CN101613274B - Method for preparing methyl acetate by carbonylating dimethyl ether - Google Patents
Method for preparing methyl acetate by carbonylating dimethyl ether Download PDFInfo
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- CN101613274B CN101613274B CN 200810011999 CN200810011999A CN101613274B CN 101613274 B CN101613274 B CN 101613274B CN 200810011999 CN200810011999 CN 200810011999 CN 200810011999 A CN200810011999 A CN 200810011999A CN 101613274 B CN101613274 B CN 101613274B
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Abstract
The invention discloses a catalyst modification method for preparing methyl acetate by carbonylating dimethyl ether. The method is applied to the reaction process in which the dimethyl ether reacts with the carbon monoxide to high selectively form methyl acetate in the presence of an acid molecular sieve catalyst, particularly a mordenite molecular sieve. Pyridine organic amines are utilized to modify the mordenite molecular sieve and modify a channel structure and the acidity of the molecular sieve, thereby effectively inhibiting carbon deposition and greatly improving the stability of catalysts. The use of the catalysts by the method can catalyze the carbonylation of dimethyl ether to obtain methyl acetate under mild conditions. The conversion rate of dimethyl ether is between 10 and 60 percent, the selectivity of the methyl acetate is over 99 percent, and the activity of the catalysts is kept steady after the reaction is performed for 48 hours.
Description
Technical field
The present invention relates to a kind of reaction process and catalyst modification method of under the condition of gentleness, utilizing solid molecular sieves catalysis dme carbonylation to produce methyl acetate; It is the process of producing methyl acetate through catalysis dme carbonylation; Used catalyzer is the H type mordenite of H type mordenite and the absorption of pyridines organic amine.
Background technology
Acetate is a kind of important Organic Chemicals, is used to produce vinyl acetate, acetate fiber, acetic anhydride etc.Its global YO is above 1,000 ten thousand tons.Industry is at present gone up the production process of acetate and is mainly used Monsanto [GB 1,277,242] and BP [EP 0,849,248] method, utilizes precious metal Rh or Ir to make catalyzer, CH
3I does promotor, under even phase condition, realizes through methanol carbonylation.But because methyl iodide has intensive corrodibility, production unit need use the special alloy of erosion resistance, and the material that contains iodine is difficult to remove with common distillating method, and catalyzer will use the Rh of costliness, precious metals such as Ir simultaneously.Though through constantly research, the method for not having iodine, non-precious metal catalyst production acetate does not at present have industriallization as yet.
Dme is a kind of good Chemicals, have nontoxic, advantage such as gas under the normal temperature.Dme is synthetic main through methyl alcohol or synthetic gas one-step synthesis at present.Synthesising gas systeming carbinol has been sophisticated heavy industrialization process, and dimethyl ether by methanol dehydration also has proven technique.Wherein synthetic gas can use non-oil resource gasification preparations such as coal, biomass or Sweet natural gas; Be very sophisticated industrial technology. so the catalyzed conversion of dme prepares the high added value chemical; Such as dme carbonylation system methyl acetate and acetate; Be the trend that dme effectively utilizes, on technology and resources economy, stronger competitive power arranged all.
Dimethyl ether carbonylation reaction has more report.German Patent German 3,606,169 has invented X and the Y molecular sieve that a kind of usefulness contains cobalt and has made catalyzer, is used for methyl alcohol and dme gas mixture carbonylation reaction, and product mainly is acetate and methyl acetate.U.S. Pat 5,763,654 have invented a kind of group VIII noble metals that utilizes is catalyzer, and methyl iodide is the carbonylation processes of the dme of promotor, and the principal reaction product is acetate (having water to exist).Volkova [Catalysis Letters 80 (2002) 175] has reported the process of the dimethyl ether catalysis carbonylation of the heteropolyacid catalyst that contains Rh, and product mainly is a methyl acetate, but catalyst deactivation is very fast.
[Angew.Chem.Int.Ed.45 (2006) 1 for nearest Iglesia etc.; J.Catal.245 (2007) 110; J.Am.Chem.Soc.129 (2007) 4919] reported that dme is in the molecular sieve system with 8 yuan of rings and 12 or 10 ring structures; Like mordenite (Mordenite) and ferrierite (Ferrierite), carry out carbonylation reaction.The result shows that the active site of catalyzed carbonylation is in the B of 8 yuan of rings acid position.Reaction has obtained to surpass the selectivity of 99% methyl acetate.U.S. Pat 2007238897 has been invented the process of dimethyl ether carbonylation reaction on the mordenite, and at 165 ℃, 1MPa, reaction gas anhydrate under the condition, have obtained 163g-MeOAC (g-zeolite) h)
-1Space-time yield.
Summary of the invention
The present invention finds that through to the carbonylation reaction research of dme on mordenite the pore passage structure and the acidic character of catalytic activity and selectivity of product and molecular sieve is closely related.Carbonylation transformation efficiency only containing dme on 10 yuan of rings or the 10 yuan of acid materials such as molecular sieve and the heteropolyacid more than the ring is very low.And have higher dimethyl ether conversion rate and methyl acetate selectivity under the condition in gentleness on the mordenite with 12 yuan of rings and 8 yuan of dual ducts of ring.Discover further that on acidic mordenites with the prolongation in reaction times, there is deactivation phenomenom in catalyzer, deactivation rate is accelerated with the rising of temperature.
The objective of the invention is duct and acid modification, improve the transformation efficiency of dme, and effectively suppress the inactivation of catalyzer through mordenite.
For realizing above-mentioned purpose, technical scheme of the present invention is following:
The catalyzer mordenite of the synthetic methyl acetate of a kind of dme carbonylation through pyridines organic amine adsorption of modification, effectively suppresses the inactivation of catalyzed reaction, prolongs the catalyst reaction life-span.Wherein mordenite is the molecular sieve with 12 yuan of ring main aperture roads and 8 yuan of ring intersection ducts.B acidic site in 12 yuan of intra-annular B acid position and 8 membered ring channels all can be as the reactive activity center, but 12 membered ring channels of larger aperture generate carbon distribution easily, the obstruction duct, thus cause the inactivation of catalyzer, be difficult to generate carbon distribution in 8 membered ring channels.Therefore through selecting a kind of suitable alkaline molecule, effectively poison 12 yuan of intra-annular B acid positions, and keep 8 yuan of intra-annular B acid positions.When effectively suppressing the carbon distribution inactivation, keep catalytic activity.
A kind of method of preparing methyl acetate by carbonylating dimethyl ether; The catalyzer that it adopted is the H type mordenite of the saturated absorption of pyridines organic amine; Mordenite is by the saturated absorption of pyridine; And under reaction conditions stable existence, it can be used for the process that catalysis dme carbonylation is produced methyl acetate as modified catalyst.
The process of the saturated absorption of said pyridines organic amine H type mordenite does, the mordenite of H type is seated in the reactor drum 300-500 ℃, H
2, He, N
2, handled 1-5 hour under argon gas or the dry air atmosphere; Cool to 100-400 ℃ then, switch to and contain the saturated H of pyridines organic amine
2, He, N
2, under argon gas or the dry air atmosphere, adsorbed 1-24 hour, and then under this temperature, use H
2, He, N
2, argon gas or dry air purged 1-5 hour, forms the H type mordenite of saturated absorption.
The optimal adsorption temperature of pyridines organic amine is 200-300 ℃.
The modification of alkaline molecule with mordenite of dual pore passage structure can be undertaken by following ordinary method: the mordenite of sodium type is passed through NH
4NO
3The mordenite of three secondary ions exchange being transformed into ammonium type.After dry and roasting, obtain the mordenite of H type.
The skeleton Si/Al of the mordenite of H type is than being 5-50.Said H type mordenite can adopt the concentration of acid or the said acid of alkali pre-treatment before adsorbing be 0.5-10mol/L, handled 1-20 hour at 25-120 ℃; The concentration of said alkali is 0.05-4mol/L, handles 1-10 hour down at 25-120 ℃.Used acid is nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetate and/or oxalic acid; Said alkali is NaOH and/or KOH.
Said pyridines organic amine be pyridine,
(wherein R is CH
3, CH
2CH
3, F, Cl, Br, I, NO
2In any functional group),
(R1 wherein, R2 is respectively CH
3, CH
2CH
3, F, Cl, Br, I, NO
2In any sense),
(R3 is respectively CH for R1 wherein, R2
3, CH
2CH
3, F, Cl, Br, I, NO
2In any sense).
The method of a kind of dme of the present invention preparing methyl acetate by carbonylating on mordenite, it is that catalyzer with modification switches to reaction gas, control reaction temperature is 100-300 ℃; Preferably 150-250 ℃; Virgin gas is dme and CO, feeds the gas mixture of dme and CO, and the mol ratio of dme and CO is 1: 1-1: 30; With the pressure 0.1-10MPa of control reaction gas, the air speed that feeds gas is 500-100000mlg
-1h
-1, promptly get methyl acetate; Methyl acetate further hydrolysis generates acetate or other acetate derivative compounds of transesterify generation.
The used reactor drum of the present invention can be the fixed bed gas-solid phase reactor, also can be the fluidized-bed gas-solid phase reactor.
The usefulness solid molecular sieves catalysis preparing methyl acetate by carbonylating dimethyl ether that the present invention proposes has avoided carbonylation of methanol to use the CH of precious metal Rh or Ir and severe corrosive
3I, and the mordenite of organic amine modification has improved the stability of carbonylation reaction greatly.
Catalyst modification method of the present invention can be applicable at acid molecular sieve catalyst, particularly the reaction process of dme and carbon monoxide highly selective generation methyl acetate on the mordenite molecular sieve.Utilize pyridines organic amine modified mordenite molecular sieve, the pore passage structure and the acidity of decorating molecule sieve, thus suppress carbon distribution effectively, increase substantially the stability of catalyzer.The present invention uses such catalyzer can be at catalysis dme carbonylation system methyl acetate under the mild conditions.Dimethyl ether conversion rate 10-60%, the selectivity of methyl acetate is greater than 99%, and keeps stable in the activity of 48 hours rear catalysts of reaction.
Description of drawings
Below in conjunction with accompanying drawing and table and embodiment the present invention is done further detailed explanation:
Fig. 1 is that HMOR (Si/Al=5.6) goes up the variation with the reaction times of dimethyl ether conversion rate and selectivity of product.Reaction conditions is: 150 ℃, and GHSV=1,250mlg
-1h
-1, CO/DME/N
2/ He=50/5/2.5/42.5.
Fig. 2 is that HMOR (Si/Al=5.6) goes up the variation with the reaction times of dimethyl ether conversion rate and selectivity of product.Reaction conditions is: 180 ℃, and GHSV=1,250mlg
-1h
-1, CO/DME/N
2/ He=50/5/2.5/42.5.
Fig. 3 is that HMOR (Si/Al=5.6) goes up the variation with the reaction times of dimethyl ether conversion rate and selectivity of product.Reaction conditions is: 200 ℃, and GHSV=1,250mlg
-1h
-1, CO/DME/N
2/ He=50/5/2.5/42.5.
Fig. 4 is that HMOR (Si/Al=5.6) goes up the variation with the reaction times of dimethyl ether conversion rate and selectivity of product.Reaction conditions is: 225 ℃, and GHSV=1,250mlg
-1h
-1, CO/DME/N
2/ He=50/5/2.5/42.5.
Fig. 5 is that the HMOR (Si/Al=5.6) of 200 ℃ of preadsorption of pyridine goes up the dimethyl ether carbonylation reaction result.Reaction conditions is: 200 ℃, and GHSV=1,250mlg
-1h
-1, CO/DME/N
2/ He=50/5/2.5/42.5.
Fig. 6 is the selectivity graphic representation over time of dimethyl ether conversion rate and product methyl acetate on the mordenite of 300 ℃ of absorption of pyridine.Reaction conditions: 200 ℃, 1MPa, DME/CO/N
2/ He=5/50/2.5/42.5, GHSV=1,250mlg
-1h
-1
The dimethyl ether conversion rate on the mordenite of 400 ℃ of absorption of Fig. 7 pyridine and the selectivity of product methyl acetate be graphic representation over time.Reaction conditions: 200 ℃, 1MPa, DME/CO/N
2/ He=5/50/2.5/42.5, GHSV=1,250mlg
-1h
-1
Embodiment
With following specific examples the present invention is done further explanation:
Embodiment 1:
100g NaMOR (Si/Al=5.6) is joined 1.5L, the NH of 1mol/L
4NO
3Solution in, keep 90 ℃ of exchanges 3 hours, then with filtering 1L deionized water wash, oven dry.Repeat above exchange process 3 times.After the last exchange, dried 12 hours for 110 ℃, 500 ℃ of roastings obtained powder catalyst in 6 hours under groom's furnace air atmosphere then.Get a part of powdered sample and be pressed into sheet, pulverize, screening 40-60 order is used for active testing, is designated as the #1 catalyzer.
Embodiment 2:
The 10g# 1 catalyzer is joined 300ml, the HNO of 2mol/L
3In the solution under vigorous stirring 80 ℃ handled 10 hours.Through filtering, the 2L deionized water wash was dried 12 hours for 110 ℃ then, and 500 ℃ of roastings of roasting are 6 hours in groom's stove.Get a part of powdered sample and be pressed into sheet, pulverize, screening 40-60 order is used for active testing, is designated as the #2 catalyzer.
Embodiment 3-4:
Be used for handling the HNO of #1
3Concentration be followed successively by 4mol/L and 8mol/L, remaining preparation condition and embodiment 2 with.And be designated as #3 and #4 catalyzer successively.
Embodiment 5:
With 10gNH
4MOR joins 300ml, in the NaOH solution of 0.05mol/L under vigorous stirring 80 ℃ handled 2 hours.Through filtering, the 2L deionized water wash was dried 12 hours for 110 ℃ then.Change the sample after the oven dry into HMOR according to embodiment 1 again, get a part of powdered sample and be pressed into sheet, pulverize, screening 40-60 order is used for active testing, is designated as the #5 catalyzer.
Embodiment 6-8:
Be used for handling NH
4The concentration of the NaOH of MOR is followed successively by 0.1mol/L, 0.2mol/L and 1.0mol/L, and remaining preparation condition and embodiment 5 are together.And be designated as #6, #7 and #8 catalyzer successively.
Embodiment 9:
Take by weighing #1 catalyst sample 0.6g, the internal diameter of packing into is the interior N of stainless steel reaction pipe of 10mm for the 8mm external diameter
2The following 500 ℃ of normal pressures of atmosphere were handled 1 hour down, cooled to 150 ℃ then naturally.Introduce CO/DME/N
2/ He=50/5/2.5/42.5 gas mixture also slowly boosts to 1MPa, control reaction velocity 1,250mlg
-1h
-1With the online detection reaction tail gas of gc.Test result is seen Fig. 1.
Embodiment 10-12:
Change different temperature of reaction and be followed successively by 180 ℃, 200 ℃ and 225 ℃, remaining reaction condition and embodiment 9 are same, and reaction result is seen Fig. 2-4 successively.
Embodiment 13:
Take by weighing #1 catalyst sample 0.6g, the internal diameter of packing into is the interior N of stainless steel reaction pipe of 10mm for the 8mm external diameter
2The following 500 ℃ of normal pressures of atmosphere were handled 1 hour down, cooled to 200 ℃ then naturally.Introduce the saturated N of pyridine
2And keep 200 ℃ of reaction tube temperatures, and adsorb after 1 hour, under this temperature, switch to pure N
2And kept 1 hour, introduce CO/DME/N then
2/ He=50/5/2.5/42.5 gas mixture also slowly boosts to 1MPa, control reaction velocity GHSV=1,250mlg
-1h
-1With the online detection reaction tail gas of gc.Test result is seen Fig. 5.
Embodiment 14-15:
The adsorption temp of pyridine is followed successively by 300 ℃ and 400 ℃, and remaining reaction condition and embodiment 13 are same, and test result is seen Fig. 6-7 successively.
Embodiment 16-22:
Change catalyzer #2-#8 successively, remaining reaction condition and embodiment 14 are same, and the steady state test result lists in table 1.
The catalyst activity and the selectivity of product result of the stable state that table 1 embodiment 17-19 measures
Claims (8)
1. the method for a preparing methyl acetate by carbonylating dimethyl ether; It is characterized in that: the catalyzer that it adopted is the H type mordenite of saturated absorption pyridine; Pyridine is by the saturated absorption of mordenite; And under reaction conditions stable existence, it can be used for the process that catalysis dme carbonylation is produced methyl acetate as modified catalyst.
2. method according to claim 1 is characterized in that: the process of said saturated absorption pyridine H type mordenite is:
The mordenite of H type is seated in the reactor drum 300-500 ℃, H
2, He, N
2, handled 1-5 hour under argon gas or the dry air atmosphere; Cool to 100-400 ℃ then, switch to and contain the saturated H of pyridine
2, He, N
2, under argon gas or the dry air atmosphere, adsorbed 1-24 hour, and then under this temperature, use H
2, He, N
2, argon gas or dry air purged 1-5 hour, forms the H type mordenite of saturated absorption.
3. method according to claim 2 is characterized in that: the optimum temps of absorption pyridine is 200-300 ℃.
4. method according to claim 2 is characterized in that: the skeleton Si/Al of the mordenite of H type is than being 5-50.
5. method according to claim 2 is characterized in that: said H type mordenite adopts acid or alkali pre-treatment before adsorbing,
The concentration of said acid is 0.5-10mol/L, handles 1-20 hour at 25-120 ℃;
The concentration of said alkali is 0.05-4mol/L, handles 1-10 hour down at 25-120 ℃.
6. method according to claim 5 is characterized in that: used acid is nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, acetate and/or oxalic acid; Said alkali is NaOH and/or KOH.
7. method according to claim 1 is characterized in that: said carbonylation reaction virgin gas is dme and CO, and the mol ratio of dme and CO is 1: 1-1: 30, and temperature of reaction is 100-300 ℃, reaction pressure 0.1-10MPa.
8. method according to claim 7 is characterized in that: the reactor drum of employing is the fixed-bed reactor or the fluidized-bed reactor of continuous flow.
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