CN101182340A - Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof - Google Patents
Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101182340A CN101182340A CNA2007101799948A CN200710179994A CN101182340A CN 101182340 A CN101182340 A CN 101182340A CN A2007101799948 A CNA2007101799948 A CN A2007101799948A CN 200710179994 A CN200710179994 A CN 200710179994A CN 101182340 A CN101182340 A CN 101182340A
- Authority
- CN
- China
- Prior art keywords
- lithium
- rhodium
- reaction
- acetic acid
- reaction system
- 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
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 222
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 42
- 230000006315 carbonylation Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 102
- 239000010948 rhodium Substances 0.000 claims abstract description 59
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 45
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 43
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 28
- 230000000694 effects Effects 0.000 claims abstract description 27
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims abstract description 15
- MPWABWAILHDPTM-UHFFFAOYSA-N [Li].NC(=O)O Chemical compound [Li].NC(=O)O MPWABWAILHDPTM-UHFFFAOYSA-N 0.000 claims abstract description 11
- VIOYXNIHLPLPMP-UHFFFAOYSA-N [Rh].[Li].NC(=O)O Chemical compound [Rh].[Li].NC(=O)O VIOYXNIHLPLPMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 19
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 19
- JUMYIBMBTDDLNG-OJERSXHUSA-N hydron;methyl (2r)-2-phenyl-2-[(2r)-piperidin-2-yl]acetate;chloride Chemical compound Cl.C([C@@H]1[C@H](C(=O)OC)C=2C=CC=CC=2)CCCN1 JUMYIBMBTDDLNG-OJERSXHUSA-N 0.000 claims description 15
- 229940099204 ritalin Drugs 0.000 claims description 15
- NSBJSRUCYQSYQO-UHFFFAOYSA-L diiodorhodium Chemical compound I[Rh]I NSBJSRUCYQSYQO-UHFFFAOYSA-L 0.000 claims description 13
- 150000003016 phosphoric acids Chemical class 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 10
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 23
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 150000002500 ions Chemical group 0.000 abstract description 17
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052740 iodine Inorganic materials 0.000 abstract description 8
- 239000011630 iodine Substances 0.000 abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000013522 chelant Substances 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- -1 pyridines quaternary ammonium salt Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012429 reaction media Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 5
- 235000004279 alanine Nutrition 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 4
- 229940006461 iodide ion Drugs 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 229920013683 Celanese Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 235000011089 carbon dioxide Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OFDCTUIOIVVFNE-UHFFFAOYSA-N [Li].NC(C(=O)O)CC Chemical compound [Li].NC(C(=O)O)CC OFDCTUIOIVVFNE-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 230000002153 concerted effect Effects 0.000 description 2
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 230000001020 rhythmical effect Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 description 2
- 238000012916 structural analysis Methods 0.000 description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JJMVYLKXFKVCDZ-UHFFFAOYSA-N [Li].[Rh] Chemical compound [Li].[Rh] JJMVYLKXFKVCDZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229940124277 aminobutyric acid Drugs 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 1
- 238000007630 basic procedure Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- SKVWXDRVFXUPJX-UHFFFAOYSA-M lithium;carbamate Chemical class [Li+].NC([O-])=O SKVWXDRVFXUPJX-UHFFFAOYSA-M 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000001394 metastastic effect Effects 0.000 description 1
- 206010061289 metastatic neoplasm Diseases 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229960004839 potassium iodide Drugs 0.000 description 1
- 235000007715 potassium iodide Nutrition 0.000 description 1
- WINGFJQHCRYKRB-UHFFFAOYSA-L potassium;sodium;diiodide Chemical compound [Na+].[K+].[I-].[I-] WINGFJQHCRYKRB-UHFFFAOYSA-L 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method of producing acetic acid by methanol carbonylation, a special catalyst and a preparation method thereof. The invention provides an amino carboxylic acid lithium-rhodium complex, a structure of which is shown in a formula (I), wherein, X equals to BPh4 or I; n equals to 1, 2 or 3. The invention considers amino carboxylic acid lithium as a ligand which matches with rhodium complex to form a positive ionic active center structure of the strong-weak coordinate bonds chelate type; the positive ion part contains N-Rh bond on a strong coordinating position and O-Rh bond on a weak coordinating position, which ensures the stability and the activity of the active center; metal lithium and metal rhodium are inside the active center structure together to form the synergetic catalysis effect and also can be used to combine with other catalysts to improve the catalytic activity; the strong assistant catalysis of iodine negative ions towards the reaction assists for providing the excellent performance of the catalyst with foundation; at the same time, the combination of lithium iodide, lithium acetate and phosphate is used as an assistant catalyst which ensures that the catalyst of the invention presents excellent comprehensive performance for catalyzing the reaction that methanol carbonylation produces the acetic acid.
Description
Technical field
The present invention relates to a kind of carbonylation of methanol and produce method and the special-purpose catalyst and the preparation method of acetic acid.
Background technology
Acetic acid is a kind of important Organic Chemicals, is mainly used in to produce Vinyl Acetate Monomer, aceticanhydride, terephthalic acid (PTA), polyvinyl alcohol, acetates, cellulose acetate etc.Has extensive use in industries such as chemical industry, light textile, medicine, dyestuffs.In recent years, because the development of PTA and acetic acid derived product, impelled acetic acid to become one of a few petroleum chemicals that minority output and demand increase rapidly.
Producing in the production technology of acetic acid in carbonylation of methanol, is one of important contents to the research of catalyzer.Carbon monoxide under the effect of catalyzer, with methyl alcohol prepared in reaction acetate be the carbonylic preparation method that grows up in the 40-50 age in 20th century.The beginning of the seventies, the people such as Paul ik of Monsanto company opened up new enforcement approach about oxo-synthesis homogeneous rhodium catalyst invention (US 3 769 329) for carbonylic synthesis technology.Through updating and perfect, with the rhodium production process route that the oxo process technology of catalyzer has become the industrial most important and output maximum of present acetate.Its reaction process is the effect that methyl alcohol passes through rhodium catalyst, prepares acetate with reaction of carbon monoxide, and catalyzer adopts [Rh (CO)
2I
2]
-Anionic small molecules title complex [Roth, J.F.et al.Chem.Technol, 1971,600].Because this class rhodium active specy is unstable in reaction, is easy to be converted in reaction process dicarbapentaborane tetraiodo rhodium (III) [Rh (CO)
2I
4]
-Anionic complex, and lose activity, all the more so when temperature is higher, and higher temperature is favourable to reaction.Therefore in industrial production, general employing keeps the dividing potential drop of carbon monoxide or adds the existence of excessive hydrogen iodide with protection rhodium (I) title complex, but this has greatly increased the corrosive nature of reaction medium to equipment again.
At existing catalyzer these deficiencies in reaction process, people are groping the better catalyzer of performance always, and hope can have advantages of high catalytic activity and better stable simultaneously.The catalyzer that Britain BP company uses in recent years becomes iridium catalyst systems [EP 849 249,19 Dec 1996] by original rhodium catalytic system, has obtained certain effect, makes catalyst performance that bigger improvement arranged.
For overcoming [Rh (CO)
2I
2]
-As the weak point of catalytic active species, investigators have carried out fruitful work, and have obtained good progress.Wherein, comparatively effective means is: adopt the small molecules contain nitrogen, phosphorus, oxygen, sulphur functional group or macromolecule ligand and Rh formation title complex as catalyzer, reach the purpose of improving rhodium active specy thermostability and improving its catalytic activity.For example, adopt the part of superpolymer, make catalyzer when keeping higher carbonylation activity, the stability of catalyzer also be improved (CN100750, US 5281359, US 6458996) as catalyzer.In the research of polymer catalyst, the homogeneous phase that is part with the homopolymer and the multipolymer of vinylpyridine and the research of heterogeneous reaction catalyzer are always people and pay close attention to.Reported that in early days (Inor Chem.1981 (20): 64), contained the 4-vinylpyridine multipolymer afterwards is part and RhCl to the catalyzer that polyvinylpyridine quaternary ammonium salt anionite-exchange resin and rhodium reactant salt form
3The catalyzer that coordination forms also is reported in media, and it adopts the homogeneous reaction form under the reaction conditions of gentleness, reached higher catalysis speed (EP-0277824).Discover that the solubility small molecules rhodium catalyst that forms with the ionic linkage binding partner has the higher catalytic activity that helps, and the part of nitrogenous family element is studied and uses morely, wherein, help catalytic effect best with the pyridines quaternary ammonium salt.Think on the carbon atom of pyridines aromatic nucleus substituting group number and position to shorten decomposition induction time, improve initial catalytic rate effect obviously (J.Mol.Catal., 1983,20:175-184).Also there is report to point out that the variation of substituent position and character is to the formed small molecules title complex of this part [[Rh (CO) on the pyridine ring in the recent period
2ClL] catalytic activity has remarkable influence (Appl.Organometal, Chem.2002; 16:258-264).
Adding one or more in catalyst system helps catalytic additive to improve and to promote that reaction is an important research contents.In numerous research, the research of salt compounded of iodine and acetate is more deep.M.Gauss[M.Gauss et al.Applied Homogeneous:Catalysis with Organometallic Compounds, New York, VHC, 1996,104.] and the M.A.Murphy[M.A.Murphy et al.JOrganomet Chem of Hoechst Celanese company, 1986,303:257-272.] and B.L.Smith[B.L.Smith et al.J MolCatal, 1987,39:115-136.] etc. the people think that by the catalytic methyl alcohol homogeneous carbonylation of rhodium is studied the promoting catalysis of salt compounded of iodine and acetate is because this salt and [Rh (CO)
2I
2]
-Formed Rh (I) the title complex negatively charged ion of pentacoordinate, this negatively charged ion can react with speed faster with MeI as reaction intermediate, and this step reaction is the committed step that influences overall reaction rates.And these salt have suppressed RhI by forming easily molten rhodium complex with catalyzer
3Sedimentary generation, thus the stability of catalyst system improved.By selecting salt compounded of iodine and suitable ritalin concentration, can than obtain under the low water content with high water content under identical reactive behavior and stability, improved the utilising efficiency of CO simultaneously.In addition, people such as M.A.Murphy is also to LiBF
4Wait other additive to study.
The industrial exemplary of significantly improving production technique by adding the inorganic salt promotor is a HoechstCelanese company.The said firm has obtained to be undertaken by the Monsanto carbonylic synthesis technology permission of commercial size acetic acid production in 1978, and it has been carried out a series of improvement.Early 1980s, the said firm has developed the Processes for Producing Acetic Acid of the low water content of independent intellectual property right, and this technology has been improved the production process of acetic acid widely.The principal feature of this technology is promptly by adding inorganic salt compounded of iodine to a higher content, and (US 5001259, EP055618) to reach the effect that improves activity of such catalysts and stability.
Summary of the invention
The purpose of this invention is to provide a kind of aminocarboxylic acid lithium rhodium complex and preparation method thereof with good carbonylation of methanol catalytic activity.
Aminocarboxylic acid lithium rhodium complex provided by the present invention, structure be suc as formula shown in the I,
Wherein, X=BPh
4Or I; N=1,2 or 3.
The preparation method of this aminocarboxylic acid lithium rhodium complex comprises the steps:
1) aminocarboxylic acid and lithium hydroxide are dissolved in methyl alcohol or the acetic acid,, disappear until aminocarboxylic acid crystallization and lithium hydroxide crystallization in 20-60 ℃ of high-speed stirring;
2) four carbonyl dichloros, two rhodiums are dissolved in methyl alcohol or the acetic acid, and slowly join and stir step 1) gained solution down, continue stirring in 10-40 ℃, form stable title complex;
3) iodide or tetraphenylboron thing are dissolved in methyl alcohol or the acetic acid, and join step 2 in stirring down) in the gained solution, continue stirring in 10-40 ℃, promptly obtain described aminocarboxylic acid lithium rhodium complex.
Another object of the present invention provides the purposes of aminocarboxylic acid lithium rhodium complex of the present invention.
Aminocarboxylic acid lithium rhodium complex of the present invention has good catalysis methanol carbonylation reaction activity, can produce in the acetic acid at the catalysis methanol carbonylation to be widely used.
The method that the present invention also provides a kind of carbonylation of methanol to produce acetic acid is methyl alcohol and CO (carbon monoxide converter) gas to be carried out methanol carbonylation obtain acetic acid under the catalyst system effect, and wherein, catalyst system contains aminocarboxylic acid lithium rhodium complex of the present invention.
Be catalysis methanol carbonylation reaction better, described catalyst system also is added with dicarbapentaborane diiodo-rhodium; Based on the reaction system gross weight, the content of described dicarbapentaborane diiodo-rhodium in reaction system is counted 200-1200ppm with rhodium.Based on the reaction system gross weight, the total content of rhodium is 200-2000ppm in the described reaction system; Be preferably 400-1200ppm; 600-1000ppm more preferably.
In order to improve the catalytic activity of catalyst system better, catalyst system also is added with promotor, and described promotor comprises methyl iodide, lithium iodide, Lithium Acetate and phosphoric acid salt.Wherein, the weight content of methyl iodide in reaction system is 8-20%, is preferably 12-18%; The weight content of lithium iodide in reaction system is 2-20%, is preferably 6-15%; The weight content of Lithium Acetate in reaction system is 0.5-10, is preferably 2-4%; Phosphatic range of choice is Na, K, NH
4Phosphoric acid normal salt and hydrate thereof, the weight content of phosphoric acid salt in reaction system is 0.01%-5%, is preferably 0.1%-0.8%.
In order to control the content of water in the reaction system better, also be added with ritalin in the reaction system, ritalin content is reaction system gross weight 0.5-13%, is preferably 3-8%.
The temperature of methanol carbonylation is controlled at 150-250 ℃, is preferably 185-210 ℃.The branch of carbon monoxide is pressed in 0.2-3.0MPa, is preferably 0.5-1.5MPa.Because all gases by product, such as carbonic acid gas and hydrogen etc., and the vapour pressure of various liquid in the reaction medium, the reaction total pressure is preferably 3.0MPa at 2.0-5.0MPa.
This catalyzer has excellent performance, is mainly reflected in following four aspects:
1. very strong stability: poor stability is an open defect of existing carbonylation of methanol catalyzer, mainly be because original catalytic active center is a dicarbapentaborane diiodo-rhodium anion structure, this structure is under reaction conditions, especially unstable under the flash conditions, generate the rhodium triiodid precipitation easily, cause the reduction of throughput, even the pipeline of obstruction production unit causes stopping production; Because special catalyst structure, the stability of catalyzer of the present invention obviously is better than original carbonylation of methanol catalyzer.
2. high activity: the Meng Shan reactive behavior of the used catalyzer of methanol carbonylation process counts about 8mol/ (Lh) with space-time yield (STY), just is improved after Celanese company improves.Through the composition and the reaction conditions of control catalyst, this activity of such catalysts can reach more than the 30mol/ (Lh), through further optimizing, can reach 40mol/ (Lh).Potentiality on the activity provide wide space for existing expanding production of full scale plant.
3. high selectivity: methanol carbonylation itself is a reaction that selectivity ratios is higher, and side reaction mainly is that water and reaction of carbon monoxide generate hydrogen and carbonic acid gas owing to contain a certain amount of water in the reactor.The hydrogen that generates is also relatively more active, and it can participate in reaction and generate other by product, such as methane, and acetaldehyde etc.The inventive method can drop to the water-content in the reaction system a quite low level, thereby can improve the selectivity of reaction greatly.
4. high adaptability: adaptability mainly is the structure that comes from catalyzer of the present invention self, and promotor makes up the over-all properties that is had.
The present invention is that part and rhodium complex form power and join key chelating type positive ion active centre structure with the aminocarboxylic acid lithium, this catalyzer positive ion partly contains strong coordinate N → Rh key and weak coordinate 0 → Rh key, guaranteed the stable and active of active centre, metallic lithium and metal rhodium are co-located in the active centre inside configuration, can form the concerted catalysis effect; And catalyzer of the present invention can also be united use with other catalyzer, improves its catalytic activity; Be aided with the strong promoting catalysis of iodine negative ion again, for the excellent properties of this catalyzer provides the foundation to this reaction; Simultaneously, lithium iodide and phosphatic combination make catalyzer of the present invention show the excellent comprehensive performance in the reaction of catalysis methanol carbonylation production acetic acid as promotor.
Embodiment
Complex structure of the present invention is shown below:
X＝BPh
4，I； n＝1，2，3
Concrete preparation method is as follows:
(1) aminocarboxylic acid of 1 molar part and the lithium hydroxide of equimolar amount are dissolved in amount of methanol or the acetic acid, in 20-60 ℃ of high-speed stirring 10-60 minute, until aminocarboxylic acid crystallization and lithium iodide crystallization completely dissolve.The solubleness of two reactants in organic solvent is less, but the aminocarboxylic acid lithium that generates has reasonable solvability.
NH
2(CH
2)
nCOOH+LiOH→NH
2(CH
2)
nCOOLi+H
2O
(2) four carbonyl dichloros, two rhodiums with 0.5 molar part are dissolved in amount of methanol or the acetic acid, and the methyl alcohol or the acetum of the aminocarboxylic acid lithium under slowly adding is stirred, continue to stir 20-60 minute in 10-40 ℃, the chlorine bridge of four carbonyl dichloros, two rhodiums ruptures, and forms stable title complex with the aminocarboxylic acid lithium.
(3) potassiumiodide (sodium) or the sodium tetraphenylborate with 1 molar part is dissolved in an amount of methyl alcohol or the acetic acid, and in stirring the solution that adds down in (2), continues stirring in 10-40 ℃ and promptly got the concrete title complex that will prepare in 10-30 minute.
Resulting title complex can be in methyl alcohol and acetic acid stable existence, because carbon monoxide is a kind of part of this composition catalyst, so its stability is better when having carbon monoxide to exist, can adapt to the reaction medium environment in the carbonylation of methanol production technique fully.In this complex solution, add ether, can obtain flaxen cotton-shaped solid complexes.When being reactant with the sodium tetraphenylborate, the solid complexes that obtains can stable in the airly exist.
Title complex of the present invention has the catalytic activity that good catalysis methanol carbonylation prepares acetic acid, can be used for the carbonylation reaction of methyl alcohol.And solvent for use is methyl alcohol, acetic acid or both mixtures during owing to the preparation title complex, and therefore this title complex can directly use by solution state in actual production, and the concentration of rhodium can be controlled by add complex solution gradually in reactor.
In the carbonylation reaction system of methyl alcohol, also can add dicarbapentaborane diiodo-rhodium tetraethylammonium difluoride, the cationic catalyst that itself and aminocarboxylic acid lithium of the present invention are part is united use, the negative ions active centre concurs, catalysis methanol carbonylation reaction better, the content of dicarbapentaborane diiodo-rhodium negative ion in reaction system is counted 200-1200ppm (based on the reaction system gross weight) with rhodium.Based on the reaction system gross weight, the total content of rhodium catalyst is controlled at 200-2000ppm in rhodium in the reaction system, is preferably 400-1200ppm, and 600-900ppm is the use of suitable existing industrial manufacture process.
The performance of catalyzer of the present invention also with the use of promotor, the control of ritalin and water-content has confidential relation.Promotor of the present invention is methyl iodide, lithium iodide, Lithium Acetate and phosphoric acid salt.Wherein methyl iodide is all necessary promotors of carbonylation of methanol catalyzer, and lithium iodide, Lithium Acetate and phosphatic being used in combination then are another sources of catalyzer excellent properties of the present invention.Promotor of the present invention and consumption thereof are as follows:
Based on the reaction system gross weight, the content of methyl iodide in reaction system is 8-20%, is preferably 12-18%; The content of lithium iodide in reaction system is 2-20%, is preferably 6-15%; The content of Lithium Acetate in reaction system is 0.5-10, is preferably 2-4%; Phosphatic range of choice is phosphoric acid normal salt and the hydrate thereof of Na, K, and the content of phosphoric acid salt in reaction system is 0.01%-5%, is preferably 0.1%-0.8%.
This catalyzer is when industrial use, in reaction system, add ritalin and be controlled at 1-10% with water-content in the control reaction system, be preferably 1.5-6% (based on the reaction system gross weight), ritalin content is controlled at 0.5-13%, is preferably 3-8% (based on the reaction system gross weight).
The temperature of methanol carbonylation device is controlled at 150-250 ℃, is preferably 185-210 ℃.The dividing potential drop of carbon monoxide is controlled at 0.2-3.0MPa in the reactor, is preferably 0.5-1.5MPa.Because all gases by product, such as carbonic acid gas and hydrogen etc., and the vapour pressure of various liquid in the reaction medium, the total pressure of reactor will be controlled at 2.0-5.0MPa, is controlled at about 3.0MPa usually.
The performance of catalyzer excellence of the present invention mainly comes from the several characteristics of catalyst themselves:
1. power is joined the stability that existence that key chelate structure: N → Rh joins key has by force guaranteed catalyzer, and under relatively harsher reaction conditions, the N atom is caught positive univalent rhodium ion tightly, makes it be in active co-ordination state all the time.Join key a little less than 0 → Rh owing to can break and bonding again in reaction, help the oxidation addition of methyl iodide, make catalyzer have higher activity, this structure is different from common negative ion active specy, also be the N monodentate rhodium complex and the N of bibliographical information, N bidentate rhodium complex can not compare.Aminocarboxylic acid is the simplest part of structure that can form strong and weak coordinate bond with rhodium, and the stability of himself is also fine, and its performance as catalyzer of using provides better basis.Be that the catalyzer that part prepares carbonylation of methanol also is an important innovations point of the present invention with the aminocarboxylic acid.
2. bimetal structure: lithium ion closely links to each other by aminocarboxylic acid with the rhodium active centre, coexists as in the catalyst molecule, and the concerted catalysis effect can take place, and activity of such catalysts is had promoter action preferably.
3. negative ions structure: the active centre is the positive ion rhodium complex, in reaction system, the content of iodide ion is higher, and the tetraphenylboron negative ion also can be replaced by iodide ion, interaction between the negative ions makes that the strong promoting catalysis of iodide ion is better brought into play.Simultaneously, dicarbapentaborane diiodo-rhodium negative ion active centre can also be arranged in the reaction system, the carrying out of itself and the common catalysis methanol carbonylation reaction in rhodium positive ion active centre.
4. promotor combination efficiently: except the necessary methyl iodide promotor of this reaction itself, the present invention has also selected lithium iodide, Lithium Acetate and highly active phosphoric acid salt promotor.Having of lithium iodide is beneficial to the ritalin that keeps higher concentration in the reaction system, can reduce the water-content in the production equipment like this, thereby reduce system loading greatly, not only saved energy consumption, and can also increase the throughput of equipment greatly.The introducing of a large amount of lithium iodide promotors is the main improvement with respect to Monsanto house journal technology (i.e. BP technology afterwards) of the AO Plus technology of Celanese company.The use of lithium iodide promotor has improved production efficiency greatly, but the too high meeting of iodine content brings the increase of the consumption of iodine in the production, has increased production cost to a certain extent, thus the present invention to have selected Lithium Acetate, phosphoric acid salt simultaneously be promotor.The adding of Lithium Acetate has suppressed (CH
3COOCH
3+ LiI → CH
3COOLi+CH
3I) Fan Ying generation has guaranteed that iodide ion has higher actual content in the reaction system.When the lower aq level, phosphoric acid salt will be far above the lithium iodide of same amount to the promoter action of reactive behavior, so, need only the phosphoric acid salt promotor that adds low levels in the reaction system, just can obtain higher activity, when keeping identical reactive behavior, can reduce the consumption of lithium iodide like this.Phosphoric acid salt and lithium iodide, Lithium Acetate are united use, can receive the better synthesis effect.
Unique catalyst structure and promotor combination efficiently make carbonylation of methanol catalyzer of the present invention have the excellent comprehensive performance.Catalyzer of the present invention can directly apply to existing low pressure methanol carbonylation method Processes for Producing Acetic Acid, and can significantly promote the throughput of original production device.It also goes for the improvement technology of existing technology, improves the structure and the type selecting that comprise nucleus equipments such as reactor and flasher, and the dilatation of subsequent processing device etc.
The use of carbonylation of methanol catalyzer of the present invention relates generally to the introducing of Preparation of catalysts and promotor.The Preparation of catalysts process is carried out in organic solvent, and this solvent is methyl alcohol, acetic acid or both mixtures.Solvent itself also is reactant, product or both combinations.The use of catalyzer is divided into is using and is using on the device intermittence two kinds of situations on the continuous apparatus:
(1) use on the continuous reaction apparatus
At continuous apparatus, can directly inject the methanol carbonylation device after Preparation of catalysts is finished, and not need other subsequent processes.Promotor can be dissolved in methyl alcohol or acetic acid, adds the methanol carbonylation device with feed stream then.Reactor is controlled at the certain reaction temperature, and under agitation, carbon monoxide is blasted reactor by distribution device in gas-fluid, methyl alcohol and the methyl iodide that returns are introduced reactor by liquid distribution device.For the carbon monoxide pressure of tension that makes the reactor upper space remains on certain level, need discharge gas continuously from the top of the vapour space of reactor, and the total pressure of controlling reactor simultaneously.
In operating process, utilize a liquid-level controller to predict liquid level in the reactor, expel liquid reaction product continuously, and will be transported in the flasher.Flasher is in lower pressure (0.1-0.6MPa) operation down.Vapor portion in the flasher mainly comprises methyl iodide and acetic acid etc., comes back to reactor after methyl iodide is separated, and to keep wherein certain methyl iodide content, rest part enters the acetic acid separated purification system in downstream, obtains acetate products.Send back in the reactor after the material of flasher bottom is discharged, this strand material mainly is acetic acid and mixture of catalysts.Continue each component concentrations in the analysis reactor, and come each component in the controlling reactor to be in the concentration range of setting by the turnover logistics.
The above is the basic procedure of reactive system in the continuous reaction apparatus.This flow process is suitable for the acetic acid industry production equipment, also can be fit to pilot plant and mold trial device.As long as can keep comprising the steady running of the reactive system of flasher, just enough be used for the performance of evaluate catalysts, subsequent separation system in addition can with the reactive system independent operation.
The reactive behavior of successive reaction can be passed through the used time of catalyzed reaction, and the growing amount of product calculates, and also can calculate by the absorption rate of carbon monoxide; Selectivity can be calculated by the result that reaction product is analyzed; Stability can be judged by observing response activity change and precipitation generation situation.
(2) use on the rhythmic reaction device
Methanol carbonylation also can carry out on the batch experiment device.After Preparation of Catalyst finishes, together with solvent impouring reactor, promotor is good according to certain cubage, directly throw in the reactor then, seal reactor, and, feed the CO (carbon monoxide converter) gas of certain pressure, and close the valve of inlet mouth with behind the air in the CO (carbon monoxide converter) gas metathesis reactor.Start stirring arm, make solid cocatalyst dissolving wherein, the temperature of the reactor that raises gradually begins to descend after gauge outfit pressure is elevated to a certain degree, the reaction beginning.Open the inlet mouth valve, and carbon monoxide pressure is adjusted to preset value, the heating unit of conditioned reaction device, make temperature of reaction remain on preset range, reaction continues to carry out, and carbon monoxide stops to absorb when methyl alcohol reacts completely, perhaps be reacted to the time of setting, stopped reaction.
Performance perameters such as the activity of rhythmic reaction, selectivity and stability, can utilize with successive reaction in similar methods obtain.
In order more clearly to illustrate technology contents of the present invention, further do some description especially exemplified by several embodiment, but it should be noted that the following examples only constitute explanation of the present invention, and be not construed as limiting the invention.
To subsequent treatment process in the catalyzer use and device, carry out too much that meticulous argumentation is nonsensical, because it has nothing to do with catalyst themselves, and the structure of different operational paths and equipment also is not quite similar.Therefore we form different catalyst system emphatically, and different working condition is discussed the influence of catalytic perfomance.By the small testing device at intermittence, than the variation that is easier to investigate each component in the reaction system, to the influence of catalyst effect.Can more press close to the catalytic performance that industrial production is investigated catalyzer practically by long run test.
Embodiment 1, Preparation of catalysts
The alanine of 0.01 molar part and 0.01 mole lithium hydroxide are dissolved in the methyl alcohol of 100ml,, form the methanol solution of alanine lithium in 30 ℃ of high-speed stirring 30 minutes; 0.005 mole four carbonyl dichloros, two rhodiums are dissolved in the 50ml methyl alcohol, and slowly add the methanol solution of the alanine lithium under stirring, continue to stir 40 minutes, form alanine lithium rhodium complex in 40 ℃; 0.01 mole potassiumiodide is dissolved in the 50ml methyl alcohol, and adds down in the above-mentioned complex solution, continue to stir 30 minutes, obtain the catalyst solution that will prepare, be designated as catalyzer (I) in 40 ℃ in stirring.
The aminobutyric acid of 0.01 molar part and 0.01 mole lithium hydroxide are dissolved in the methyl alcohol of 100ml,, form the methanol solution of aminobutyric acid lithium in 40 ℃ of high-speed stirring 40 minutes; 0.005 mole four carbonyl dichloros, two rhodiums are dissolved in the 50ml acetic acid, and slowly add the methanol solution of the aminobutyric acid lithium under stirring, continue to stir 60 minutes, form aminobutyric acid lithium rhodium complex in 30 ℃; NaBPh with 0.01 mole
4Be dissolved in the mixing solutions of 20ml methyl alcohol and 30ml acetic acid, and add down in the above-mentioned complex solution, continue to stir 50 minutes, obtain the catalyst solution that will prepare, be designated as catalyzer (II) in 30 ℃ in stirring.
In above-mentioned complex solution, add ether, obtain flaxen cotton-shaped solid complexes respectively.Resulting title complex is carried out structural analysis: acid-base reaction generates the basic general knowledge that salt is chemistry, so the generation of aminocarboxylic acid lithium salts need not analysis of experiments.Can form if power is joined bond structure, then the chlorine atom must be taken off, and forms the positive ion complex structure, so the structure that the key issue of structural analysis is a power joins key chelating type title complex is determined and the determining of rhodium carbonyl structure.
Resulting catalyzer is carried out x-ray photoelectron spectroscopy test, the N of amino nitrogen atom
1sBound energy rises to the 399.1-399.9eV of title complex, the O of carbonylic oxygen atom by the 398.6eV of part
1sBound energy also rises to 532.2-533.0eV by the 532.0eV of part.In addition, Rh3d in the title complex
5/2Bound energy all the bound energy than corresponding four carbonyl dichloros, two rhodiums is low, show that rhodium atom accepted the metastatic electron that comes from N and O atom as receptor in complex formation, form N → Rh and O → Rh coordinate bond respectively.Composition catalyst to gained carries out examination of infrared spectrum, on its infrared spectra, and 1990 and 2070cm
-1There are two groups of absorption peaks at the place, matches with the terminal carbonyl absorption peak of rhodium.
The result of analytical test proves that the catalyst structure formula matches among the title complex of gained and the present invention.
Embodiment 2, catalyzed reaction
The catalyzer (I) of catalyst system therefor for making among the embodiment 1.Batch test carries out in the zirconium matter autoclave of 250ml, controls different reaction systems and forms, and can obtain different reaction results.Discuss the performance of catalyzer below by the response data in the table 1.The acetic acid productive rate refers to the percentage that material benzenemethanol generates acetic acid.
Methyl alcohol is the raw material of reaction, and the adding of ritalin mainly is the water-content for conditioned reaction process medium, and the add-on of ritalin is high more, and actual water content is low more in the reaction.Part remaining in the reaction medium is an acetic acid.The content of the rhodium complex catalyst of aminocarboxylic acid lithium (embodiment 1 preparation) calculates with the mass fraction (ppm) of rhodium in reaction system.The reactor pressure of test 1 is 5.0MPa, and the reactor pressure of test 2 is 2.0Mpa, and the reactor pressure of all the other tests is 4.0Mpa.Reaction times is 20 minutes.Phosphoric acid salt is by selection respectively among Na, the K, and phosphatic promoting catalysis is mainly phosphate anion and produces.
Table 1 batch test response data
| Sequence number | Each component concentration (wt%) in the reaction system | Temperature of reaction (℃) | STY mol/L·h | Selectivity (%) | ||||||
| Rh content/ppm | Methyl iodide | Lithium iodide | Lithium Acetate | Phosphoric acid salt | Ritalin | Methyl alcohol | ||||
| 1 | 200 | 20 | 20 | 10 | 5 | 13 | 30 | 250 | 6.4 | 99.8 |
| 2 | 300 | 8 | 2 | 0.5 | 0.01 | 0.5 | 60 | 150 | 6.9 | 99.1 |
| 3 | 400 | 15 | 10 | 3 | 0.1 | 4 | 40 | 190 | 10.4 | 99.5 |
| 4 | 400 | 15 | 10 | 3 | 0.4 | 1 | 40 | 190 | 12.9 | 99.1 |
| 5 | 400 | 15 | 10 | 3 | 0.4 | 4 | 40 | 190 | 12.3 | 99.3 |
| 6 | 700 | 15 | 10 | 3 | 0.4 | 4 | 40 | 190 | 20.6 | 98.9 |
| 7 | 700 | 15 | 10 | 8 | 0.4 | 4 | 40 | 190 | 21.9 | 99.4 |
| 8 | 700 | 15 | 13 | 3 | 0.4 | 4 | 40 | 190 | 22.1 | 99.2 |
| 9 | 900 | 15 | 10 | 3 | 0.4 | 4 | 40 | 190 | 30.7 | 99.5 |
| 10 | 900 | 10 | 10 | 3 | 0.4 | 4 | 40 | 190 | 28.5 | 99.6 |
| 11 | 900 | 10 | 5 | 3 | 0.4 | 4 | 40 | 190 | 25.1 | 99.7 |
| 12 | 1200 | 15 | 10 | 3 | 0.4 | 4 | 40 | 190 | 38.3 | 99.3 |
| 13 | 1600 | 15 | 10 | 3 | 0.4 | 4 | 40 | 190 | 45.6 | 99.2 |
| 14 | 2000 | 15 | 10 | 3 | 0.4 | 4 | 40 | 190 | 50.4 | 98.9 |
The result shows that rhodium concentration raises and helps the raising of reactive behavior, and the rising of ritalin content can reduce the water-content in the reaction system, but reactive behavior is descended.The content of lithium iodide and Lithium Acetate raises and helps the raising of reactive behavior.The rising of the content of methyl iodide also helps reactive activity and raises, but too high levels can make the stability of catalyzer reduce.The selectivity of methanol carbonylation is very high, all can reach more than 98%.
Embodiment 3, catalyzed reaction
Catalyst system therefor is selected the catalyzer (II) that makes among the embodiment 1 for use.Utilization mold trial device at intermittence is estimated the continuous use properties of carbonylation of methanol catalyzer.Catalyzed reaction is carried out in the 250ml reactor in this device, after reaction for some time reaction mother liquor is extruded and enters a glass multistage rectification device, after steaming a certain amount of mother liquor (being mainly methyl iodide and acetic acid), remaining catalyzer mother liquor is together with a certain amount of methyl iodide, enter a high voltage bearing filling body of stainless steel together, and being pressed into reactor by the highly compressed CO (carbon monoxide converter) gas, the new reaction of beginning that heats up so moves in circles.All can calculate reactive activity by the uptake rate of carbon monoxide and the amount of acetic acid product in the reaction, can calculate the selectivity of reaction by the composition of assay products, stability can judge by the precipitation situation of glass water distilling apparatus observation rhodium complex.
The rhodium complex concentration of aminocarboxylic acid lithium is in rhodium 900ppm in the controlling reactor, methyl iodide concentration 12wt%, and lithium iodide content 15wt%, Lithium Acetate 3wt%, sodium phosphate 0.5wt%, ritalin 3.5wt%, methyl alcohol 50wt%, all the other media are acetic acid.Temperature of reaction is controlled at 180-190 ℃, and the reaction total pressure is controlled at 3.0MPa, and the reaction times is 30 minutes, circulating reaction 10 times, and the reactive behavior and the selective data of each time are as shown in table 2:
Table 2 catalyst recirculation number of times and reactive behavior and selective data
| Cycle index | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| STY mol/(L·h) | 29.3 | 33.7 | 30.9 | 35.2 | 31.6 | 32.4 | 36.8 | 33.4 | 31.5 | 32.4 |
| Selectivity % | 98.4 | 99.0 | 98.6 | 99.1 | 99.5 | 99.3 | 99.6 | 99.1 | 99.4 | 99.5 |
Above result shows that the catalytic activity of catalyzer and selectivity are all higher, and under the isolating condition of catalyzer mother liquor of harshness, catalyzer still has stability preferably.
Embodiment 4, catalyzed reaction
The aminocarboxylic acid lithium is the rhodium catalyst of part, also can unite use with dicarbapentaborane diiodo-rhodium, and can reach better catalytic effect.Dicarbapentaborane diiodo-rhodium can be used the preparation of document (ZL 85101460) reported method: about 110 ℃, rhodium triiodid is dissolved in acetic acid or the hydroiodic acid HI, simultaneously under 0.1MPa or higher pressure, in the gained mixture, blast CO (carbon monoxide converter) gas, dissolve fully and generate dicarbapentaborane diiodo-rhodium until rhodium triiodid.
After the rhodium complex catalyst solution (catalyst I) of alanine lithium and dicarbapentaborane diiodo-rhodium catalyst solution prepared according to a certain percentage, unite and use the catalysis methanol carbonylation reaction.Change the content of different rhodium complexs, and calculate catalyst levels with the mass content of rhodium in reaction medium.
Other reaction conditions is with the test in the table 15:
Methyl iodide concentration 15wt%, lithium iodide content 10wt%, Lithium Acetate 3wt%, sodium phosphate 0.4wt%, ritalin 4wt%, methyl alcohol 40wt%, all the other media are acetic acid; Temperature of reaction is 190 ℃, and reaction pressure is 4MPa, and the reaction times is 20 minutes.
The data of batch test reaction result are as shown in table 3.
Table 3 catalyzer of the present invention and dicarbapentaborane diiodo-rhodium are united the use experimental result
| Sequence number | The rhodium complex of aminocarboxylic acid lithium (ppm) | Dicarbapentaborane diiodo-rhodium (ppm) | STY mol/(L·h) | Acetic acid selectivity (%) |
| 1 | 300 | 200 | 12.5 | 99.4 |
| 2 | 100 | 1200 | 40.9 | 99.5 |
| 3 | 200 | 700 | 30.4 | 99.2 |
| 4 | 700 | 200 | 35.6 | 99.8 |
The result shows that two catalyzer all have the catalytic activity of methanol carbonylation, but the catalytic activity of catalyzer of the present invention is better than traditional dicarbapentaborane diiodo-rhodium.
Claims (10)
1. the aminocarboxylic acid lithium rhodium complex of formula I structure,
Wherein, X=BPh
4Or I; N=1,2 or 3.
2. the preparation method of the described aminocarboxylic acid lithium of claim 1 rhodium complex comprises the steps:
1) aminocarboxylic acid and lithium hydroxide are dissolved in methyl alcohol or the acetic acid,, disappear until aminocarboxylic acid crystallization and lithium hydroxide crystallization in 20-60 ℃ of high-speed stirring;
2) four carbonyl dichloros, two rhodiums are dissolved in methyl alcohol or the acetic acid, and slowly join and stir step 1) gained solution down, continue stirring in 10-40 ℃, form stable title complex;
3) iodide or tetraphenylboron thing are dissolved in methyl alcohol or the acetic acid, and join step 2 in stirring down) in the gained solution, continue stirring in 10-40 ℃, promptly obtain described aminocarboxylic acid lithium rhodium complex.
3. the method for acetic acid is produced in a carbonylation of methanol, is methyl alcohol and CO (carbon monoxide converter) gas to be carried out methanol carbonylation obtain acetic acid under the catalyst system effect, and it is characterized in that: described catalyst system contains the aminocarboxylic acid lithium rhodium complex of formula I structure.
4. method according to claim 3 is characterized in that: described catalyst system also is added with dicarbapentaborane diiodo-rhodium; Based on the reaction system gross weight, the content of described dicarbapentaborane diiodo-rhodium in reaction system is counted 200-1200ppm with rhodium.
5. according to claim 3 or 4 described methods, it is characterized in that: based on the reaction system gross weight, rhodium content is 200-2000ppm in the described reaction system; Be preferably 400-1200ppm; 600-1000ppm more preferably.
6. according to claim 3 or 4 described methods, it is characterized in that: described catalyst system also is added with promotor, and described promotor comprises methyl iodide, lithium iodide, Lithium Acetate and phosphoric acid salt.
7. method according to claim 6 is characterized in that: the weight content of methyl iodide in reaction system is 8-20%, is preferably 12-18%; The weight content of lithium iodide in reaction system is 2-20%, is preferably 6-15%; The weight content of Lithium Acetate in reaction system is 0.5-10, is preferably 2-4%; Phosphatic range of choice is phosphoric acid normal salt and the hydrate thereof of Na, K, and the weight content of phosphoric acid salt in reaction system is 0.01%-5%, is preferably 0.1%-0.8%.
8. according to claim 3 or 4 described methods, it is characterized in that: also be added with ritalin in the reaction system, ritalin content is reaction system gross weight 0.5-13%, is preferably 3-8%.
9. according to claim 3 or 4 described methods, it is characterized in that: the temperature of methanol carbonylation is controlled at 150-250 ℃, is preferably 185-210 ℃.
10. according to claim 3 or 4 described methods, it is characterized in that: the reaction total pressure is preferably 3.0MPa at 2.0-5.0MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101799948A CN101182340B (en) | 2007-12-20 | 2007-12-20 | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101799948A CN101182340B (en) | 2007-12-20 | 2007-12-20 | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101182340A true CN101182340A (en) | 2008-05-21 |
| CN101182340B CN101182340B (en) | 2010-04-21 |
Family
ID=39447779
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101799948A Expired - Fee Related CN101182340B (en) | 2007-12-20 | 2007-12-20 | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101182340B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266795A (en) * | 2011-06-15 | 2011-12-07 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof |
| CN103012500A (en) * | 2011-09-28 | 2013-04-03 | 上海开复精细化工科技有限公司 | Pyridine nickel rhodium catalyst as well as preparation method and application thereof |
| WO2013096624A1 (en) * | 2011-12-23 | 2013-06-27 | Dow Global Technologies Llc | Methanol homologation |
| CN103977834A (en) * | 2014-06-03 | 2014-08-13 | 江苏索普（集团）有限公司 | Preparation method of catalyst used in synthesizing of propionic acid by carbonylating ethyl alcohol and application of catalyst |
| JP2016117708A (en) * | 2014-11-14 | 2016-06-30 | セラニーズ・インターナショナル・コーポレーション | Process for producing acetic acid by introducing lithium compound |
| US9540303B2 (en) | 2015-04-01 | 2017-01-10 | Celanese International Corporation | Processes for producing acetic acid |
| CN108290814A (en) * | 2015-11-25 | 2018-07-17 | 利安德巴塞尔乙酰有限责任公司 | Additive for carboxylic acid production process |
| CN109970815A (en) * | 2019-05-06 | 2019-07-05 | 宁夏大学 | Pyridyl group rhodium catalyst and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053392C (en) * | 1994-01-21 | 2000-06-14 | 中国科学院化学研究所 | Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use |
| CN100522362C (en) * | 2004-03-25 | 2009-08-05 | 香港理工大学 | Double active species catalyst and its application |
-
2007
- 2007-12-20 CN CN2007101799948A patent/CN101182340B/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102266795B (en) * | 2011-06-15 | 2013-09-11 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof |
| CN102266795A (en) * | 2011-06-15 | 2011-12-07 | 陕西煤业化工技术开发中心有限责任公司 | Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof |
| CN103012500A (en) * | 2011-09-28 | 2013-04-03 | 上海开复精细化工科技有限公司 | Pyridine nickel rhodium catalyst as well as preparation method and application thereof |
| WO2013096624A1 (en) * | 2011-12-23 | 2013-06-27 | Dow Global Technologies Llc | Methanol homologation |
| CN103977834A (en) * | 2014-06-03 | 2014-08-13 | 江苏索普（集团）有限公司 | Preparation method of catalyst used in synthesizing of propionic acid by carbonylating ethyl alcohol and application of catalyst |
| JP2017075160A (en) * | 2014-11-14 | 2017-04-20 | セラニーズ・インターナショナル・コーポレーション | Methods for producing acetic acid by introducing lithium compound |
| JP2016117708A (en) * | 2014-11-14 | 2016-06-30 | セラニーズ・インターナショナル・コーポレーション | Process for producing acetic acid by introducing lithium compound |
| US9580377B2 (en) | 2014-11-14 | 2017-02-28 | Celanese International Corporation | Process for producing acetic acid by introducing a lithium compound |
| US9540303B2 (en) | 2015-04-01 | 2017-01-10 | Celanese International Corporation | Processes for producing acetic acid |
| CN108290814A (en) * | 2015-11-25 | 2018-07-17 | 利安德巴塞尔乙酰有限责任公司 | Additive for carboxylic acid production process |
| CN108290814B (en) * | 2015-11-25 | 2021-03-12 | 利安德巴塞尔乙酰有限责任公司 | Additive for carboxylic acid production process |
| CN109970815A (en) * | 2019-05-06 | 2019-07-05 | 宁夏大学 | Pyridyl group rhodium catalyst and its preparation method and application |
| CN109970815B (en) * | 2019-05-06 | 2021-10-19 | 宁夏大学 | Pyridyl rhodium catalyst and its prepn and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101182340B (en) | 2010-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101182340B (en) | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof | |
| CN111054443B (en) | Zirconium-based MOF catalyst loaded with double active sites and preparation method and application thereof | |
| CN1127245A (en) | Catalytic systems and methods for carbonylation | |
| CN110252405A (en) | A kind of carbon monoxide-olefin polymeric for reducing the positive structure isomer ratios of alkene hydroformylation products | |
| CN101376650A (en) | Method for directly preparing gamma-valerolactone from acetylpropionic acid and aminic acid | |
| CN1978055B (en) | Hydroformylation catalytic system and use | |
| CN104529783A (en) | Efficient and safe method for synthesizing carbonic ester by using oxidative carbonyl | |
| CN202700501U (en) | Stirring-free oxidating and deep-oxidating reaction system applicable to KPTA (Kunlun pure terephthalic acid) production | |
| CN100522362C (en) | Double active species catalyst and its application | |
| CN1876239A (en) | Catalyst system for synthesizing acetic acid and acetic anhydride from carbonyl compound and its uses | |
| CN103180281B (en) | Coproduction of acetic acid and acetic anhydride | |
| CN110975941A (en) | Hydroformylation reaction catalyst composition and method for preparing aldehyde through propylene hydroformylation reaction | |
| CN101411997A (en) | Single teeth syn-dicarbonyl rhodium-triphenylphosphine complex catalyst for carbonyl group combined to acetic acid as well as preparation method and use thereof | |
| CN114751813B (en) | Method for preparing glycolaldehyde by hydroformylation of formaldehyde | |
| CN113134362B (en) | Heterogeneous catalyst for preparing lactaldehyde by non-ligand hydroformylation of acetaldehyde and synthesis gas and preparation method and application thereof | |
| CN102964248A (en) | Method for producing nitric oxide and synthesizing dimethyl oxalate through carbonylation | |
| CN1104285C (en) | homogeneous rhodium catalyst for carbonyl synthesis and preparation method thereof | |
| CN109438199A (en) | A kind of method that continuous high-efficient oxidation prepares 2,6,6- trimethyl -2- cyclohexene -1,4- diketone | |
| CN101362103A (en) | Unidentate rhodium carbonyl complexes catalyst of carbonyl synthesis acetic acid, acetic anhydride | |
| CN101716527B (en) | High-stability catalyst for producing acetic acid by carbonylation method and application method thereof | |
| CN111632592A (en) | Catalyst for preparing methylal by low-temperature oxidation of methanol and preparation method and application thereof | |
| CN105884598A (en) | Method for performing biomimetic catalysis and air oxidation on cyclohexane with pure natural preparation | |
| CN101293213B (en) | Rhodium catalyst for carbonyl synthesis of acetic anhydride and preparation method thereof | |
| CN107469860A (en) | A kind of method for improving rhodium/biphosphinate catalyst stability | |
| CN101954295A (en) | Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Shanghai Pu Jing electromechanical complete equipment Co., Ltd. Assignor: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES|China Perfect Machinery Industry Co.,Ltd. Contract fulfillment period: 2007.12.15 to 2021.4.12 Contract record no.: 2008110000007 Denomination of invention: Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof License type: Exclusive license Record date: 20080310 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENCE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.12.15 TO 2021.4.12 Name of requester: SHANGHAI PUJING ELECTRICAL AND MECHANICAL EQUIPME Effective date: 20080310 |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: SHANGHAI PUJING CHEMICAL CO., LTD. Free format text: FORMER OWNER: CHINA PERFECT MACHINERY INDUSTRY CORP., LTD. |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 100080 NO.2, ZHONGGUANCUN NORTH NO.1 STREET, HAIDIAN DISTRICT, BEIJING TO: 100190 NO.2, ZHONGGUANCUN NORTH NO.1 STREET, HAIDIAN DISTRICT, BEIJING |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20100630 Address after: 100190 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Co-patentee after: Pujing Chemical Industry (Shanghai) Ltd. Patentee after: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Address before: 100080 Haidian District, Zhongguancun, North Street, No. 1, No. 2, Beijing Co-patentee before: China Perfect Machinery Industry Co.,Ltd. Patentee before: Institute of Chemistry, Chinese Academy of Sciences |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100190 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee after: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee after: PUJING CHEMICAL INDUSTRY Co.,Ltd. Address before: 100190 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Patentee before: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Patentee before: Pujing Chemical Industry (Shanghai) Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100421 |