CN104138768A - A preparing method of a ZSM-35 molecular sieve catalyst used for dimethyl ether carbonylation - Google Patents
A preparing method of a ZSM-35 molecular sieve catalyst used for dimethyl ether carbonylation Download PDFInfo
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Abstract
A preparing method of a ZSM-35 molecular sieve catalyst used for dimethyl ether carbonylation is provided. The method includes step of: treating a Na-type ZSM-35 molecular sieve with an ammonium nitrate solution, washing with water, drying and calcinating to obtain an H-type molecular sieve; heating the H-type ZSM-35 molecular sieve in an alkali having a concentration of 0.1-1.0 mol/L and a mixed solution of organic surfactants with different chain lengths with a water bath at 40-90 DEG C for 0.5-6 h; washing the obtained product until the product is neutral; and exchanging with an ammonium nitrate solution, filtering, washing with deionized water, drying and calcinating to obtain an H-type catalyst. When compared with unmodified ZSM-35 molecular sieve catalysts or ZSM-35 molecular sieve catalysts modified only with the alkali, the ZSM-35 molecular sieve catalyst modified with the alkali and the mixed solution of the organic surfactants with the different chain lengths is obviously improved in catalytic activity under the premise of maintaining stability.
Description
Technical field
The invention belongs to molecular sieve catalyst field, be specifically related to a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst.
Background technology
Methyl acetate is a kind of broad-spectrum fine chemical product, there is excellent dissolubility, of many uses, be a kind of very important Organic Chemicals and fabulous industrial solvent, become gradually in the world a kind of product of maturation, for replacing acetone, butanone, ethyl acetate, pentamethylene etc.The downstream product of methyl acetate mainly contains acetic acid, aceticanhydride, methyl acrylate, vinyl acetate and acetamide etc.Along with going deep into of research, the production technology of methyl acetate has obtained great development.With regard to traditional handicraft, adopt methyl alcohol and this method of acetic acidreaction generation methyl acetate under sulphuric acid catalysis more.The concentrated sulfuric acid cheap and easy to get is as catalyst, and its catalytic activity is higher.But, because it has compared with severe corrosive, strong oxidizing property and dehydration, can cause harmful effect to equipment and environment, and can produce a series of accessory substances, the post processing of product is very difficult.Therefore, finding new catalyst and new reaction system is the current research topic receiving much concern.
The synthetic method of methyl acetate has a lot, as the methanol dehydrogenation synthetic method taking methyl alcohol as raw material; Reaction rectification method taking methyl alcohol and acetic acid as raw material; Methanol Carbonylation one-step method taking methyl alcohol and CO as raw material; The homologation of methyl formate and dimethyl ether carbonyl process etc.Traditional carbonylation of methanol catalyst is taking loaded by heteropoly acid noble metal as main, but the type catalyst is expensive, and cost is higher.Through exploring for many years, researcher finds, can on acidic zeolite material, carry out dimethyl ether carbonylation reaction, has realized dimethyl ether Halogen, By Non-precious Metal Catalysts carbonylation process.Wherein acidic mordenites (MOR) shows good reactivity and selectivity of product at low temperatures, but less stable, and deactivation rate is fast.The ZSM-35 molecular sieve with FER structure shows good reaction stability.
The US Patent No. 20070238897A1 (2007) that is entitled as " carbonylation of alkyl ethers process " discloses the molecular sieve to have octatomic ring pore passage structure, such as MOR, FER and OFF are as ethers carbonylating catalyst, and the size in octatomic ring duct is greater than
Liu Junlong etc. have contrasted the difference of dimethyl ether carbonylation methyl acetate reactivity processed on MOR and ZSM-35 catalyst in article (Catal.Lett.2010,13933-37), find that ZSM-35 molecular sieve has better reaction stability and selectivity of product.At 200 ° of C, 1Mpa, DME/CO/N2/He=5/50/2.5/42.5, under the reaction condition of 12.5ml/min, methyl acetate selectively reaches 96%, but its dimethyl ether conversion rate is only 11%, therefore, urgently modification of this molecular sieve analog, is keeping, under good stability prerequisite, improving its catalytic activity.
In above-mentioned open source literature, only the ZSM-35 molecular sieve with FER structure is applied in dimethyl ether carbonylation reaction, do not relate to the application of ZSM-35 molecular sieve after modification, and some novel method of modifying is not applied on ZSM-35 molecular sieve.For ZSM-35 molecular sieve active experimental result effectively improving in dimethyl ether carbonylation reaction after alkali and different chain length organic surface active agent mixed solution processing modification, the present invention lays special stress on protecting a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst.
Summary of the invention
The object of this invention is to provide a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst, the method has adopted alkali and different chain length organic surface active agent mixed solution to process ZSM-35 molecular sieve catalyst, compared with the ZSM-35 molecular sieve catalyst of untreated or independent alkali treatment, keeping under good stability prerequisite, its reactivity is significantly improved.
The invention provides a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst, concrete steps are as follows: by the ammonium nitrate solution processing of Na-type ZSM-35 molecular sieve, after washing, dry, roasting, make H-type molecular sieve; The H-type molecular sieve obtaining is processed 0.5～6 hour with mixed solution heating water bath under 40～90 ° of C of aqueous slkali and different chain length organic surface active agent; Product obtained above washing, to neutral, with ammonium nitrate solution exchange, is filtered, and with making catalyst after deionized water washing, dry, roasting.
Preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst provided by the invention, the concentration of the aqueous slkali in described step (1) is 0.1～1.0mol/L.Described aqueous slkali is one or more (aqueous slkali is preferably NaOH) in NaOH, potassium hydroxide or ammonia spirit.
Preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst provided by the invention, different chain length organic surface active agent in described step (1) is softex kw (CTAB), one or more (different chain length organic surface active agent is preferably softex kw (CTAB)) in TTAB (TTAB) or DTAB (DTAB).
Preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst provided by the invention, the aqueous slkali in described step (1) and the concentration ratio of different chain length organic surface active agent are that 20:1～0.1:1(is preferably 10:1～1:1).
Preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst provided by the invention, the mixed solution treatment temperature of described aqueous slkali and different chain length organic surface active agent is preferably 40～90 ° of C, and the processing time is preferably 0.5～6 hour.
Preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst provided by the invention, in described step (1), baking temperature is 90～120 ° of C, be 6～12 hours drying time, sintering temperature is 450～600 ° of C, roasting time is 2～6 hours, and the concentration of ammonium nitrate solution is 1.0mol/L.
Preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst provided by the invention, in described step (2), baking temperature is 90～120 ° of C, be 6～12 hours drying time, sintering temperature is 450～600 ° of C, roasting time is 2～6 hours, and the concentration of ammonium nitrate solution is 1.0mol/L.
Na in ZSM-35 molecular sieve catalyst prepared by the present invention
2o content is less than or equal to 0.05wt%.
Alkali prepared by the present invention and different chain length organic surface active agent mixed solution modified ZSM-5-35 molecular sieve catalyst react for dimethyl ether and carbon monoxide carbonylation methyl acetate processed, can keep, under good stability prerequisite, improving its catalytic activity.
Brief description of the drawings
Fig. 1 is the catalyst prepared of the present invention for the conversion ratio of dimethyl ether carbonylation reaction Raw dimethyl ether with reaction time variation diagram, wherein, reaction condition: carbon monoxide/dimethyl ether (mol ratio)=10:1, P=2.0MPa, T=235 ° of C, WHSV (dimethyl ether)=0.13h
-1;
Fig. 2 is the selective temporal evolution figure of the catalyst prepared of the present invention for dimethyl ether carbonylation reaction object product methyl acetate, wherein, reaction condition: carbon monoxide/dimethyl ether (mol ratio)=10:1, P=2.0MPa, T=235 ° of C, WHSV (dimethyl ether)=0.13h
-1.
Detailed description of the invention
Following examples will be further described the present invention, but not thereby limiting the invention.Comparative example 1
60g ZSM-35 molecular sieve, in three times (1 hour/time) of ammonium nitrate solution exchange of 1mol/L, is washed twice (1 hour/time), and 110 DEG C are dried 12 hours, make catalyst Cat-A after roasting.Wherein ammonium nitrate exchange and washing temperature are 85 ° of C, and sintering temperature is 540 DEG C, 3 hours.Gained catalyst Cat-A detects through XRF, the Na in this catalyst
2o is less than 0.05wt%.
Comparative example 2
In the sodium hydroxide solution that is 0.2mol/L in 120ml concentration by 20g H-type ZSM-35 molecular sieve, under 80 ° of C, utilize heating water bath to process 4h, filter and wash to neutral.Three times (1 hour/time) of ammonium nitrate solution exchange by prepared molecular sieve with 1mol/L, washes twice (1 hour/time), makes catalyst Cat-B after roasting.Gained catalyst detects through XRF, the Na in this catalyst
2o is less than 0.05wt%.
Comparative example 3
Be in 0.04mol/L softex kw (CTAB) solution by 20g H-type ZSM-35 molecular sieve in 120ml concentration, utilize heating water bath to process 4h under 80 ° of C, filter and wash to neutral, 110 DEG C dry, 540 DEG C of roasting 6h.Three times (1 hour/time) of ammonium nitrate solution exchange by prepared molecular sieve with 1mol/L, washes twice (1 hour/time), makes catalyst Cat-C after roasting.Gained catalyst detects through XRF, the Na in this catalyst
2o is less than 0.05wt%.
Embodiment 1
The NaOH that is 0.4mol/L in 120ml concentration by 20g H-type ZSM-35 molecular sieve and concentration are in 0.04mol/L softex kw (CTAB) mixed solution, under 80 ° of C, utilize heating water bath to process 4h, filter and wash to neutral, 110 DEG C dry, 540 DEG C of roasting 6h.Three times (1 hour/time) of ammonium nitrate solution exchange by prepared molecular sieve with 1mol/L, washes twice (1 hour/time), makes catalyst Cat-D after roasting.Gained catalyst detects through XRF, the Na in this catalyst
2o is less than 0.05wt%.
Embodiment 2
The potassium hydroxide that is 0.3mol/L in 120ml concentration by 20g H-type ZSM-35 molecular sieve and concentration are in 0.08mol/L TTAB (TTAB) mixed solution, under 80 ° of C, utilize heating water bath to process 4h, filter and wash to neutral, 110 DEG C dry, 540 DEG C of roasting 6h.Three times (1 hour/time) of ammonium nitrate solution exchange by prepared molecular sieve with 1mol/L, washes twice (1 hour/time), makes catalyst Cat-E after roasting.Gained catalyst detects through XRF, the Na in this catalyst
2o is less than 0.05wt%.
Embodiment 3
The NaOH that is 0.8mol/L in 120ml concentration by 20g H-type ZSM-35 molecular sieve and concentration are in 0.08mol/L DTAB (DTAB) mixed solution, under 80 ° of C, utilize heating water bath to process 4h, filter and wash to neutral, 110 DEG C dry, 540 DEG C of roasting 6h.Three times (1 hour/time) of ammonium nitrate solution exchange by prepared molecular sieve with 1mol/L, washes twice (1 hour/time), makes catalyst Cat-F after roasting.Gained catalyst detects through XRF, the Na in this catalyst
2o is less than 0.05wt%.
Comparative example 1～3 and embodiment 1～3 reaction evaluating:
The reactivity worth evaluation of catalyst is carried out on conventional fixed bed reactors, and tube inner diameter is 16mm, and length is 33cm, catalyst loading amount 7g.Catalyst is at N
2the lower 520 ° of C pretreatment 2h of atmosphere, then at N
2under atmosphere, be cooled to reaction temperature.Raw material is dimethyl ether and carbon monoxide mixtures, from top to bottom by beds, generates object product methyl acetate, and reaction afterproduct adopts the on-line analysis of Aglient-7890A gas-chromatography.Dimethyl ether conversion rate temporal evolution on the ZSM-35 molecular sieve catalyst of different chain length organic surface active agent modification is as Fig. 1, and the selective temporal evolution of object product methyl acetate is as Fig. 2.As can be seen from Figure, the upper dimethyl ether conversion rate of ZSM-35 catalyst (Cat-D, Cat-E) after modification obviously improves, object product methyl acetate selectively improves by a small margin, process catalyst compared with untreated or independent alkali treatment through alkali and different chain length organic surface active agent mixed solution, under stability remains unchanged prerequisite, carbonylation activity is improved significantly.
Claims (9)
1. for a preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst, it is characterized in that: concrete steps are as follows:
(1) by Na-type ZSM-35 molecular sieve, use ammonium nitrate solution processing, after washing, dry, roasting, make H-type molecular sieve; This molecular sieve is processed 0.5～6 hour under 40～90 ° of C with alkali and different chain length organic surface active agent mixed solution;
(2) by the product washing of step (1) to neutral, with ammonium nitrate solution exchange, and with making catalyst after deionized water washing, dry, roasting.
2. according to a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst described in claim 1, it is characterized in that: the alkaline concentration in described step (1) is 0.1～1.0mol/L.
3. according to a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst described in claim 1, it is characterized in that: the aqueous slkali in described step (1) is one or more in NaOH, potassium hydroxide or ammonia spirit.
4. according to a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst described in claim 1, it is characterized in that: the different chain length organic surface active agent in described step (1) is softex kw (CTAB) one or more in TTAB (TTAB) or DTAB (DTAB).
5. according to a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst described in claim 1, it is characterized in that: the aqueous slkali in described step (1) and different chain length organic surface active agent concentration ratio are 20:1～0.1:1.
According to described in claim 5 for the preparation method of dimethyl ether carbonylation ZSM-35 molecular sieve catalyst, it is characterized in that: the aqueous slkali in described step (1) and the concentration ratio of different chain length organic surface active agent are 10:1～1:1.
7. according to a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst described in claim 1, it is characterized in that: in described step (1) and (2), baking temperature is 90～120 ° of C, and be 6～12 hours drying time.
8. according to a kind of preparation method for dimethyl ether carbonylation ZSM-35 molecular sieve catalyst described in claim 1, it is characterized in that: in described step (1) and (2), sintering temperature is 450～600 ° of C, and roasting time is 2～6 hours.
According to described in claim 1 for the preparation method of dimethyl ether carbonylation ZSM-35 molecular sieve catalyst, it is characterized in that: the concentration of described ammonium nitrate solution is 1.0mol/L.
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Cited By (2)
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| CN106311336A (en) * | 2016-08-11 | 2017-01-11 | 西南化工研究设计院有限公司 | Method for making methyl acetate through carbonylation of dimethyl ether and the modified molecular sieve catalyst and modification method thereof |
| CN112121847A (en) * | 2019-06-25 | 2020-12-25 | 高化学株式会社 | Catalyst for preparing methyl acetate by dimethyl ether carbonylation and preparation and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106311336A (en) * | 2016-08-11 | 2017-01-11 | 西南化工研究设计院有限公司 | Method for making methyl acetate through carbonylation of dimethyl ether and the modified molecular sieve catalyst and modification method thereof |
| CN106311336B (en) * | 2016-08-11 | 2019-02-15 | 西南化工研究设计院有限公司 | The method and its modified molecular sieve catalyst and method of modifying of Dimethyl ether carbonylation methyl acetate |
| CN112121847A (en) * | 2019-06-25 | 2020-12-25 | 高化学株式会社 | Catalyst for preparing methyl acetate by dimethyl ether carbonylation and preparation and application thereof |
| CN112121847B (en) * | 2019-06-25 | 2024-01-05 | 高化学株式会社 | Catalyst for preparing methyl acetate by dimethyl ether carbonylation and preparation and application thereof |
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