- 150000001768 cations Chemical group 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 239000004088 foaming agent Substances 0.000 claims description 2
- 239000002243 precursor Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 112
- 238000006243 chemical reaction Methods 0.000 abstract description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 23
- 230000006315 carbonylation Effects 0.000 abstract description 6
- 238000005810 carbonylation reaction Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 17
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 16
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 14
- 238000002156 mixing Methods 0.000 description 10
- 238000011160 research Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000010792 warming Methods 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 7
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000000470 constituent Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 235000011837 pasties Nutrition 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Abstract
The present invention is one kind of methanol oxo-synthesis rhodium catalyst with crosslinked porous microspherical polymer as ligand. The polymer is formed with vinyl pyridine and glycol acrylate and through crosslinking copolymerization. The N and O donor atom in the ligand and tetracarbonyl dirhodium dihalide, under the action of sodium tetraphenylborate, form square planar cis-bicarbonyl Rh(I) structure as positive active center. The negative ion is (BPh4)-. During the methanol carbonylation, the catalyst can convert methanol into acetic acid and acetic anhydride at relatively low temperature and the CO2 producing amount in the reaction system is lower than 0.005 mol%.
Description
Technical field
The present invention relates to the synthetic rhodium catalyst of carbonyl, relate in particular to the macromolecule ligand heterogeneous rhodium catalyst of carbonyl synthesis of acetic acid and acetic anhydride.
Background technology
In the reaction of methanol carbonyl synthesis of acetic acid, the research of catalyst is one of important contents.For a long time, in numerous all kinds of catalyst researches, the kind of catalyst relates to reaction formations such as homogeneous phase, heterogeneous, gas/solid phase.The selection of reactive metal is except that rhodium, and many transition metal such as iridium, ruthenium, nickel, cobalt all have been carried out research.The success of the homogeneous catalyst of rhodium on commercial Application makes the methanol carbonyl synthesis of acetic acid form a large-scale ripe industry.Simultaneously, catalyst heterogeneous and the gas and solid phase catalyzing form is also studied widely by people.In the research report of heterogeneous and homogeneous catalyst, be the trial of catalyst ligand with the macromolecular compound, be the interested problems of a lot of people.A large amount of high polymers that contain donor atoms such as N, O, S, P are studied, and the so-called polymer catalyst of this class has advantages of excellent stability mostly in reaction, but relative activity is compared with the homogeneous phase micromolecule catalyst and existed tangible gap.In the research of these polymer catalysts, the homogeneous phase that is part with the homopolymers and the copolymer of vinylpyridine and the research of heterogeneous reaction catalyst are always people and pay close attention to.(Inor Chem.1981 (20): the 64) catalyst of Bao Dao polyvinylpyridine quaternary ammonium salt anion exchange resin and rhodium reactant salt formation, people (EP-0277824) such as Marston Chahes R finally are part and RhCl with containing the 4-vinylpyridine copolymer from early stage people such as RussellsDrago
3The catalyst that coordination forms under 180～195 reaction temperature conditions, adopts the homogeneous reaction form, and its catalysis speed reaches 867 (g AcOH/gRhh).(US 6458995, and EP 1268059) are selected for use with iridium is the catalyst research of reactive metal, and the research work of catalyst is better expanded.
Above-mentioned research work has all obtained good progress in many aspects, but the performance indications of its catalyst of overall merit, the industrialized application of distance also has certain distance.
Summary of the invention
The present invention relates to the synthetic rhodium catalyst of a kind of carbonyl, wherein this catalyst comprises cation part and anion part, and described cation partly comprises crosslinked porous polyethylene pyridyloxy acrylic acid diethylene glycol dilaurate copolymer ligand and rhodium carbonyl.
According to the synthetic rhodium catalyst of carbonyl of the present invention, wherein said anion partly comprises tetraphenylboron acid group or acetate.
According to the synthetic rhodium catalyst of carbonyl of the present invention, wherein, the N with the rhodium coordination in catalyst molecule is the N on the pyridine ring in the vinylpyridine, with the O of rhodium coordination be carbonyl O in the acrylic acid diethylene glycol dilaurate.
According to the synthetic rhodium catalyst of carbonyl of the present invention, the therein ethylene yl pyridines is 2-vinylpyridine or 4-vinylpridine.
According to the synthetic rhodium catalyst of carbonyl of the present invention, wherein rhodium carbonyl is [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2
According to the synthetic rhodium catalyst of carbonyl of the present invention, the precursor of wherein said anion is NaBPh
4, NaOOCCH
3
The method for preparing the crosslinked porous microsphere shape copolymer ligand in the synthetic rhodium catalyst of carbonyl of the present invention is comprising vinylpyridine monomers, crosslinking agent, initator and perforating agent are mixed.
According to method of the present invention, wherein crosslinking agent is the acrylic acid diethylene glycol dilaurate.
According to method of the present invention, wherein the inventory of crosslinking agent is 1～9 times of vinylpyridine by weight.
According to method of the present invention, wherein said inventory is 2.3 times.
According to method of the present invention, wherein the ratio of vinylpyridine and acrylic acid diethylene glycol dilaurate is 3:7 by weight.
According to method of the present invention, wherein initator is azodiisobutyronitrile or benzoyl peroxide.
According to method of the present invention, wherein the consumption of initator be vinylpyridine and acrylic acid diethylene glycol dilaurate weight and 1～5%.
According to method of the present invention, wherein the consumption of initator be vinylpyridine and acrylic acid diethylene glycol dilaurate weight and 2%.
According to method of the present invention, wherein pore-foaming agent is the mixture of kerosene, toluene and isoamyl alcohol.
According to method of the present invention, wherein the kerosene consumption is 30～80% of a total monomer amount weight by weight.
According to method of the present invention, wherein the kerosene consumption is 65% of a total monomer amount weight by weight.
According to method of the present invention, wherein the toluene consumption is a total monomer amount 10～40% by weight.
According to method of the present invention, wherein the toluene consumption is 25% by weight.
According to method of the present invention, wherein the isoamyl alcohol consumption is 1～15% of a total monomer amount by weight.
According to method of the present invention, wherein the toluene consumption is 8% by weight.
According to method of the present invention, wherein this method further comprises the step that adds condensation polymer.
According to method of the present invention, wherein said condensation polymer is that TEPA and epoxychloropropane condensation form.
According to method of the present invention, wherein the condensation polymer consumption is 5～15% of a monomer total amount by weight.
According to method of the present invention, wherein the condensation polymer consumption is 8% of a monomer total amount by weight.
According to method of the present invention, wherein this method further comprises the step that adds dispersant.
According to method of the present invention, wherein dispersant is the bentonite of water furnishing oar shape.
According to method of the present invention, wherein the consumption of bentonite is 10～30% of a monomer total amount by weight.
According to method of the present invention, wherein, the consumption of bentonite is 20% of a monomer total amount by weight.
According to method of the present invention, wherein adopt the suspension polymerisation mode.
According to method of the present invention, wherein water is for containing 10% weight Na
2SO
4The aqueous solution.
According to method of the present invention, wherein Na
2SO
4Amount of aqueous solution used is 3～10 times of organic facies volume.
According to method of the present invention, wherein Na
2SO
4Amount of aqueous solution used is 5 times of organic facies volume.
The method for preparing the synthetic rhodium catalyst of carbonyl of the present invention comprising the solution that will contain copolymer ligand and four carbonyl dihalo-s, two rhodiums, adds NaBPh
4Or CH
3In the aqueous solution of COONa.
A kind of method for preparing acetate has wherein been used according to the synthetic rhodium catalyst of carbonyl of the present invention.
A kind of method for preparing acetic anhydride has wherein been used according to the synthetic rhodium catalyst of carbonyl of the present invention.
Meaning of the present invention is, in part is synthetic, in the past methods of using divinylbenzene to do the crosslinking copolymers agent have been changed more, the acrylic acid diethylene glycol dilaurate of introducing in the copolymer is as crosslinking agent the time, the ketonic oxygen in its molecule (=C=O) can participate in coordination with the reactive metal rhodium as the donor atom.In complex, have two kinds and join key, be i.e. Rh → N, O → Rh.Wherein O → Rh join key since binding energy relatively a little less than, easy fracture in reaction, thus make co-catalyst CH
3The addition reaction of I is more easy, has promoted its reactive activity intermediate CH
3The generation of COI, thus make catalyst have higher activity.And the conjugation N on the pyridine ring provides the ability of electronics stronger, and N → Rh coordinate bond that itself and rhodium form is improved the reaction stability of catalyst.The result proves, uses such catalyst in the time of 135～140 ℃, can successfully methyl alcohol be catalytically conveted to acetate, even directly obtain acetic anhydride.When reaction temperature was 180 ℃, its space-time yield (mol AcOH/Lh) reached 40, and catalytic rate (g AcOH/gRh-h) reaches more than 1200.
The active specy structure of rhodium of the present invention is a cation coordination structure, and its anion has partly been selected carbonylation is had the borate of facilitation and with reaction system the acetate ion that well dissolves each other and act on arranged.
Technology of the present invention constitutes, mainly comprise being used for formation and the preparation method that methanol carbonylation prepares the crosslinked spherical copolymer rhodium catalyst of acetate and acetic anhydride, and the composition and the using method of the reaction system of carbonyl synthesis of acetic acid that adapts therewith and acetic anhydride.
The microspherical copolymer that the present invention relates to is that the preparation method of the synthetic rhodium catalyst of the carbonyl of part is as follows:
1. the 2-vinylpyridine (4-vinylpridine) that takes by weighing 1.0 Unit Weights is with after the acrylic acid diethylene glycol dilaurate of 2.5 Unit Weights mixes, add the kerosene of 1.35 Unit Weights, the toluene of 0.5 Unit Weight, the isoamyl alcohol of 0.17 Unit Weight and the azodiisobutyronitrile of 0.04 Unit Weight successively, mix the back and be organic facies.
2. 10% Na of 50 Unit Weights
2SO
4The aqueous solution joins in the polymerization bottle, starting the lodicule formula stirs, when being warming up to 40 ℃, add organic facies, reaction temperature is continued to rise to 65～70 ℃, mixing speed transfers to 300～500 rev/mins, the condensation polymer that adds 0.04 Unit Weight stirred 10～20 minutes, the adding water is modulated into the bentonite of 1.0 Unit Weights of pasty state, continues to stir after 10 minutes stirring is transferred to 100～150 rev/mins, reacts 24 hours.
3. after reaction finishes, the macromolecule bead of polymerization is leached.Remove bentonite with the hot water cyclic washing, acetone extracting 48 hours are used in dry back, and drying obtains spherical part.
4. take by weighing a certain amount of spherical part and be suspended in the methyl alcohol, under agitation add [Rh (CO)
2X]
2, be 3% of spherical part in its weight of rhodium.The stirring at room reaction added NaBPh after 10～20 minutes
4The aqueous solution, wherein NaBPh
4: [Rh (CO)
2X]
2=2:1 (mol).Continue reaction after 10 minutes, filter, drying obtains the high polymer rhodium catalyst of lemon yellow.
Above-mentioned institute controlling catalyst has good performance in the catalysis methanol carbonylation prepares the reaction of acetate, acetic anhydride, wherein following is with the obvious advantage:
1. reaction temperature is low,, not only can obtain very high acetic acid yield, even can directly obtain a certain amount of acetic anhydride during in 135～140 ℃ in reaction temperature.
2. this catalyst is applicable to low water reaction system, need not to add water in course of reaction, has promptly reduced the consumption of water gas reaction to CO.Water that its reaction generates self and the effect of CO are not obvious, CO
2Growing amount all less than 0.005% (mol).
Crosslinked spherical porous copolymers rhodium catalyst of the present invention is when the catalysis methanol carbonylation prepares acetate, acetic anhydride, and reactant is a methyl alcohol, and iodomethane is a co-catalyst.Its content is between 1～5mol/L scope in overall reaction liquid, and after acetate in the reaction system generated, along with the increase of acetic acid content, its reaction speed was accelerated, and when having hydroiodic acid and water to exist in the reaction system, also can obviously improve its reaction rate.
Specifically, the present invention includes a kind of synthetic rhodium catalyst of carbonyl that is part with crosslinked porous polyethylene pyridyloxy acrylic acid diethylene glycol dilaurate copolymer microsphere, wherein the crosslinking agent of copolymer is the acrylic acid diethylene glycol dilaurate, adopts the method for suspension polymerisation to obtain.After this crosslinked porous microsphere shape part and rhodium carbonyl coordination formed the monodentate coordination structure, through the sodium salt effect, the double coordination that forms rhodium was along dicarbapentaborane cation coordination structure.The anion of this catalyst partly is tetraphenylboron acid group or acetate.
Crosslinked as described in the present invention porous microsphere shape copolymer rhodium catalyst, wherein crosslinked porous microsphere shape copolymer ligand follows these steps to be prepared: take by weighing quantitative vinylpyridine monomers, crosslinking agent, initator and perforating agent, after mixing, join and contain 10% Na
2SO
4In the polymerization bottle of the aqueous solution, adopt leaf slurry formula to stir 300～500 rev/mins of mixing speeds.Stirred 5～10 minutes, and added condensation polymer, be warmed up to 65～70 ℃, continue to stir 10～20 minutes, add the bentonite of water furnishing oar shape.Reacted 10～15 minutes, and stirred and reduce to 100 rev/mins, reacted 24 hours.After reaction finishes, the high polymer bead is leached, use the distilled water cyclic washing, acetone extracting 48 hours are used in dry back, crosslinked porous microsphere shape copolymer ligand.
Crosslinked as described in the present invention porous microsphere shape copolymer rhodium catalyst, by the preparation of following method: take by weighing a certain amount of copolymer ligand, be suspended in the methyl alcohol, wherein the methyl alcohol volume is 10～30 times of part volume, is generally 20 times.The methanol solution that under agitation adds four carbonyl dihalo-s, two rhodiums, inventory are in rhodium, and its weight is 2～6% of part, and the best is 3%.After 10 minutes, add NaBPh in the stirring at room reaction
4Or CH
3The aqueous solution of COONa, wherein NaBPh
4Or CH
3The COONa consumption is 2 times (moles) of four carbonyl dihalo-s, two rhodiums.Continue reaction after 10 minutes, filter, with methanol wash twice, the room temperature vacuum drying promptly obtains the catalyst finished product to constant weight.
Crosslinked as described in the present invention porous microsphere shape copolymer rhodium catalyst, also can directly obtain acetic anhydride when wherein the catalysis methanol carbonylation prepares acetate, reactant is a methyl alcohol in the reaction system, co-catalyst is an iodomethane, and need not add other any auxiliary agents, co-catalyst iodomethane content in reaction system is 1～5mol/L scope.Catalyst amount is in the reaction system: in rhodium 200～2000ppm scope, reaction temperature is 120～180 ℃, and carbon monoxide pressure is 3.0～5.0MPa.
The specific embodiment
Embodiment 1
Take by weighing 2～vinylpyridine (or 4-vinylpridine) 18g, acrylic acid diethylene glycol dilaurate 42g, kerosene 40g, toluene 15g, isoamyl alcohol 5g, azodiisobutyronitrile 1.2g mixes the back and is organic facies.Na with 500g aqueous solution dissolving 50g
2SO
4, join then in the polymerization bottle, be warming up to 40 ℃, organic facies is added.The paddle formula stirs and transfers to 250～300 rev/mins, adds the 1.2g condensation polymer, is warming up to 65～70 ℃, reacts 10～20 minutes, adds the 30g bentonite that water is modulated to pasty state.Continue reaction 10 minutes, stirring is transferred to 100～150 rev/mins, reacted 24 hours.Filtration obtains the copolymer bead.The copolymer bead is through boiling water agitator treating 5 times, and each 30～40 minutes, to remove bentonite.After the drying,, obtain copolymer ligand with acetone extracting 48 hours.
The spherical part of copolymer is suspended in the methyl alcohol, adds [Rh (CO)
2Cl]
2, be 2%～6% scope of copolymer bead in its weight of rhodium.Behind the room temperature reaction 10～20 minutes, add NaBPh
4Or NaOOCCH
3The aqueous solution (wherein, NaBPh
4Or NaOOCCH
3Molal quantity be [Rh (CO)
2Cl]
22 times of molal quantity).React after 10 minutes, filter, drying promptly obtains finished catalyst.
Embodiment 2
In the 500ml reactor, add methyl alcohol 6.02mol, iodomethane 1.02mol, made 2-vinylpyridine among the embodiment 1/acrylic acid ethylene glycol bis ester copolymer rhodium catalyst 8g (100～120 orders, Rh=4%), CO constant voltage 3.0MPa, 155 ℃ of reaction temperatures, 300 rev/mins of mixing speeds, 20 minutes reaction time.Each constituent content is in the system of reaction end back: methyl alcohol 2.18mol (methanol conversion is 63.8%), and iodomethane 0.97mol, methyl acetate 0.7mol, acetate 0.19mol, water 2.19mol, dimethyl ether 0.90mol, acetic anhydride 0.024mol, carbon dioxide are 0.
Embodiment 3
In reactor, add methyl alcohol 6.0mol, iodomethane 1.0mol, made 4-vinylpridine among the embodiment 1/acrylic acid ethylene glycol bis ester copolymer rhodium catalyst 8g (100～120 orders, Rh=4%), be warming up to 130 ℃ after feeding CO, CO constant voltage 3.0MPa, 400 rev/mins of mixing speeds, 120 minutes reaction time.Each constituent content is in the system of reaction end back: methyl alcohol 0.22mol, and iodomethane 0.90mol, methyl acetate 1.39mol, acetate 1.20mol, water 2.14mol, dimethyl ether 0.61mol, acetic anhydride 0.05mol, carbon dioxide are 0.
Embodiment 4
In reactor, add methyl alcohol 6.0mol, iodomethane 1.0mol, made 2-vinylpyridine among the embodiment 1/acrylic acid ethylene glycol bis ester copolymer rhodium catalyst 7g (40～60 orders, Rh=5%), be warming up to 140 ℃ after feeding CO, CO constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 130 minutes reaction time.Each constituent content is in the system of reaction end back: methyl alcohol 0mol (methanol conversion is 100%), and iodomethane 0.93mol, methyl acetate 0.92mol, acetate 3.46mol, water 0.98mol, dimethyl ether 0.073mol, acetic anhydride 0.172mol, carbon dioxide are 0.
Embodiment 5
In reactor, add methyl alcohol 6.0mol, iodomethane 1.0mol, made 2-vinylpyridine among the embodiment 1/acrylic acid ethylene glycol bis ester copolymer rhodium catalyst 8g (40～60 orders, Rh=3.5%), be warming up to 135 ℃ after feeding CO, CO constant voltage 3.5MPa, 500 rev/mins of mixing speeds, 120 minutes reaction time.Each constituent content is in the system of reaction end back: methyl alcohol 0mol (methanol conversion is 100%), iodomethane 0.89mol, methyl acetate 1.11mol, acetate 2.84mol, water 1.36mol, dimethyl ether 0.23mol, acetic anhydride 0.125mol, carbon dioxide are 0.005mol.
Embodiment 6
In reactor, add methyl alcohol 6.0mol, iodomethane 1.0mol, made 4-vinylpridine among the embodiment 1/acrylic acid ethylene glycol bis ester copolymer rhodium catalyst 8g (100～120 orders, Rh=4%), be warming up to 170 ℃ after feeding CO, CO constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 50 minutes reaction time.Each constituent content is in the system of reaction end back: methyl alcohol 0mol (methanol conversion is 100%), iodomethane 0.90mol, methyl acetate 1.07mol, acetate 2.82mol, water 1.36mol, dimethyl ether 0.29mol, acetic anhydride 0.152mol, carbon dioxide are 0.003mol.
Embodiment 7
In reactor, add methyl alcohol 6.0mol, iodomethane 1.0mol, made 2-vinylpyridine among the embodiment 1/acrylic acid ethylene glycol bis ester copolymer rhodium catalyst 8.1g (60～80 orders, Rh=4%), be warming up to 170 ℃ after feeding CO, CO constant voltage 4.0MPa, 500 rev/mins of mixing speeds, 30 minutes reaction time.Each constituent content is in the system of reaction end back: methyl alcohol 0.06mol (methanol conversion is 99%), iodomethane 0.90mol, methyl acetate 1.12mol, acetate 1.52mol, water 2.05mol, dimethyl ether 0.75mol, acetic anhydride 0.137mol, carbon dioxide are 0.001mol.
Embodiment 8
In reactor, add methyl alcohol 6.0mol, iodomethane 1.0mol, made 2-vinylpyridine among the embodiment 1/acrylic acid ethylene glycol bis ester copolymer rhodium catalyst 8.0g (80～100 orders, Rh=3.0%), be warming up to 180 ℃ after feeding CO, CO constant voltage 4.5MPa, 500 rev/mins of mixing speeds, 25 minutes reaction time.Each constituent content is in the system of reaction end back: methyl alcohol 0mol (methanol conversion is 100%), and iodomethane 1.09mol, methyl acetate 1.12mol, acetate 4.02mol, water 1.24mol, dimethyl ether 0.17mol, acetic anhydride 0.07mol, carbon dioxide are 0.003mol.
Claims (36)
1. the synthetic rhodium catalyst of carbonyl is characterized in that this catalyst comprises cation part and anion part, and described cation partly comprises crosslinked porous polyethylene yl pyridines acrylic acid diethylene glycol dilaurate copolymer ligand and rhodium carbonyl.
2. carbonyl according to claim 1 synthesizes rhodium catalyst, it is characterized in that described anion partly comprises tetraphenylboron acid group or acetate.
3. carbonyl according to claim 1 synthesizes rhodium catalyst, it is characterized in that, the N with the rhodium coordination in catalyst molecule is the N on the pyridine ring in the vinylpyridine, with the O of rhodium coordination be carbonyl O in the acrylic acid diethylene glycol dilaurate.
4. carbonyl according to claim 1 synthesizes rhodium catalyst, it is characterized in that vinylpyridine is 2-vinylpyridine or 4-vinylpridine.
5. carbonyl according to claim 1 synthesizes rhodium catalyst, it is characterized in that rhodium carbonyl is [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2Or [Rh (CO)
2I]
2
6. carbonyl according to claim 1 synthesizes rhodium catalyst, and the precursor that it is characterized in that described anion is NaBPh
4Or NaOOCCH
3
7. the method for preparing the crosslinked porous copolymers part in the synthetic rhodium catalyst of the described carbonyl of claim 1 is comprising vinylpyridine monomers, crosslinking agent, initator and perforating agent are mixed.
8. method according to claim 7 is characterized in that crosslinking agent is the acrylic acid diethylene glycol dilaurate.
9. method according to claim 7, the inventory that it is characterized in that crosslinking agent are 1～9 times of vinylpyridine by weight.
10. method according to claim 9 is characterized in that described inventory is 2.3 times of vinylpyridine by weight.
11. method according to claim 8 is characterized in that the ratio of vinylpyridine and acrylic acid diethylene glycol dilaurate is 3:7 by weight.
12. method according to claim 7 is characterized in that initator is azodiisobutyronitrile or benzoyl peroxide.
13. method according to claim 8, the consumption that it is characterized in that initator be vinylpyridine and acrylic acid diethylene glycol dilaurate weight and 1～5%.
14. method according to claim 13, the consumption that it is characterized in that initator be vinylpyridine and acrylic acid diethylene glycol dilaurate weight and 2%.
15. method according to claim 7 is characterized in that pore-foaming agent is the mixture of kerosene, toluene and isoamyl alcohol.
16. method according to claim 15 is characterized in that the kerosene consumption is 30～80% of a total monomer amount weight by weight.
17. method according to claim 15 is characterized in that the kerosene consumption is 65% of a total monomer amount weight by weight.
18. method according to claim 15 is characterized in that the toluene consumption is 10～40% of a total monomer amount by weight.
19. method according to claim 18 is characterized in that the toluene consumption is 25% of a total monomer amount by weight.
20. method according to claim 15 is characterized in that the isoamyl alcohol consumption is 1～15% of a total monomer amount by weight.
21. method according to claim 20 is characterized in that the toluene consumption is 8% of a total monomer amount by weight.
22. method according to claim 7 is characterized in that this method further comprises the step that adds condensation polymer.
23. method according to claim 22 is characterized in that said condensation polymer is that TEPA and epoxychloropropane condensation form.
24. method according to claim 23 is characterized in that the condensation polymer consumption is 5～15% of a monomer total amount by weight.
25. method according to claim 23 is characterized in that the condensation polymer consumption is 8% of a monomer total amount by weight.
26. method according to claim 7 is characterized in that this method further comprises the step that adds dispersant.
27. method according to claim 26 is characterized in that dispersant is the bentonite of water furnishing oar shape.
28. method according to claim 27 is characterized in that the consumption of bentonite is 10～30% of a monomer total amount by weight.
29. method according to claim 28 is characterized in that, the consumption of bentonite is 20% of a monomer total amount by weight.
30. method according to claim 7 is characterized in that adopting the suspension polymerisation mode.
31. method according to claim 30 is characterized in that water is for containing 10% weight Na
2SO
4The aqueous solution.
32. method according to claim 31 is characterized in that Na
2SO
4Amount of aqueous solution used is 3～10 times of organic facies volume.
33. method according to claim 32 is characterized in that Na
2SO
4Amount of aqueous solution used is 5 times of organic facies volume.
34. prepare the method for the synthetic rhodium catalyst of the described carbonyl of claim 1,, add NaBPh comprising the solution that will contain copolymer ligand and four carbonyl dihalo-s, two rhodiums
4Or CH
3In the aqueous solution of COONa.
35. a method for preparing acetate has wherein used carbonyl according to claim 1 to synthesize rhodium catalyst.
36. a method for preparing acetic anhydride has wherein used carbonyl according to claim 1 to synthesize rhodium catalyst.
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