CN103831124A - Phosphorus zeolite catalyst for synthesizing methyl acetate by dimethyl ether carbonylation and method using catalyst - Google Patents
Phosphorus zeolite catalyst for synthesizing methyl acetate by dimethyl ether carbonylation and method using catalyst Download PDFInfo
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- CN103831124A CN103831124A CN201210488092.3A CN201210488092A CN103831124A CN 103831124 A CN103831124 A CN 103831124A CN 201210488092 A CN201210488092 A CN 201210488092A CN 103831124 A CN103831124 A CN 103831124A
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Abstract
The invention provides a phosphorus zeolite catalyst for synthesizing methyl acetate by dimethyl ether carbonylation reaction. The catalyst comprises zeolite and phosphorus, wherein the zeolite is mordenite or ferrierite; the weight of phosphorus in the catalyst accounts for 0.1%-15% of the total weight of the catalyst by P2O5; the silicon-aluminum molar ratio of a framework of the mordenite or the ferrierite is (5: 1) to (20: 1) of SiO2/Al2O3; the mordenite or the ferrierite is hydrogen type mordenite or ferrierite. The invention further provides a method for synthesizing methyl acetate through the dimethyl ether carbonylation reaction by using the catalyst. According to the catalyst and the method, the reaction activity and selectivity are improved and the reaction process is simplified.
Description
Technical field
The present invention relates to a kind of P-contained zeolite catalyst for the synthetic methyl acetate of dimethyl ether carbonylation, also relate to the method that uses this catalyst.
Background technology
Methyl acetate is a kind of important Organic Ingredients intermediate, is widely used in the industries such as weaving, spices and medicine.Can produce numerous downstream product by methyl acetate, as methyl acetate hydrolysis is produced acetic acid, methyl acetate hydrogenation is produced ethanol etc.
Dimethyl ether is a kind of important industrial chemicals, at present very ripe by the technical matters of producing dimethyl ether by dehydrating methanol, synthesize the methyl acetate of high added value by carbonylation take dimethyl ether as raw material, be the good approach of one that dimethyl ether effectively utilizes, have technically and economically obvious advantage.
It is catalyst that dimethyl ether uses the VIII family metal of loaded by heteropoly acid the earliest by the technique of carbonylation synthesis of acetic acid methyl esters, severe reaction conditions and product methyl acetate selectively not high.2006, the discovery modenites such as Iglesia (8 rings and 12 rings) and ferrierite (8 rings and 10 rings) have very high catalytic activity to the carbonylation of dimethyl ether, product methyl acetate selectively exceed 90%(Angew.Chem.Int.Ed 2006 (45): 1).
The catalytic activity of the molecular sieve that US20070238897 has reported various different structures in dimethyl ether carbonylation reaction, finds that the activity of modenite is the highest, and the structure of molecular sieve, pore distribution directly affect the activity of catalyst.
CN200810011999.4 has reported the modification such as the organic base that utilizes pyridine pore structure, and the method can make the stability of catalyst greatly improve.
CN200880121481.4 has reported that microcrystal mordenites is for catalysis dimethyl ether carbonylation reaction.The particle diameter of zeolite is not more than 3 microns, shows higher activity and stability.
CN20098015305.X has proposed the method for the aluminium in a kind of selectively removing modenite 12 ring structures.First the method loads monovalent metal on modenite, then steam dealuminzation, and the aluminium atom in like this can selectively removing modenite 12 ring structures, the aluminium atom in 8 ring structures affects less.By above-mentioned processing, improve the stability of catalyst.
The modenite that US20100274045 has reported load IB family metallic atom shows very high catalytic activity during for dimethyl ether carbonylation reaction as catalyst.It is higher that the catalyst activity that adopts ion-exchange process to prepare is prepared than infusion process, and tenor still less.
Up to now, the catalyst for the synthetic methyl acetate reaction of dimethyl ether carbonylation of reporting in document mainly concentrates on modenite, ferrierite and with the modenite of the metals such as supported copper etc.The metals such as copper can increase the absorption of reactant CO, thereby cause reaction rate accelerates, and catalytic activity is improved.But, still cannot be satisfactory in activity aspect active and selectivity of product as modenite and the ferrierite etc. of base catalyst.Phosphorus is introduced modenite or ferrierite by first passage of the present invention, significantly improved activity and the selectivity of product of catalyst, simplified processing step simultaneously, improved industrial economic benefit.
Summary of the invention
The present invention, by phosphorus-containing compound being introduced to modenite or magnesium alkali zeolite catalyst, provides a kind of catalyst of novelty, and this catalyst shows high reaction activity and selective in the reaction of the synthetic methyl acetate of catalysis dimethyl ether carbonylation.
Of the present invention aspect first, provide a kind of for dimethyl ether carbonylation reaction the catalyst with synthesis of acetic acid methyl esters, described catalyst comprises zeolite and phosphorus, described zeolite is modenite or ferrierite, take the gross weight of described catalyst as benchmark, with P
2o
5meter, the phosphorus content in described catalyst is 0.1-15 % by weight, wherein, the framework silicon-aluminum mol ratio of described modenite or ferrierite is SiO
2/ Al
2o
3=5:1 to 20:1.
In one embodiment, described modenite or ferrierite are Hydrogen.Preferably, described framework silicon-aluminum mol ratio is SiO
2/ Al
2o
3=10:1 to 20:1.In one embodiment, the phosphorus content in described catalyst is 1-10 % by weight.
In one embodiment, described catalyst is prepared in the following manner: i) phosphorus-containing compound is water-soluble or organic solvent, to be mixed with solution; Ii) described modenite or ferrierite are flooded in described solution; Iii) to dipping after described modenite or ferrierite is dried and roasting.Described phosphorus-containing compound is preferably containing trivalent or phosphoric inorganic or organic compound, as phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, triethyl phosphate, triphenylphosphine.In one embodiment, step I i) be immersed in 20-100 ℃, more preferably at the temperature of 40-90 ℃, carry out; The dipping duration is 1-24 hour.In one embodiment, step I ii) baking operation at the temperature of 300-600 ℃, carry out, described baking operation carries out in air or inert gas, described inert gas is nitrogen, argon gas or other.
It is a kind of by the method for the synthetic methyl acetate of dimethyl ether carbonylation that another aspect of the present invention provides, described method comprises: in the situation that there is catalyst of the present invention, dimethyl ether is contacted with the unstripped gas that comprises carbon monoxide, thereby reaction generate methyl acetate, described in comprise carbon monoxide unstripped gas be pure CO gas or synthesis gas.
In an embodiment of the invention, described method is carried out under the following conditions: the mol ratio of CO and dimethyl ether is 1-100, is preferably 1-50, more preferably 1-9; Reaction temperature is 100-350 ℃, preferably 150-250 ℃, more preferably 180-220 ℃; Reaction pressure is 0.1-10MPa; The cumulative volume air speed of the described unstripped gas that comprises carbon monoxide and dimethyl ether is 1000-10000 hour
-1.
The specific embodiment
" scope " disclosed herein is with the form of lower limit and the upper limit.Can be respectively one or more lower limits, and one or more upper limit.Given range limits by a selected lower limit and a upper limit.Selected lower limit and the upper limit define the border of special scope.All scopes that can limit by this way comprise with capable of being combined, and any lower limit can be combined to form a scope with any upper limit.For example, list the scope of 60-120 and 80-110 for special parameter, be interpreted as that the scope of 60-110,60-80,110-120 and 80-120 also expects.In addition, if the minimum zone value of listing 1 and 2, and if listed maximum magnitude value 3,4 and 5, scope below can all expect: 1-2,1-3,1-4,1-5,2-3,2-4,2-5,3-4 and 4-5.In the present invention, if not special explanation, all embodiments mentioned in this article and preferred embodiment can be combined to form new technical scheme mutually.
In the present invention, if not special explanation, all technical characterictics mentioned in this article and preferred feature can be combined to form new technical scheme mutually.
In the present invention, if not special explanation mentioned in this article can sequentially be carried out in steps, also can carry out at random, but preferably in sequence.For example, described method comprises step (a) and (b), represents that described method can comprise in sequence step (a) and (b), also can comprise in sequence step (b) and (a).For example, describedly mention described method and also can comprise step (c), represent that step (c) can random order join described method, for example, described method can comprise step (a), (b) and (c), also step (a), (c) and (b) be can comprise, step (c), (a) and (b) etc. also can be comprised.
Catalyst of the present invention mainly comprises zeolite and loads on the phosphorus component on zeolite, and described phosphorus component is that phosphorus-containing compound forms after roasting.One preferred embodiment in, described in the phosphorus component that loads on zeolite be the oxide of phosphorus.In another embodiment, described catalyst is made up of the oxide of zeolite and phosphorus, and does not comprise other component.
Zeolite of the present invention can comprise the zeolite of any kind with dimethyl ether carbonylation reaction, for example modenite, ferrierite, analcime, chabasie, scolecite, heulandite, sodalite or foresite, preferably modenite or ferrierite.Can change the cation on zeolite by modes such as ion-exchanges, for example, the zeolite of preparing under neutrality or alkaline pH value condition is often Na type or K type zeolite, be that the counter cation connecting on the Al-Si skeleton of zeolite is sodium or potassium, by it being processed with acid solution, can make these ions be exchanged by hydrogen ion, thereby obtain h-type zeolite.Similarly, also can make the cation on zeolite by the mode of ion-exchange is Mg, Ca etc.Of the present invention one preferred embodiment in, preferably h-type zeolite of the zeolite in catalyst of the present invention.For the various zeolites of natural origin, due to the difference of its place of production natural conditions, may there is larger variation in the framework silicon-aluminum mol ratio in zeolite.And for synthetic zeolite, by regulating the condition such as mol ratio and acid-base value of the components such as raw material mesosilicic acid sodium, aluminium salt, also can effectively regulate the zeolitic frameworks silica alumina ratio making.The framework silicon-aluminum mol ratio of the zeolite using in described catalyst in a preferred embodiment of the present invention, is SiO
2/ Al
2o
3=5:1 to 20:1, more preferably 10:1 to 20:1.
Catalyst of the present invention loads on phosphorus on above-mentioned zeolite and makes.Specifically, catalyst of the present invention makes by following steps substantially: i) phosphorus-containing compound is water-soluble or other solvent, to be mixed with solution, described phosphorus-containing compound is preferably containing trivalent or phosphoric inorganic or organic compound, as phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, triethyl phosphate, triphenylphosphine; Ii), at 20-100 ℃, preferably at the temperature of 40-90 ℃, described zeolite is flooded to 1-24 hour in described solution; Iii) to the described modenite after dipping or ferrierite is dried and roasting, this baking operation carries out at the temperature of 300-600 ℃, and described baking operation carries out in air or inert gas, and described inert gas is nitrogen, argon gas or other.Can infer, after described baking operation, there is thermal decomposition in described phosphorus-containing compound, often loads on zeolite with the form of phosphorous oxide.
Catalyst of the present invention carrys out reacting of synthesis of acetic acid methyl esters for dimethyl ether (DME) with the carbonylation of carbon monoxide (CO), and reaction equation is shown below.
Specifically, this course of reaction can be undertaken by the reaction system of any appropriate.For example, can use fixed bed reactors, catalyst of the present invention is filled in reactor with the form of bed, dimethyl ether and the unstripped gas containing carbon monoxide are passed in described reactor, make the two reaction generate methyl acetate.The described unstripped gas containing carbon monoxide can be pure CO gas, can be also from any conventional of industrial source containing CO gas, for example key component is CO and H
2synthesis gas.In a preferred embodiment of the present invention, the mol ratio of CO and dimethyl ether is CO/DME=1-100, is preferably CO/DME=1-50, promotes the conversion ratio of reaction with selective by the excessive application of dimethyl ether; Reaction temperature is 100-350 ℃, preferably 150-250 ℃, more preferably 180-220 ℃; Reaction pressure is 0.1-10MPa; The cumulative volume air speed of the described unstripped gas that comprises carbon monoxide and dimethyl ether is 1000-10000 hour
-1.Those skilled in the art can carry out further conventional adjustment to reaction process according to the actual conditions of reaction and required conversion ratio, requirements such as selective.
Embodiment
The zeolite catalyst of having prepared exemplary phosphorus doping in following examples 1-10, comparative example 1-4 is unadulterated zeolite, is used in following reaction embodiment catalyst as a comparison.
Embodiment 1
Take 80 grams of framework silicon-aluminum mol ratio (SiO
2/ Al
2o
3) be 15 the sodium type modenite purchased from Tianjin Nan Hua catalyst Co., Ltd, it is stirred in the ammonium nitrate solution of 1 liter of 0.2M to 3 hours to carry out ion-exchange, then dry at 80 ℃, obtain h-mordenite 550 ℃ of roastings.
Taking 30 grams of described h-mordenites joins in the phosphate aqueous solution of 0.5 mol/L, at 60 ℃, flood 2 hours, sample is placed in to baking oven, dry at 120 ℃, then put into Muffle furnace, roasting 8 hours under 550 ℃, air atmosphere, takes out compressing tablet by the sample after roasting, and is sized to 20-40 order.In the catalyst sample that the ICP device measuring that uses Spectro Analypical Instruments GmbH to produce makes, the weight content of phosphorus is (with P
2o
5meter), record P
2o
5content accounts for 4.9 % by weight of catalyst sample gross weight.
Embodiment 2
Adopt the step Kaolinite Preparation of Catalyst sample identical with embodiment 1, difference part is, the solution that is used for flooding zeolite is the ammonium phosphate solution of 1 mol/L.Record P
2o
5content accounts for 10.3 % by weight of catalyst sample gross weight.
Embodiment 3
Adopt the step Kaolinite Preparation of Catalyst sample identical with embodiment 2, difference part is, the solution that is used for flooding zeolite is the ammonium phosphate solution of 2 mol/L.Record P
2o
5content accounts for 14.9 % by weight of catalyst sample gross weight.
Embodiment 4
Adopt the step Kaolinite Preparation of Catalyst sample identical with embodiment 1, difference part is, the solution that is used for flooding zeolite is the tripotassium phosphate aqueous solution of ester of 1 mol/L.Record P
2o
5content accounts for 11.4 % by weight of catalyst sample gross weight.
Embodiment 5
Take 80 grams of nominal framework silicon-aluminum mol ratio (SiO
2/ Al
2o
3) be 20 the sodium type modenite purchased from Tianjin Nan Hua catalyst Co., Ltd, it is stirred in the ammonium nitrate solution of 1 liter of 0.2M to 3 hours to carry out ion-exchange, then dry at 80 ℃, obtain h-mordenite 200 ℃ of roastings.
Taking 30 grams of described h-mordenites joins in the phosphate aqueous solution of 0.5 mol/L, at 60 ℃, flood 2 hours, then sample is placed in to baking oven, at 120 ℃, be dried 2 hours, then put into Muffle furnace, roasting 8 hours under 550 ℃, air atmosphere, takes out compressing tablet by the sample after roasting, and is sized to 20-40 order.In the catalyst sample that the ICP device measuring that uses Spectro Analypical Instruments GmbH to produce makes, the weight content of phosphorus is (with P
2o
5meter), record P
2o
5content accounts for 5.2 % by weight of catalyst sample gross weight.
Comparative example 1
The sample of this comparative example 1 is the h-mordenite shown in embodiment 1, and this zeolite is not with phosphorus dipping, its framework silicon-aluminum mol ratio (SiO
2/ Al
2o
3) be 15.
Comparative example 2
The sample of this comparative example 2 is the h-mordenites shown in embodiment 5, and this zeolite is not with phosphorus dipping, its framework silicon-aluminum mol ratio (SiO
2/ Al
2o
3) be 20.
Embodiment 6
According to the synthetic Hydrogen ferrierite of the disclosed method of document Ind.Eng.Chem.Res (2007) 46:2006, the XRF equipment that uses PHILIPS company to produce records its framework silicon-aluminum mol ratio (SiO
2/ Al
2o
3) be 20.
Take 30 grams of described Hydrogen ferrierites, joined in the phosphate aqueous solution of 0.5 mol/L, at the temperature of 60 ℃, stir dipping 2 hours, then within sample being put into baking oven, be dried 2 hours at 120 ℃, within then putting it into Muffle furnace, roasting 8 hours under the air atmosphere of 550 ℃, take out compressing tablet, and screening is 20-40 order.Record P
2o
5content accounts for 5.4 % by weight of catalyst sample gross weight.
Embodiment 7
The present embodiment adopts the mode identical with embodiment 6 to carry out catalyst preparation, distinguishes part and is, the solution that is used for zeolite to flood is the ammonium phosphate solution of 1 mol/L.Record P
2o
5content accounts for 10.2 % by weight of catalyst sample gross weight.
Embodiment 8
The present embodiment adopts the mode identical with embodiment 7 to carry out catalyst preparation, distinguishes part and is, the solution that is used for zeolite to flood is the ammonium phosphate solution of 2 mol/L.Record P
2o
5content accounts for 15.3 % by weight of catalyst sample gross weight.
Embodiment 9
The present embodiment adopts the mode identical with embodiment 6 to carry out catalyst preparation, distinguishes part and is, the solution that is used for zeolite to flood is the tripotassium phosphate aqueous solution of ester of 1 mol/L.Record P
2o
5content accounts for 11.5 % by weight of catalyst sample gross weight.
Embodiment 10
According to the synthetic Hydrogen ferrierite of the disclosed method of document Ind.Eng.Chem.Res (2007) 46:2006, the XRF equipment that uses PHILIPS company to produce records the framework silicon-aluminum mol ratio (SiO of end product Hydrogen ferrierite
2/ Al
2o
3) be 14.5.
Take 30 grams of described Hydrogen ferrierites, joined in the phosphate aqueous solution of 0.5 mol/L, at the temperature of 60 ℃, stir dipping 2 hours, use Buchner funnel suction filtration separating solids, within then solid sample being put into baking oven, be dried 2 hours at 120 ℃, then within putting it into Muffle furnace, roasting 8 hours under the air atmosphere of 550 ℃, takes out compressing tablet, and screening is 20-40 order.Record P
2o
5content accounts for 5.1 % by weight of catalyst sample gross weight.
Comparative example 3
The Hydrogen ferrierite that does not carry out phosphorus doping that this comparative example is used embodiment 6 to prepare, its framework si-al ratio (SiO
2/ Al
2o
3) be 20.
Comparative example 4
The Hydrogen ferrierite that does not carry out phosphorus doping that this comparative example is used embodiment 10 to prepare, its framework si-al ratio (SiO
2/ Al
2o
3) be 14.5.
In following reaction embodiment, use the catalyst sample of above embodiment 1-10 and comparative example 1-4 to carry out dimethyl ether carbonylation reaction.
This reaction is used micro fixed-bed reactor, and reactor is the stainless steel tube of 12 millimeters of internal diameters, loads therein 8 grams of catalyst, and reactor feed gas is CO and DME, and this two mol ratio is CO/DME=9/1, and the total reaction volume air speed of the two is 2500 hours
-1.Reaction temperature 195-200 ℃, reaction pressure is 0.8-1.3Mpa.
Gas chromatograph on-line analysis, TDX post is analyzed inorganic component, detects with thermal conductivity cell detector; Parapok R post is analyzed organic component, detects with hydrogen flame detector.
Result gathers the 1-5 that is listed in the table below.
Table 1
Table 2
Table 3
Table 4
Table 5
Can see from above experimental data, compare with ferrierite with the modenite of Doping Phosphorus not, by Doping Phosphorus component in zeolite, dimethyl ether conversion rate and methyl acetate selectively all obtained significant raising.
Claims (10)
1. the catalyst with synthesis of acetic acid methyl esters for dimethyl ether carbonylation reaction, described catalyst comprises zeolite and phosphorus, and described zeolite is modenite or ferrierite, take the gross weight of described catalyst as benchmark, with P
2o
5meter, the phosphorus content in described catalyst is 0.1-15 % by weight, wherein, the framework silicon-aluminum mol ratio of described modenite or ferrierite is SiO
2/ Al
2o
3=5:1 to 20:1.
2. catalyst as claimed in claim 1, is characterized in that, described modenite or ferrierite are Hydrogen.
3. catalyst as claimed in claim 1, is characterized in that, described framework silicon-aluminum mol ratio is SiO
2/ Al
2o
3=10:1 to 20:1.
4. catalyst as claimed in claim 1, is characterized in that, the phosphorus content in described catalyst is 1-10 % by weight.
5. catalyst as claimed in claim 1, is characterized in that, described catalyst is prepared in the following manner:
I) phosphorus-containing compound is water-soluble or other solvent, to be mixed with solution;
Ii) described modenite or ferrierite are flooded in described solution;
Iii) to dipping after described modenite or ferrierite is dried and roasting.
6. catalyst as claimed in claim 5, is characterized in that, described phosphorus-containing compound is selected from containing trivalent or phosphoric inorganic or organic compound, as phosphoric acid, phosphorous acid, ammonium hydrogen phosphate, triethyl phosphate, triphenylphosphine.
7. catalyst as claimed in claim 5, is characterized in that, step I i) be immersed in 20-100 ℃, more preferably at the temperature of 40-90 ℃, carry out; The dipping duration is 1-24 hour.
8. catalyst as claimed in claim 5, is characterized in that, step I ii) baking operation at the temperature of 300-600 ℃, carry out, described baking operation carries out in air or inert gas, described inert gas is nitrogen or argon gas.
9. one kind is synthesized the method for methyl acetate by dimethyl ether carbonylation, described method comprises: in the case of existing the catalyst as described in any one in claim 1-8, dimethyl ether is contacted with the unstripped gas that comprises carbon monoxide, thereby reaction generate methyl acetate, described in comprise carbon monoxide unstripped gas be pure CO gas or synthesis gas.
10. method as claimed in claim 9, is characterized in that, described method is carried out under the following conditions: the mol ratio of CO and dimethyl ether is 1-100, is preferably 1-50, more preferably 1-9; Reaction temperature is 100-350 ℃, preferably 150-250 ℃, more preferably 180-220 ℃; Reaction pressure is 0.1-10MPa; The cumulative volume air speed of the described unstripped gas that comprises carbon monoxide and dimethyl ether is 1000-10000 hour
-1.
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| CN106890668A (en) * | 2015-12-18 | 2017-06-27 | 中国科学院大连化学物理研究所 | A kind of catalyst for producing methyl acetate, its preparation method and application |
| CN106890668B (en) * | 2015-12-18 | 2019-05-17 | 中国科学院大连化学物理研究所 | A kind of catalyst producing methyl acetate, preparation method and application |
| CN106964396A (en) * | 2017-04-14 | 2017-07-21 | 中触媒新材料股份有限公司 | RTH type topological structure molecular sieve catalysts for dimethyl ether carbonylation reaction and its preparation method and application |
| CN106964396B (en) * | 2017-04-14 | 2019-06-28 | 中触媒新材料股份有限公司 | RTH type topological structure molecular sieve catalyst and its preparation method and application for dimethyl ether carbonylation reaction |
| CN109574839A (en) * | 2017-09-29 | 2019-04-05 | 中国科学院大连化学物理研究所 | A kind of method that synthesis gas directly produces methyl acetate and/or acetic acid |
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