ay United States Patent 1US010287233B2 ao) Patent No: US 10,287,233 B2 Liu et al. (45) Date of Patent: *May 14, 2019 eens S a eae Oe ene Gee te Set ey opens Youming Ni, Shabekou Dalian (CN); &X ieee ‘Zoongmin Li & ro1vosses es ie coaseaes une pee This patent is subject to a terminal dis- ‘Methyl Acetate with Nickel-Active Carbon Catalysts”, Applied (21) Appl. No. 18/743,936 ‘Wegman, Richard W., “Vapour Phase Carbonylation of Methanol or 2) porta mee 8201 Dore og ert em foe ao G0) Foreign Application Priority Data Assistant Examiner — Mark R Luderer et ane BEC. carcezmcorson.a0u mem Tacaesaen nora ee here ce BOLI 2917019; BO) 29/7438; BOL 29/7638; BOL) 2229/186; BOLI 2220/42; COTE 6737; COTE 69114 ‘See application file for complete search history production. 16 Claims, No DrawingsUS 10,287,233 B2 Page 2 66) References Cited (OTHER PUBLICATIONS ‘Cheung et al "Site sequiemens and elementary steps in dimethy «ther caronyltion catalyzed by acidic zeolites, ural of Catal) fis, Oct 27,2006, pp 110 to 123, vol 248, Elsevier, Bhan etal. “Specieity of Ses within EightMembere Ring Zest Chanel for Carbonyation of Methyl to Aesyle 1A. (Chem. Soe 2007p. 4919 to 4924, vol 129. American Chemie Soviet Donghti, Wang, “Reseach om application of Co-exystlization “Molecular Sieve Cala in the Reacon of DME Castonsation 9 McONC™, Chomical Production tod Technology, Ape 3201. pp iets i al, “Activity enhancement of ZSM38 in dimethyl ber ‘actonytion eatin rough alalise medications” RSC Advance, a9, 2013, pp 16549 t0 T6SS7, vol 3. The Royal Society of Chemisty Liu et al, "Dimethyl Ether Cbonyation to Methyl Acetate over zsMeess", Cat. Latt, Ju 22.2010, pp. 3349 37, vol 19, Springer Sconces Busines Meta LLC * cited by examinerUS 10,287,233 B2 PI METHOD PARATION, PRIORITIES AND CROSS REFERENCES. This Application claims priority from International Appl cation No, PCTICN2O15/096683 filed on 8 Dec. 2018 ad Chinese Application No. 2015104270907 filed on 20 Jul 2015; de teachings of each of which are incorpornted herein by reference in thei entirety. TECHNICAL FIELD The present invention refers to a method for producing methyl acetate and the derivatives theo by earbonyTation of dimethyl ether BACKGROUND Accompanied with the apd development of the modern industry the confiction between supplying and demanding ‘of energy has become increasingly acute. Cina is major energy constmer and meanwhile a major country of energy shortage with an urgent desire for searching replaceable ‘energy sources Fuhanol s clean enemy source witha good ‘ual solubility which can he used as blending component added into gasoline, 10 partially replace gasoline and Jimprove the ‘octane umber and the oxygen content of ison Itean also promote gasoline humming sulficieally find decrease the emission of eatbon monoxide and kyr eathons in vehicle exhaust, AS a patil replacement of Vehicle fuel, ethanol may make the vehicle fuel ia China more diversified. Currently, in China cereals, especially coms, has mostly been wed as raw materi to manlc- ture fel ethanol. Chis has become the thin largest country ff ethanol producing and consuming, alter Breil and ‘America However, according 1 Chinese national condition, there are many unfavorable factors using ceteals as raw ‘material o produce ethanol. Inthe Future, non-ceeal routes Toe producing ethanol will he developed preferably in Chins ‘Started with coal resoures, producing thanol via syngas js an important direction to develope coal chemical engi noering industry in China with a broad market prospect. It has great strategie meanings and farreaching impacts on clean utilization of coal resources, relieving the pressure of | lacking oil resourees and enhancing energy sori in our country. Currently, there ae mainly tWo process routes of preparing ethanol from coal, one of which is preparing ethanol from syngas directly. However, a previous meta, thodum, is needed to serve as the catalyst in this rout, 50 the cost of the catalyst is relatively high, Moreover, the ‘wpa of shodium is fimited, The other oute is preparing ‘ethanol fom syngas through hydrogenation of scetie aed i ‘hich acetic acid is preformed by liquid phase methanol carbonylation from the syngss, and then converts to ethanol by hydrogenation, The second route is mature, bu the device Used in this route needa o he made of special allay Which is amticorrsive, so the cost is high Using dimethyl ether os ew material, methy acetate ca be direty symthoized by earbonylation of dimethyl ether, ‘and methyl acetate can be hydrogenated. to. ethanol Ahugh the route i stil in research sige, i 8 brand new route with great application prospect. In 1983, Fujimoto (ppl Catal 1983, 7 (3), 361-368) used NiiAe a catalyst 10 ty out a gaesolid phase reaction of dimethyl ther ‘atbonylation, It was discovered that dimethyl ether can react wih CO to generate methyl aetate when the molar 2 ratio of COPDME isin range from 2104, with selectivity jn range from 80% to 92% and the highest yield of 20%. In 1994, Weyman (J Chem Soe Chem Comm 1994, (8), 947-948) carried out a dimethyl ether carbonylation reaction using heteropolyacid RAW, PO/SiO; as the eatalyst. The Yiekd of methyl acetate was 16% and nearly no other side Pprxducts were generated. In 2002, Russian researchers, Notkova_and her colleagues (Catalysis Leners 2002, 80 G-4), 175-179) used a cesium phosphotungstate modified Rh aS catalyst to cary out the earbonylation reaction of dimethyl ether and the rection rte isan onder of magnitude higher than the Weyman's reaction using RhW,,PO,SiO, a8 catalyst In 2006, Enrique Iglesia's research group in Berkeley (Anger: Chem, nt. Fd, 43(2006) 10, 1617-1620, J. Catal 243 (2007) 110, Jn, Chem. Sac. 129 (2007) 4919) carried ‘out dimethyl ether carbonylation on the molecular sieves with 8 membered ring and 12 membered ring or 10 mem: bere ring, such as Morente and Ferieite As a result it ‘was considered that the earbonglation reaction happencs on the B ocid active center of 8 membered ring The selectivity fof methyl acetate was quite good, reaching 99%, but the fctivty of dimethyl ether carbonylation is very Ko. American application US2007238897 dselosed that using moleculae sieves with 8 membered ring pore svete, such as MOR, FER and OFF, as eatalyst for the carbo: ylation of ethers, the pore sizeof the 8 membered ring should be larger than 0.25x0.36 am. Using mondenite as catalyst under the reaction conditions of 168° Cand 1 MPa, spacetime yield of O.163-MeOAc(e-Cathy! was achieved. WO2008132450AI (2008) disclosed a MOR eata- Iyst modified by copper and silver, whose performance is obviously beter than unmoved MOR catalyst, on reaction conditions of hydrogen atmosphere and temperature ranging Tom 250° C. to 350° €. WO20H0SIO99AT disclosed that the carbonylation periormance of MOR catalyst with smaller grains is beter than MOR catalyst with bigger sins, WO20I0130972A2 disclosed an MOR catalyst treated by desilication and dealuminzation, and the aetvity and the reaction stability of the MOR catalyst can be ‘gnileanly enhanced by an optimized combination of acid tesvtment and alka teatment. Moroover, CNIO3S96760 disclosed a method for preparing methyl acetate by carbo- ylation of dimethyl ether in which mordenite andor fer Fierite were wed as the caalyst. CNIOI903325A disclosed a carbonylation process of preparing acetic acid andor ‘methy> acetate in which the molecular sieves with MOR Framework structure were used as the eatalyst. Waa Doa uhui (Application of a coerysalization molecular sieve catalyst in preparing methy! acetate by carbonylation of dimethyl ether’, Chenical Production and Techniques (2013), No. 3, Vl 20. 14-18) disclosed an application of a coeeysalizaion molecular sieve catalyst" in preparing iets] acetate by earbonylation of dimethyl ether, in Which the catalyst was a cocrystllization molecular sieve contain- ing 2 phases of BEAMOR, Ane coerytallization molecular seve vomiting 2 phases of EMT/FAU was mentioned in the fist paragraph, without being wed for carbonation of | dimethyl ether 19 methyl acetate. CN102080018A disclosed the resction data of dimethyl ether carbnylation on a coe ‘ystallization molecular sieve of rare eath ZSM-35/MOR, The results show thatthe activity and stability oF eoerystal- Tiztion molecular seve was significantly beter than ZSM- 35 catalyst, and the stability of cocrystalization molecular eve war’ significantly better than MOR catalyst. Xu Longya and his colleagues (RSC Adv, 2013, 316840- 16587) also reported the reaction propedies of ZSM-35.US 10,287,233 B2 3 treated by alkali in carbonylation of dimethyl ether The results show tat after being treated by alkali, 2SM-3S has an apparent mesoporous structure, enhancing the dilfasion fells of reactants and prodvets on the catalyst. and the Stability and activity ofthe catalyst was improved, InCNIOI613274A. pyridine organic antines were used 10 modify mordenite molecular sieve catalyst, and it was Aiscovered that the modiieaion of molecular sieve ean dramatically enkance the stability of catalyst. The percent conversion of dimethyl ether was in a range from 10% 10 60%, and the selectivity of methyl acetate was over 99%. “Moreover. the activity ofthe catalyst remsined stable ater reacting for 48h, Shen Wenjie (Catal. Lert 2010, 139.33 537) and his colleagues made a research on preparing meth ‘acetate by earhonylation of dimethyl ther, comparing the rection activity on MOR and. ZSM-35 catalyst. It was ‘iscovered that ZSM.8S molecular sieve has better eeacton Stability and products selectivity, and under the reaction conditions of 250 (2 1 MPa, DMBICON e-5/50°25/ 425 and 125 mL/min, the percent conversion of dimethyl eter could reach 11%, and the selectivity of methyl acetate could reach 96%. “The shove references has disclosed a lot of research results on dimethyl ether carbonylation, and research on the catalyst has mainly focused on MOR, FER, andthe like with 8 structure of © membered ring. In the results reported Publicly those catalysts are very easy’ to become instvatod ‘vith catalyst life of less than 100 h. And ationally. the reaction reslts eannot meet the requirement of industrial production, ‘SUMMARY OF THE INVENTION The purpose ofthe present invention isto provide # new method for proccing melhyl aceate The inventors of the present invention found hat the carbonylation reaction of low alkyl ether isa typical acid ‘atalyzed reaction, and the acidity and pore structure prop- ery of the catalyst have a decisive inlence on the earbo- ylation performance ofthe catalyst. BMT zeolite belongs to the hexeponal system, the space group of Pafmme with the coll paumeters of -b= 1.7974 nm anid e-2.836S nm, and the lamework density of 12.9 Van’. Is framework structure is a simple hexagonal analogue of faujasite zeolite FAU, ‘composed of 12 membered rings, 6 membered rings and 4 ‘membered rings. As olive with a beter topology stevcture than EAU, ithas a stronger acidity and a bags eid quantity At the same time, EMT has two sos oF intersecting cavities which are connected by 2 dimensional exoss channels. Its superior pore connectivity is more conducive to the adsorp fof reactants and the difsion of product molecules, Therefore, the present invention provides a method for producing methyl seotate, which comprises a step carving ‘ut carbonylation reaction of dimethyl ether and a rae gas vaining carbon monoxide in the presence of a estalyst aining an aeidie EMT zeolite molecular seve Tn a prefered embodiment, the molar rio of silicon toms t¢alumioum atoms inthe aidie PMT zeolite molct- lar sieve is ina ange from 1.5 to 30, Preferably, the molar ratio of silicon atoms to aluminum atoms inthe acidic EMT Zeolite molectiar sieve isin a range from 210 15, In a prefered embodiment, the acidic EMT. zeolite ‘molecular sieve eontans catalyst promoter which is one or ‘more metals selected from gallium, ion, copper and silver. Preferably, the catalyst promoter i introduced to the acidic EMT zeolite molecular sieve by a method sclected from insta synthesis, metal jon exchange or impregnation load 4 ‘ing. Proferaby, hase on the total weight ofthe catalyst, the ‘weight faction of the catalyst promoter calculated by weight of metal elementary substance isin a ange from 0.01 wt % to 10-wt%. More preferably, based on te otal weight ofthe catalyst, the weight Iration of the catalyst promoter calew ted by weight of motl elementary substance isin range fom 008 wt % to 1.0 wt % In a peefered embodiment, the acidic EMT zeolite molecular sieve contains a binder which is one of more compounds slocte from alumina, silicon dioxide and mag: nesium oxide. Preferably, based on the total weight of the catalyst, the weight faction ofthe binder i in a range from O wt % 0 50 wt %. Ina prefered embodiment, the carbonylation reaction is carried out at a temperature range from 160 C]t0 250 Cand at a pressure range fom 0.5 MPa 10 200 MPa, and the Teeding muss space velocity of dimethyl ether isin a range fom 0.05 bh! to 3 br, and the molar ratio of carbon sionowide to dimethyl ethers ina range from 20:1 to O.5:1 Ina peeferred embodiment, the carbonylation reaction is carried out at a temperature range from 170 C)t0 240 Cand fat 8 pressure range from 1.0 MPs to 150 MPa, and the Teding ass space velocity of dimethyl eter is ina range fom 0.1 I! to 25h”, and the molar ratio of carbon monoxide to dimethyl ether isin a range from 15:1 t0 1:1 Ina prefered embodiment, thera gas cntaiing carbon mono contains carbon monoxide. hydrogen and one oF ore inactive gases selected from nitrogen, helium, argon, carbon dioxide, methane and ethane, Preferably, based on the total Volume the raw gas containing carbon monoxide, the volume fraction of carbon monoxide is in a range from '50P% to 100%, and the Volume Fraction of hydrogen isi range from 09% to $0%, and the volume fraction of the inert fis 8 in a range from 0% t0 50%. Tina preferred embodiment, the methyl scotte is hydro lyzed 10 acetic ai. ‘in preferred embodiment, the methyl sootte is hydro- nated to ethyl aleobol Tn prefered embodiment, the carbonylaton reaction is carried out ina fied bed reactor, « Buidized bod rescor or ‘moving bed reactor, The present invention provides « new method fr produc: Jing methyl acotte. Inthe method ofthe present invention, the carhonylation is carried out in the presence of the cztalyst containing the acidie EMT zeolite molecular sieve, and the reaction setivity is high, and the stability has been Significantly improved, meeting the requirement of indus ‘eal production, DETAILED DESCRIPTION OF THE EMBODIMENT “The present invention provides « method for synthesizing methyl acetate, Which comprises step carrying out a cerbonylation reaction of dimethy] ether and a ra gas containing carbon monoxide and hydrogen on catalyst containing an acidic EMT zeolite molecular seve Preferably, the carbonylation reaction is carried out at a temperature range from 160 1 250 and at pressure range fiom 05 MPa to 200 MPs, and the feeding mass space velocity of dimethyl ethee i ina range fom 0.05 1" Wo 3 Ie, and the mola ratio-of earbon monoxide to dimethyl eer isin a range from 20:10 0.8:1. More preferably, the ‘eeding mass space velocity of dimethyl ether isin a range fiom 0.1 br! fo 25h”, and the molar ratio of carbon ‘monoxide to dimethyl ether isin range fom 13:1 10 1:1,US 10,287,233 B2 5 and the reaction temperature is in a range from 170 CI 10 22400) and the reaction pressure is ina range from 1.0 MPa (o 18.0 MPs, Preferably, the molar ratio of silicon atoms to aluminum stom in the acidic FMT zeolite molecular sieve used in the presen invention is in range ftom 15 0 30. Preferably. the ‘molar ratio of silicon atoms to aluminum atoms in the acidic EMT zeolite molecul seve of the preset invention i n'a range from 210 1S. Preferably, the acidic EMT zeolite molecule sieve used in the present invention contains a catalyst promoter which is fone oF more metals selected from gallium, ima, copper ad silver (which may exist in the form of metal elementary Substance or metal compounds stch as metal oxides). For instance, the eaialyst promoter is inte 10 the acidic EMT zeolite molecular sieve by a method selected from insta synthesis, metal ion exchange or impregnation load ing. Preferably, based on the total weight ofthe catalyst, the ‘weight faction of the catalyst promoter calculated by weight ‘of metal elementary substanee isin «range fom 0.01 wt tw 10 wt %. More profeably, the weight faction of the catalyst promoter calculated by weight of metal elementary substance isin a range from 0.05 wt % to 1.0 wt %. Preferably, the acidic EMT molecular sive used in the preseat invention contains a binder which is ene or more ‘Compounds selected from alumins, slioon dioxide and mag: resinm oxide. Preferably, the weight fraction ofthe binds fin the total weight ofthe catalyst sina range Irom O wt 9 50m %, Preferably, the raw gas containing carbon monoxide wsed Jn the presen invention contains carbon monoxide, hydro- ten and one or more inte pases selected from nitrogen, helium, argon, carbon dioxide, methane and ethane. Prefer ably, based of the total volume of the raw gas containing tatbon monoxide, the volume fraction of earbon monoxide Js na range from 30% to 100%, andthe volume fraction of hydrogen isin 2 range from 0°% to 50%, and the volume Faction of the inert gas is in a range from 03% 10 50% Preferably, the carbonylation reaction in the present ‘invention seared ont ina fixed bed resto, uidized bed reactor or a moving bed reactor EXAMPLES. The present invention will be deseribed in details by Examples, but the present invention is not limited to these Examples. nthe examples, the calculation of percent conversion of imethyl ether and selectivity of methyl acetate was based fn the carbon mole number: Percent conversion of dimethyl ether-{(he carbon mole umber of dimethyl ether in the feed gas)=(the carbon mole ‘number of dimethyl ethor inthe prodiuet)(the carbon mole number of dimetiyl ether in the feed g3s)x(100%) Selectivity of methyl acetste-(23)x(the carbon ‘anmber of methyl acetate i the prodct)o[(the carbon ‘umber of dimethyl ether in the feed gas)=(the carbon mole number of dimethyl eer in the product) (100%) Tour samples of Na-EMT zeolite molecular sieve whose ‘molar ratios of silicon atom 10 aluminum atom respectively ate 2,4, 1S and 25, a sample of Na-EMT zeolite molecular Seve eonlaining Ga whose molar ratio of silicon atom 10 ‘aluminum is 4, and a sample of Na-EMT zeolite molecular sieve containing Fe whose molar rato of silicon atom 10 sluminum is 4 have been ws inthe Examples, lof them ‘were produced and proves by Dalian Insite of Chemical Physics. 6 ales for Preparing the Caalyst HLEMT Catalyst 100 gofa simple of Na-EMT zeolite molecular sieve wos exchanged with 0.5 mol/L of ammonium nitrate for three times and each time was for 2 hours. And then the sold preluct was washed with deionized water, ried, calcined at 550° C. for 4b, pressed, crushed and sieved to 20-40 mesh ‘sed as the caalyst sample. Four sumples of Na-EMT zeolite molecular sieve with molar ratios of silicon atom 10 iuminum atom of 2,4, 15 and 28 were usod, to obtain the Samples of Catalyst 1, Catalyst 2¢, Catalyst 3 and Catalyst 48, respectively. GaEMT Catalyst 100 g ofthe sample of Na-EMT zeolite molecular sieve containing Ga (he molecular ratio of silicon atom to alt minum is 4) was exchanged with 0.5 mol/L of ammonium nitrate for three times and each time was for 2 ours. And then the solid product was washed with deionized water, dried, caleind at 580° C, for 4 h, pressd, crushed and sieved 10 20-40 mesh to obtain the sample of Catalyst S# FeEMT Catalyst 100 g ofthe sample of Na-EMT zeolite molecular sieve containing Fe (he molecular rato of sifcon tom to ale rum is 4) was exchanged with 0.5 mol/L of ammonium nitrate for three limes and eae time was for 2 hours, Aad then the solid product was washed with deionized water, ded, caleind at 580°C, for 4 h, pressd, crushed and sieved to 20-40 mesh to obtain the sample of Catalyst 6 Supported Catalyst of MIEMT ‘The supported catalyst of MEMT was prepared using ‘uivatent-volume impregnation method. 432 gof Fe(NO,) fy 432 g of Cu(NO,},311,0 and 3.04 g of AgNO,.3H,0 ‘were respectively dissolved in 18 ml. of deionized water 10 form the Fe(NO,), aqueous solution, Cu(NO,), aqueous solution and AgNO, aqueous solution 20 g of Catalyst 24 (HEMT zeolite molecular sieve catalyst) was added ino the Fe{NO,), aqueous solution, Cu(NO,), aqueous solution and ‘AgNO, aquents solution, respectively. After standing foe 24 hours, the solid products were separated by iltration, ‘washed by deionized water, die inthe oven at 120 Coe 12 hours, and then the stmples obtained were pt into sulle famace whose temperature was heated 10 S80] ata heating rate of Cin, caleined at 550° C. in at for 4h to obtain the samples of Catalyst 74 Catalyst 8# and Catalyst 94 Jon Exchange Catalyst of M-EMT 20 x of Catalyst 24 (H-EMT zeolite molecular sieve catalyst) and 300 mil of 0.18 mol ferric nitrate aqueous Solution were placed in a flask, being sired for 2 hours st SOC) under the conltion of cooling. and refluxing with idliquid ratio of 1:15. The solid product was separated by fikation and washed by deionized water. Repeating the hove steps for 2 times, the sample obtained was dred at 1209 for 12 hours, and the dried sample was put into a rule fumace whose temperature was heated to SSO} at a heating rate of 2° C min, ealeined at S50? C. in ar for 4h o obtain the sample of Catalyst 108 Molded Catalyst of H-EMT $0 g of Na-EMT zeolite molecular sieve with molar ratio of silicon atom © aluminum of 4, 28g of psendo-boehmite and 10% of eluted nitric acid were uniformly mixed, and then the mixtuee was molded through extrusion. Afler being ealeinod at 380 C] Tor 4 hours, the molded sample Was exchanged with 0.5 mol/L of ammonium nitrate for dare times 2 hourstime). And then the soli prodct was washed by deionized water, dried, calcined at $80° C. for 4 to bia the sample of Catalyst 114US 10,287,233 B2 7 80g of Na-EMT zeolite molecular sieve with molar ratio of silicon atom to alumium of 4,20 g of magnesium oxide 1d 10% of dilated nitric acid were uniformly mixed, and then the mixture was molded through extrusion. After being calcined at $80 [1 for 4 hours, the molded sample was exchanged with 0.5 mol/L of ammonitim nitrate for thre dimes and each time was for 2 hours. And thea the solid prlict was washed by deionized water, died, caleined at 550° C. for 4h to obiain the sample of Catalyst 12% 80 g of No-EMT zeolite molecular sieve with molar ratio ofsilcon atom to aluminum of 4, $0 g of silicon sol and 10% bf diltted site acid were uniformly mixed, snd then the ‘mixture was molded through extrusion. ARer being calcined sat 550 [1 for 4 hours, the molded sample was exchanged ‘with 0 mol/L, of ammonium nitate for three times (2 hhoursiime). And then the solid product was washed by deionized water, dried, calcined at $50°C. for 4h to obi the sample of Catalyst 13 Examples of Synthesis Comparative Example HLMOR (molar ratio of silicon tom to aluminum atom SiAT=6.7) Was used as a comparative catalyst. 10 g of the comparative catalyst was put ino a tubular fixed bod reactor ‘with inner diameter of 28 mm, and thea was heated to 580 ata heating rate ofS Chmin under nitrogen gas. Afler being kept at $80 C1 for 4 ours, the temperature 38 reduced 10 the reaction temperature of 199 Cin nitrogen gas, and thon the pressure was ineresed wo the reaction pressure of 5 MPa by introducing CO. The space velocity of feeding dimetty] ether was 0.10 ir! andthe molar rato of carbon monoxide to dimethyl ether was 6:1, and the molar ratio of carbon monoxide to hydrogen in the maw gas containing earhon ‘monoxide was 2:1. The results tthe reaction times when the catalytic reaction ran on for 1h, 0h and 100 b, are shown in Table 1 TABLE | ‘Sse af mei ace) ws ras Example 1 According to Table 2,10 g ofthe catalyst was put into a tubular fixed bed reactor with inner diameter of 28 mmm, and then was heated to 550 (ata eating rate of SC}min under nitogen gis. After being kept at $50) for 4 hours, the temperature was reduced tothe reaction lemperature of 190 ‘Din nitrogen gas, and then the pressure was increased to the reaction pressure of § MPa by introducing CO. The raw ‘material Went through the catalyst bed rom top to bottom. The space velocity of feeding dimethyl ether was 0.10", and the molae ratio of dimethyl eter t carbon monoxide ‘was 1'6, and the molae ratio of earbon monoxide 1 hydro~ ten inthe aw gas containing carbon monoxide was 21, and the reaction temperature was 190 C]. The results at the ection time when te catalytic reaction ran on for 100 are shown in Table 2 8 TABLE 2 an faa nt a nn » Example 2 Reaction Results of Dinthy! Ether Carbonyation ot Di ferent Reaetion Tempenitines 10 g of Catalyst wos sc. The raeton temperatures were 70. 210 ©) and 240 C1, respectively, and other txperinicnal conditions were same as Example 1. The result the reaction time when the catalytic reaction ran on Tar 100 haze shown in Table 3, TABLE 3 Sty of my act 5). Stk 909 Shs So Example 3 Reoetion Results of Dimethyl Ether Carbonylation at Dif ferent Reaction Pressures The Catalyst 4¥ va8 ued, The reaetion pressures were 1 MPa, 6 MPs, 10 MPa and 15 MPa, rspectvely, and the reaction temperature Was 190 CI, and other experimental conditions were same as Example 1, The rests a¢ the ‘ction tne when the catalytic reaction ran on for 100 b are shown in Table 4 TABLE 4 nc ee tine etiam ‘cert comenion of dina aie) Example 4 Reaction Results of Dimethyl Ether Carbonylation at Dif erent Space Velocities of Dimethyl Ether The Catalyst 6 was used. The space velocities of dim cyl ether were 0.25 h", Thr and'2 h™, respectively, ad the reaction temperature Was 190 [nd other experimental conditions were same as Example I. The resus atthe time fon steant of 100 hare shown in Table 5.US 10,287,233 B2 9 TABLES Spe yl of Gina eet) 025 Rrotconenionctaimiyi ait 63143 ‘Savy of me sce). #7 1 ae 10 Example 7 Reaction Results in Different Type of Reactors The Catalyst 6? was used. The reaction temperature was 230 Cand the reactors were a fluidized bed reactor anda ‘moving bod reactor, respectively, and othor experimental conditions were same as Example 1. The reaction ests are shown in Table 8 Fxample 5 TABLE 8 Reaction Results of Dimethyl Ether Carbonylaton Under Different Molar Ratio of Carbon Monoxide #9 Dimethyl 2% fraser fit _ nevis be Biher 18 Recen comenioefofaimeayteeO) 92 ous ‘The Catalyst $# was used. The molar ratios of carbon SASHA ohne wees) a monoxide 10 dimethyl ether were 12:1, 81,421 and 21, respectively, and the reaction temperature was 190 Cand : tothe experimental conditions were same as Example 1 They Example 8 results athe reaction time when te eatalytic rection anon Saree Meihyl Acetate Hyulysis t Acetic Acid “The carbonvlation predt methyl acetate was hydrolyzed tw acatic avid inthe presence of hydeoiyzng catalyst. The mABIE rato of water to ester was 4, and space velocity of methy estos ean dive alsa 25 cette was Oh", and loading amount ofthe catalyst was Siding ci ena mone 10g. The reetion results are shown in Table 10. Mole sino on nonosddetnl e : TABLE 9 ae Feanconenin was] uy |e Saenger) \ Resion mou Sceciiy of sa\ oa \ ms 0 ee ei see (8) | 0 » Pample 6 a Reaction Results of Dimethyl EtberCarbonylation when the 4 en ; : : 4 Methyl Aewate Hydmgenaton to Ethanol Raw Gas Containing Carbon Monoxide Also Contains an ee ee an oo sate was hyope re nated to ethanol inthe presence of hydrogenation catalyst The Catalyst 9# was used, The molar ratios of eahon ‘The reaction pressure war 5.5 MP, andthe molar ratio of monoxide to hydrogen was 12 and 15, respectively, and the hydrogen tp metyl acetate in ra gas was 2021, and the Space velocities of dimethyl cher was 0.1". and the molar moar rato of hydrogen to carbon monoxide was 20:1, and ‘ato of dimethyl ether to earbon monoxide was 1:9. and the the space veleity’ of may acetate was 3h, ad reaction temperature Was 190 C1 and other experimental amount ofthe caalyst was 10 p The reaction msl Conditions were same as Example 1. The rests at the shown in Table IL reaeton time when the catalytic reetion ran on for 200 hare showa in Tale 7. 0 TABLE 10 TABLET Boe il ie min taal ‘estne eof ieee oe ICEMT ea whe i Remon Mt site dension a = 7 58. teopeatus Fone omenionofSdesnn of Seeitiy of shine Tolune Poses emvemion Sci of co” "oetpsceae 2) oar Meno! 0) {cect aiowof ‘ofan aher— er te 7 rT = as = Bt oat The present invention is been describe in details hove, but the invention is not fiited « he detailed so na oe tembedimeats desribed in this text, Those skilled in the at 6s will understand tht other changes and deformations can be ‘made without deviating from the scope of the invention. The scope of the invention is limited! by the appended claims.US 10,287,233 B2 uw The invention claimed is 1.8 method for prodcing methyl acetate, whieh com> ses a step in which dimethyl ether and a raw pas eon: ining carbon monoxide go through a eactr loaded with a catalyst for carrying outs carboaylation reaction; wherein the ealalyst contains an acide FMT zeolite molecular sieve. 2. A method for producing methyl acetate according 10 claim 1, wherein in the side EMT zeolite molecular sieve, the molar ratio of silicon atoms to aluminum atoms is ina range from 1 1030. 3A method for producing methyl acetate according 10 claim 1, wherein the acidic EMT zeolite molec sieve contains a catalyst promotor whichis one or more metal Selected rom gallium, iron, copper and silver. 44 method for producing methyl acetate according 10 any of claims 110 3, wherein the acide EMT zeolite ‘molecular sieve contiins binder which is ane oF more ‘compounds selected from alumina, silicon dioxide and mag: resi oxide 5. A method for producing methyl acctate according to claim 1, wherein the carbonylation reaction i carried out at ‘temperature range from 160°C. 10 250° C. and aa pressure range from 0.5 MPs to 20.0 MPa, and the feeding mass space veloity of dimethyl ether sin range from 0.05 “to 3h, and the molar ratio of carbon monoxide 10 imetiyl ether is ina range from 2041 to 05:1 6. A method for producing methyl acetate according to claim 1, wherein the carboaylation reaction is earid out at f temperature range fom 170° C. 10 240°C. and a a pressure range from 1.0 MPs to 15.0 MPa, and the feeding mass space velocity of dimethy] ether is in a range from O.1h~ to 2.Sh, and the mole rato of carbon monoxide 10 Aimethyl ether i ina range from 15:1 10 1:1 7. A method for producing methyl acetate according to claim 1, wherein the mW gas containing carbon monoxide contains carbon monoxide, hydrogen and one or more Instive gases selected from nitrogen, helium, argon, carbon ddioxide, methane and ethane. 8, A method for produeing methyl acetate aeconing 10 lain 1, wherein the methyl aeetate is hydrolyzed to acetic cid. 12 9. A method for producing meth] acetate according to claim 1. wherein the methyl acetate is hydrogenated to ety leak 10, A method for producing methyl acetate according 10 claim 1, wherein the carbonylaton reaction is arried out in 8 fixed bed reactor, a Huidized bed reactor or a moving bed reactor 1. A method for producing methyl acetate aeording to claim 1, wherein in the aidie EMT zeolite molecalr sieve, the molar rato of silicon atoms to aluminum atoms is in'8 range fom 2 to 1S 12, A method for producing methy! acetate cording 10 claim 3, wherein te catalyst promoter i introduced to the fcidie EMT zeolite molectlar sieve by # method scleced from insta synthesis, metal jon exchange or impregnation loading, 13. A method for producing methyl acetate according 10 lim 3, wherein based onthe total weight of theeatalys, he ‘weight action of the catalyst promover calculated by weight ‘of metal elementary substance isin a range fom 0.01 wt % to 1o.wt%, 14. A method for producing methy] acetate scording 10 lim 3, wherein bast onthe total weight ofthe catalyst the ‘weight fraction of the catalyst promoter calculated by weight of mica elementary substance isin a range fom 0.05 wt % to 10 wt% 1S. A method for producing methy] acetate aecording to any of claims 4, wherein based on the total weight of the aly, dhe weight faction ofthe binder i ina range from Owe 96 10 50 wt %, 16. method for producing metiy] acetate according to cli 7, wherein based on the foal volume ofthe rw gs containing carbon monoxide, the volume fraction of carbon monoxide is in. range fom 50% to 100%, and the volume traction of hydrogen is ina range from 0% to 50%, and the volume fraction ofthe inert gas isin a range from 0% to 50%