CN101659607B - Method for preparing acetic acid and acetic anhydride respectively or synchronously - Google Patents
Method for preparing acetic acid and acetic anhydride respectively or synchronously Download PDFInfo
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- CN101659607B CN101659607B CN 200810042294 CN200810042294A CN101659607B CN 101659607 B CN101659607 B CN 101659607B CN 200810042294 CN200810042294 CN 200810042294 CN 200810042294 A CN200810042294 A CN 200810042294A CN 101659607 B CN101659607 B CN 101659607B
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- acetic acid
- diacetyl oxide
- rhodium
- iridium
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 704
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 225
- 238000000034 method Methods 0.000 title claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 287
- 239000010948 rhodium Substances 0.000 claims abstract description 147
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 127
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 126
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 125
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 105
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 103
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims abstract description 81
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims abstract description 80
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 65
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 64
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 239000000203 mixture Substances 0.000 claims abstract description 47
- 239000001257 hydrogen Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 38
- 150000001413 amino acids Chemical class 0.000 claims abstract description 22
- 150000003862 amino acid derivatives Chemical class 0.000 claims abstract description 18
- 150000003284 rhodium compounds Chemical class 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims abstract description 6
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 29
- GDFAOVXKHJXLEI-VKHMYHEASA-N N-methyl-L-alanine Chemical compound C[NH2+][C@@H](C)C([O-])=O GDFAOVXKHJXLEI-VKHMYHEASA-N 0.000 claims description 27
- 235000001014 amino acid Nutrition 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 230000036571 hydration Effects 0.000 claims description 13
- 238000006703 hydration reaction Methods 0.000 claims description 13
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 13
- HGPLKKVQTVJBHF-UHFFFAOYSA-K I(=O)(=O)[O-].[Rh+3].I(=O)(=O)[O-].I(=O)(=O)[O-] Chemical compound I(=O)(=O)[O-].[Rh+3].I(=O)(=O)[O-].I(=O)(=O)[O-] HGPLKKVQTVJBHF-UHFFFAOYSA-K 0.000 claims description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical group 0.000 claims description 11
- 230000031709 bromination Effects 0.000 claims description 8
- 238000005893 bromination reaction Methods 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- PHHYVYYBYXVXHH-UHFFFAOYSA-K iridium(3+) triiodate Chemical compound [Ir+3].I(=O)(=O)[O-].I(=O)(=O)[O-].I(=O)(=O)[O-] PHHYVYYBYXVXHH-UHFFFAOYSA-K 0.000 claims description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 6
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 5
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 4
- XGUXJMWPVJQIHI-YFKPBYRVSA-N (2s)-2-azaniumyl-3-cyclopropylpropanoate Chemical compound [O-]C(=O)[C@@H]([NH3+])CC1CC1 XGUXJMWPVJQIHI-YFKPBYRVSA-N 0.000 claims description 3
- 239000004471 Glycine Substances 0.000 claims description 3
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 3
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 claims description 3
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 claims description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 2
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- AYFVYJQAPQTCCC-GBXIJSLDSA-N L-threonine Chemical compound C[C@@H](O)[C@H](N)C(O)=O AYFVYJQAPQTCCC-GBXIJSLDSA-N 0.000 claims description 2
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims description 2
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- AYFVYJQAPQTCCC-UHFFFAOYSA-N Threonine Natural products CC(O)C(N)C(O)=O AYFVYJQAPQTCCC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004473 Threonine Substances 0.000 claims description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 claims description 2
- 239000006035 Tryptophane Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- MBRRYUQWSOODEO-LBPRGKRZSA-N benzyl (2s)-2-amino-4-methylpentanoate Chemical compound CC(C)C[C@H](N)C(=O)OCC1=CC=CC=C1 MBRRYUQWSOODEO-LBPRGKRZSA-N 0.000 claims description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 2
- HLYTZTFNIRBLNA-LNTINUHCSA-K iridium(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ir+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O HLYTZTFNIRBLNA-LNTINUHCSA-K 0.000 claims description 2
- MIZXGHSRLLJEET-UHFFFAOYSA-N iridium;oxalic acid Chemical compound [Ir].OC(=O)C(O)=O MIZXGHSRLLJEET-UHFFFAOYSA-N 0.000 claims description 2
- 229940059936 lithium bromide Drugs 0.000 claims description 2
- KQSSATDQUYCRGS-UHFFFAOYSA-N methyl glycinate Chemical compound COC(=O)CN KQSSATDQUYCRGS-UHFFFAOYSA-N 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims description 2
- DIGHFXIWRPMGSA-NSHDSACASA-N tert-butyl (2s)-2-amino-3-(4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 DIGHFXIWRPMGSA-NSHDSACASA-N 0.000 claims description 2
- 229960004799 tryptophan Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 27
- 238000001556 precipitation Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
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- 238000005260 corrosion Methods 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 150000002504 iridium compounds Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 102
- 239000002994 raw material Substances 0.000 description 64
- 238000002360 preparation method Methods 0.000 description 42
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- 230000008569 process Effects 0.000 description 34
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 32
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- 230000004044 response Effects 0.000 description 31
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 28
- 230000000007 visual effect Effects 0.000 description 26
- 239000007788 liquid Substances 0.000 description 25
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- 230000000052 comparative effect Effects 0.000 description 14
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- -1 acetic acid acid anhydride Chemical class 0.000 description 8
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- 229910052751 metal Inorganic materials 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
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- LEKJTGQWLAUGQA-UHFFFAOYSA-N acetyl iodide Chemical compound CC(I)=O LEKJTGQWLAUGQA-UHFFFAOYSA-N 0.000 description 3
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- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
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- ZDYCQQFBTFDFOK-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O ZDYCQQFBTFDFOK-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 150000001868 cobalt Chemical class 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
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- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for preparing an acetic acid and an acetic anhydride respectively and synchronously, which is characterized in that: a methanol, a methylacetate or a mixture of the methanol and the methylacetate and a mixed gas of carbon monoxide and hydrogen are reacted at 150 to 250 DEG C and 2.0 to 6.0 MPa; and a catalyst system used in the reaction comprises a mixture of rhodium or one of rhodium compounds and iridium or one of iridium compounds, a methyl iodide, at least one selected from mixtures of an amino acid and an amino acid derivative, the amino acid or the amino acid derivative, and an accelerant. The method for preparing the acetic acid and the acetic anhydride in the invention has the advantages of: (1) reducing the generated tar, (2) reducing substance content of the acetic anhydride product, and (3) improving the stability of the catalyst system in the invention and avoiding the precipitation phenomenon. Due to the fact that the reaction system has no water, the corrosion to devices is also reduced.
Description
Technical field
The present invention relates to a kind of method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide.
Background technology
As the important basic organic chemical raw material of a class, acetic acid and diacetyl oxide and downstream derived product thereof are widely used in the synthetic of medicine, synthon, light industry, weaving, leather, agricultural chemicals, explosive, rubber and metal processing, food and Fine Organic Chemical product.At present, the market outlook of world's acetic acid and diacetyl oxide are quite had an optimistic view of.
Producing the method for acetic acid and diacetyl oxide in the prior art, is to take continuous production equipment, is made by methyl alcohol and methyl acetate or dme and methyl alcohol and reaction of carbon monoxide.
Catalyst system by carbonyl synthesis of acetic or diacetyl oxide has experienced 3 stages, fs is the cobaltous iodide catalyzer, the earliest be nineteen sixty BASF AG on the Research foundation of Reppe etc., develop first take cobalt-carbonyl as catalyzer, methyl iodide is the cobalt series catalyst of promotor, this catalyst system shortcomings such as condition harshness (65MPa, 250 ℃), acetic acid selectivity low (counting 87% with methyl alcohol), by product are many that respond fail to realize industrialization.Subordinate phase is that U.S. Monsanto company in 1970 has succeeded in developing rhodium base catalyst, and its technique relies on the advantages such as reaction conditions relatively gentle (3～4MPa, 175 ℃), acetic acid selectivity higher (counting 99% with methyl alcohol), by product are few to realize rapidly industrialization.But rhodium base catalyst exists water-gas reforming reaction, by product propionic acid content relatively high, ethanoyl iodide and hydrogen iodide effect generation acetaldehyde occurs, and is settled out RhI
3Make the defectives such as catalyst deactivation.Rhodium base catalyst is used for then synthesis of acetic acid acid anhydride of methyl acetate carbonylation, improves oxonation speed by adding auxiliary agent LiI or lithium acetate, equally also exist the defective that reaction system tar formation speed is fast, rhodium catalyst is separated out precipitation.Phase III is Britain BP company succeeded in developing, realized in 1996 industrial application in nineteen ninety a kind of novel carbinol carbonylation acetic acid process processed, this process using iridium catalyst based (Cativa catalyzer), compare with rhodium base catalyst, have higher speed of reaction, higher catalyst stability, carbonylation reaction and the significantly advantage such as can under low water content, finish, become at present the most rising technique in this field.At present applying to the unique patent of carbonyl synthesis of acetic anhydride with regard to iridium base catalyst system is the GB2333773 of BP company.As seen the iridium catalyst system is relatively less for the research of methyl acetate synthesizing acetic acid by carbonylation acid anhydride, reason is that the diacetyl oxide itself that (1) generates is a good part, diacetyl oxide and rhodium have certain weak coordination ability, the coordination ability of iridium is higher than rhodium, so diacetyl oxide and iridium are stablized coordination and then formed the inertia species; (2) diacetyl oxide can carry out oxidative addition with the species of iridium, forms the inertia species; (3) in the rhodium system, produce diacetyl oxide and need to add a certain amount of an alkali metal salt, such as LiI or Li (OAc), be conducive on the one hand methyl acetate and LiI effect, form methyl iodide, the Li (OAc) that generates on the other hand and acetyliodide effect are conducive to the generation of diacetyl oxide, but in the iridium system, add too much lithium salts, can cause more I
-Ion is free, causes the inertia species to generate.Because severe reaction conditions, catalyst levels are large, replace rhodium production diacetyl oxide difficulty larger with the iridium catalyst system.
With rhodium as the patent of the catalyzer of preparation acetic acid and diacetyl oxide mixture also wide coverage, referring to for example United States Patent (USP) 3,927,078,4,046807,4,115,444,4,252,741,4374070,4,430,273,4,559,183,5,003,104,5,292,948 and European patent 8,396,8,7869,87,870.If these patent disclosures rhodium catalytic system comprised such as some amine and quarternary ammonium salt compound, phosphine and phosphorus compound, mineral compound (such as an alkali metal salt: promotor lithium iodide), the content of methyl iodide account for the reaction solution gross weight 12～30% between, carbonylation rate can improve.If add methyl alcohol and/or water in the reaction raw materials, acetic acid also is one of product of carbonylation.Therefore, the diacetyl oxide product liquid that obtains of this carbonylation method is the mixture that contains diacetyl oxide and acetic acid.
There are following three problems in the mixture that adopts this rhodium base catalyst carbonylation method to prepare diacetyl oxide or acetic acid, diacetyl oxide: can produce tar (mixture of macromole organic polymer) in the time of (1) reaction; (2) acetic acid that obtains of this carbonylation method and diacetyl oxide product permanganate indices are high, the purity difference of product; (3) the rhodium catalyst poor stability of this carbonylation method use, easily precipitation.
The price of rhodium metal climbs up and up year after year at present, and the cost of producing acetic acid and diacetyl oxide is significantly risen, and many manufacturers are about to face the problem of selecting a kind of low price, catalytic performance can replace rhodium base catalyst.And BP has at first found iridium catalyst based in acetic acid production.But the research for the diacetyl oxide new catalyst does not have very large breakthrough.
Be still rhodium base catalyst and the carbonylation reaction device of world production acetic acid associating diacetyl oxide adopts, production cost is still in continuous rising.Novel catalyzer replaces the research of rhodium base catalyst to become very urgent thus.
Summary of the invention
The present invention is according to deficiency of the prior art, provides a kind of cheaply for the preparation of the catalyst system of acetic acid and diacetyl oxide.
For achieving the above object, the present invention is achieved through the following technical solutions:
Prepare acetic acid, diacetyl oxide or prepare simultaneously the method for acetic acid and diacetyl oxide, it is characterized in that, the mixed gas that makes the mixture of methyl alcohol, methyl acetate or methyl alcohol and methyl acetate and carbon monoxide and hydrogen reacts under 150～250 ℃ and 2.0～6.0MPa, and the catalyst body that uses in the reaction is:
In selected from rhodium or the rhodium compound one or more and one or more the mixture that is selected from iridium or the iridic compound;
Methyl iodide;
Amino acid and amino acid derivative mixture, amino acid or amino acid derivative;
And promotor.
Wherein, the mass concentration of the compound of rhodium or rhodium in mixed reaction solution is 200～1000ppm; The mass concentration of the compound of iridium or iridium in mixed reaction solution is 500～2000ppm.
Wherein, the consumption of methyl iodide is 5～16% of mixed reaction solution weight.
Wherein, the mass concentration of lithium salts in mixed reaction solution is 50～500ppm.
Wherein, amino acid or amino acid derivative consumption be iridium or iridic compound mole number 0.1～3.0.
Wherein, hydrogen usage be carbon monoxide mole number 1～10%.
Wherein, the weight ratio of methyl acetate in mixed reaction solution is 5～30%.
Wherein, described rhodium compound selected from rhodium metal, iodate rhodium, hydration iodate rhodium, bromination rhodium, hydration bromination rhodium, rhodium chloride, hydration rhodium chloride, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, RhCl
33H
2O, Rh (OAc)
3, Rh
2O
3, Rh (acac) (CO)
2, Rh
4(CO)
12Or Rh
6(CO)
16
Wherein, described iridic compound is selected from iridium metals, iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, hydration iridium chloride, oxalic acid iridium, etheric acid iridium, iridium oxide, iridous oxide, Ir (acac) (CO)
2, Ir (acac)
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, Ir
4(CO)
12, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+Or [Ir (CH
3) (CO)
2I
3]
-H
+
Wherein, described amino acid is selected from glycine, L-Ala, proline(Pro), Threonine, tryptophane, leucine or tyrosine.
Wherein, described amino acid derivative is selected from N, N-N-methylsarcosine, N-methylalanine, leucine benzyl ester, tyrosine tert-butyl ester, glycine methyl ester or cyclopropyl alanine.
Wherein, described promotor is selected from lithium salts.
Wherein, described lithium salts is selected from lithium iodide, lithiumbromide, lithium chloride or lithium acetate.
Wherein, described catalyst system also comprises one or both in nickel salt and the platinum salt.
Catalyst system among the present invention, add together in the reactor by precursor, amino acid or Amino acid derivatives, acetic acid, methyl iodide and a small amount of water with rhodium and iridium, under 150～250 ℃ and 2.0～6.0MPa, stir, the catalyst precursor of rhodium and iridium, by with I
-The rhodium that ion, CO reaction namely form and the coordination compound [Rh (CO) of iridium
2I
2]
-[Ir (CO)
2I
2]-.
Catalyst system among the present invention, manufacturing cost has descended 40% on the one hand, can avoid on the other hand rhodium base catalyst to produce the defective of acetic acid and diacetyl oxide.
The method for preparing acetic acid and diacetyl oxide among the present invention, solved the shortcoming that the coal-tar middle oil generation of reaction solution is many, product purity is poor and catalyst stability is not good that rhodium base catalyst production acetic acid and diacetyl oxide exist, be in particular in that (1) tar growing amount has reduced, every generation 1kg acetic acid, diacetyl oxide mix product, the tar of generation is lower than 0.0002kg; (2) reducing substances content is low in the diacetyl oxide product, by the method among the present invention, not needing increases the device of processing reducing substances, and namely the permanganate indices of available diacetyl oxide product just can reach the requirement of premium grads among the GB10668-89, is lower than 60mg/100ml; (3) stability of the catalyst system among the present invention improves, and deposited phenomenon does not occur.And the anhydrous corrosion to device of reaction system has also reduced.
The present invention also will solve the problem that iridium catalyst is produced diacetyl oxide.In the iridium catalyst system, add lithium salts so that the I-stable existence, I
-With CO competition and the coordination of iridium central atom, thereby restrain speed of response, thereby be called as catalyzer influential " poisonous " reagent.But in the rhodium catalyst system, add lithium salts so that thereby the easier generation diacetyl oxide of acetyliodide and lithium acetate promotes oxonation, improve speed of response.Pass through in the iridium catalyst system to add a certain amount of amino acid or amino acid derivative, so that the hydrogen bond action of the amino cationic moiety of amino acid and amino acid derivative and amino acid whose-COOH group comes complexing I jointly
-Ion, thus part I reduced
-Free, weaken the impact on speed of response.
Patent CN02102066.3 proposes to stablize rhodium catalyst by nitrogenous oxygen organic compound, stablizes rhodium catalyst by the organic ligand complexing of nitrogenous oxygen, thereby in order to increase stabilising effect, needs to add the organic ligand that adds a large amount of nitrogenous oxygen.And in the present invention as long as add a small amount of amino acid and amino acid derivative thereof contain oxynitrides, the amino of amino acid and amino acid derivative and the H in the system
+Or Me
+Form positively charged ion, play the effect of the active iridium anionic species of partially stabilized catalyzer, the simultaneously cationic formation of amino acid has also suitably increased I
-Dissociating of ion, thus iridium catalyst further stablized.
Method of the present invention can feed change methyl alcohol and the content of the methyl acetate ratio of regulating acetic acid and diacetyl oxide in addition, to satisfy specific economic needs.
Description of drawings
Fig. 1 is the process flow sheet of preparation acetic acid and diacetyl oxide.
Embodiment
The present invention further specifies below in conjunction with accompanying drawing.
As shown in Figure 1, use present method to prepare acetic acid and the diacetyl oxide mixture normally carries out in the device in three districts.First district comprises a high-pressure reactor 1 for reaction zone, also has to use the second reactor, and for example Yi Si Man is in the patent CN1 of China's application, 298,380.Second Region is the disengaging zone of reaction mixture, generally include one or two flasher 2, at this, catalyzer separates with reaction solution, light constituent methyl acetate, methyl iodide and a part of acetic acid, diacetyl oxide enter the 3rd district as gas phase, return reaction zone and carry catalyzer, promotor, stablizer as acetic acid, the diacetyl oxide of restructuring minute, namely the first district.The 3rd district is rectification zone, and the realization product separates with light constituent methyl acetate, methyl iodide, and light constituent returns the first district.
According to the concentration of need of production, squeeze into a kind of and iridium in rhodium or the rhodium compound or a kind of mixture in the iridic compound by pump toward reactor 1, that squeezes into simultaneously reactor 1 also has methyl iodide, acetic acid, diacetyl oxide, lithium salts.The purpose that adds diacetyl oxide is to consume the water of bringing into when catalyzer prepares.After the catalyzer of reactive system needs comprises that promotor, stablizer and methyl iodide, acetic acid meet production requirement, reactor 1 be filled with CO and an amount of hydrogen to reactor pressure at 1.0MPa, then reactor and flasher are set up catalyst recirculation, and reactor 1 heats up, is filled with CO and a certain proportion of hydrogen.After temperature of reaction, reaction pressure satisfy the production technique index, formally drop into material benzenemethanol and methyl acetate.
Catalyst system among the present invention, in the time of can or preparing simultaneously acetic acid and diacetyl oxide at preparation acetic acid, diacetyl oxide each raw material is joined in the reaction solution, it is suitable that temperature and pressure is adjusted to, and can catalysis prepare acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide.In order to save time, also can before preparing acetic acid, diacetyl oxide or preparing simultaneously acetic acid and diacetyl oxide, make in advance each raw material reaction for some time of catalyst system.
All embodiment carry out in continuous apparatus as shown in Figure 1, by such continuous apparatus, can make the composition of reaction solution relatively stable, and carry out macrocyclic test, the generating rate that the test reaction system is coal-tar middle oil, the permanganate indices of diacetyl oxide product.Need to prove that there are three rectifying tower in the 3rd district shown in the accompanying drawing 1, first rectifying tower is lights column, separating acetic acid methyl esters, methyl iodide and acetic acid, diacetyl oxide, the methyl acetate of cat head, methyl iodide Returning reactor; Second rectifying tower separating acetic acid and diacetyl oxide, the acetic acid that cat head or side line obtain making with extra care; The 3rd rectifying tower is the diacetyl oxide rectifying tower, and the acetic acid described in this specification sheets and diacetyl oxide mixing prod are light constituent rectifying tower bottom product.
From the detailed description that hereinafter provides, will further specify scope of the present invention and practicality.Yet, should know when narration optimum implementation of the present invention, detailed description and specific embodiments only are to provide in order to say something, the professional of the art from this is described in detail with distinct various changes and modifications in the scope of the invention and spirit.
Embodiment A
Add rhodium precursor iodate rhodium and iodate iridium in the reactor of catalyzer preparation, make the mass ratio of rhodium and iridium be (2～10): (5～20) add N-methylalanine and water with iridium molfraction 1:1; Add the methyl iodide, the solvent acetic acid that meet production technique; Then pass into CO, 150 ℃ of temperature of reaction, stirred 2 hours under the pressure 3.0MPa.Detect with infrared spectrometer after the cooling, rhodium is with [Rh (CO) in the catalyst solution
2I
2]
-Form exist, iridium is with [Ir (CO)
2I
2]
-Form exist.
Embodiment B
In the reactor of catalyzer preparation, add rhodium precursor iodate rhodium, add again amount, the solvent acetic acid of the methyl iodide that meets production technique, then pass into CO, 150 ℃ of temperature of reaction, reaction is 2 hours under the pressure 3.0MPa, prepares the coordination compound of rhodium, and this coordination compound is the solution shape.
This embodiment is not embodiments of the invention, because do not have amino acid or amino acid derivative stablizer in this catalyst system.
Embodiment 1
In the continuous apparatus of flow process such as accompanying drawing 1, the product of embodiment A preparation is added in the reactor together with methyl iodide, acetic acid, diacetyl oxide, lithium acetate, the add-on visual response of methyl iodide, acetic acid, diacetyl oxide need to be determined, the water that adds in the purpose spent catalyst preparation of diacetyl oxide.It is 190 ℃ in temperature of reaction, pressure is 4.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Device moves 500 hours continuously, the about 8.9mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00015kg, permanganate indices is 35mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.After device moves 500 hours continuously, extract reaction solution and make rhodium, iridium content analysis, find that content does not descend.
Need to prove that in the device of flow process such as accompanying drawing 1, the control method of methyl acetate and methyl iodide content is: before (1) reaction beginning, drop into methyl acetate and the methyl iodide of desired component concentration to reactor; (2) after the reaction beginning, (such as one hour) extracts reaction solution analysis at regular intervals, calculates speed of reaction, requires to adjust corresponding raw material according to reaction process and drops into ratio, to guarantee the requirement of reaction solution component.
It should be noted that also the mass concentration of reacting rear acetic acid and diacetyl oxide only refers to acetic acid and the diacetyl oxide that generates, and does not comprise the concentration of the solvent acetic acid that contains in the reactive system.
Comparative Examples 1
In the continuous apparatus of flow process such as accompanying drawing 1, with the product of Embodiment B preparation together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, it is 190 ℃ in temperature of reaction, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 6.7mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00032kg, permanganate indices is 75mg/100ml, product acetic acid and diacetyl oxide are brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Need explanation because under rhodium catalyst in carbonyl reaction synthesis of acetic acid and the diacetyl oxide process, a part of catalyzer has been wrapped up in the generation of tar, causes catalyst precipitation to be separated out, and the reactive system catalyst concn descends.
Embodiment C
Repeat the method for catalyzer Preparation Example A, change the processing condition of preparation, adopt 200 ℃ of temperature of reaction, the technique that stirred 5 hours under the pressure 4.5MPa prepares rhodium and iridium mixed ligand complex.Detect with infrared spectrometer after the catalyst solution cooling of preparation, rhodium is with [Rh (CO)
2I
2]
-Form exist, iridium is with [Ir (CO)
2I
2]
-Form exist.
Adopt the method for preparing catalyst of Embodiment C, change the consumption of the iodate rhodium that adds, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 150 ℃, pressure is 2.0MPa, the rhodium mass concentration is 200ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 50ppm, the mol ratio of N-methylalanine and iridium is 1.0, and the methyl iodide consumption is 12% of mixed reaction solution weight, and methyl acetate is 15% of mixed reaction solution weight, reaction raw materials is 43% methyl alcohol and 57% methyl acetate of calculating by weight, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 5.3mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00003kg, permanganate indices is 40mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.Device continuously operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not descend.
Comparative Examples 2
Repeat Embodiment B, change the consumption of the iodate rhodium that adds, making the rhodium mass concentration is 200ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 150 ℃, pressure is 2.0MPa, the rhodium mass concentration is 200ppm in the control reaction solution, the lithium mass concentration is 50ppm, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, and reaction raw materials is 43% methyl alcohol and 57% methyl acetate of calculating by weight, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Continuously operation is 500 hours, the about 0.55mol/lh of speed of reaction, and average every kilogram of diacetyl oxide product correspondence generates to such an extent that tar content is 0.00001kg, and permanganate indices is 65mg/100ml, and product after placement for some time is faint yellow.Because the speed of reaction of carbonyl synthesis of acetic or diacetyl oxide is directly relevant with the concentration of rhodium catalyst, rhodium content is low, and speed of response is slow.So after the successive reaction 500 hours, reaction solution tar formation speed is slower, the reaction solution rhodium content does not obviously descend.
Embodiment 3
Repeat Embodiment C, only change the iodate rhodium of adding and the consumption of iodate iridium, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 250 ℃, pressure is 6.0MPa, the rhodium mass concentration is 200ppm in the control reaction solution, iridium mass concentration 500ppm, the lithium mass concentration is 500ppm, the mol ratio of N-methylalanine and iridium is 1.0, and the methyl iodide consumption is 12% of mixed reaction solution weight, and the methyl acetate consumption is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 3.9mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00019kg, permanganate indices is 48mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.Device continuously operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 3
Repeat Embodiment B, change the consumption of the iodate rhodium that adds, making the rhodium mass concentration is 200ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 250 ℃, pressure is 6.0MPa, the rhodium mass concentration is 1000ppm in the control reaction solution, the lithium mass concentration is 500ppm, the methyl iodide consumption is 12% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 0.59mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00003kg, permanganate indices is 70mg/100ml, product acetic acid and diacetyl oxide are weak yellow liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 850ppm.。
Embodiment 4
Repeat embodiment A, changing the precursor that adds rhodium is Rh (acac)
3, the iridium precursor is Ir (acac)
3In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium chloride adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 8.8mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00014kg, permanganate indices is 32mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 4
Repeat Embodiment B, changing the adding precursor is Rh (acac)
3, the rhodium mass concentration is 800ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium chloride adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 3.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide consumption is 12% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 42% methyl alcohol and 58% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 6.6mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00031kg, permanganate indices is 70mg/100ml, product acetic acid and diacetyl oxide are brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 680ppm.
Embodiment D
Repeat the method for catalyzer Preparation Example A, change the processing condition of preparation, adopt 250 ℃ of temperature of reaction, the technique that stirred 8 hours under the pressure 6.0MPa prepares rhodium and iridium mixed ligand complex.Detect with infrared spectrometer after the catalyst solution cooling of preparation, rhodium is with [Rh (CO)
2I
2]
-Form exist, iridium is with [Ir (CO)
2I
2]
-Form exist.
Embodiment 5
Adopt the method for preparing catalyst of embodiment D, changing the precursor that adds rhodium is Rh
4(CO)
12, changing the iridium precursor is Ir
4(CO)
12In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 8.9mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00019kg, permanganate indices is 35mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 5
Repeat Embodiment B, changing the rhodium precursor that adds is Rh
4(CO)
12, making the rhodium mass concentration is 800ppm.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 5.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide consumption is 15% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 42% methyl alcohol and 58% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 4.1mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00035kg, permanganate indices is 80mg/100ml, product acetic acid and diacetyl oxide are brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Embodiment 6
Repeat embodiment D, changing the precursor that adds rhodium is Rh
2O
3, changing the iridium precursor that adds is iridous oxide.In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 200 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0,12% of methyl iodide consumption mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 9.1mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 45mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 6
Repeat Embodiment B, changing the rhodium precursor that adds is Rh
2O
3In the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 200 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide consumption is 12% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 4.0mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00036kg, permanganate indices is 82mg/100ml, product acetic acid and diacetyl oxide are brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 670ppm.
Embodiment 7
Repeat embodiment A, change the iodate rhodium and the iodate one ground amount that add, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 170 ℃, pressure is 4.0MPa, the rhodium mass concentration is 1000ppm in the control reaction solution, iridium mass concentration 2000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, and the methyl iodide consumption is 12% of mixed reaction solution weight, and the methyl acetate consumption is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 9.2mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00013kg, permanganate indices is 30mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The device operation extracted reaction solution and makes rhodium, iridium content analysis after 500 hours, found that content does not obviously descend.
Comparative Examples 7
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 170 ℃, pressure is 4.0MPa, the rhodium mass concentration is 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the methyl iodide consumption is 12% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 7.1mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00041kg, permanganate indices is 68mg/100ml, product acetic acid and diacetyl oxide are weak yellow liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 690ppm.
Embodiment 8
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium iodide adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 5% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Device moves 500 hours continuously, the about 8.6mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00011kg, permanganate indices is 30mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 30.4% and 29.6% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 8
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium iodide adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide consumption is 5% of mixed reaction solution weight, and methyl acetate is 12% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 3.2mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00024kg, permanganate indices is 55mg/100ml, product acetic acid and diacetyl oxide are colourless transparent liquid, and the acetic acid of generation and diacetyl oxide account for respectively 30.4% and 29.% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 750ppm.
Embodiment 9
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 16% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Device moves 500 hours continuously, the about 9.2mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 45mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 24.8% and 24.2% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 9
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide consumption is 16% of mixed reaction solution weight, and methyl acetate is 12% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 7.0mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00038kg, permanganate indices is 85mg/100ml, product acetic acid and diacetyl oxide are light brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 24.8% and 24.2% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Embodiment 10
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 5% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Device moves 500 hours continuously, the about 5.5mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00010kg, permanganate indices is 35mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 31.9% and 31.1% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 10
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide consumption is 12% of mixed reaction solution weight, and methyl acetate is 5% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 3.5mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00023kg, permanganate indices is 75mg/100ml, product acetic acid and diacetyl oxide are brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 31.9% and 31.1% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 760ppm.
Embodiment 11
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 50ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 30% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Device moves 500 hours continuously, the about 9.2mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 35mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 19.2% and 18.8% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 11
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 50ppm, and the methyl iodide consumption is 12% of mixed reaction solution weight, and methyl acetate is 30% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Operation is 500 hours continuously, the about 5.1mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00036kg, permanganate indices is 75mg/100ml, product acetic acid and diacetyl oxide are brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 19.2% and 18.8% of whole reaction solution.The rhodium concentration of 500 hours afterreaction liquid is 650ppm.
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 16% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 1% of carbon monoxide mole number.Device moves 200 hours continuously, the about 4.9mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00017kg, permanganate indices is 35mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 200 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 12
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 250ppm, and the methyl iodide consumption is 16% of mixed reaction solution weight, and methyl acetate is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 1% of carbon monoxide mole number.Operation is 200 hours continuously, the about 4.3mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00041kg, permanganate indices is 75mg/100ml, product acetic acid and diacetyl oxide are brown liquid after placing for some time, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution.The rhodium concentration of 200 hours afterreaction liquid is 550ppm.
Embodiment 13
Repeat embodiment A, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, the rhodium mass concentration is 800ppm in the control reaction solution, iridium mass concentration 1000ppm, the lithium mass concentration is 500ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, and reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, and solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 10% of carbon monoxide mole number.Device moves 200 hours continuously, the about 9.1mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00021kg, permanganate indices is 38mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 200 hours in the continuous apparatus operation, find that content does not descend.
Comparative Examples 13
Repeat Embodiment B, in the continuous apparatus of flow process such as accompanying drawing 1, with the preparation product together with methyl iodide, acetic acid, lithium acetate adds in the reactor together, methyl iodide, acetic acid, the add-on visual response of diacetyl oxide need to be determined, temperature of reaction is 190 ℃, pressure is 4.0MPa, rhodium concentration is 800ppm in the control reaction solution, the lithium mass concentration is 500ppm, and the methyl iodide consumption is 12% of mixed reaction solution weight, and methyl acetate is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 10% of carbon monoxide mole number.Operation is 200 hours continuously, the about 7.7mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00033kg, permanganate indices is 46mg/100ml, product acetic acid and diacetyl oxide are colourless transparent liquid, and the acetic acid of generation and diacetyl oxide account for respectively 25.8% and 25.2% of whole reaction solution.Also there is simultaneously 2% EDA in the reaction solution.The rhodium concentration of 200 hours afterreaction liquid is 750ppm.
Result from above embodiment and Comparative Examples thereof, when in reaction solution, adding a certain amount of iridium catalyst and amino acid stabilizers, in any case change temperature of reaction, reaction pressure, rhodium concentration, lithium concentration, methyl iodide content, the hydrogen ratio, methyl acetate content, the result is that the speed of response of carbonylation method of the production acetic acid of this invention and acetate mixture is fast, the tar formation speed, the permanganate indices of product is lower than the carbonylation method that adopts rhodium base catalyst production acetic acid and acetate mixture all the time, and after device moved continuously, the catalyst content of reaction solution did not significantly descend.
Embodiment's spirit of the present invention 14～25 is listed in the table below in order better to illustrate.Embodiment 14～25, and method for preparing catalyst provides according to embodiment A, and wherein the kind of the mass concentration of rhodium and iridium, amino acid or amino acid derivative stablizer and add-on add by embodiment 14～25 requirements.Reaction conditions is identical, 190 ℃ of temperature of reaction, pressure is 4.0MPa, lithium mass concentration 250ppm, the methyl iodide consumption is 8% of mixed reaction solution weight, the methyl acetate consumption is 15% of mixed reaction solution weight, variation be rhodium and iridium concentration, amino acid or amino acid derivative stabilizer types with and with the mass ratio of mol ratio, material benzenemethanol and the methyl acetate of iridium catalyst.
| Embodiment | Methanol/methyl acetate w/w | Rhodium content amount ppm | Iridium content amount ppm | Amino acid stabilizers | Stablizer/iridium mol ratio | STYmol/l·h | Acetic acid/acetic anhydride w/w | Tar generating rate Kg/Kg | Permanganate indices mg/100ml |
| 14 | 10/90 | 400 | 1000 | N-methylalanine | 1.0 | 6.4 | 7.5/49.5 | 0.00011 | 35 |
| 15 | 43/57 | 400 | 1000 | N-methylalanine | 1.0 | 9.1 | 28.9/28.1 | 0.00009 | 35 |
| 16 | 83/17 | 400 | 1000 | N-methylalanine | 1.0 | 12.3 | 49.5/7.5 | 0.00007 | 30 |
| 17 | 43/57 | 400 | 1000 | Glycine | 1.0 | 8.9 | 28.9/28.1 | 0.00010 | 35 |
| 18 | 43/57 | 400 | 1000 | Proline(Pro) | 1.0 | 8.4 | 28.9/28.1 | 0.00012 | 40 |
| 19 | 43/57 | 400 | 1000 | Tyrosine | 1.0 | 7.9 | 28.9/28.1 | 0.00013 | 35 |
| 20 | 43/57 | 400 | 1000 | Cyclopropyl alanine | 1.0 | 8.3 | 28.9/28.1 | 0.00015 | 38 |
| 21 | 43/57 | 400 | 1000 | N-methylalanine | 0.5 | 8.1 | 28.9/28.1 | 0.00013 | 45 |
| 22 | 43/57 | 400 | 1000 | N-methyl-prop | 2.0 | 9.0 | 28.9/28.1 | 0.00011 | 40 |
| Propylhomoserin | |||||||||
| 23 | 43/57 | 200 | 2000 | N-methylalanine | 1.0 | 8.7 | 28.9/28.1 | 0.00005 | 30 |
| 24 | 43/57 | 1000 | 500 | N-methylalanine | 1.0 | 9.1 | 28.9/28.1 | 0.00021 | 65 |
| 25 | 43/57 | 800 | 1200 | N-methylalanine | 1.0 | 9.2 | 28.9/28.1 | 0.00014 | 40 |
Embodiment 14～25, after for some time is carried out in reaction, extract reaction solution and analyze rhodium and iridium concentration, and is consistent with the concentration of initial reaction stage.
Embodiment E
Add rhodium precursor iodate rhodium in catalyzer preparation feedback still, making the rhodium mass concentration is 800ppm; Add iridium precursor iodate iridium, make iridium mass concentration 1000ppm; Add platinum precursor acetic acid platinum, making the platinum mass concentration is 500ppm; Add N-methylalanine and water with iridium molfraction 1:1; The amount, the solvent acetic acid that add the methyl iodide that meets production technique.Then pass into CO, 150 ℃ of temperature of reaction, reaction is 1 hour under the pressure 3.0MPa, prepares the coordination compound of rhodium and iridium, and this coordination compound is the solution shape.
Embodiment 26
In the continuous apparatus of flow process such as accompanying drawing 1, the product that Embodiment C is prepared adds in the reactor together with methyl iodide, acetic acid, a small amount of diacetyl oxide, lithium acetate.It is 190 ℃ in temperature of reaction, pressure is 5.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, reaction raw materials is for calculating by weight 43% methyl alcohol and 57% methyl acetate, solvent is acetic acid, another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Device moves 500 hours continuously, the about 8.4mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00016kg, permanganate indices is 40mg/100ml, product acetic acid and diacetyl oxide are water white transparency, and the acetic acid of generation and diacetyl oxide account for respectively 26.8% and 26.2% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Embodiment 27
In the continuous apparatus of flow process such as accompanying drawing 1, the product that embodiment A is prepared adds in the reactor together with methyl iodide, acetic acid, lithium acetate, water.It is 190 ℃ in temperature of reaction, pressure is 3.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, and the lithium mass concentration is 250ppm, and the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, methyl acetate is 15% of mixed reaction solution weight, and water is 4.5% of mixed reaction solution weight, and reaction raw materials is simple methyl alcohol, solvent is acetic acid, and another raw material is the mixed gas of carbon monoxide or carbon monoxide and hydrogen.Device moves 500 hours continuously, the about 15.0mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00005kg, permanganate indices is 30mg/100ml, product acetic acid is water white transparency, and the acetic acid of generation accounts for 78.5% (containing 20% acetic acid solvent) of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Embodiment 28
In the continuous apparatus of flow process such as accompanying drawing 1, the product that embodiment A is prepared adds in the reactor together with methyl iodide, acetic acid, lithium acetate, a small amount of diacetyl oxide, and the purpose of diacetyl oxide is the water that spent catalyst is brought reaction system into.It is 190 ℃ in temperature of reaction, pressure is 5.0MPa, the rhodium mass concentration is 800ppm, iridium mass concentration 1000ppm in the control reaction solution, the lithium mass concentration is 250ppm, the mol ratio of N-methylalanine and iridium is 1.0, the methyl iodide consumption is 12% of mixed reaction solution weight, and methyl acetate is 15% of mixed reaction solution weight, and solvent acetic acid is 25% of mixed reaction solution weight.Reaction raw materials is simple methyl acetate, and another raw material is for containing carbon monoxide and hydrogen gas mixture, and hydrogen usage is 5% of carbon monoxide mole number.Device moves 500 hours continuously, the about 4.5mol/lh of speed of reaction, average every kilogram of acetic acid and diacetyl oxide product correspondence generate to such an extent that tar content is 0.00019kg, and permanganate indices is 35mg/100ml, the product diacetyl oxide is water white transparency, and the diacetyl oxide of generation accounts for 48% of whole reaction solution., extract reaction solution and make rhodium, iridium content analysis after 500 hours in the continuous apparatus operation, find that content does not descend.
Among the present invention, the content of used rhodium compound all is take rhodium content as benchmark, the content of used iridic compound, all be content take iridium as benchmark, the amount of used lithium salts all is that content take lithium is as benchmark.
Among the embodiment 1-28, described catalyst system also can not use the product of embodiment A or C preparation, but change into directly the raw material of catalyst system is added in the reaction vessel with preparation acetic acid, diacetyl oxide or the raw material for preparing simultaneously acetic acid and diacetyl oxide, under the reaction conditions of each embodiment, can play same katalysis.
Above-described embodiment only for the present invention will be described, does not consist of the restriction to the claim scope, and other substantial equivalence means that it may occur to persons skilled in the art that are all in claim scope of the present invention.
Claims (9)
1. prepare acetic acid, diacetyl oxide or prepare simultaneously the method for acetic acid and diacetyl oxide, it is characterized in that, the mixed gas that makes the mixture of methyl alcohol, methyl acetate or methyl alcohol and methyl acetate and carbon monoxide and hydrogen reacts under 150～250 ℃ and 2.0～6.0MPa, and the catalyst body that uses in the reaction is:
In selected from rhodium or the rhodium compound one or more and one or more the mixture that is selected from iridium or the iridic compound;
Methyl iodide;
Amino acid and amino acid derivative mixture, amino acid or amino acid derivative;
And promotor;
Described amino acid is selected from glycine, L-Ala, proline(Pro), Threonine, tryptophane, leucine or tyrosine; Described amino acid derivative is selected from DMG, N-methylalanine, leucine benzyl ester, tyrosine tert-butyl ester, glycine methyl ester or cyclopropyl alanine; Described promotor is selected from lithium salts;
Wherein, the mass concentration of the compound of described rhodium or rhodium in mixed reaction solution is 200～1000ppm; The mass concentration of the compound of described iridium or iridium in mixed reaction solution is 500～2000ppm; The consumption of described methyl iodide is 5～16% of mixed reaction solution weight; Described amino acid or amino acid derivative consumption be iridium or iridic compound mole number 0.1～3.0; The mass concentration of described lithium salts in mixed reaction solution is 50～500ppm.
2. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 1 is characterized in that, hydrogen usage be carbon monoxide mole number 1～10%.
3. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 1 is characterized in that the weight ratio of methyl acetate in mixed reaction solution is 5～30%.
4. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 1, it is characterized in that described rhodium compound is selected from iodate rhodium, hydration iodate rhodium, bromination rhodium, hydration bromination rhodium, rhodium chloride, hydration rhodium chloride, [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, Rh (OAc)
3, Rh
2O
3, Rh (acac) (CO)
2, Rh
4(CO)
12Or Rh
6(CO)
16
5. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 4 is characterized in that described hydration rhodium chloride is RhCl
33H
2O.
6. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 1, it is characterized in that described iridic compound is selected from iodate iridium, hydration iodate iridium, bromination iridium, hydration bromination iridium, iridium chloride, hydration iridium chloride, oxalic acid iridium, etheric acid iridium, iridium oxide, Ir (acac) (CO)
2, Ir (acac)
3, [Ir (CO)
2I]
2, [Ir (CO)
2Cl]
2, [Ir (CO)
2Br]
2, Ir
4(CO)
12, [Ir (CO)
2I
2]
-H
+, [Ir (CO)
2Br
2]
-H
+, [Ir (CO)
2I
4]
-H
+Or [Ir (CH
3) (CO)
2I
3]
-H
+
7. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 6 is characterized in that described iridium oxide is iridous oxide.
8. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 1 is characterized in that described lithium salts is selected from lithium iodide, lithiumbromide, lithium chloride or lithium acetate.
9. the method for preparing acetic acid, diacetyl oxide or prepare simultaneously acetic acid and diacetyl oxide according to claim 1 is characterized in that described catalyst system also comprises one or both in nickel salt and the platinum salt.
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| CN104250210A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Method for production of acetic acid by methanol carbonylation |
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| CN1100087A (en) * | 1993-03-31 | 1995-03-15 | 罗纳·布朗克化学公司 | Process for the preparation of carboxylic acids or corresponding esters in the presence of a catalyst based on reodium and iridium |
| CN1134397C (en) * | 1998-10-23 | 2004-01-14 | 国际人造丝公司 | Methanol carbonylation process in the presence of rhodium/iridium/iodide ion catalyst system |
| CN1166615C (en) * | 2002-01-21 | 2004-09-15 | 中国石油化学工业开发股份有限公司 | Process for preparing carboxylic acids |
| WO2007145795A3 (en) * | 2006-06-09 | 2008-03-27 | Eastman Chem Co | Production of acetic acid and mixtures of acetic acid and acetic anhydride |
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