CN104610028A - Method for preparing polymethoxydimethyl ether - Google Patents
Method for preparing polymethoxydimethyl ether Download PDFInfo
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- CN104610028A CN104610028A CN201510103577.XA CN201510103577A CN104610028A CN 104610028 A CN104610028 A CN 104610028A CN 201510103577 A CN201510103577 A CN 201510103577A CN 104610028 A CN104610028 A CN 104610028A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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Abstract
The invention provides a method for preparing polymethoxydimethyl ether. The method comprises the following steps: adding methylal and trioxymethylene into a first-stage reactor, controlling the reaction temperature and pressure of the first-stage reactor, and starting a circulating pump to enable materials to produce a self-circulation reaction in the first-stage reactor; after reacting the materials in the first-stage reactor for a period of time, enabling the materials in the first-stage reactor to enter a buffer bin, and regulating the temperature and the pressure of the buffer bin; closing a switch valve between the first-stage reactor and the buffer bin and continuously feeding the materials into the first-stage reactor; after the temperature and the pressure of the buffer bin are the same as those of a next-stage reactor, enabling the materials to enter the next-stage reactor; controlling the reaction temperature and pressure of the next-stage reactor and starting the circulating pump to enable the material to produce the circulation reaction in the reactor; enabling the materials to enter multiple stages of reactors in sequence for reaction, wherein different catalysts are arranged in the reactors. With adoption of the method for preparing polymethoxydimethyl ether, the catalytic efficiency is high, energy is saved, and after-treatment is simple.
Description
Technical field
The present invention relates to chemical field, in particular to a kind of method preparing polymethoxy dimethyl ether.
Background technology
Polymethoxy dimethyl ether, as diesel oil additive, effectively can improve diesel oil at in-engine burning quality, improves thermo-efficiency, reduces pollutant emission, is considered to the diesel-dope having application prospect.
China is energy consumption big country, but China is also the energy country that especially hydrocarbon resources is relatively poor, and this contradiction brings challenge and hidden danger greatly to the energy security of China.On the one hand, readjust the energy structure, on the other hand, find the road that fungible energy source becomes an important alleviation Pressure on Energy.
Many research is carried out for synthesis polymethoxy dimethyl ether product both at home and abroad.Can carry out effecting reaction in the presence of a catalyst owing to preparing polymethoxy dimethyl ether needs, therefore, a kind of suitable catalyzer has great significance for preparing polymethoxy dimethyl ether.
At present, the common catalyzer for the preparation of polymethoxy dimethyl ether is divided into liquid catalyst and the large class of solid catalyst two, liquid catalyst mainly comprises acid catalyst as the vitriol oil, and ionic-liquid catalyst, and the representative of solid catalyst is molecular sieve catalyst and cation resin catalyzing agent.
High cost, high energy consumption, high pollution bring great puzzlement to the production of polymethoxy dimethyl ether.Production method common at present uses single catalyzer to react.But above-mentioned catalyzer all exists certain problem, the reaction conditions as the acid catalyst in liquid catalyst is violent, aftertreatment more complicated, and energy consumption is high, pollutes large; Ionic-liquid catalyst is not easily separated, high to equipment corrosion, expensive etc.; The catalytic efficiency of molecular sieve catalyst and cation resin catalyzing agent is lower, recycles rate low, and cost is higher.
Due in polymethoxy dimethyl ether (DMMn) production, the product that n value is different has series multiple, and only has the product of n=3-8 to meet the requirements.Therefore, the selectivity in production process is also extremely important, and the problem that current catalyzer ubiquity selectivity is not high.
Summary of the invention
For Problems existing in existing method, the invention provides a kind of method preparing polymethoxy dimethyl ether, to solve the problem.
The present invention is achieved in that
The application provides a kind of method preparing polymethoxy dimethyl ether, said method comprising the steps of:
A. reactant methylal and trioxymethylene are added in A reactor, control temperature of reaction and the reaction pressure of described A reactor respectively, and the recycle pump opening described A reactor makes material self-circulating reaction in described A reactor;
B., after material reacts for some time in described A reactor, the opening-closing valve opened between described A reactor and surge bunker makes the material in a described reactor enter the described surge bunker be arranged between described A reactor and next stage reactor; Close described opening-closing valve, regulate the temperature and pressure of described surge bunker; Continue to charging in described A reactor;
C. the temperature of reaction of surge bunker temperature and surge bunker pressure and described next stage reactor and reaction pressure consistent after, the opening-closing valve opened between described surge bunker and described next stage reactor makes the material in described surge bunker enter described next stage reactor;
D. control temperature of reaction and the reaction pressure of described next stage reactor, and the recycle pump opening described next stage reactor makes material react at described next stage reactor internal recycle;
E. material enters reaction in staged reactor successively, arranges different catalyzer in each stage reactor.
Multiple catalysts is combined by the application, utilizes solid catalyst easily to process, the advantage that liquid catalyst catalytic efficiency is high, solid, liquid catalyst are combined, can catalytic efficiency be improved on the one hand, can aftertreatment technology be simplified on the other hand, reduce production cost.In addition, use the reaction unit of special classification, band surge bunker, the temperature and pressure that can effectively utilize upper level to react, save energy, reduces costs further; The reaction unit of classification, band surge bunker is conducive to the stability ensureing whole reactive system, improves the degree of safety of producing.
Preferably, described catalyzer is selected from the group of molecular sieve catalyst, acid cation exchange resin catalyst, acid ion exchange fibre catalyst and ionic-liquid catalyst composition; When using ionic-liquid catalyst, described ionic-liquid catalyst is arranged in last step reactor.
Preferably, described molecular sieve catalyst is selected from Y zeolite and type ZSM 5 molecular sieve; Described acid cation exchange resin catalyst is sulfonic group strong-acid Zeo-karb; Described acid ion exchange fibre catalyst is selected from polypropylene-base sulfonic group cation exchange fibre and polyvinylsulfonic acid base positively charged ion changes fiber.
Further preferably, the temperature of reaction being provided with the reactor of described acid cation exchange resin catalyst is 80-140 DEG C, and reaction pressure is 0.5-3.0MPa, and the reaction times is 0.5h-20h.
More preferably, the amount of described acid cation exchange resin catalyst is the 3%-10% of the quality of reactant methylal and trioxymethylene.
Preferably, the temperature of reaction being provided with the reactor of described molecular sieve catalyst is 90-150 DEG C, and reaction pressure is 0-3.0MPa, and the reaction times is 5h-25h.
More preferably, the amount of described molecular sieve catalyst is the 5%-15% of the quality of reactant methylal and trioxymethylene.
Preferably, the temperature of reaction being provided with the reactor of ionic-liquid catalyst is 30-130 DEG C, and reaction pressure is 0-0.5MPa, and the reaction times is 1h-10h.
More preferably, the mol ratio of described ionic-liquid catalyst and trioxymethylene is 1:20-300.
Alternatively, the mass ratio of described reactant methylal and trioxymethylene is 0.5-3:1.
A kind of method preparing polymethoxy dimethyl ether using the application to provide, at least one in following beneficial effect can be brought:
The first, combinationally use solid-liquid catalyzer, can reaction efficiency be improved; The second, use the solid catalyst Substitute For Partial liquid catalyst of relative moderate, greatly can reduce production cost; 3rd, use the reaction unit that surge bunker is set, stability and the degree of safety of reaction unit entirety can be improved; 4th, rational selecting catalyst arranges order, can greatly reduce energy consumption and post-processing difficulty; 5th, select rational reaction conditions, the reasonable disposition between each level reactor can be ensured, further improve reaction efficiency, reduce production cost, save energy, protection of the environment.
Embodiment
Below in conjunction with embodiment, the application is described in further detail.Be understandable that, specific embodiment described herein is only for explaining the application, but not the restriction to the application.
Many for the preparation of the catalyzer of polymethoxy dimethyl ether at present.The general strong acid that adopts is as catalyzer in early days, as sulfuric acid, hydrochloric acid; But the corrodibility of strong acid is higher, higher to the requirement of equipment, input cost is large, maintenance difficulties is large, and production security is poor, and aftertreatment also relatively bothers.In order to simplify aftertreatment technology, a lot of researcher is devoted to the exploitation of solid catalyst, the such as metal oxide catalyst etc. of molecular sieve catalyst, cation exchange resin catalyst, loading type, the relative merits of these solid catalysts are different, some catalytic efficiency is lower, as molecular sieve catalyst; Some complete processing is complicated, high cost, as some metal oxide catalyst; Some recyclabilities are also had to compare poor.In a word, the factor such as catalytic efficiency, cost, aftertreatment, recyclability more or less governs promoting the use of of various catalyzer, and several factor is difficult to effectively unite.
For this situation, catalyzer relatively low for low for cost catalytic efficiency and the high catalyzer of cost height catalytic efficiency are combined, to reach the balance of above-mentioned factor by the application.Multiple catalysts uses several aspect to need to consider together: 1. several catalyzer used successively should interact, the catalyzer of previous utilization should noresidue or low residue in reaction system; 2. the use of multiple catalysts should not increase the difficulty that final product is separated; 3. the condition of multiple catalysts catalyzed reaction not should difference excessive, the burden of increase reactive system that should be not too much.
For above-mentioned several aspect: for 1-2 point, adopt solid catalyst in front, the posterior reactive mode of liquid catalyst, minimizing interacts, and does not increase separating difficulty; For the 2nd point, select suitable reaction conditions, and add surge bunker between every A reactor, regulate the difference of the aspects such as the temperature between each order reaction, pressure, the stability of reaction system is strengthened.
With specific embodiment, the present invention is set forth below.
Embodiment 1
By reactant methylal and trioxymethylene according to mass ratio be 0.5:1 add be fixedly installed Y zeolite catalyst (quality is 5% of reactant) A reactor in, the temperature of reaction controlling A reactor is 90 DEG C, reaction pressure is 3.0MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 5h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and second reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Pyrrolidone acidic ionic liquid catalysts (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:20) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 30 DEG C, pressure is 0.5MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 10h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 2
By reactant methylal and trioxymethylene according to mass ratio be 3:1 add be fixedly installed type ZSM 5 molecular sieve catalyzer (quality is 15% of reactant) A reactor in, the temperature of reaction controlling A reactor is 150 DEG C, reaction pressure is 0MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 25h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Glyoxaline ion liquid catalyzer (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:300) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 130 DEG C, pressure is 0MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 1h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Molecular sieve catalyst and ionic-liquid catalyst combinationally use, and catalytic efficiency is higher than single catalyst.
Embodiment 3
By reactant methylal and trioxymethylene according to mass ratio be 1:1 add be provided with sulfonic group strong-acid cation resin catalyzing agent (quality is 10% of reactant) A reactor in, the temperature of reaction controlling A reactor is 80 DEG C, reaction pressure is 0.5MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 0.5h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Pyridine ionic liquid catalyzer (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:200) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 100 DEG C, pressure is 0.3MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 5h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 4
By reactant methylal and trioxymethylene according to mass ratio be 2:1 add be provided with sulfonic group acidulous cation resin catalyzer (quality is 3% of reactant) A reactor in, the temperature of reaction controlling A reactor is 140 DEG C, reaction pressure is 3MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 20h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Alkyl quaternaries ionic-liquid catalyst (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:100) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 120 DEG C, pressure is 0.1MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 7h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 5
By reactant methylal and trioxymethylene according to mass ratio be 2.5:1 add be provided with sulfonic group strong-acid cation exchange resin catalyst (quality is 7% of reactant) A reactor in, the temperature of reaction controlling A reactor is 100 DEG C, reaction pressure is 2.5MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 10h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
HMCM-22 molecular sieve catalyst (quality is 10% of reactant) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 100 DEG C, pressure is 1MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 15h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 6
By reactant methylal and trioxymethylene according to mass ratio be 1.5:1 add be provided with sulfonic group strong-acid cation resin catalyzing agent (quality is 4% of reactant) A reactor in, the temperature of reaction controlling A reactor is 90 DEG C, reaction pressure is 1.5MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 5h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Polypropylene-base sulfonic group cation exchange fibre (quality is 2% of reactant) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 100 DEG C, pressure is 0.3MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 25h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 7
By reactant methylal and trioxymethylene according to mass ratio be 1.5:1 add be fixedly installed Y zeolite catalyst (quality is 8% of reactant) A reactor in, the temperature of reaction controlling A reactor is 120 DEG C, reaction pressure is 2MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 12h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Polyvinylsulfonic acid base cation exchange fibre (quality is 4% of reactant) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 90 DEG C, pressure is 0.5MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 20h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 8
By reactant methylal and trioxymethylene according to mass ratio be 2:1 add be provided with polypropylene-base sulfonic group cation exchange fibre (quality is 5% of reactant) A reactor in, the temperature of reaction controlling A reactor is 105 DEG C, reaction pressure is 1MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 10h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Pyrrolidinone compounds ionic-liquid catalyst (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:150) is provided with in second reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and second reactor and reaction pressure (temperature 110 DEG C, pressure is 0.2MPa) consistent after, the opening-closing valve opened between surge bunker and second reactor makes the material in surge bunker enter second reactor;
Control temperature of reaction and the reaction pressure of second reactor, and the recycle pump opening second reactor makes material at second reactor internal recycle reaction 6h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 9
By reactant methylal and trioxymethylene according to mass ratio be 2.5:1 add be fixedly installed Y zeolite catalyst (quality is 9% of reactant) A reactor in, the temperature of reaction controlling A reactor is 95 DEG C, reaction pressure is 0.5MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 7h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Polyvinylsulfonic acid base cation exchange fibre (quality is 4% of reactant) is provided with in second reactor, the temperature of reaction controlling second reactor is 100 DEG C, reaction pressure is 1MPa, and the recycle pump opening second reactor makes material self-circulating reaction in second reactor;
After reaction 3h, the opening-closing valve opened between second reactor and surge bunker makes the material in two reactors enter the surge bunker be arranged between second reactor and three reactor; Close the opening-closing valve between second reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in second reactor;
Pyrrolidinone compounds ionic-liquid catalyst (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:30) is provided with in three reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and three reactor and reaction pressure (temperature 50 C, pressure is 0.4MPa) consistent after, the opening-closing valve opened between surge bunker and three reactor makes the material in surge bunker enter three reactor;
Control temperature of reaction and the reaction pressure of three reactor, and the recycle pump opening three reactor makes material at three reactor internal recycle reaction 2h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
Embodiment 10
By reactant methylal and trioxymethylene according to mass ratio be 2.5:1 add be fixedly installed Y zeolite catalyst (quality is 7% of reactant) A reactor in, the temperature of reaction controlling A reactor is 100 DEG C, reaction pressure is 0.5MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 10h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Storng-acid cation exchange resin (quality is 4% of reactant) is provided with in second reactor, the temperature of reaction controlling second reactor is 110 DEG C, reaction pressure is 0.5MPa, and the recycle pump opening second reactor makes material self-circulating reaction in second reactor;
After reaction 2h, the opening-closing valve opened between second reactor and surge bunker makes the material in two reactors enter the surge bunker be arranged between second reactor and three reactor; Close the opening-closing valve between second reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in second reactor;
Polypropylene-base sulfonic group cation exchange fibre (quality is 3% of reactant) is provided with in three reactor, the temperature of reaction controlling reactor is 95 DEG C, reaction pressure is 0.5MPa, and the recycle pump opening three reactor makes material self-circulating reaction in three reactor;
After reaction 3h, the opening-closing valve opened between three reactor and surge bunker makes the material in three reactor enter the surge bunker be arranged between three reactor and fourth-order reaction device; Close the opening-closing valve between three reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in three reactor;
Pyrrolidinone compounds ionic-liquid catalyst (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:250) is provided with in fourth-order reaction device; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and three reactor and reaction pressure (temperature 70 C, pressure is 0.5MPa) consistent after, the opening-closing valve opened between surge bunker and fourth-order reaction device makes the material in surge bunker enter fourth-order reaction device;
Control temperature of reaction and the reaction pressure of fourth-order reaction device, and the recycle pump opening fourth-order reaction device makes material at fourth-order reaction device internal recycle reaction 1h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency and selectivity.
The result of embodiment 1-10 is as shown in table 1 below:
Table 1 transformation efficiency and selectivity
| Embodiment | Transformation efficiency/% | Selectivity/% |
| 1 | 90.1 | 69.4 |
| 2 | 91.8 | 68.8 |
| 3 | 92.3 | 68.5 |
| 4 | 91.4 | 69.5 |
| 5 | 89.2 | 68.9 |
| 6 | 93.5 | 70.1 |
| 7 | 90.7 | 69.9 |
| 8 | 93.6 | 71.2 |
| 9 | 95.8 | 75.3 |
| 10 | 96.9 | 77.1 |
In order to contrast the advantage of the application relative to single catalyst, choose Y zeolite catalyst, acidic cation exchanges macroporous resin, polypropylene-base sulfonic group strong-acid ion-exchange fiber, methyl-2-pyrrolidone sulfate ion liquid catalyst in contrast, often kind of catalyzer carries out 50 tests according to most preferred condition, obtain its transformation efficiency and optionally mean value, the mean value that the method provided with embodiment 9 carries out testing for 50 times contrasts, and its result is as shown in table 2 below:
Table 2 controlled trial result
From upper table 2, the method that the application provides, its transformation efficiency and selectivity are all than the height of single catalyst.
In addition, contriver finds in process of the test, in this 3 class catalyzer of ion exchange resin, ion-exchange fiber, ionic-liquid catalyst, there is some transformation efficiencys and the higher catalyzer of selectivity, the method that some (such as Chinese Academy of Sciences's orchidization invent some ionic-liquid catalysts under optimum condition) has even exceeded the application to be provided carries out the transformation efficiency that reacts and selectivity, but these catalyzer also exist production cost high, yield poorly, one or more problem such as aftertreatment difficulty.
Present application contemplates production cost, output, catalytic efficiency, the problem such as requirement, aftertreatment, environmental pollution to production unit, multiple catalysts is comprehensively used.Such as, the catalytic efficiency of molecular sieve catalyst is very low, but its cost is low, output is large, aftertreatment is simple, low for equipment requirements, be difficult to during single use meet higher production efficiency, it is high with cost, yield poorly, aftertreatment bothers relatively, the ionic-liquid catalyst high to equipment requirements is combined, while enhancing productivity, also can effectively production control cost and the harm to environment, comprehensive benefit is high.
In addition, generally ionic-liquid catalyst is arranged in last step reactor, the setting of each stage reactor is before not limited to the order that the embodiment of the present application provides, should reaction conditions be considered and match with actual production equipment, the order of rational preparation catalyzer, effectively to utilize the energy, reduce production cost further.
Through repetition test, consider the factor of catalyzer cost, energy consumption, aftertreatment and all respects such as transformation efficiency and selectivity, obtaining most preferred scheme is:
Embodiment 11
By reactant methylal and trioxymethylene according to mass ratio be 3:1 add be fixedly installed Y zeolite catalyst (quality is 15% of reactant) A reactor in, the temperature of reaction controlling A reactor is 90 DEG C, reaction pressure is 0.5MPa, and the recycle pump opening A reactor makes material self-circulating reaction in A reactor;
After reaction 25h, the opening-closing valve opened between A reactor and surge bunker makes the material in A reactor enter the surge bunker be arranged between A reactor and next stage reactor; Close the opening-closing valve between A reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in A reactor;
Polyvinylsulfonic acid base cation exchange fibre (quality is 5% of reactant) is provided with in second reactor, the temperature of reaction controlling second reactor is 90 DEG C, reaction pressure is 0.5MPa, and the recycle pump opening second reactor makes material self-circulating reaction in second reactor;
After reaction 5h, the opening-closing valve opened between second reactor and surge bunker makes the material in two reactors enter the surge bunker be arranged between second reactor and three reactor; Close the opening-closing valve between second reactor and surge bunker, regulate the temperature and pressure of surge bunker; Continue to charging in second reactor;
Pyrrolidinone compounds ionic-liquid catalyst (mol ratio of ionic-liquid catalyst and trioxymethylene is 1:300) is provided with in three reactor; The temperature of reaction of storehouse to be buffered temperature and surge bunker pressure and three reactor and reaction pressure (temperature 90 DEG C, pressure is 0.5MPa) consistent after, the opening-closing valve opened between surge bunker and three reactor makes the material in surge bunker enter three reactor;
Control temperature of reaction and the reaction pressure of three reactor, and the recycle pump opening three reactor makes material at three reactor internal recycle reaction 5h.
Reaction terminates rear discharging, aftertreatment reaction mass, detects transformation efficiency 95.2% and selectivity 70.3%.
Although the transformation efficiency of the program, selectivity are not the highest, when ensureing transformation efficiency and selectivity is higher, its cost, energy consumption, system stability etc. are best.
Consider the complicacy of production, and interacting between various catalyzer, in order to weaken the impact of the problems referred to above on reaction, general use three kinds of catalyzer carry out reacting, four kinds can be used at most, exceed four kinds and will bring labile factor to production unit, also bring certain difficulty to actually operating.Because actual production often might not pursue high conversion and highly selective, each key element of production be considered, to improve comprehensive benefit.
The foregoing is only the preferred embodiment of the application, be not limited to the application, for a person skilled in the art, the application can have various modifications and variations.Within all spirit in the application and principle, any amendment done, equivalent replacement, improvement etc., within the protection domain that all should be included in the application.
Claims (10)
1. prepare a method for polymethoxy dimethyl ether, wherein, said method comprising the steps of:
A. reactant methylal and trioxymethylene are added in A reactor, control temperature of reaction and the reaction pressure of described A reactor respectively, and the recycle pump opening described A reactor makes material self-circulating reaction in described A reactor;
B., after material reacts for some time in described A reactor, the opening-closing valve opened between described A reactor and surge bunker makes the material in a described reactor enter the described surge bunker be arranged between described A reactor and next stage reactor; Close described opening-closing valve, regulate the temperature and pressure of described surge bunker; Continue to charging in described A reactor;
C. the temperature of reaction of surge bunker temperature and surge bunker pressure and described next stage reactor and reaction pressure consistent after, the opening-closing valve opened between described surge bunker and described next stage reactor makes the material in described surge bunker enter described next stage reactor;
D. control temperature of reaction and the reaction pressure of described next stage reactor, and the recycle pump opening described next stage reactor makes material react at described next stage reactor internal recycle;
E. material enters reaction in staged reactor successively, arranges different catalyzer in each stage reactor.
2. method according to claim 1, wherein, described catalyzer is selected from the group of molecular sieve catalyst, acid cation exchange resin catalyst, acid ion exchange fibre catalyst and ionic-liquid catalyst composition; When using ionic-liquid catalyst, described ionic-liquid catalyst is arranged in last step reactor.
3. method according to claim 2, wherein, described molecular sieve catalyst is selected from Y zeolite and type ZSM 5 molecular sieve; Described acid cation exchange resin catalyst is sulfonic group strong-acid Zeo-karb; Described acid ion exchange fibre catalyst is selected from polypropylene-base sulfonic group cation exchange fibre and polyvinylsulfonic acid base positively charged ion changes fiber.
4. method according to claim 3, wherein, the temperature of reaction being provided with the reactor of described acid cation exchange resin catalyst is 80-140 DEG C, and reaction pressure is 0.5-3.0MPa, and the reaction times is 0.5h-20h.
5. method according to claim 4, wherein, the amount of described acid cation exchange resin catalyst is the 3%-10% of the quality of reactant methylal and trioxymethylene.
6. method according to claim 3, wherein, the temperature of reaction being provided with the reactor of described molecular sieve catalyst is 90-150 DEG C, and reaction pressure is 0-3.0MPa, and the reaction times is 5h-25h.
7. method according to claim 6, wherein, the amount of described molecular sieve catalyst is the 5%-15% of the quality of reactant methylal and trioxymethylene.
8. method according to claim 3, wherein, the temperature of reaction being provided with the reactor of ionic-liquid catalyst is 30-130 DEG C, and reaction pressure is 0-0.5MPa, and the reaction times is 1h-10h.
9. method according to claim 8, wherein, the mol ratio of described ionic-liquid catalyst and trioxymethylene is 1:20-300.
10. the method according to any one of claim 2-9, wherein, the mass ratio of described reactant methylal and trioxymethylene is 0.5-3:1.
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| CN105753666A (en) * | 2016-05-10 | 2016-07-13 | 中国人民解放军总后勤部油料研究所 | Method for preparing polyoxymethylene dimethyl ether |
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| CN101198576A (en) * | 2005-06-15 | 2008-06-11 | 巴斯福股份公司 | Method for the production of polyoxymethylene dialkyl ethers from trioxan and dialkylethers |
| CN102249869A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for catalytically synthesizing polymethoxy dimethyl ether by ionic liquid |
| CN104119210A (en) * | 2014-06-27 | 2014-10-29 | 北京东方红升新能源应用技术研究院有限公司 | Method for preparing polymethoxy dimethyl ether by virtue of slurry bed in combination with fixed bed |
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| CN101198576A (en) * | 2005-06-15 | 2008-06-11 | 巴斯福股份公司 | Method for the production of polyoxymethylene dialkyl ethers from trioxan and dialkylethers |
| CN102249869A (en) * | 2010-05-18 | 2011-11-23 | 中国科学院兰州化学物理研究所 | Technical process for catalytically synthesizing polymethoxy dimethyl ether by ionic liquid |
| CN104119210A (en) * | 2014-06-27 | 2014-10-29 | 北京东方红升新能源应用技术研究院有限公司 | Method for preparing polymethoxy dimethyl ether by virtue of slurry bed in combination with fixed bed |
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