CN100337750C - Catalyst system for carbonylation of methanol for synthesizing ethanol, and application - Google Patents
Catalyst system for carbonylation of methanol for synthesizing ethanol, and application Download PDFInfo
- Publication number
- CN100337750C CN100337750C CNB2004100801557A CN200410080155A CN100337750C CN 100337750 C CN100337750 C CN 100337750C CN B2004100801557 A CNB2004100801557 A CN B2004100801557A CN 200410080155 A CN200410080155 A CN 200410080155A CN 100337750 C CN100337750 C CN 100337750C
- Authority
- CN
- China
- Prior art keywords
- acetate
- catalyst
- reaction
- carbonylation
- rhodium
- 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.)
- Expired - Lifetime
Links
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 18
- 230000006315 carbonylation Effects 0.000 title claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000010948 rhodium Substances 0.000 claims abstract description 46
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 23
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 9
- 239000010452 phosphate Substances 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 62
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 26
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 26
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 16
- 230000000694 effects Effects 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000003426 co-catalyst Substances 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- 229910000318 alkali metal phosphate Inorganic materials 0.000 claims 2
- 239000002253 acid Chemical class 0.000 claims 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 48
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 15
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- WJIBZZVTNMAURL-UHFFFAOYSA-N phosphane;rhodium Chemical compound P.[Rh] WJIBZZVTNMAURL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- PZSJYEAHAINDJI-UHFFFAOYSA-N rhodium(3+) Chemical compound [Rh+3] PZSJYEAHAINDJI-UHFFFAOYSA-N 0.000 description 2
- 229920013683 Celanese Polymers 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 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
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 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
- 238000012423 maintenance Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a catalytic system for synthesizing acetic acid through the carbonylation of methanol. A rhodium complex is used as an active component of a catalyst, and phosphate and methyl iodide are used as a cocatalyst, wherein the molar ratio of the phosphate to the active component is from 1 to 1000, and the molar ratio of the methyl iodide to the active component is from 1 to 800. In the carbonyl synthesis reaction, the catalytic system can fast catalyze the carbonylation reaction of the methanol under the correspondingly moderate condition, and simultaneously, the catalytic system has good stability.
Description
Technical field
The present invention relates to the preparation method of a class methanol carbonylation to synthesize acetic acid.
Background technology
Acetic acid is a kind of important Organic Chemicals, is mainly used in to produce VAM, aceticanhydride, terephthalic acid (TPA) (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 downstream product, impelled acetic acid to become one of a few petroleum chemicals that minority output and demand increase rapidly.
Carbon monoxide under the effect of catalyst, 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 Paulik of Monsanto company opened up new enforcement approach about oxo-synthesis homogeneous rhodium catalyst invention (US 3769329) for carbonylic synthesis technology.Through updating and perfect, with the rhodium production process route that the carbonyl synthetic technology of catalyst has become the industrial most important and output maximum of present acetate.Its course of reaction is the effect that methyl alcohol passes through rhodium catalyst, prepares acetate with reaction of carbon monoxide, and catalyst adopts [Rh (CO)
2I
2]
-The little molecular complex of anionic [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 course of reaction 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) complex, but this has greatly increased the corrosiveness of reaction medium to equipment again.
At existing catalyst these deficiencies in course of reaction, people are groping the better catalyst of performance always, and hope can have advantages of high catalytic activity and better stable simultaneously.The catalyst 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 great improvement arranged.
Institute of Chemistry, Academia Sinica, once having proposed a kind of metallo-organic compound that contains nitrogen, oxygen is part, the chelating type that forms new square plane with rhodium carbonyl along the dicarbapentaborane bimetal complexes [Chinese patent 1105603A).This system can be used for the catalysis methanol carbonyl and turns to acetate and methyl acetate, also can obtain acetic anhydride by the catalysis methyl acetate.
In existing suitability for industrialized production, adopt square plane anion structural coordination compound with rhodium as catalytic active species, so the improvement Journal of Sex Research based on this catalyst is devoted in a large amount of work more.Adding one or more in catalyst system and catalyzing 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 withOrganometallic Compounds, New York, VHC, 1996,104.] and the M.A.Murphy[M.A.Murphy et al.J Organomet Chem of HoechstCelanese company, 1986,303:257～272.] and B.L.Smith[B.L.Smith et al.J Mol Catal, 1987,39:115～136.] etc. the people think that by the methyl alcohol homogeneous carbonylation of rhodium catalysis 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 complex anion of pentacoordinate, this anion 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 catalyst
3The generation of precipitation, thus the stability of catalyst system and catalyzing improved.By selecting salt compounded of iodine and suitable methyl acetate concentration, can than obtain under the low water content with high water content under identical reactivity and stability, improved the utilization ratio 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 technology by adding the inorganic salts co-catalyst is a Hoechst Celanese company.The said firm has obtained to be undertaken by the Monsanto carbonylic synthesis technology permission of commercial size production of acetic acid 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 main feature of this technology is promptly by adding inorganic salt compounded of iodine to a higher content, reach the effect (US5 001 259, and EP 055 618) of having put forward activity of such catalysts and stability.
Summary of the invention
The object of the present invention is to provide a kind of liquid phase reactor catalyst system that acetate is produced in carbonylation of methanol that is used for.Help catalytic additive by add phosphate in this catalyst system and catalyzing, this catalyst system and catalyzing has advantages of high catalytic activity and stability, and under gentle relatively condition, the catalysis methanol carbonyl turns to acetate quickly and efficiently.Simultaneously, this catalyst system and catalyzing can also be used for the higher homologue of methyl alcohol is carried out the course of reaction that catalyzed carbonylation generates the higher homologue of acetate.The present invention turns to example with the methyl alcohol catalysis of carbonyl and launches to discuss.
Common methyl alcohol liquid phase catalyzed carbonylation technical process comprises: in the liquid phase medium of rhodium-containing salt catalyst and water, acetate, iodomethane, methyl acetate and ionic iodide catalyst stabilizer/co-promoter, the synthetic reaction of catalysis carbon monoxide and methyl alcohol generates carbonylation product acetate.At the rhodium complex catalyst of different ligands, researchers have carried out fruitful exploration, and in the last few years, many rhodium complex salt were synthesized out, and have shown and can compare favourably with the Monsanto catalyst or than its better catalytic activity.Wherein contain such as PEt
3Rhodium complex etc. simple organophosphor ligand is considered to most important gang [Christophe M.Thomas, etal Coordin.Chem.Rev., 2003,243:125-142].People such as Cole-Hamijlton have studied the use trialkyl phosphine as rhodium base carbonylating catalyst, and they are the strong electronics parts of giving.Water has played the activated state of maintenance catalyst at its rhodium (I) complex in reaction system, its existence has reduced [Rh (CO)
2I
4]
-Or Rh (PEt
3)
2(CO) I
3Etc. the generation of nonactive attitude rhodium (III) complex, therefore, higher water content can improve carbonylation rate significantly.Under low water content, with Rh (PEt
3)
2(CO) Cl replaces [Rh (CO)
2Cl]
2There is not obvious benefit as catalyst precarsor.
The biphosphine ligand rhodium complex also is proved to be carbonylating catalyst preferably.People such as Pringle [C.-A.Carraz etal, Chem.Commun., 2000,14,1277] have reported that the two phosphine rhodium complexs of asymmetric ethene are than its symmetrical homologue catalysis methanol carbonylation more efficiently.And under the industrial production condition, the two phosphine rhodium complexs of asymmetric ethene have better stability than the catalyst of other change part that all were reported.But the carbonylation rate of these pairs phosphine composition catalyst catalysis but is lower than [the Rh (CO) of Monsanto
2I
2]
-Catalyst.Studies have shown that asymmetry is vital for the biphosphine ligand rhodium complex.And, it should be noted that the P that is used for carbonylation of methanol, N-[K.Vkatti, etal.Inorg.Chem., 1993,32,5919], P, O-[R.W.Wegman, etal.J.Chem.Soc.Chem.Commun., 1987,1,1891] and P, S-[M.J.Baker, etal.J.Chem.Soc.Chem.Commun., 1995,197] etc. the sub-part of power supply all is asymmetric, and they all have a strong donor atom and a medium or more weak donor atom.
Catalyst system and catalyzing provided by the invention, with rhodium complex as the activity of such catalysts component, phosphate and iodomethane are co-catalyst, and wherein the mole of phosphate and active component is than between 1～1000, and the mole of iodomethane and active component is than between 1～800.This phosphate co-catalyst is cheap and easy to get, and stable in properties, and stronger industrial promotional value is arranged.
Catalyst of the present invention has good performance when the catalysis methanol carbonylation, in the following aspects than traditional Monsanto catalyst with study many organophosphor ligand catalyst in recent years and have remarkable advantages:
(1) water gas reaction that can not monitor in the system.
(2) reacting initial temperature is low, and reaction temperature reaches to react about 120 ℃ and promptly begins to carry out.
(3) catalysis high activity, as can be seen, in the time, methyl alcohol all is converted into acetate rapidly at shorter reaction in appended embodiment.
(4) do not need higher water content can keep the stability and the high activity of catalyst in the reaction system.This provides a great convenience for the separating technology of simplifying follow-up acetate and water.
(5) the Preparation of catalysts process is simple, does not need catalyst precarsor is carried out any processing.
When catalyst of the present invention prepared acetate at the catalysis methanol carbonylation, the co-catalyst iodomethane content of adding was in overall reaction liquid between 1～5mol/L model week.Add acetate and make solvent, can improve reaction speed, the acetate consumption is between 3～97% (Wt) of methyl alcohol and acetate total amount.When having hydroiodic acid and water to exist in the reaction system, reaction speed is improved.Catalyst consumption in the reaction system is counted 200～2000ppm scope with rhodium, 120～180 ℃ of reaction temperatures, and carbon monoxide pressure is 2～6MPa.
From appended examples of the present invention, as can be seen, add and demonstrate high activity when phosphatic caltalyst ties up to catalysis methanol carbonylation system acetate.
The specific embodiment
Embodiment 1
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetate 1.12mol, iodomethane 0.19mol, (NH
4)
3PO
44H
2O 0.5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 20min.Methanol conversion 88.6%, methyl acetate content is 0.02mol in the product, and the acetate increment is 0.68mol, and the acetate space-time yield is 19.4mol AcOH/ (Lh).
Embodiment 2
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetate 1.12mol, iodomethane 0.19mol, (NH
4)
3PO
44H
2O 5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 15min.Methanol conversion 89.8%, methyl acetate content is 0.03mol in the product, and the acetate increment is 0.68mol, and the acetate space-time yield is 19.7mol AcOH/ (Lh).
Embodiment 3
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.136g, methyl alcohol 1.24mol, acetate 0.87mol, iodomethane 0.21mol, (NH
4)
3PO
44H
2O 1.2g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 25min.Ethanol conversion 90%, methyl acetate content is 0.03mol in the product, and the acetate increment is 1.09mol, and the acetate space-time yield is 23.7mol AcOH/ (Lh).
Embodiment 4
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetate 1.12mol, iodomethane 0.19mol, Zn
3(PO
4)
24H
2O 0.5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 25min.Methanol conversion 87.5%, methyl acetate content is 0.03mol in the product, and the acetate increment is 0.66mol, and the acetate space-time yield is 16.0mol AcOH/ (Lh).
Embodiment 5
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetate 1.12mol, iodomethane 0.19mol, Zn
3(PO
4)
24H
2O 5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 30min.Methanol conversion 94.8%, methyl acetate content is 0.04mol in the product, and the acetate increment is 0.71mol, and the acetate space-time yield is 14.9mol AcOH/ (Lh).
Embodiment 6,
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetate 1.12mol, iodomethane 0.19mol, Na
3PO
412H
2O 0.5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 15min.Methanol conversion 89.7%, methyl acetate content is 0.04mol in the product, and the acetate increment is 0.67mol, and the acetate space-time yield is 19.7mol AcOH/ (Lh).
Embodiment 7
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetate 1.12mol, iodomethane 0.19mol, Na
3PO
412H
2O 5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 15min.Methanol conversion 95.4%, methyl acetate content is 0.03mol in the product, and the acetate increment is 0.72mol, and the acetate space-time yield is 20.9mol AcOH/ (Lh).
Embodiment 8
In 250ml zirconium matter autoclave pressure, add Rh (OAc)
20.144g, methyl alcohol 0.79mol, acetate 1.12mol, iodomethane 0.19mol, Na
3PO
412H
2O 10g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 15min.Methanol conversion 98.0%, methyl acetate content is 0.04mol in the product, and the acetate increment is 0.74mol, and the acetate space-time yield is 21.5mol AcOH/ (Lh).
Embodiment 9
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.136g, methyl alcohol 1.04mol, acetate 0.75mol, iodomethane 0.19mol, K
3PO
47H
2O 1.0g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 30min.Methanol conversion 88.0%, methyl acetate content is 0.03mol in the product, and the acetate increment is 0.88mol, and the acetate space-time yield is 19.1mol AcOH/ (Lh).
Embodiment 10
In 250ml zirconium matter autoclave pressure, add [Rh (CO)
2Cl]
20.15g, methyl alcohol 1.15mol, acetate 0.90mol, iodomethane 0.19mol, Li
3PO
40.5g; Behind twice of the air in the carbon monoxide replacement reaction kettle, charge into carbon monoxide and seal this system to system, setting mixing speed is 500 rev/mins, control reaction pressure 4.0Mpa, 140 ℃ of reaction temperatures, the reaction time is 30min.Methanol conversion 86.3%, methyl acetate content is 0.04mol in the product, and the acetate increment is 0.95mol, and the acetate space-time yield is 18.5mol AcOH/ (Lh).
Claims (3)
1. the preparation method of a methanol carbonylation to synthesize acetic acid, with rhodium complex as the activity of such catalysts component, phosphate and iodomethane are co-catalyst, and wherein the mole of phosphate and active component is than between 1～1000, and the mole of iodomethane and active component is than between 1～800; Reaction temperature is 120～180 ℃, and carbon monoxide pressure is 2.0～6.0Mpa, and the consumption of rhodium complex in reaction system counted 200～2000ppm by rhodium;
Described rhodium complex is [Rh (CO)
2Cl]
2, [Rh (CO)
2Br]
2, [Rh (CO)
2I]
2, or Rh (OAc)
2
Described co-catalyst is Zn, ammonium or alkali-metal phosphate.
2. preparation method as claimed in claim 1 is characterized in that used alkali-metal phosphate is Li
3PO
4, Na
3PO
4, K
3PO
4And their moisture salt or acid salt.
3. preparation method as claimed in claim 1 is characterized in that the phosphate of used Zn or ammonium is respectively Zn
3(PO
4)
2, (NH
4)
3PO
4Or its moisture salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100801557A CN100337750C (en) | 2004-09-24 | 2004-09-24 | Catalyst system for carbonylation of methanol for synthesizing ethanol, and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100801557A CN100337750C (en) | 2004-09-24 | 2004-09-24 | Catalyst system for carbonylation of methanol for synthesizing ethanol, and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1751796A CN1751796A (en) | 2006-03-29 |
| CN100337750C true CN100337750C (en) | 2007-09-19 |
Family
ID=36678871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100801557A Expired - Lifetime CN100337750C (en) | 2004-09-24 | 2004-09-24 | Catalyst system for carbonylation of methanol for synthesizing ethanol, and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100337750C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153002B (en) * | 2006-09-28 | 2011-04-20 | 中国石油化学工业开发股份有限公司 | Method for producing carboxylic acid |
| CN101658801B (en) * | 2008-08-29 | 2013-03-06 | 上海焦化有限公司 | Catalysis system for synthesis of acetic acid by using carbonylation and application thereof |
| CN111195514B (en) * | 2018-11-20 | 2021-03-30 | 中国科学院大连化学物理研究所 | Monoatomic dispersion rhodium-based catalyst, preparation method thereof and application thereof in methane low-temperature oxidation reaction |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1131110C (en) * | 2001-04-12 | 2003-12-17 | 中国科学院化学研究所 | Homogeneous carbonylation reaction catalyst and its preparation and application |
| WO2003104179A1 (en) * | 2002-06-06 | 2003-12-18 | Bp Chemicals Limited | Process for the production of acetic acid |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
| US20040068131A1 (en) * | 2000-07-27 | 2004-04-08 | Matthias Beller | Production of novel phosphane ligands and use in catalytical reactions |
| CN1517150A (en) * | 2003-01-17 | 2004-08-04 | 中国科学院化学研究所 | Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application |
-
2004
- 2004-09-24 CN CNB2004100801557A patent/CN100337750C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040068131A1 (en) * | 2000-07-27 | 2004-04-08 | Matthias Beller | Production of novel phosphane ligands and use in catalytical reactions |
| CN1131110C (en) * | 2001-04-12 | 2003-12-17 | 中国科学院化学研究所 | Homogeneous carbonylation reaction catalyst and its preparation and application |
| US20040059153A1 (en) * | 2002-05-23 | 2004-03-25 | Institut Francais Du Petrole | Process for carbonylating alcohols, employing a catalyst based on rhodium or iridium in a non-aqueous ionic liquid, with efficient catalyst recycling |
| WO2003104179A1 (en) * | 2002-06-06 | 2003-12-18 | Bp Chemicals Limited | Process for the production of acetic acid |
| CN1517150A (en) * | 2003-01-17 | 2004-08-04 | 中国科学院化学研究所 | Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application |
Non-Patent Citations (1)
| Title |
|---|
| 铑配合物催化甲醇羰基化反应的性能和机理 潘平来等，催化学报，第17卷第1期 1996 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1751796A (en) | 2006-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101053841A (en) | Rhodium catalyst with organometallic lithium salts as ligand | |
| CN1117628C (en) | Bimetallic catalyst for homogeneous methanol carbonylation and its prepn | |
| CN103861643B (en) | A kind of catalyst system for acetic acid synthesis from methanol carbonylation and application thereof | |
| CN1876239A (en) | Catalyst system for synthesizing acetic acid and acetic anhydride from carbonyl compound and its uses | |
| CN101857608A (en) | Imidazole ionic liquid phosphine ligand and application of coordination compound thereof in hydroesterification | |
| CN100337750C (en) | Catalyst system for carbonylation of methanol for synthesizing ethanol, and application | |
| CN1053392C (en) | Methyl alcohol carbonylation homogeneous rhodium catalyst and its preparing method and use | |
| CN1032133C (en) | Continuous process for simultaneous preparation of acetic acid and acetic anhydride | |
| CN102218343A (en) | Lithium pyridine carboxylate-rhodium acetate complex catalyst for synthesizing acetic acid and acetic anhydride through carbonylation, and preparation method and application thereof | |
| CN1212197C (en) | Catalytic system used for homogeneous hydroxylation reaction and its manufacturing method and application | |
| CN115090308B (en) | Metal-doped sodium super-ionic catalyst and preparation method and application thereof | |
| CN1131110C (en) | Homogeneous carbonylation reaction catalyst and its preparation and application | |
| CN1778468A (en) | Catalyst system of catalytic methylester acetate or methylether synthetic acetoanhy dride and use thereof | |
| CN102166531B (en) | A catalyst system for acetic acid synthesis through methanol carbonylation and an application of the catalyst system | |
| CN101391232B (en) | Pyrazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof | |
| CN1939586A (en) | Homogeneous rhodium catalytic system of oxo-acetic anhydride and its use | |
| CN1418729A (en) | Catalyst for producing isobutene by cracking methyl tert-butyl ether | |
| CN101954295B (en) | Catalyst system for methanol low-pressure carbonyl synthesis of acetic acid and application thereof | |
| CN100443173C (en) | Catalyst system for synthetizing acetic acid from methanol or synthetizing ethylanhydride from methyl acetate and use thereof | |
| CN102259028A (en) | Iridium catalyst for homogeneously catalyzing carbonylation of methanol to synthesize acetic acid as well as preparation method and application thereof | |
| CN102294265B (en) | Catalyst for synthesis of acetic acid through carbonylation at low water concentration, preparation method and application thereof | |
| CN101391231B (en) | Imidazole acetic-acid rhodium complexes catalyst capable of catalyzing carbonylation reaction to preparing acetic acid and acetic anhydride and preparation method and use thereof | |
| CN103012500B (en) | A kind of pyridine nickel rhodium catalyst and its preparation method and application | |
| CN100569788C (en) | Rhodium acetic anhydride complex and preparation method thereof and application | |
| CN111558395A (en) | Bimetallic catalyst for methanol carbonylation reaction, preparation method 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 | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: CHEMISTRY INSTITUTE, CHINESE ACADEMY OF SCIENCES; Free format text: FORMER OWNER: CHEMISTRY INSTITUTE, CHINESE ACADEMY OF SCIENCES; ZHENJIANG SUOPU ACETATE CO., LTD. Effective date: 20081031 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20081031 Address after: No. 2, North First Street, Zhongguancun, Beijing, Haidian District: 100080 Co-patentee after: JIANGSU SOPO (Group) Co.,Ltd. Patentee after: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Address before: No. 2, North First Street, Zhongguancun, Beijing, Haidian District: 100080 Co-patentee before: Zhenjiang Soap Acetic Acid Co.,Ltd. Patentee before: Institute of chemistry, Chinese Academy of Sciences |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200120 Address after: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Co-patentee after: JIANGSU SOPO CHEMICAL Co.,Ltd. Patentee after: INSTITUTE OF CHEMISTRY, CHINESE ACADEMY OF SCIENCES Address before: 100080 No. 2 North First Street, Haidian District, Beijing, Zhongguancun Co-patentee before: JIANGSU SOPO (Group) Co.,Ltd. Patentee before: Institute of Chemistry, Chinese Academy of Sciences |
|
| CX01 | Expiry of patent term |
Granted publication date: 20070919 |