CN112574035A - Catalyst and method for synthesizing methyl acetate/acetic acid - Google Patents
Catalyst and method for synthesizing methyl acetate/acetic acid Download PDFInfo
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 title claims abstract description 28
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims description 22
- 230000002194 synthesizing effect Effects 0.000 title description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims abstract description 102
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000002808 molecular sieve Substances 0.000 claims abstract description 34
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 33
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000006315 carbonylation Effects 0.000 claims abstract description 14
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001307 helium Substances 0.000 claims abstract description 5
- 229910052734 helium Inorganic materials 0.000 claims abstract description 5
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract 3
- 229910052697 platinum Inorganic materials 0.000 claims abstract 3
- 229910052709 silver Inorganic materials 0.000 claims abstract 3
- 229910001428 transition metal ion Inorganic materials 0.000 claims abstract 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052593 corundum Inorganic materials 0.000 claims abstract 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract 2
- 239000012298 atmosphere Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 8
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 6
- 239000010457 zeolite Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims 7
- 150000003624 transition metals Chemical class 0.000 claims 6
- 238000005342 ion exchange Methods 0.000 claims 3
- -1 HNO)3 Chemical class 0.000 claims 1
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- 125000004429 atom Chemical group 0.000 claims 1
- 230000008021 deposition Effects 0.000 claims 1
- 238000005470 impregnation Methods 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 11
- 238000003756 stirring Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910001657 ferrierite group Inorganic materials 0.000 description 3
- 239000003502 gasoline Substances 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052680 mordenite Inorganic materials 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
- C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
Abstract
The invention provides a catalyst for preparing methyl acetate/acetic acid by carbonylation of methanol/dimethyl ether. The catalyst has ten-membered ring and eight-membered ring channel structure, and the skeleton topological structure of the catalyst is SZR type by International molecular Sieve Association (IZA), and SiO of the molecular sieve2/Al2O3The ratio is 8-40; the molecular sieve catalyst is in the hydrogen form; the hydrogen form isThe sub-sieve catalyst can be modified by transition metal ions (such as Cu, Ag, Pt and the like). The methyl acetate/acetic acid synthesis method comprises the following steps: introducing the mixed gas of methanol/dimethyl ether, carbon monoxide and helium or hydrogen into a reactor filled with a catalyst for reaction to obtain methyl acetate/acetic acid. The catalyst shows higher activity and better selectivity for dimethyl ether carbonylation reaction, and has better stability in a long-time reaction process.
Description
Technical Field
The invention relates to the field of catalytic chemistry, in particular to a method for preparing methyl acetate by methanol/dimethyl ether carbonylation, which adopts a hydrogen type SUZ-4 molecular sieve with an SZR topological structure to carry out carbonylation reaction.
Background
With the rapid development of modern industry, the contradiction between energy supply and demand is more and more prominent. As a country with large energy consumption, China also has energy shortage, so that alternative energy needs to be searched. Ethanol is a good gasoline additive recognized in the world as a clean energy source, improves the octane number and the oxygen content of gasoline, effectively promotes the full combustion of the gasoline, reduces the emission of CO and CH in automobile exhaust, and is also an important basic chemical. Currently, annual production of ethanol worldwide is about one hundred million tons, produced mainly by corn and sugar cane in the united states and brazil. The annual output of fuel ethanol in China is only 250 ten thousand tons, and grains are mainly utilized and the national subsidy is relied on for production. The use of fossil resources for ethanol production has long been a goal and challenge of worldwide efforts. However, according to the national conditions, a plurality of limiting factors exist in the preparation of ethanol by using grains as raw materials, and the fuel ethanol in China is developed more and more in the future and is a non-grain route.
From coal resources, the production of ethanol by synthesis gas is an important direction for the development of novel coal chemical industry in China, and has wide market prospect. The method has the advantages of clean utilization of coal resources, relieving the contradiction of shortage of petroleum resources, improving the energy safety of China, and having important strategic significance and profound influence. At present, the process routes for preparing ethanol from coal are mainly divided into 2 types: firstly, ethanol is directly prepared from synthesis gas, but a noble metal rhodium catalyst is needed, the cost of the catalyst is high, and the yield of rhodium is limited; the other is that the synthetic gas is hydrogenated to prepare the ethanol through the acetic acid, the synthetic gas is firstly subjected to the methanol liquid phase carbonylation to prepare the acetic acid, and then is hydrogenated to synthesize the ethanol. The process of the route is mature, but the equipment needs special alloy with corrosion resistance and has higher cost. The method is an energy-saving and efficient ethanol preparation path, and the success in the first coal-based ethanol preparation demonstration project in 2017 in China marks that the ethanol preparation from coal is realized, and the large-scale popularization of ethanol gasoline in China is possible.
The Enrique igleia research group (angle. chem. int. ed.45(2006)10,1617-1620, j.catal.245(2007),110, j.am. chem. soc.129(2007),4919) performed the carbonylation of dimethyl ether in molecular sieve systems having 8-and 12-or 10-membered rings, such as Mordenite (Mordenite) and Ferrierite (Ferrierite), with the result that the active site was believed to be located on the B acid active center of the 8-membered ring. The selectivity of methyl acetate is very good and reaches 99 percent. Of these, ferrierite exhibits high stability but lower conversion than mordenite. Because the molecular sieve catalyst does not need to load noble metal, the production cost of methyl acetate is effectively reduced, and the molecular sieve catalyst becomes a research hotspot for preparing methyl acetate by a dimethyl ether carbonylation method.
Disclosure of Invention
The invention mainly utilizes the SUZ-4 zeolite molecular sieve with the topological structure of SZR to carry out methanol/dimethyl ether carbonylation reaction test, the molecular sieve with the SZR structure has pore canal structures of 8 rings and 10 rings, and shows better stability and higher activity in continuous reaction.
In order to achieve the purpose, the zeolite molecular sieve is hydrogen type SUZ-4, the gas is methanol/dimethyl ether, CO and the mixture of CO and helium or hydrogen in a certain proportion, and the hydrogen type SUZ-4 is activated.
The silicon-aluminum atomic ratio of the hydrogen SUZ-4 is 4-20: 1.
the temperature of the methanol/dimethyl ether carbonylation reaction is 150-300 ℃, and the pressure of the methanol/dimethyl ether carbonylation reaction is 0.5-10 MPa.
The space velocity of the mixed gas in the methanol/dimethyl ether carbonylation reaction is 800-10000 mL/(g.h).
The invention provides a method for preparing methyl acetate by carbonylation of methanol/dimethyl ether, which comprises the following steps: and carrying out dimethyl ether carbonylation on the mixed gas of methanol/dimethyl ether, carbon monoxide and helium or hydrogen through an activated hydrogen type SUZ-4 zeolite molecular sieve to obtain methyl acetate, wherein the hydrogen type SUZ-4 has an SZR topological structure. The invention takes a hydrogen SZU-4 zeolite molecular sieve with an SZR topological structure as a catalyst, the catalyst has pore canal structures of 8 rings and 10 rings, the silicon-aluminum ratio is lower, and the catalyst can keep higher activity for a long time in the dimethyl ether carbonylation reaction process, thereby realizing the continuity and stability of preparing acetic acid/methyl acetate by methanol/dimethyl ether carbonylation and simultaneously having higher activity.
Drawings
FIG. 1 is a graph showing the results of detection of the product of the reaction process of example 1;
FIG. 2 is a graph showing the results of detection of the products of the reaction process of example 2;
FIG. 3 is a graph showing the results of detection of the products of the reaction process of example 3;
FIG. 4 is a graph showing the results of detection of the product of the reaction process of example 4;
FIG. 5 is a graph showing the results of detection of the product of the reaction process of example 5;
FIG. 6 is a graph showing the results of detection of the products of the reaction process of example 6;
FIG. 7 is a graph showing the results of detection of the reaction product of example 7.
Detailed Description
The invention provides a method for preparing methyl acetate by carbonylation of methanol/dimethyl ether, which comprises the following steps: dimethyl ether (abbreviated as DME), carbon monoxide and helium mixed gas are subjected to dimethyl ether carbonylation reaction through hydrogen type SUZ-4 to obtain methyl acetate (abbreviated as MA), and the hydrogen type SUZ-4 zeolite has an SZR topological structure.
[1] SUZ-4 used in the examples was synthesized using TEAOH as a templating agent. The specific synthesis steps are as follows: KOH is used as an alkali source, aluminum powder is used as an aluminum source, tetraethylammonium hydroxide (TEAOH) is used as a template agent and silica sol is used as a silicon source, and the materials are mixed together and hydrothermally crystallized for a certain time.
[2] The SUZ-4 molecular sieves used in the examples had a silicon to aluminum atomic ratio of 8 or 10.
[3]DME carbonylation mixtures used in the examplesThe volume ratio of the synthesized gas is DME/CO/H25/50/45 or DME/CO/Ar/He 5/50/2.5/42.5; the methanol carbonylation mixture ratio was 16.7/83.3 MeOH/CO.
[4] The carbonylation temperature of dimethyl ether adopted in the embodiment is 210-260 ℃, and the reaction pressure is 1-2 MPa.
[5] The gas space velocity of dimethyl ether carbonylation reaction adopted in the embodiment is 800-10000 mL/(g.h).
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
[1]3g of KOH and 0.45g of Al powder were mixed and 35g H was added2O, stirring to dissolve, then adding 5.8g of TEAOH (35 wt%), continuing stirring, finally adding 20g of silica sol (40 wt%), stirring at room temperature for 3h, and crystallizing at 150 ℃ for 1 day.
[2]Roasting the freshly synthesized SUZ-4 in the step 1 in the air atmosphere, roasting at 550 ℃ for 10h to obtain K-SUZ-4(1), and then adding a certain amount of K-SUZ-4 into 1mol/L NH4NO3Mass of molecular sieves and NH in solution4NO3The volume ratio of the solution is 1: 50. exchanging for 6h at the temperature of 100 ℃, filtering and washing, and repeating for three times to obtain NH4-SUZ-4 (1). Then roasting at 540 ℃ for 5H in an air atmosphere to obtain H-SUZ-4 (1).
[3] And (3) performing dimethyl ether carbonylation reaction on the HSUZ-4 obtained in the step (2) in a fixed bed reactor, firstly activating for 1h at 500 ℃ under a nitrogen atmosphere, and then reacting at 220 ℃, wherein the volume composition of reaction gas is DME/CO/Ar/He which is 5/50/2.5/42.5, the pressure of a bed layer is controlled to be 2MPa, and the space velocity of mixed gas is controlled to be 1250 ml/(g.h).
[4] The reaction process of the preparation method of this example is detected, and the obtained result is shown in fig. 1, in the preparation method provided in this example, the initial conversion rate of dimethyl ether can reach 2.5%, the initial maximum conversion rate is 22.3%, the initial selectivity of methyl acetate can reach 97%, after 20 hours of reaction, the conversion rate of dimethyl ether can still be maintained at 21.5%, and the selectivity of methyl acetate is always over 97%.
Example 2
[1] 3g of KOH and 0.45g of Al powder are mixed, 35g H2O is added and stirred until dissolved, then 5.8g of TEAOH (35%) is added and stirring is continued, finally 20g of silica sol (40%) is added and stirring is carried out for 3h at room temperature, and crystallization is carried out for 3 days at 150 ℃.
[2]Roasting the freshly synthesized SUZ-4 in the step 1 in the air atmosphere, roasting at 550 ℃ for 10h to obtain K-SUZ-4(3), and then adding a certain amount of K-SUZ-4 into 1mol/L NH4NO3Mass of molecular sieves and NH in solution4NO3The volume ratio of the solution is 1: 50. exchanging for 6h at the temperature of 100 ℃, filtering and washing, and repeating for three times to obtain NH4-SUZ-4 (3). Then roasting at 540 ℃ for 5H in an air atmosphere to obtain H-SUZ-4 (3).
[3] And (3) performing dimethyl ether carbonylation reaction on the HSUZ-4(3) obtained in the step (2) in a fixed bed reactor, firstly activating for 1h at 500 ℃ under a nitrogen atmosphere, then reacting at 220 ℃, wherein the reaction gas product is DME/CO/Ar/He (5/50/2.5/42.5), the bed layer pressure is controlled to be 2MPa, and the space velocity of mixed gas is 1250 ml/(g.h).
The reaction process of the preparation method of this embodiment is detected, and the obtained result is shown in fig. 2, in the preparation method provided by this embodiment, the initial conversion rate of dimethyl ether can reach 2.5%, the highest conversion rate can reach 22%, the initial selectivity of methyl acetate can reach 97%, after 20 hours of reaction, the conversion rate of dimethyl ether can still be maintained at 21.9%, and the selectivity of methyl acetate is always over 97%.
Example 3
[1]3g of KOH and 0.45g of Al powder were mixed and 35g H was added2O, stirring to dissolve, then adding 5.8g of TEAOH (35%), continuing stirring, finally adding 20g of silica sol (40%), stirring at room temperature for 3h, and crystallizing at 150 ℃ for 5 days.
[2]Roasting the freshly synthesized SUZ-4 in the step 1 in the air atmosphere, roasting at 550 ℃ for 10h to obtain K-SUZ-4(5), and then taking a certain amount of K-SUZ-4 to 1mol/L NH4NO3Mass of molecular sieves and NH in solution4NO3The volume ratio of the solution is 1: 50. exchanging for 6h at the temperature of 100 ℃, filtering and washing, and repeating for three times to obtain NH4-SUZ-4 (5). Then roasting at 540 ℃ for 5H in an air atmosphere to obtain H-SUZ-4 (5).
[3] And (3) performing dimethyl ether carbonylation reaction on the HSUZ-4(5) obtained in the step (2) in a fixed bed reactor, activating for 1h at 500 ℃ under a nitrogen atmosphere, then reacting at 220 ℃, wherein the reaction gas product is DME/CO/Ar/He (5/50/2.5/42.5), the bed layer pressure is controlled to be 2MPa, and the space velocity of mixed gas is 1250 ml/(g.h). The reaction process of the preparation method of this example is detected, and the obtained result is shown in fig. 3, in the preparation method provided in this example, the initial conversion rate of dimethyl ether can reach 2.5%, the initial maximum conversion rate is 23.4%, the initial selectivity of methyl acetate can reach 97%, after 20 hours of reaction, the conversion rate of dimethyl ether can still be maintained at 22.6%, and the selectivity of methyl acetate is always over 97%.
Example 4
[1] The H-SUZ-4(5) prepared in example 3 was used for methanol carbonylation in a fixed bed reactor, the specific steps were as follows: introducing pure CO into methanol liquid at the temperature of 24 ℃ to carry out mixed gas reaction in a bubbling mode, controlling the reaction temperature to be 220 ℃, controlling the bed pressure to be 2MPa, controlling the reaction space velocity to be 2500 ml/(g.h), and after the reaction is carried out for 26h, carrying out temperature programming to 240 ℃ to continue the reaction. The results of examining the reaction process of the preparation method of this example are shown in fig. 4, and in the preparation method provided in this example, at 220 ℃, the initial conversion rate of methanol can reach 87.6%, the maximum conversion rate is 88.5%, the maximum selectivity of methyl acetate can reach 25%, the selectivity of acetic acid is about 3%, and the conversion rate of dimethyl ether can still be maintained at the same level after 24 hours of reaction. When the temperature is increased to 240 ℃, the conversion rate is slightly increased, the conversion rate is increased from 88.5 percent to 90.4 percent and is stabilized at 89.8 percent, the selectivity of the methyl acetate is obviously increased from 25 percent to 47 percent at most and is slowly reduced, and the selectivity of the methyl acetate is still 40 percent after the reaction is carried out for 18 hours at 240 ℃; the selectivity of acetic acid is improved to 8-9%.
Example 5
[1] 3g of KOH and 0.45g of Al powder are mixed, 35g H2O is added and stirred until dissolved, then 5.8g of TEAOH (35%) is added and stirring is continued, finally 20g of silica sol (40%) is added and stirred for 3h at room temperature and crystallized for 7 days at 150 ℃.
[2]Roasting the freshly synthesized SUZ-4 in the step 1 in the air atmosphere, roasting at 550 ℃ for 10h to obtain K-SUZ-4(7), and then adding a certain amount of K-SUZ-4 into 1mol/L NH4NO3Mass of molecular sieves and NH in solution4NO3The volume ratio of the solution is 1: 50. exchanging for 6h at the temperature of 100 ℃, filtering and washing, and repeating for three times to obtain NH4-SUZ-4 (7). Then roasting at 540 ℃ for 5H in an air atmosphere to obtain H-SUZ-4 (7).
[3]Taking the HSUZ-4(7) obtained in the step 2 to carry out dimethyl ether carbonylation reaction in a fixed bed reactor, firstly activating for 1H at 500 ℃ under the nitrogen atmosphere, then reacting at 260 ℃, controlling the bed pressure at 2MPa, and controlling the volume ratio of reaction mixed gas to be 5% DME/50% CO/45% H2The space velocity of the mixed gas is controlled at 1250 ml/(g.h).
The reaction process of the preparation method of the embodiment is detected, and the obtained result is shown in fig. 5, in the preparation method provided by the embodiment, after the induction period, the conversion rate of dimethyl ether can reach 26%, the selectivity of methyl acetate can reach 90%, the reaction starts to be slowly inactivated along with the reaction, the conversion rate of dimethyl ether is reduced to 15.4% after 8h, but the catalyst can be reused after regeneration.
Example 6
[1]An amount of K-SUZ-4(3) from example 2 was added to 4mol/L HNO3Molecular sieve mass and HNO in solution3The volume ratio of the solution is 1: 50. exchanging for 6h at the temperature of 100 ℃, filtering and washing, and repeating for three times. Then roasting at 540 ℃ for 5H in the air atmosphere to obtain H-SUZ-4 (HNO)3)。
[2]Taking the H-SUZ-4 (HNO) obtained in the step 13) Performing dimethyl ether carbonylation reaction in a fixed bed reactor, firstly activating for 1h at 500 ℃ under the nitrogen atmosphere, then reacting at 220 ℃,the volume ratio of the reaction mixed gas is DME/CO/Ar/He which is 5/50/2.5/42.5, the bed pressure is controlled at 2MPa, and the space velocity of the reaction mixed gas is controlled at 1250 ml/(g.h).
The reaction process of the preparation method of this embodiment is detected, and the obtained result is shown in fig. 6, in the preparation method provided in this embodiment, after the induction period, the conversion rate of dimethyl ether can reach 23.4%, and the selectivity of methyl acetate can reach 97%, along with the progress of the reaction, the reaction starts to slowly deactivate, and after 24 hours, the conversion rate of dimethyl ether is reduced to 21.8%, but the catalyst can be reused after regeneration.
Example 7
[1] The 2g H-SUZ-4(7) obtained in example 5 was added to 20ml of 0.03mol/L Cu salt solution at 80 ℃ for 2H to obtain Cu/H-SUZ-4 (7).
[2]Taking the Cu/H-SUZ-4(7) obtained in the step 1 into a fixed bed reactor to carry out dimethyl ether carbonylation reaction, firstly raising the temperature to 100 ℃ at 5 ℃/min under the nitrogen atmosphere, then raising the temperature to 260 ℃ at 1 ℃/min, cutting into reaction gas, reacting at 260 ℃, wherein the volume ratio of the reaction mixed gas is 5% DME/50% CO/45% H2The bed pressure is controlled at 2MPa, and the space velocity of the reaction mixture gas is controlled at 1250 ml/(g.h).
The reaction process of the preparation method of the embodiment is detected, and the obtained result is shown in fig. 7, in the preparation method provided by the embodiment, after an induction period, the conversion rate of dimethyl ether can reach 39.5%, and the selectivity of methyl acetate can reach 90.5%, along with the reaction, the reaction starts to be rapidly inactivated, and after 4 hours, the conversion rate of dimethyl ether is reduced to 13.8%, but the catalyst can be reused after regeneration.
The catalyst shows higher activity and better selectivity for dimethyl ether carbonylation reaction, and has better stability in a long-time reaction process.
Claims (10)
1. A process for the carbonylation of methanol and/or dimethyl ether to produce methyl acetate and/or acetic acid comprising the steps of:
reacting methanol and/or dimethyl ether with mixed gas containing carbon monoxide gas by using an activated hydrogen type SUZ-4 molecular sieve or a transition metal ion modified hydrogen type SUZ-4 molecular sieve as a catalyst to prepare methyl acetate and/or acetic acid, wherein the SUZ-4 zeolite molecular sieve has an SZR topological structure; the gas containing carbon monoxide is carbon monoxide or the mixture of carbon monoxide and other gases, and the other gases are one or more than two of Ar, helium or hydrogen.
2. The method according to claim 1, wherein the reaction is carried out by using a fixed bed reactor, the temperature of the methanol and/or dimethyl ether carbonylation reaction is 150-300 ℃, and the pressure of the methanol and/or dimethyl ether carbonylation reaction is 0.5-10 MPa.
3. The method according to claim 2, wherein the mixed gas space velocity of the methanol and/or dimethyl ether carbonylation reaction is 800-10000 mL/(g-h).
4. A process according to claim 1, 2 or 3, wherein the carbon monoxide-containing gas has a carbon monoxide content of 50-100% by volume.
5. The method of claim 1, wherein: the activating atmosphere of the hydrogen type SUZ-4 molecular sieve catalyst is nitrogen atmosphere, the activating temperature is 350-550 ℃, and the activating time is 0.5-6 h.
6. The method according to claim 1, wherein the hydrogen-type SUZ-4 molecular sieve has a silicon-aluminum atomic ratio of 4 to 20: 1.
7. The catalyst according to claim 1, wherein the hydrogen-type SUZ-4 molecular sieve modified by transition metal comprises one or more of but not limited to Cu, Ag, Pt, etc.; the mass content of the transition metal in the hydrogen type SUZ-4 molecular sieve catalyst modified by the transition metal is 0.1-5%.
8. A catalyst for use in the process of any one of claims 1 to 7The catalyst is characterized in that the catalyst has a ten-membered ring and/or eight-membered ring channel structure, the framework topological structure of the catalyst is determined as SZR type by International molecular Sieve Association (IZA), and the SiO of the molecular sieve2/Al2O3The molar ratio is 8-40, and preferably, the atomic ratio of silicon to aluminum is 4-20: 1; the molecular sieve catalyst is in the hydrogen form.
9. The method according to claim 8, wherein the SUZ-4 molecular sieve is in hydrogen form, and the method for obtaining the hydrogen SUZ-4 molecular sieve is performed by using inorganic acid (such as HNO)3，HCl，H3PO4One or more than two of them) directly treating one or more than two of K type, Na type or Na/K mixed SUZ molecular sieves;
alternatively, ammonium salts (e.g., NH) may also be used4NO3、NH4One or more than two of Cl) is subjected to ion exchange and then is heated and roasted to be converted into the hydrogen type molecular sieve, wherein the roasting temperature is 400-540 ℃, and the time is 3-20 h.
10. The catalyst of claim 8 or 9, wherein the hydrogen-type molecular sieve catalyst can be modified with transition metal ions, the transition metal elements include but are not limited to one or more of Cu, Ag, Pt, etc.; the mass content of the transition metal in the hydrogen type SUZ-4 molecular sieve catalyst modified by the transition metal is 0.1-5%; the supporting method of the transition metal includes, but is not limited to, one or more of impregnation, ion exchange, and atom deposition, and the ion exchange method is preferred.
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