WO2021255671A1 - Method for producing aromatic dicarboxylic acid using iron co‑catalyst - Google Patents
Method for producing aromatic dicarboxylic acid using iron co‑catalyst Download PDFInfo
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- WO2021255671A1 WO2021255671A1 PCT/IB2021/055325 IB2021055325W WO2021255671A1 WO 2021255671 A1 WO2021255671 A1 WO 2021255671A1 IB 2021055325 W IB2021055325 W IB 2021055325W WO 2021255671 A1 WO2021255671 A1 WO 2021255671A1
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- catalyst
- solvent
- aromatic compound
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003426 co-catalyst Substances 0.000 title claims abstract description 54
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 33
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title description 7
- -1 dimethyl aromatic compound Chemical class 0.000 claims abstract description 96
- 239000003054 catalyst Substances 0.000 claims abstract description 82
- 238000000034 method Methods 0.000 claims abstract description 79
- 239000011572 manganese Substances 0.000 claims abstract description 71
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 67
- 239000010941 cobalt Substances 0.000 claims abstract description 67
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 59
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 46
- 230000001590 oxidative effect Effects 0.000 claims abstract description 41
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 37
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 37
- 239000007800 oxidant agent Substances 0.000 claims abstract description 23
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 51
- 229930195733 hydrocarbon Natural products 0.000 claims description 48
- 150000002430 hydrocarbons Chemical class 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 46
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 46
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 10
- 239000001569 carbon dioxide Substances 0.000 claims description 10
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- YGYNBBAUIYTWBF-UHFFFAOYSA-N 2,6-dimethylnaphthalene Chemical compound C1=C(C)C=CC2=CC(C)=CC=C21 YGYNBBAUIYTWBF-UHFFFAOYSA-N 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 6
- 150000004965 peroxy acids Chemical class 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 claims description 3
- YNJSNEKCXVFDKW-UHFFFAOYSA-N 3-(5-amino-1h-indol-3-yl)-2-azaniumylpropanoate Chemical compound C1=C(N)C=C2C(CC(N)C(O)=O)=CNC2=C1 YNJSNEKCXVFDKW-UHFFFAOYSA-N 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 239000012933 diacyl peroxide Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 60
- 230000015572 biosynthetic process Effects 0.000 description 36
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 26
- 230000009467 reduction Effects 0.000 description 26
- 238000007254 oxidation reaction Methods 0.000 description 21
- 239000006227 byproduct Substances 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000008240 homogeneous mixture Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- RVHSTXJKKZWWDQ-UHFFFAOYSA-N 1,1,1,2-tetrabromoethane Chemical compound BrCC(Br)(Br)Br RVHSTXJKKZWWDQ-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
- B01J27/13—Platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/14—Monocyclic dicarboxylic acids
- C07C63/15—Monocyclic dicarboxylic acids all carboxyl groups bound to carbon atoms of the six-membered aromatic ring
- C07C63/26—1,4 - Benzenedicarboxylic acid
Definitions
- Aromatic dicarboxylic acids e.g., terephthalic acid
- dimethyl aromatic compounds e.g., para-xylene
- U.S. Patent Number 5,453,538 discloses a process for the manufacture of aromatic dicarboxylic acids that uses bromine facilitated by the use of cerium along with the cobalt and manganese catalyst.
- U.S. Patent Number 4,754,062 discloses a process for the manufacture of polycarboxylic acids, and where polycaxboxylic acids such as pseudocumene are converted to tiimeliitic acid which is used to manufacture plasticizers and polyamide-imide polymers used as molding compounds for replacement of metals.
- the present disclosure provides improved systems and methods for oxidizing dimethyl aromatic compounds (e.g., para-xylene) to produce aromatic dicarboxylic acids (e.g., terephthalic acid).
- dimethyl aromatic compounds e.g., para-xylene
- aromatic dicarboxylic acids e.g., terephthalic acid
- a method for oxidizing a dimethyl aromatic compound including reacting the dimethyl aromatic compound and an oxidant in the presence of a catalyst system in a solvent to produce a reaction product including an aromatic dicarboxylic acid, such as terephthalic acid.
- the catalyst system includes a catalyst and a co-catalyst.
- the catalyst includes bromine, cobalt, and manganese.
- the co-catalyst includes iron.
- the iron is present in an amount of 10 to 100 parts per million by weight (ppm), such as 10 to 90 ppm, more particularly 10 to 50 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- the bromine is present in an amount of 160 to 730 ppm, such as 200 to 400 ppm, more particularly 200 to 330 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- the manganese is present in an amount of 100 to 450 ppm, such as 100 to 400 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- the cobalt is present in an amount of 100 to 450 ppm, such as 300 to 400 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- a total amount of cobalt and manganese in the catalyst can be greater than 300 to 900 ppm, such as greater than 300 to 800 ppm, more particularly greater than 300 to 400 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- a reaction mixture for the oxidation of a dimethyl aromatic compound by the method can include the dimethyl aromatic compound; the oxidant; the catalyst; the co-catalyst; water; and the solvent.
- a reaction product can be produced by the method or using the reaction mixture.
- FIG. 1 is a process flow diagram of an embodiment of a process for oxidation of para-xylene to obtain terephthalic acid.
- FIG. 2A is a graphical illustration of the mole percent of carbon monoxide and carbon dioxide (collectively “COx”) formed as over-oxidation products also referred to as by-products based on the total moles of reaction product, in Comparative Example A and Example 1 ; and the percent reduction in the moles of COx formed in Example 1 as compared to Comparative Example A.
- COx carbon monoxide and carbon dioxide
- FIG. 2B is a graphical illustration of the mole percent of COx formed as by products, based on the total moles of reaction product, in Comparative Example B and Example 2; and the percent reduction in the moles of COx formed in Example 2 as compared to Comparative Example B.
- FIG. 2C is a graphical illustration of the mole percent of COx formed as by products, based on the total moles of reaction product, in Comparative Example C and Examples 3-4; and the percent reduction in the moles of COx formed in Examples 3-4 as compared to Comparative Example C.
- FIG. 3A is a graphical illustration of the percent reduction in the weight of Cio+ hydrocarbons formed as by-products in Comparative Example A and Example 1 ; and the percent increase in the weight of terephthalic acid produced in Example 1 as compared to Comparative Example A; as used herein “Cio+ hydrocarbons” refers to hydrocarbons including 10 or more carbon atoms.
- FIG. 3B is a graphical illustration of the percent reduction in the weight of Cio+ hydrocarbons formed as by-products of Comparative Example B and Example 2; and the percent increase in the weight of terephthalic acid produced in Example 2 as compared to Comparative Example B.
- FIG. 3C is a graphical illustration of the percent reduction in the weight of Cio+ hydrocarbons formed as by-products of Comparative Example C and Examples 3-4; and the percent increase in the weight of terephthalic acid produced in Examples 3-4 as compared to Comparative Example C.
- FIG. 3D is a graphical illustration of the percent reduction in the weight of Cio+ hydrocarbons formed as by-products of Comparative Example C and Examples 3-4 as compared to Comparative Example A; and the percent increase in the weight of terephthalic acid produced in Comparative Example C and Examples 3-4 as compared to Comparative Example A.
- aromatic dicarboxylic acids e.g., terephthalic acid
- dimethyl aromatic compounds e.g., para-xylene
- by-products can be formed.
- consumption of the dimethyl aromatic compounds and solvent e.g., acetic acid
- solvent e.g., acetic acid
- the methods of the present disclosure use a catalyst system that includes a catalyst and a co-catalyst, the co-catalyst including iron.
- the methods for oxidizing dimethyl aromatic compounds to obtain aromatic dicarboxylic acids facilitate the reduction of the amount of carbon monoxide, carbon dioxide, and/or Cio+ hydrocarbons in the reaction product, and increase the purity of the aromatic dicarboxylic acids as compared to previous methods for oxidizing dimethyl aromatic compounds that did not utilize a co-catalyst including iron.
- the methods of the present disclosure can achieve a reduction in the total moles of COx produced equal to or greater than 5 mole %, such as equal to or greater than 10 mole %, more particularly at equal to or greater than 15 mole %, as compared to the total moles of COx produced in previous methods for oxidizing dimethyl aromatic compounds that did not utilize a co-catalyst including iron.
- the methods of the present disclosure can achieve a reduction in the amount of Cio+ hydrocarbons produced equal to or greater than 10 weight percent (wt%), such as equal to or greater than 20 wt%, more particularly at equal to or greater than 30 wt%, as compared to the amount of Cio+ hydrocarbons produced in previous methods for oxidizing dimethyl aromatic compounds that did not utilize a co-catalyst including iron.
- wt% weight percent
- the methods of the present disclosure can achieve an increase in the wt% of aromatic dicarboxylic acid produced equal to or greater than 0.5 wt%, such as equal to or greater than 1.0%, more particularly equal to or greater than 1.5 wt%, as compared to the moles of aromatic dicarboxylic acid produced in previous methods for oxidizing dimethyl aromatic compounds that did not utilize a co-catalyst including iron.
- the amount of catalyst can be reduced as compared to previous methods.
- the present disclosure provides methods that allow for the inclusion of a lesser amount of manganese and/or bromine in the catalyst, while maintaining or improving the quality of aromatic dicarboxylic acid produced per milligram of catalyst.
- a reduction in the amount of manganese present can be equal to or greater than 25 wt%, such as equal to or greater than 50 wt%, more particularly equal to or greater than 75 wt%, as compared to the ppm of manganese present in previous methods for oxidizing dimethyl aromatic compounds.
- manganese can be present in an amount in a range of 100 to 450 ppm, such as 100 to 400 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- a reduction in the amount of bromine present can reduce, mitigate, or avoid corrosion of the equipment used for the oxidation or allow for use of different materials of construction for the equipment.
- a reduction in the amount of bromine present can be equal to or greater than 25 wt%, such as equal to or greater than 50 wt%, more particularly equal to or greater than 75 wt%, as compared to the ppm of bromine present in previous methods for oxidizing dimethyl aromatic compounds.
- bromine can be present in the catalyst in an amount of 160 to 730 ppm, such as 200 to 400 ppm, more particularly 200 to 330 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- a method for oxidizing a dimethyl aromatic compound can include reacting the dimethyl aromatic compound and an oxidant in the presence of a catalyst system (e.g., a catalyst and a co-catalyst) in a solvent to produce a reaction product including an aromatic dicarboxylic acid.
- a catalyst system e.g., a catalyst and a co-catalyst
- the dimethyl aromatic compound can include at least one of xylene (e.g., least one of para-xylene, meta-xylene, or ortho-xylene), or 2,6-dimethylnaphthalene; such as para- xylene.
- xylene e.g., least one of para-xylene, meta-xylene, or ortho-xylene
- 2,6-dimethylnaphthalene such as para- xylene.
- a catalyst is used.
- the catalyst includes bromine and manganese.
- the catalyst can include bromine, cobalt, and manganese.
- the catalyst can comprise no added titanium, chromium, vanadium, molybdenum, tin, cerium and zirconium. “No added” refers to the element being present in trace amounts as an impurity.
- the catalyst can be unsupported and sources of the catalyst can be combined to form the catalyst as a catalyst mixture.
- Sources of the catalyst can include salts of cobalt (e.g., cobalt (II) acetate tetrahydrate) and manganese (e.g., manganese (II) acetate tetrahydrate).
- a bromine source can be at least one of hydrobromic acid, sodium bromide, ammonium bromide, or tetrabromoethane .
- the total amount of catalyst e.g., bromine, cobalt and manganese
- the total amount of catalyst can be present in an amount of greater than 460 to 1,630 ppm, such as 600 to 1,200 ppm, more particularly 600 to 1,130 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- the catalyst can include an amount of cobalt of 100 to 450 ppm, such as 300 to 400 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- the catalyst can include an amount of manganese of, for example, 100 to 450 ppm, such as 100 ppm to 400 ppm, based on a total weight of the dimethyl aromatic compound and the solvent.
- a total amount of cobalt and manganese in the catalyst can be greater than 300 to 900 ppm, such as greater than 300 to 800 ppm, more particularly greater than 300 to 400 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- the catalyst can include cobalt, manganese, and bromine and a molar ratio of bromine to (cobalt and manganese) can be in a range of 0.3: 1 to 3: 1, such as 0.3: 1 to 2: 1, more particularly 0.3:1 to 1:1.
- the method uses a co-catalyst.
- the co-catalyst can include iron in an amount of 10 to 100 ppm, such as 10 to 90 ppm, more particularly 10 to 50 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- the catalyst can include cobalt and manganese and a weight ratio of iron to the total amount of cobalt and manganese can be in a range of 0.05: 1 to 0.25:1, such as 0.05: 1 to 0.20: 1, more particularly 0.05:1 to 0.15:1.
- the co-catalyst can further include at least one of ruthenium, tantalum, tungsten, or nickel.
- the co-catalyst comprises no added titanium, chromium, vanadium, molybdenum, tin, cerium, or zirconium.
- a solvent is used to at least partially dissolve the dimethyl aromatic compound, the catalyst, and the oxidant.
- the solvent can include a Ci-7 aliphatic carboxylic acid, such as acetic acid.
- the solvent can further include water (e.g., the solvent can be an aqueous solution).
- a weight ratio of solvent to dimethyl aromatic compound can be in a range of l5:l to 1:1, such as 10 : 1 to 1:1, more particularly 5 : 1 to 1:1.
- the method uses an oxidant.
- the oxidant can include at least one of hydrogen peroxide, dioxygen, ozone, an anthraquinone, a C2-32 alkyl peroxide, a C2-32 alkyl hydroperoxide, a C2-32 ketone peroxide, a C2-32 diacyl peroxide, a C3-22 diperoxy, a ketal, a C2-32 peroxyester, a C2-32 peroxydicarbonate, a C2-32 peroxy acid, a C6-32 perbenzoic acid, a C2-32 peracid, a periodinane, or a periodate, such as dioxygen (e.g., in air).
- dioxygen e.g., in air
- the reacting of the dimethyl aromatic compound and the oxidant can be at a temperature in a range of 170 °C to 200 °C, such as 180 °C to 200 °C, more particularly 190 °C to 200 °C.
- the reacting of the dimethyl aromatic compound and the oxidant can be at a pressure in a range of 1 to 1.8 MegaPascals (MPa), such as 1 to 1.7 MPa, more particularly 1 to 1.6 MPa.
- MPa MegaPascals
- a residence time in the reactor can be in a range of 20 minutes to 200 minutes, such as 40 minutes to 150 minutes, more particularly 60 minutes to 100 minutes.
- the method can be carried out in a reactor such as a batch reactor, a continuous reactor, or semi-continuous reactor.
- the reactor can include an inlet for feeding at least one of the dimethyl aromatic compound, the solvent, the catalyst, or the co-catalyst continuously for a period of time and an outlet for removing the reaction product continuously for a period of time or at specific times.
- the reacting of the dimethyl aromatic compound and the oxidant can be in a continuous stirred-tank reactor.
- the aromatic dicarboxylic acid produced by the methods of the present disclosure can be at least one of terephthalic acid, isophthalic acid, ori/io-phthalic acid, or 2,6-naphthalenedicarboxylic acid.
- the aromatic dicarboxylic acid can be terephthalic acid.
- the aromatic dicarboxylic acid can be present in the reaction product in an amount equal to or greater than 90 wt%, such as equal to or greater than 92 wt%, more particularly equal to or greater than 94 wt%, based on the total weight of solids in the reaction product.
- the reaction product can include by-products such as carbon monoxide and carbon dioxide (collectively “COx”).
- COx carbon monoxide and carbon dioxide
- a total amount of COx present in the reaction product can be reduced by equal to or greater than 5 mole %, such as equal to or greater than 10 mole %, more particularly equal to or greater than 15 mole %, as compared to a total amount of carbon monoxide and carbon dioxide present in a conventional reaction product of a method for oxidizing the dimethyl aromatic compound.
- the reaction product can further include by-products such as Cio+ hydrocarbons.
- Cio+ hydrocarbons can be present in the reaction product in an amount greater than 0 and equal to or less than 1.5 wt%, such as equal to or less than 1.0 wt%, more particularly equal to or less than 0.5 wt%, based on the total weight of solids in the reaction product.
- Cio+ hydrocarbons can be present in the reaction product in an amount of 0.1 to 1.5 wt%, such as 0.5 to 1.0 wt%, more particularly 1 to 0.5 wt%, based on the total weight of solids in the reaction product.
- Cio+ hydrocarbon refers to a hydrocarbon including 10 or more carbon atoms. Any number of Cio+ hydrocarbons can be present in a reaction product, such as at least five different Cio+ hydrocarbons, or at least fifteen different Cio+ hydrocarbons, or at least twenty different Cio+ hydrocarbons.
- the method can further include separating the solvent, the catalyst, and the co-catalyst from the reaction product, and recycling the solvent, the catalyst, and the co-catalyst to the reactor.
- the catalyst and the co-catalyst can be in solution in the solvent and separation of the catalyst and the co-catalyst from the solvent can be performed via filtration or a solid-liquid separation method.
- a reaction mixture for the oxidation of a dimethyl aromatic compound by the above-described methods can include the dimethyl aromatic compound, the oxidant, the catalyst, the co-catalyst, water, and the solvent.
- a reaction product can be produced by the above-described methods, or using the above-described reaction mixture.
- FIG. A more complete understanding of the components, processes, and apparatuses disclosed herein can be obtained by reference to the accompanying drawings.
- FIG. These figures (also referred to herein as “FIG.”) are merely schematic representations based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and/or to define or limit the scope of the exemplary embodiments.
- specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings, and are not intended to define or limit the scope of the disclosure.
- FIG. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.
- a reaction mixture 6 including para-xylene, solvent, water, catalyst, and co-catalyst can be fed into reactor 10.
- An oxidant 8 also can be fed into reactor 10.
- reaction product 12 including terephthalic acid can be removed from reactor 10.
- Reaction product 12 can be fed into first crystallizer 20 to produce first crystallized stream 22.
- First crystallized stream 22 can be fed into second crystallizer 30 to produce second crystallized stream 32.
- Second crystallizer stream 32 can be fed into third crystallizer 40 to produce third crystallized stream 42 including crystallized terephthalic acid.
- Cio+ hydrocarbons can be reacted with the oxidant to obtain terephthalic acid.
- Solvent, catalyst, and co-catalyst stream 44 can be separated from third crystallized stream 42 and recycled to reaction mixture 6.
- the oxidation reactions were carried out in a semi-continuous stirred-tank batch reactor.
- the catalyst included cobalt, manganese, and bromine and the co-catalyst included iron.
- the catalyst and co-catalyst were prepared by dissolving cobalt acetate, manganese acetate, and iron acetate in 63 grams of water. Hydrobromic acid was then added to the catalyst/co-catalyst solution. The resulting homogeneous mixture was used as the catalyst and co-catalyst for oxidizing the para-xylene.
- the reactants were prepared by mixing 120 grams of p-xylene, 600 grams of acetic acid, and 8 wt% water (63 grams of water) to form a reactant mixture. The reaction mixture was mixed with catalyst and charged in the reactor.
- Example 1-4 iron co-catalyst was used in an amount of 50 ppm, based on the total weight of the para-xylene, water, and the acetic acid.
- Comparative Examples A-C the iron co-catalyst was not present.
- Table 2 and for Example 2 and Comparative Example B a lower reaction temperature of 180 °C was used.
- a lesser amount of catalyst was used than in Examples 1-2 and Comparative Examples A-B.
- Example 4 a different amount of bromine was used than in Example 3.
- Example 2 the oxidation reaction at 180 °C produced, e.g., formed, 34.8 mole % less COx than in Example 1 at 190 °C.
- Example 3 exhibited a reduction in COx formation of about 12 mole % as compared to Comparative Example C.
- Example 4 which included a greater amount of bromine as compared to Example 3, exhibited a greater reduction of COx formation as compared to Example 3, and as compared to Comparative Example C (24.2 mole %).
- iron co-catalyst e.g., at 50 ppm Fe and based on the total weight of the dimethyl aromatic compound and the solvent
- COx formation can be reduced.
- the reduction in COx formation can be accompanied by an improvement in selective consumption of para-xylene and acetic acid.
- the presence of iron can also reduce the amount of Cio+ hydrocarbons produced.
- the reduction in formation of Cio+ hydrocarbons will lead to improved terephthalic acid yield.
- iron can allow for a reduction in the total metal content (e.g., cobalt and manganese) in the catalyst and improve product selectivity.
- the reduced total metal content can also reduce the bromine amount used, which helps to reduce corrosion in the production equipment.
- Example 5 Example 5
- Comparative Examples D-H Example. D-H in Table 3 below
- para-xylene was oxidized in the presence of different compositions of catalyst and co catalyst (the co-catalyst was utilized in Example 5 only) in acetic acid.
- the oxidation reactions were carried out in a semi -continuous stirred-tank batch reactor.
- the catalyst included cobalt, manganese, and bromine and the co-catalyst included iron (Example 5 only).
- the catalyst and co-catalyst were prepared by dissolving cobalt acetate, manganese acetate, and iron acetate in 63 grams of water. Hydrobromic acid was then added to the catalyst/co-catalyst (if present) solution. The resulting homogeneous mixture was used as the catalyst and co-catalyst (if present) for oxidizing the para-xylene.
- the reactants were prepared by mixing 120 grams of p-xylene, 600 grams of acetic acid, and 8 wt% water (63 grams of water) to form a reactant mixture. The reaction mixture was mixed with catalyst and charged in the reactor.
- Example 5 Example 5
- iron co-catalyst was used in an amount of 50 ppm, based on the total weight of the para-xylene, water, and the acetic acid. In Comparative Examples D- H, the iron co-catalyst was not present.
- Each weight ratio of cobalt to manganese is provided as Co/Mn.
- Each oxidation reaction time is provided as “Exp. Time” in minutes.
- the COx formation is provided in mole % (mol%), and the terephthalic acid yield is provided in weight percent (“TPA (wt%)”).
- Cio+ hydrocarbons refers to hydrocarbons including 10 or more carbon atoms.
- Example 5 had a total content of cobalt and manganese of 400 ppm (300 ppm cobalt and 100 ppm manganese), and had the formation of the Cio+ hydrocarbons at 0.21 wt% and the formation of the COx at 0.1333 mol%.
- Comparative Example E having a total content of cobalt and manganese of 300 ppm (200 ppm cobalt and 100 ppm manganese)
- the formation of the Cio+ hydrocarbons (2.41 wt%) and the COx (0.1949 mol%) were higher than compared to Comparative Example F, which had a total content of cobalt and manganese of 400 ppm (300 ppm cobalt and 100 ppm manganese), and had the formation of the Cio+ hydrocarbons at 1.13 wt% and the formation of the COx at 0.1759 mol%.
- Comparative Example E having a total content of cobalt and manganese of 300 ppm (200 ppm cobalt and 100 ppm manganese), the formation of the Cio+ hydrocarbons (2.41 wt%) and the COx (0.1949 mol%) were higher than compared to Example 5, which had a total content of cobalt and manganese of 400 ppm (300 ppm cobalt and 100 ppm manganese), and had the formation of the Cio+ hydrocarbons at 0.21 wt% and the formation of the COx at 0.1333 mol%.
- Example 5 the use of a catalyst comprising: (i) bromine in an amount of 160 to 730 ppm (e.g., 342 ppm), (ii) manganese in an amount of 100 to 450 ppm (e.g., 100 ppm), and (iii) cobalt in an amount of 100 to 450 ppm (e.g., 300 ppm) and wherein the cobalt and manganese is present in an amount of greater than 300 to 900 ppm, along with a co-catalyst comprising iron (e.g., 50 ppm), this enables the production of aromatic dicarboxylic acids (e.g., terephthalic acid), while reducing the amount of the undesired 4-carboxybenzaldehyde, Cio+ hydrocarbons and COx, and while advantageously increasing the yield of the aromatic dicarboxylic acid.
- aromatic dicarboxylic acids e.g., terephthalic acid
- the iron co-catalyst can allow for a reduction in the total metal content (e.g., cobalt and manganese) in the catalyst system and improve product selectivity.
- the reduced total metal content can also reduce the bromine amount used, which facilitates reducing corrosion in the reactor.
- a method for oxidizing a dimethyl aromatic compound comprising: reacting the dimethyl aromatic compound and an oxidant in the presence of a catalyst system in a solvent to produce a reaction product comprising an aromatic dicarboxylic acid, such as terephthalic acid; wherein the catalyst system comprises a catalyst and a co-catalyst; wherein the catalyst comprises bromine, cobalt, and manganese; wherein the co-catalyst comprises iron; wherein the iron is present in an amount of 10 to 100 ppm, such as 10 to 90 ppm, more particularly 10 to 50 ppm, based on a total weight of the dimethyl aromatic compound and the solvent; wherein the bromine is present in an amount of 160 to 730 ppm, such as 200 to 400 ppm, more particularly 200 to 330 ppm, based on the total weight of the dimethyl aromatic compound and the solvent; wherein the manganese is present in an amount of 100 to 450 ppm, such as 100 to 400
- Aspect 2 The method of Aspect 1, wherein the dimethyl aromatic compound comprises at least one of para-xylene, meta-xylene, ortho-xylene, or 2,6-dimethylnaphthalene.
- Aspect 3 The method of any one or more of the preceding aspects, wherein the aromatic dicarboxylic acid is present in the reaction product in an amount of equal to or greater than 90 wt%, such as equal to or greater than 92 wt%, more particularly equal to or greater than 94 wt%, based on a total weight of solids in the reaction product.
- Aspect 4 The method of any one or more of the preceding aspects, wherein a total amount of carbon monoxide and carbon dioxide present in the reaction product is reduced by equal to or greater than 5 mole percent, such as equal to or greater than 10 mole percent, more particularly equal to or greater than 15 mole percent, as compared to a total amount of carbon monoxide and carbon dioxide present in a reaction product of a method for oxidizing a dimethyl aromatic compound outside the presence of the iron.
- Aspect 5 The method of any one or more of the preceding aspects, wherein Cio+ hydrocarbons are present in the reaction product in an amount equal to or less than 1.5 wt%, such as equal to or less than 1.0 wt%, more particularly equal to or less than 0.5 wt%, based on a total weight of solids in the reaction product.
- Aspect 6 The method of any one or more of the preceding aspects, wherein the catalyst is present in an amount of greater than 460 to 1,630 ppm, such as 600 to 1,200 ppm, more particularly 600 to 1,130 ppm, based on the total weight of the dimethyl aromatic compound and the solvent.
- Aspect 7 The method of any one or more of the preceding aspects, wherein the co-catalyst further comprises at least one of ruthenium, tantalum, tungsten, or nickel.
- Aspect 8 The method of any one or more of the preceding aspects, wherein the oxidant comprises at least one of hydrogen peroxide, dioxygen, ozone, an anthraquinone, a C2-32 alkyl peroxide, a C2-32 alkyl hydroperoxide, a C2-32 ketone peroxide, a C2-32 diacyl peroxide, a C3-22 diperoxy, a ketal, a C2-32 peroxyester, a C2-32 peroxydicarbonate, a C2-32 peroxy acid, a C6-32 perbenzoic acid, a C2-32 peracid, a periodinane, or a periodate, such as dioxygen.
- the oxidant comprises at least one of hydrogen peroxide, dioxygen, ozone, an anthraquinone, a C2-32 alkyl peroxide, a C2-32 alkyl hydroperoxide, a C2-32 ketone peroxide,
- Aspect 9 The method of any one or more of the preceding aspects, wherein the solvent comprises a C1-7 aliphatic carboxylic acid, such as acetic acid.
- Aspect 10 The method of any one or more of the preceding aspects, wherein the solvent further comprises water.
- Aspect 11 The method of any one or more of the preceding aspects, wherein a weight ratio of solvent to dimethyl aromatic compound is in a range of 15: 1 to 1: 1, such as 10: 1 to 1: 1, more particularly 5 : 1 to 1: 1.
- Aspect 12 The method of any one or more of the preceding aspects, wherein a molar ratio of bromine to cobalt and manganese is in a range of 0.3:1 to 3: 1, such as 0.3: 1 to 2: 1, more particularly 0.3 : 1 to 1: 1.
- Aspect 13 The method of any one or more of the preceding aspects, wherein a weight ratio of iron to the total amount of cobalt and manganese is in a range of 0.05: 1 to 0.25: 1, such as 0.05: 1 to 0.20: 1, more particularly 0.05: 1 to 0.15: 1.
- Aspect 14 The method of any one or more of the preceding aspects, wherein the reacting is at a temperature in a range of 170 °C to 200 °C, such as 180 °C to 200 °C, more particularly 190 °C to 200 °C.
- Aspect 15 The method of any one or more of the preceding aspects, wherein the reacting is at a pressure in a range of 1 to 1.8 MegaPascals, such as 1 to 1.7 MegaPascals, more particularly 1 to 1.6 MegaPascals.
- Aspect 16 The method of any one or more of the preceding aspects, further comprising separating the solvent, the catalyst, and the co-catalyst from the reaction product, and recycling the solvent, the catalyst, and the co-catalyst separated from the reaction product to a reactor in which the dimethyl aromatic compound and the oxidant are reacted to produce the reaction product.
- Aspect 17 The method of any one or more of the preceding aspects, further comprising reacting the aromatic dicarboxylic acid and hydrogen in the presence of a hydrogenation catalyst.
- Aspect 18 The method of any one or more of the preceding aspects, wherein the catalyst system comprises no added titanium, chromium, vanadium, molybdenum, tin and zirconium.
- compositions, methods, and articles can alternatively comprise, consist of, or consist essentially of, any appropriate components or steps herein disclosed.
- the compositions, methods, and articles can additionally, or alternatively, be formulated so as to be devoid, or substantially free, of any steps, components, materials, ingredients, adjuvants, or species that are otherwise not necessary to the achievement of the function or objectives of the compositions, methods, and articles.
- test standards are the most recent standard in effect as of the filing date of this application, or, if priority is claimed, the filing date of the earliest priority application in which the test standard appears.
Abstract
Description
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CN202180033014.1A CN115551826A (en) | 2020-06-16 | 2021-06-16 | Process for producing aromatic dicarboxylic acids using iron promoters |
GB2300329.6A GB2612472B (en) | 2020-06-16 | 2021-06-16 | Method for producing aromatic dicarboxylic acid using iron co-catalyst |
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WO2024003044A3 (en) * | 2022-06-30 | 2024-04-04 | Sabic Global Technologies B.V. | Catalyst system for preparing terephthalic acid |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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GB1542231A (en) * | 1976-11-08 | 1979-03-14 | Toray Industries | Process for producing fibre grade terephthalic acid |
US4754062A (en) | 1985-05-24 | 1988-06-28 | Amoco Corporation | Iron-enhanced selectivity of heavy metal-bromine catalysis in the oxidation of polyalkylaromatics |
US5453538A (en) | 1994-02-14 | 1995-09-26 | Amoco Corporation | Process for the manufacture of aromatic dicarboxylic acids utilizing cerium to facilitate a low bromine to metals catalyst ratio |
WO2000037406A1 (en) * | 1998-12-22 | 2000-06-29 | Samsung General Chemicals Co., Ltd. | Method of producing aromatic carboxylic acids |
WO2020144517A1 (en) * | 2019-01-08 | 2020-07-16 | Sabic Global Technologies B.V. | Method for producing dicarboxylic acid using cerium co-catalyst |
-
2021
- 2021-06-16 KR KR1020227039173A patent/KR20230023618A/en unknown
- 2021-06-16 CN CN202180033014.1A patent/CN115551826A/en active Pending
- 2021-06-16 WO PCT/IB2021/055325 patent/WO2021255671A1/en active Application Filing
- 2021-06-16 GB GB2300329.6A patent/GB2612472B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1542231A (en) * | 1976-11-08 | 1979-03-14 | Toray Industries | Process for producing fibre grade terephthalic acid |
US4754062A (en) | 1985-05-24 | 1988-06-28 | Amoco Corporation | Iron-enhanced selectivity of heavy metal-bromine catalysis in the oxidation of polyalkylaromatics |
US5453538A (en) | 1994-02-14 | 1995-09-26 | Amoco Corporation | Process for the manufacture of aromatic dicarboxylic acids utilizing cerium to facilitate a low bromine to metals catalyst ratio |
WO2000037406A1 (en) * | 1998-12-22 | 2000-06-29 | Samsung General Chemicals Co., Ltd. | Method of producing aromatic carboxylic acids |
WO2020144517A1 (en) * | 2019-01-08 | 2020-07-16 | Sabic Global Technologies B.V. | Method for producing dicarboxylic acid using cerium co-catalyst |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2024003044A3 (en) * | 2022-06-30 | 2024-04-04 | Sabic Global Technologies B.V. | Catalyst system for preparing terephthalic acid |
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GB2612472B (en) | 2024-04-24 |
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