CN109433146A - A kind of continuous catalysis annulation device - Google Patents
A kind of continuous catalysis annulation device Download PDFInfo
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- CN109433146A CN109433146A CN201811484122.7A CN201811484122A CN109433146A CN 109433146 A CN109433146 A CN 109433146A CN 201811484122 A CN201811484122 A CN 201811484122A CN 109433146 A CN109433146 A CN 109433146A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
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Abstract
The present invention relates to one kind to be catalyzed into loop reactor, belongs to catalysis annulation field.It is catalyzed into heating device, reaction unit, separator and the reception device that loop reactor includes piping connection.Reaction unit is mainly tower reactor, inside reactor is provided with catalytic bed of the aperture at 1 micron -5 millimeters, the overall thickness of catalytic bed accounts for the 30%-85% of the total effective height of reactor, the channel surfaces load of catalytic bed is sulfonic group containing catalytic activity group, carboxyl, the solid catalyst of phenolic group, reaction raw materials steam is contacted with catalyst surface to react, enter separator by the top duct of reaction unit, the catalytic separation film for being 100 nanometers -300 nanometers by aperture, it is separated in separator, unreacted feedstock circulation, which flows into reaction unit, continues vaporization participation reaction, the condensation of product steam enters in product reception device.Realize the low-cost industrial preparation of exotic fuel.
Description
Technical field
The present invention relates to a kind of continuous catalysis annulation devices for liquid rocket propellant exotic fuel, belong to
Annulation field.
Background technique
Exotic fuel is to be put aside energy in the molecular structure by synthetic method based on the raw material of industry,
In a kind of high-energy pure hydrocarbon that combustion process releases again.Compared with traditional rocket kerosene, have than leaping high
(improve 7s or more), the advantages that density is big, viscosity is small.
Intramolecular annulation is an important link of exotic fuel preparation.For current technique, due to
The reasons such as raw molecule steric hindrance is larger, yield become the bottleneck for restricting exotic fuel synthesis, cause only less than 40%
The yield of exotic fuel is relatively low, and cost is excessively high, and product purity is low (about 50%), and the production quantity of by-product is higher than 50%, together
When, due to using liquid catalyst, catalyst not can be recycled, and waste liquid production quantity is larger, influences the scale of exotic fuel
Using.
The present invention is directed to exotic fuel intramolecular annulation Track character, targetedly develops a kind of for height
Energy rocket fuel intramolecular cyclization continuous catalysis synthesis reactor breaks through exotic fuel intramolecular annulation operation hardly possible,
The bottleneck problems such as low efficiency realize the low-cost industrial preparation of exotic fuel.
Summary of the invention:
It is an object of the invention to provide a kind of continuous catalysis annulation device, with solve existing annulation process operation it is difficult,
The problems such as low efficiency.
The present invention solves the problems, such as that it can reach by following technical solution:
(1) exotic fuel intramolecular annulation uses tower reactor, and reaction raw materials are placed in heating kettle, pass through
The reaction raw materials of liquid are become gaseous state by heating, and feedstock vapor enters reactor bottom from heating kettle, connect with catalytic bed
Touching reaction.
(2) catalyst used in exotic fuel intramolecular annulation is solid acid catalyst, using high score subtree
Rouge prepares the catalyst bed of cellular structure using polymerization methods as substrate, and reaction gas is real by catalyst bed duct
Show according to different molecular size from separated structure.Solid acid catalyst is fixed on above fixed bed, realizes heterogeneous urge
Change reaction, catalyst is avoided to mix with material liquid, it is difficult to separate, realize the recycling of catalyst, mitigate post-processing burden.Instead
The channel diameter for answering catalytic bed in device is 100 microns -1 millimeter, and the aperture diameter of seperation film is 100 nanometers -300 nanometers, is urged
The mass content of the effective catalytic active component of agent is about the 1%-30% of material quantity, and the overall thickness of catalytic bed accounts for reactor
The 30%-85% of total effective height, while the thickness degree of different pore size diameter respectively accounts for total catalytic bed thickness in catalytic bed
1/3, the channel diameter of different beds be respectively 1 millimeter -5 millimeters, 100 microns -1 millimeter, 10 microns -1 micron.Pass through leaching
Catalyst active component is carried on catalytic bed duct by the mode of stain.
(3) active group of catalyst used in exotic fuel intramolecular annulation be containing sulfonic group, carboxyl,
Phenolic group, the content of effective catalytic group are 10%-50%, can carry out efficient catalytic with reaction raw materials and react.
(4) exotic fuel intramolecular cyclization continuous catalysis synthetic method uses continuous feeding and discharging system, tower reaction
The Product liquid that device top steams passes through separator, and separator middle part and lower part are filled with filler, according to reaction solution
It measures with the size of separator and adjusts amount of filler, separation unit overhead is equipped with the polymer base material with a thickness of 2-3 millimeters
Porous separation resin film, aperture are 100 nanometers -300 nanometers, realize the separation of product and raw material.Product and unreacted is complete
Material liquid separated, product access product tank, for fully reacting material liquid by tower bottom reenter reaction kettle progress
Reaction.So that reaction product is continuously available separation during this, promotes reaction balance to move to right, increase reaction conversion ratio.
Effective bottleneck for breaking through exotic fuel intramolecular annulation is realized the work of exotic fuel by the present invention
Industryization amplification production, has the beneficial effect that:
(1) continuous catalysis annulation device provided in an embodiment of the present invention is urged by the way that duct formula is arranged in reaction unit
Change bed, adjusts different apertures, realize reaction raw materials gas in the abundant reaction on catalytic bed surface, while realizing preliminary
The separation of raw produce, increases reaction contact area, effectively increases reaction efficiency；
(2) by setting separator, efficiently solve the problems, such as that product Central Plains feed collet band is serious；
(3) by setting seperation film, fine separation effectively has been carried out to product and raw material, has improved product purity；
(4) by setting reflux, the circular response of raw material is realized, product is continuously available separation, further mitigates cold
The burden of solidifying device, improves product purity；
(5) continuous catalysis annulation may be implemented whole day automation stable operation, from average daily feather weight output increased to
Hundred feather weight, tonne scale；
(6) corrosive raw materials reacted realize automatic feed, product, intermediate product and other impurities using automatic material connection and
Switch storage tank, reduces the chance of operator's contact corrosion chemicals；
(7) exotic fuel passes through the separating-purifying of product, and the purity of product is increased to 99.5% or more, product cost
Reduce by 80%.
Detailed description of the invention:
Fig. 1 is continuous catalysis annulation device schematic diagram.
Fig. 2 is catalytic separation membrane structure diagram
Specific embodiment:
The working principle of the invention is further explained and is illustrated with reference to the accompanying drawing.
Referring to Fig. 1 and 2, the embodiment of the invention provides one kind to be catalyzed into loop reactor, for being catalyzed annulation, especially
Intramolecular cyclization suitable for exotic fuel is catalyzed reaction.Described is catalyzed into the reaction that loop reactor includes piping connection
Device V2 and separator V3, pipeline 1 include feeding pipe, discharging pipeline and control valve.
Specifically, in embodiments of the present invention, reaction unit V2 is tower reactor, and preferably main structure is Ni-based stainless
The reaction kettle of steel material, such as main structure are 304 stainless steels, 316 stainless steels or Hastelloy material, and nickel element content is
1 ‰ -10%, which is resistant to 300 DEG C of high temperature, has acid-proof alkali chemical corrosion resistance；Reactor volume is preferred
10L~2000L；
In the embodiment of the present invention, separator V3 (including V31 and V32) is rectifying column, preferred filler formula rectifying column, rectifying
The preferred DN10-DN50 of inlet duct bore of tower, discharge the preferred DN10-DN50 of bore, and rectifying column converts theoretical stage as 10-40
Grade, filler Ceramics filler, metal packing, plastic filler, in reaction unit high-temperature steam by rectifying column realize product and
The condensation separation of raw material, impurity；
It can also include condensing unit V4 (including condenser in the embodiment of the present invention to be collected convenient for product referring to Fig. 1
V41 and V42) and collection device V5, condensing unit V4 use multi-stage condensing shell and tube condensing mode, preferably 2~10 grades of series, change
Thermal medium is water or oil；Collection device is collecting tank, for collecting the final products cooling through condensing unit V4.
Provided in an embodiment of the present invention to be catalyzed into loop reactor at work, liquid and material are added instead by feeding device
Reaction in device is answered, the gas of generation flows out reaction unit by feeding pipe.
Further, referring to Fig. 1, described is catalyzed into loop reactor, further includes return line, return line one end with point
It exports and connects from device, the other end is connect with reaction unit V2.
By the way that return line is arranged, the complete raw material of unreacted enters in reaction unit V2 by return line to be continued to participate in instead
It answers.
Further, referring to Fig. 1 and 2, the outlet of separator V31, V32 provided in an embodiment of the present invention are equipped with micropore point
From film, condensing unit V41 and V42 are flowed into after microporous separation membrane filtering screening from separator V31, V32 escaping gas.
It is provided with reheater V6 between reaction unit V2 and separator V32, enters for heating from reaction unit V2
Liquid material in the pipeline of separator V32, makes gaseous state, into separator V32.
By be arranged catalytic separation film, can by catalytic separation membrane aperture limit different boiling, the component of molecular weight into
Row separation, further mitigates the burden of subsequent condensation device etc., further improves product purity.
In an alternative embodiment, the catalytic separation film is polyvinylidene fluoride-polyvinyl alcohol composite high-molecular film.It is poly-
For vinylidene fluoride-polyvinyl alcohol composite high-molecular film using polyvinylidene fluoride as substrate, polyvinyl alcohol is flexible macromolecule, poly- second
Enol in conjunction with substrate, is formed firm film bulk structure, small-bore duct is covered on membrane body by way of interpenetrating networks, the knot
Structure polymeric membrane high temperature resistant, acid-alkali-corrosive-resisting, widely applicable, long service life；It is preferred that under normal pressure state aperture be 80 microns-
300 microns of polyvinylidene fluoride-polyvinyl alcohol composite high-molecular film, since polyvinyl alcohol has flexibility, with the increasing of pressure
Greatly, polyvinylidene fluoride-polyvinyl alcohol composite high-molecular membrane aperture is up to 500 microns -5000 microns.When there is multi-component vapor logical
When crossing catalytic separation film, small molecule light component is easier the duct by catalytic separation film, the heavy constituent of relatively large molecule
Condensation or reflux easily occur at duct for substance, since polyvinyl alcohol has flexibility, when throughput increases or air pressure increases, and hole
Road diameter can be expanded to 500-5000 microns automatically, thus, it can be adjusted by throughput in control separator or pressure
Pore size realizes the distillation to different boiling, molecular weight component.
In an alternative embodiment, by the ratio for being 1: 1-4 according to mass ratio by polyvinylidene fluoride and polyvinyl alcohol,
It is dissolved in 5-10 times of solvent, solvent selects methanol, ethyl alcohol, ether, n,N-Dimethylformamide, is placed on 80-120 DEG C of environment
Lower 16-24h drying, obtains polymeric membrane.
Referring to Fig. 1, the outlet separator V31 and V32 is also connect by pipeline with condensing unit V41 and V42 respectively.Pass through
4th pipeline is set, it can be in throughput where appropriate, the 4th pipeline of unlatching, makes the gas in separator fully enter condensation dress
It sets, improves production efficiency.
Further, the continuous catalysis annulation device provided in an embodiment of the present invention further includes controller (in figure
It is not shown), controller is for controlling above-mentioned each valve switch.By the way that control device is arranged, throughput can be automatically adjusted, is improved
Production efficiency.
In an alternative embodiment, the continuous catalysis annulation device further includes feeding device, and the controller is also
It is fed for controlling the feeding device to the reaction unit.Automatic feed is controlled by setting controller, automatically adjusts gas
Flow avoids manual operation, not only improves production efficiency, but also ensured worker safety.
The following are specific embodiments of the present invention:
Embodiment 1
As shown in Figure 1, the embodiment of the invention provides a kind of continuous catalysis annulation devices, including feed system is (in figure
Be not shown), heating kettle V1, reaction unit V2, separator V3 (including V31 and V32), condensing unit V4, product receiving tank V5
And controller (not shown)；
For reaction unit V2 and separator V3 by piping connection, pipeline includes feeding pipe, discharging pipeline, separator
Return line is additionally provided between the outlet V3 and reaction unit V2, return line is equipped with reflux controlled valve；
In the present embodiment, feed system includes storage tank, feeding device, material inlet valve and feed control unit, it is described into
Material control unit control feeding device, which work and controls the material inlet valve, to be switched, make raw material in storage tank by preset flow or
Rate enters in reaction kettle, and the volume of the storage tank is 100L；Liquid feeding device uses anticorrosion membrane pump, and feed rate is
10-200L/min；
Reaction unit V2 is 304 stainless steel cauldrons of 100L nickel material content 3 ‰, using enamel dasher；Point
It is material filling type rectifying column from device V3 (including V31 and V32), the inlet duct bore of rectifying column is DN50, and discharging bore is
DN50, rectifying column conversion theoretical stage is 40 grades；Condensing unit V4 (including V41 and V42) is 5 grades of shell and tube condensers, heat exchange
Medium is water；
The outlet of separator V3 is connect by pipeline with condensing unit V4, and microporous separation membrane, the micropore separation are equipped with
Film be polyvinylidene fluoride-polyvinyl alcohol composite high-molecular film, the preparation method of polymeric membrane include: by polyvinylidene fluoride with
The ratio that polyvinyl alcohol is 1: 4 according to mass ratio, is dissolved in 10 times of DMF N,N-Dimethylformamide, is placed on 100 DEG C of environment
Lower 20h drying, obtains polymeric membrane；The outlet separator V3 is also connect by pipeline with condensing unit V4, and pipeline is equipped with valve
Door；
The outlet condensing unit V5 is connect by pipeline with product receiving tank, and electric-controlled switch valve is equipped on each pipeline.
In the present embodiment, each controlled valve is all made of explosion-proof grade electric control valve, and controller controls each valve switch, realize into
Material control and the control of system interior air-flow amount.
Provided in this embodiment to be catalyzed into loop reactor, whole day automation stable operation may be implemented in catalysis annulation,
From average daily feather weight output increased to hundred feather weight to a tonne scale；Be catalyzed annulation corrosive raw materials realize automatically into
Material, product, intermediate product and other impurities reduce operator's contact corrosion chemicals using automatic material connection and switching storage tank
Chance；Exotic fuel passes through the separating-purifying of product, and the purity of product is increased to 99.5% or more, and product cost reduces
80%.
Reference examples
Using 15L glass material reaction kettle, 10kg liquid charging stock and 0.2kg liquid catalyst, the disposable hand of liquid charging stock
Dynamic charging, solid material are disposably fed manually, speed of agitator 80rpm, and reaction temperature is 90 DEG C, and reaction time 5h is obtained
It is 30% to exotic fuel intramolecular annulation intermediate product yield.
The content that description in the present invention is not described in detail belongs to the well-known technique of professional and technical personnel in the field.
Claims (6)
1. a kind of continuous catalysis annulation device, including passing through the heating device of piping connection, reaction unit, separator, cold
Solidifying device and product reception device, it is characterised in that reaction unit is mainly tower reactor, and inside reactor is provided with multiple
The channel surfaces of the catalytic bed of different pore size structure, catalytic bed load the solid catalyst containing catalytic activity group, instead
It answers feedstock vapor to contact with catalyst surface to react, enters separator by the top duct of reaction unit, separating
Separated in device, unreacted feedstock circulation, which flows into reaction unit, to be continued vaporization and participates in reaction, product steam condense into
Enter in product reception device.It can be realized exotic fuel continuous catalysis intramolecular annulation, realize that intramolecular cyclization is anti-
High yield serialization is answered to carry out.
2. continuous catalysis annulation device according to claim 1, it is characterised in that include having multilayer in reaction unit
The catalytic bed of different pore size, active catalytic specie is loaded in catalytic bed, and the active group of catalyst used is sulfonic group, carboxylic
Base, phenolic group；The content of effective catalytic group is 10%-50%, and the mass content of the effective catalytic active component of catalyst is about original
The 1%-30% of doses.
3. continuous catalysis annulation device according to claim 4, it is characterised in that the catalytic bed substrate uses
Macromolecule resin, by polymerization means, a kind of catalyst film of cellular structure of preparation, the duct of catalytic bed is straight in reactor
Diameter is 1 micron -5 millimeters, and the aperture diameter of seperation film is 100 nanometers -300 nanometers, and the overall thickness of catalytic bed accounts for reactor
The 30%-85% of total effective height, while the thickness degree of different pore size diameter respectively accounts for total catalytic bed thickness in catalytic bed
1/3, the channel diameter of different beds be respectively 1 millimeter -5 millimeters, 100 microns -1 millimeter, 10 microns -1 micron.
4. continuous catalysis annulation device according to claim 1, it is characterised in that in the middle part of the separator under
Portion is filled with filler, and filler is ceramic packing, metal packing, plastic filler.Separation unit overhead is equipped with a thickness of 2-3 milli
The porous catalytic seperation film of the polymer base material of rice, aperture are 100 nanometers -300 nanometers, realize the separation of product and raw material.
5. continuous catalysis annulation device according to claim 1, it is characterised in that the catalytic separation film is poly- inclined
Difluoroethylene-polyvinyl alcohol composite high-molecular film, polyvinylidene fluoride and polyvinyl alcohol are 1 according to mass ratio in preparation process:
The ratio of 1-4, solvent select methanol, ethyl alcohol, ether, n,N-Dimethylformamide, and solvent extension rate is 5-10 times, drying temperature
Degree is 80-120 DEG C, drying time 16-24h.
6. continuous catalysis annulation device according to claim 1, it is characterised in that reaction unit material is Ni-based stainless
The reaction kettle of steel material, main structure are 304 stainless steels, 316 stainless steels or Hastelloy material, and nickel element content is 1 ‰-
10%；Reactor volume preferably 10~2000L.
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| CN101314719A (en) * | 2008-07-09 | 2008-12-03 | 东南大学 | Method for preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst |
| CN101528725A (en) * | 2006-10-18 | 2009-09-09 | 巴斯夫欧洲公司 | Method for producing lactones from diols |
| US20100192453A1 (en) * | 2009-02-02 | 2010-08-05 | VERT CAPITAL LLC, dba VERT BIODIESEL | Production of biodiesel |
| CN102093312A (en) * | 2010-12-20 | 2011-06-15 | 浙江大学 | Epoxyethane synthesis method and production device thereof |
| CN104591956A (en) * | 2014-12-30 | 2015-05-06 | 山东东岳化工有限公司 | System and method for producing trifluoro-dichloride ethane and tetrafluoro-monchloride ethane by using tetrachloroethylene method |
| CN206783561U (en) * | 2017-05-04 | 2017-12-22 | 宁夏凤城永生锅炉有限公司 | Higher alcohols etherification reaction equipment |
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2018
- 2018-12-06 CN CN201811484122.7A patent/CN109433146A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128415A (en) * | 2005-02-25 | 2008-02-20 | Lg化学株式会社 | Method of producing unsaturated aldehyde and/or unsaturated acid |
| CN101528725A (en) * | 2006-10-18 | 2009-09-09 | 巴斯夫欧洲公司 | Method for producing lactones from diols |
| CN101314719A (en) * | 2008-07-09 | 2008-12-03 | 东南大学 | Method for preparing biological diesel oil with series double-fixed bed and catalysis of solid catalyst |
| US20100192453A1 (en) * | 2009-02-02 | 2010-08-05 | VERT CAPITAL LLC, dba VERT BIODIESEL | Production of biodiesel |
| CN102093312A (en) * | 2010-12-20 | 2011-06-15 | 浙江大学 | Epoxyethane synthesis method and production device thereof |
| CN104591956A (en) * | 2014-12-30 | 2015-05-06 | 山东东岳化工有限公司 | System and method for producing trifluoro-dichloride ethane and tetrafluoro-monchloride ethane by using tetrachloroethylene method |
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Application publication date: 20190308 |