CN100467126C - Solid catalyst for synthesizing dimethyl ether by gas-phase method, its preparation and reactive process - Google Patents
Solid catalyst for synthesizing dimethyl ether by gas-phase method, its preparation and reactive process Download PDFInfo
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- CN100467126C CN100467126C CNB2006100143903A CN200610014390A CN100467126C CN 100467126 C CN100467126 C CN 100467126C CN B2006100143903 A CNB2006100143903 A CN B2006100143903A CN 200610014390 A CN200610014390 A CN 200610014390A CN 100467126 C CN100467126 C CN 100467126C
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- molecular sieve
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Abstract
A solid catalyst for the gas-phase synthesis of dimethylether is composed of ZSM-5 molecular sieve (50-90 Wt%) and zirconium oxide or MCM-41 molecular sieve (10-50 Wt%). Its preparing process and reaction technology are also disclosed.
Description
Technical field
The present invention relates to a kind of solid catalyst and preparation method and reaction process of synthesizing dimethyl ether by gas-phase.
Background technology
Dimethyl ether is called for short DME, is the simplest aliphatic ether, and important Organic Chemicals is widely used in industries such as pharmacy, fuel, agricultural chemicals, household chemicals.
In the quite a long time, dimethyl ether is to make through rectifying as the accessory substance that height is pressed into methyl ether, along with the low rise that is pressed into methyl ether technology, external high pressure methyl ether device is almost replaced by low-pressure process, thereby develops the technology of methyl alcohol catalytic dehydration and synthesizing dimethyl ether by synthetic gas.
Along with the attention of the Chinese government to environmental protection, domestic dimethyl ether production begins starting in recent years.Nearest some domestic research units, begin to develop production technology with natural gas or the direct dimethyl ether synthesis of coal gas, but still be in the development phase, domestic still do not have industrialized unit and formally produce, this type of technology also is subjected to the restriction of aspects such as raw material sources, equipment investment in addition, is not suitable for domestic penetration and promotion.
At present domestic production producer adopt substantially liquid phase, intermittently, sulfuric acid catalysis method dimethyl ether synthesis.Because this method technology is backward, equipment is perishable, contaminated environment is serious, is just eliminated gradually abroad.Adopting fixed bed reactors, is raw material with methyl alcohol, and under cryogenic conditions, the gas phase production technology of gas phase, continuous dimethyl ether synthesis becomes the first-selected production technology of dimethyl ether.
We have prepared the ZSM-5 molecular sieve catalyst and have been used for the methanol vapor phase dimethyl ether synthesis in work before this, and obtained result preferably, but because this catalyst has significant heat release temperature runaway phenomenon in initial reaction stage, cause the interior temperature of fixed bed reactors too high, the catalyst in reactor bed temperature can improve in 2～5 minutes about 50 ℃～100 ℃, and the reaction temperature of initial reaction stage control difficulty is bigger in the industrial production.So the manufacturing condition by changing initial reaction stage and develop a kind of not only had the molecular sieve catalyst high activity but also effectively the catalyst of inhibitory reaction initial stage temperature runaway phenomenon be significant.
Summary of the invention
The solid catalyst and preparation method and the reaction process that the purpose of this invention is to provide a kind of synthesizing dimethyl ether by gas-phase.Its characteristics are to add metal oxide in molecular sieve ZSM-5 molecular sieve solid catalyst, and the gained composite catalyst had not only had ZSM-5 molecular sieve catalyst high activity but also effective inhibitory reaction initial stage temperature runaway phenomenon.
Another object of the present invention provides several manufacturing conditions, by change to production technology, and under the prerequisite that guarantees high activity of catalyst, the temperature runaway phenomenon at effective inhibitory reaction initial stage, and be easy to industrial practical operation.
The solid composite catalyst of a kind of synthesizing dimethyl ether by gas-phase provided by the invention is made up of ZSM-5 molecular sieve and MCM-41 type molecular sieve, and the additional proportion of MCM-41 type molecular sieve is 10%～50% of a total catalyst weight.
The preparation method of the solid composite catalyst of described synthesizing dimethyl ether by gas-phase comprises the steps: the ZSM-5 molecular sieve powder and the MCM-41 type molecular sieve powder of metering are carried out mechanical mixture, add and intend thin water aluminium as adhesive, extruded moulding on banded extruder, natural air drying, 80 ℃～150 ℃ down oven dry 5～20 hours, 300 ℃～500 ℃ following roastings 5～10 hours.Described adhesive additional proportion (total catalyst weight) is: 5-20%.
The application of described solid composite catalyst in the methanol vapor phase dimethyl ether synthesis comprises the steps:
(1) above-mentioned solid composite catalyst is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 180 ℃, and in 180 ℃ of following purgings 30 minutes of beds, the adding weight content is 10%～30% water in material benzenemethanol, feed the mixed material of methyl alcohol and water, the liquid air speed of mixed material is 1.0h
-1, treat that temperature stabilization after 180 ℃, switches to methyl alcohol with raw material again, methanol feedstock liquid air speed is 0.5～2.0h
-1(the methyl alcohol volume that per hour passes through on the per volume of catalyst), reactant are collected sample and are adopted gas chromatographic analysis behind condenser; Or
(2) above-mentioned solid composite catalyst is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 100-150 ℃, and purged 30 minutes down at 150 ℃ in beds, feeding methanol feedstock then, methanol feedstock liquid air speed is 0.5～2.0h
-1, treat temperature stabilization after 150 ℃, again reaction temperature is brought up to 180 ℃ gradually and react.Reactant is collected sample and is adopted gas chromatographic analysis behind condenser; Or
(3) above-mentioned solid composite catalyst is seated in the normal pressure continuous fixed bed reactor, flows down at nitrogen and be warming up to 180 ℃, and purged 30 minutes down for 180 ℃ in beds, feed methanol feedstock then, methanol feedstock liquid air speed is 0.5～2.0h
-1, reactant is collected sample and is adopted gas chromatographic analysis behind condenser.
Technique effect of the present invention and superiority:
(1) by adding molecular sieve, catalyst activity is not affected, and still has very high catalytic activity under low-temperature condition, methanol conversion is more than 85%, and the temperature runaway phenomenon of initial reaction stage has obtained effective control, and the beds temperature runaway is reduced to 18 ℃ by original 50 ℃～100 ℃;
(2) by adding 10～30% water in raw material, the beds temperature runaway is reduced to 20 ℃ by original 50 ℃～100 ℃, after raw material is switched to methyl alcohol, tangible temperature rise phenomenon do not occur, and methanol conversion reaches more than 85%;
(3) by reacting initial temperature is reduced to 100 ℃～150 ℃ from 160 ℃～200 ℃, the beds temperature runaway is reduced to 20 ℃ by original 50 ℃～100 ℃, and reaction temperature is increased to 160 ℃～200 ℃, not seeing has the temperature runaway phenomenon, and methanol conversion reaches more than 85%;
(4) above Preparation of catalysts method is simple, is easy to accomplish the repeatability preparation, is convenient to industrial-scale production;
(5) above manufacturing condition in commercial plant operation, control simply, is convenient to industrial implementation.
The specific embodiment
The present invention can describe in detail by embodiment, but they are not that the present invention is done any restriction.
Embodiment 1
Preparation of Catalyst
Take by weighing 100 gram ZSM-5 molecular sieve catalyst powder and the deionized water 100g 30min that under high speed machine stirs, pulls an oar, then with the ZrOCl of speed (can use peristaltic pump) the adding 60g of 2ml/min
28H
2The O aqueous solution, the concentration of the aqueous solution is about 5ml H
2O/1.0g ZrOCl
28H
2O).After continue stirring 10min, slowly add (0.5ml/min, peristaltic pump) concentration and be 12.5% ammoniacal liquor (general merchandise ammoniacal liquor is 25%, dilutes one times and gets final product), solidify up to liquid mixed system moment.With the Cl in the deionized water flush away gained solids
-(with the AgNO of 0.2N
3Liquid under the solution check filter, naked-eye observation does not have white precipitate and gets final product), embathe three times with absolute ethyl alcohol again.At room temperature dry in the air to suitable degree extruded moulding.The strip solid is dried back (about 48h) naturally, at 120 ℃ of oven dry 3h, 550 ℃ of roasting 4h.
Reaction process:
Take by weighing 60 milliliters of above-mentioned catalyst and be seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and be warming up to 180 ℃, and purged 30 minutes down for 180 ℃ in beds, raw material is a methyl alcohol, methanol liquid air speed 1.0h
-1, reactant is collected sample and is adopted gas chromatographic analysis behind condenser, calculate methanol conversion.By the temperature-measuring casing at beds middle part, with the real reaction temperature of K type thermocouple measurement beds, the temperature runaway situation at observing response initial stage.The results are shown in Table 1.
Embodiment 2
Take by weighing 100 gram ZSM-5 molecular sieve catalyst powder,, add 20 grams and intend thin water aluminium as adhesive with 100 gram MCM-41 type molecular sieve powder mechanical mixture at normal temperatures.Other the results are shown in Table 1 with example 1.
The MCM-41 preparation method: being raw material with the metakaolin, be the template agent with the surfactant softex kw, after hydro-thermal reaction, 120 ℃ of crystallization are after 48 hours, and the Al-MCM-41 molecular sieve is synthesized in oven dry after 550 ℃ of roastings.
Concrete steps are: metakaolin, silica gel, alkali and water are mixed into gel, H
2O and surfactant mix, and mixed gel and surfactant solution are mixed again, stir, and aged at room temperature 1.5-3 hour, place stainless steel cauldron to carry out hydro-thermal reaction then, reaction finishes after suction filtration, washing, 120 ℃ of dryings.
Embodiment 3
Take by weighing 100 gram ZSM-5 molecular sieve catalyst powder, the direct tablet compressing moulding.Other the results are shown in Table 1 with example 1.
Several catalyst activity evaluation results of table 1 and temperature runaway situation
| Embodiment | 1 | 2 | 3 |
| Methanol conversion (mol%) | 88 | 86 | 89 |
| The temperature runaway amplitude (℃) | 14 | 22 | 47 |
Embodiment 4
Reaction process is investigated
Catalyst is seated in catalyst in the normal pressure continuous fixed bed reactor with example 3, flows down at nitrogen and is warming up to 180 ℃, and purged 30 minutes down for 180 ℃ in beds, feeds methanol feedstock, and the liquid air speed of methanol feedstock is 1.0h
-1, treat that temperature stabilization after 180 ℃, switches to methyl alcohol with raw material again, methanol feedstock liquid air speed is 1.0h
-1Reactant is collected sample and is adopted gas chromatographic analysis behind condenser.The results are shown in Table 2.
Embodiment 5
Reaction process is investigated
Catalyst is with example 3, catalyst is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 180 ℃, and in 180 ℃ of following purgings 30 minutes of beds, the adding weight content is 10% water in material benzenemethanol, feed the mixed material of methyl alcohol and water, the liquid air speed of mixed material is 1.0h
-1, treat that temperature stabilization after 180 ℃, switches to methyl alcohol with raw material again, methanol feedstock liquid air speed is 1.0h
-1Reactant is collected sample and is adopted gas chromatographic analysis behind condenser, other is with example 4.The results are shown in Table 2.
Embodiment 6
Reaction process is investigated
Catalyst is with example 3, catalyst is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 180 ℃, and in 180 ℃ of following purgings 30 minutes of beds, the adding weight content is 20% water in material benzenemethanol, feed the mixed material of methyl alcohol and water, the liquid air speed of mixed material is 1.0h
-1, treat that temperature stabilization after 180 ℃, switches to methyl alcohol with raw material again, methanol feedstock liquid air speed is 1.0h
-1Reactant is collected sample and is adopted gas chromatographic analysis behind condenser, other is with example 4.The results are shown in Table 2.
Embodiment 7
Reaction process is investigated
Catalyst is with example 3, catalyst is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 180 ℃, and in 180 ℃ of following purgings 30 minutes of beds, the adding weight content is 30% water in material benzenemethanol, feed the mixed material of methyl alcohol and water, the liquid air speed of mixed material is 1.0h
-1, treat that temperature stabilization after 180 ℃, switches to methyl alcohol with raw material again, methanol feedstock liquid air speed is 1.0h
-1Reactant is collected sample and is adopted gas chromatographic analysis behind condenser, other is with example 4.The results are shown in Table 2.
Embodiment 8
Reaction process is investigated
Catalyst is with example 3, and catalyst is seated in catalyst in the normal pressure continuous fixed bed reactor with example 3, flows down at nitrogen and is warming up to 180 ℃, and purged 30 minutes down for 180 ℃ in beds, feeds H earlier
2O, H
2The liquid air speed of O is 1.0h
-1, treat that temperature stabilization after 180 ℃, switches to methyl alcohol with raw material again, methanol feedstock liquid air speed is 1.0h
-1Reactant is collected sample and is adopted gas chromatographic analysis behind condenser, other is with example 4.The results are shown in Table 2.
Embodiment 9
Reaction process is investigated
Catalyst is seated in catalyst in the normal pressure continuous fixed bed reactor with example 3, flows down at nitrogen and is warming up to 150 ℃, and purged 30 minutes down at 150 ℃ in beds, feeds methanol feedstock then, and methanol feedstock liquid air speed is 1.0h
-1, treat temperature stabilization after 150 ℃, again reaction temperature is brought up to 180 ℃ gradually and react.Reactant is collected sample and is adopted gas chromatographic analysis behind condenser.Other is with example 4.The results are shown in Table 2.
Table 2 differential responses technology assessment result and temperature runaway situation
| Embodiment | 4 | 5 | 6 | 7 | 8 | 9 |
| Methanol conversion (after recovering normal charging) (mol%) | 89 | 90 | 90 | 90 | 88 | 89 |
| The temperature runaway amplitude (℃) | 47 | 20 | 21 | 21 | 18 | 23 |
| Recover temperature runaway amplitude after the normal charging | 0 | 0 | 0 | 0 | 0 |
Claims (4)
1, a kind of solid composite catalyst of synthesizing dimethyl ether by gas-phase, it is characterized in that it intends thin water aluminium roasting afterproduct by ZSM-5 molecular sieve and MCM-41 type molecular sieve and adhesive and form, the additional proportion of MCM-41 type molecular sieve is 10%～50% of a total catalyst weight.
2, the preparation method of the solid composite catalyst of the described synthesizing dimethyl ether by gas-phase of claim 1, it is characterized in that comprising the steps: the ZSM-5 molecular sieve powder and the MCM-41 type molecular sieve powder of metering are carried out mechanical mixture, add and intend thin water aluminium as adhesive, extruded moulding on banded extruder, natural air drying, 80 ℃～150 ℃ down oven dry 5～20 hours, 300 ℃～500 ℃ following roastings 5～10 hours.
3, according to the preparation method of the solid composite catalyst of the described synthesizing dimethyl ether by gas-phase of claim 2, it is characterized in that described adhesive additional proportion is the 5-20% of total catalyst weight.
4, the application of the described solid composite catalyst of claim 1 in the methanol vapor phase dimethyl ether synthesis is characterized in that comprising the steps:
(1) the described solid composite catalyst of claim 1 is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 180 ℃, and in 180 ℃ of following purgings 30 minutes of beds, the adding weight content is 10%～30% water in material benzenemethanol, feed the mixed material of methyl alcohol and water, the liquid air speed of mixed material is 1.0h
-1, treat that temperature stabilization after 180 ℃, switches to methyl alcohol with raw material again, methanol feedstock liquid air speed is 0.5～2.0h
-1, reactant is collected sample and is adopted gas chromatographic analysis behind condenser; Or
(2) the described solid composite catalyst of claim 1 is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 100-150 ℃, and purged 30 minutes down at 150 ℃ in beds, feeding methanol feedstock then, methanol feedstock liquid air speed is 0.5～2.0h
-1, treat temperature stabilization after 150 ℃, again reaction temperature to be brought up to 180 ℃ gradually and react, reactant is collected sample and is adopted gas chromatographic analysis behind condenser; Or
(3) the described solid composite catalyst of claim 1 is seated in the normal pressure continuous fixed bed reactor, flow down at nitrogen and to be warming up to 180 ℃, and, feeding methanol feedstock then in 180 ℃ of following purgings 30 minutes of beds, methanol feedstock liquid air speed is 0.5～2.0h
-1, reactant is collected sample and is adopted gas chromatographic analysis behind condenser.
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|---|---|---|---|
| CNB2006100143903A CN100467126C (en) | 2006-06-20 | 2006-06-20 | Solid catalyst for synthesizing dimethyl ether by gas-phase method, its preparation and reactive process |
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|---|---|---|---|
| CNB2006100143903A CN100467126C (en) | 2006-06-20 | 2006-06-20 | Solid catalyst for synthesizing dimethyl ether by gas-phase method, its preparation and reactive process |
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| CN102233266A (en) * | 2010-04-26 | 2011-11-09 | 边俊民 | N,N-dimethylaniline gaseous phase synthesis solid catalyst and preparation method and reaction process thereof |
| CN104841479B (en) * | 2015-04-15 | 2017-09-08 | 西安近代化学研究所 | A kind of compound solid-acid amination catalysis and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5182242A (en) * | 1992-06-02 | 1993-01-26 | Mobil Oil Corp. | Catalysts bound with low acidity refractory oxide |
| US5684213A (en) * | 1996-03-25 | 1997-11-04 | Chemical Research & Licensing Company | Method for the preparation of dialkyl ethers |
-
2006
- 2006-06-20 CN CNB2006100143903A patent/CN100467126C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5182242A (en) * | 1992-06-02 | 1993-01-26 | Mobil Oil Corp. | Catalysts bound with low acidity refractory oxide |
| US5684213A (en) * | 1996-03-25 | 1997-11-04 | Chemical Research & Licensing Company | Method for the preparation of dialkyl ethers |
Non-Patent Citations (2)
| Title |
|---|
| 氧化物-NaZSM-5催化剂的研究. 杨民，徐柏庆.催化学报，第17卷第1期. 1996 |
| 氧化物-NaZSM-5催化剂的研究. 杨民，徐柏庆.催化学报，第17卷第1期. 1996 * |
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