CN110237777A - A kind of concentric circles isothermal reactor and its process suitable for strong exothermal reaction - Google Patents

Abstract

A kind of concentric circles isothermal reactor and its process suitable for strong exothermal reaction is related to a kind of reactor and its process, and reactor is constructed using concentric circles, and every layer of concentric circles collet is relatively independent.For Catalyst packing among random layer collet, contacting with catalyst chuck layer is the refrigerants such as vapor or conduction oil.Reactor feed gas enters catalyst bed by the top of concentric circles or bottom, the refrigerant for keeping the most strongly exothermic amount corresponding temperature of initial reaction stage minimum.Catalyst bed upper end or lower end are equipped with the quadratic distribution plate of regulating gas flow velocity, concentric circles periphery loaded catalyst maximum corresponds to maximum heat exchange area, each chuck layer can regard relatively independent reaction compartment as, be discharged after the convergence of product gas from reactor bottom end or top.Ideally realize the stability contorting of reaction bed temperature gradient and non-equal field of flow, for strong exothermal reactions such as typical methanol-fueled CLC, preparing methane by synthetic gas and oxidation or nitration reactions, the catalyst entirety bed temperature difference is 5 degrees Celsius small.

Description

A kind of concentric circles isothermal reactor and its process suitable for strong exothermal reaction

Technical field

The present invention relates to a kind of reactor and its processes, more particularly to a kind of suitable for the concentric of strong exothermal reaction Circle isothermal reactor and its process.

Background technique

With human society continuous development and people's living standard it is constantly improve, the requirement to chemical industry gradually mentions Height, trend is safe and environment-friendly, efficient, energy saving and sustainable development, as far as possible by reaction raw materials under the premise of essential safety It is completely converted into target product, realizes production process zero-emission, shortens reaction process, improves production efficiency.

Since C-H, C-O and H-O key bond energy typical in compound is significantly different, lead to reaction raw materials and target product Standard molar formation enthalpy difference it is larger, thus chemical reaction process usually just with heat absorption and heat release carry out.

In the synthesis process of most of energetic materials, such as: methanol-fueled CLC, preparing methane by synthetic gas, oxidation reaction, nitrification are anti- It answers and chlorination or fluorination reaction etc., is frequently accompanied by violent exothermic reaction.If reaction heat can not be in time from anti- It answers the interior removal of device to will lead to reaction heat largely to accumulate, reaction temperature is difficult to control, and causes reaction bed overtemperature, temperature runaway, or even draw Play the serious consequences such as explosion.

For the strong exothermal reaction for having catalyst to participate in, high temperature will lead to catalyst overheating sintering and a large amount of carbon deposits in surface, Significantly reduce catalytic efficiency and catalyst service life.Surface high dispersive, high activity catalyst often it is resistance to sintering and anti-product Charcoal ability is poor.Meanwhile being limited by thermodynamical equilibrium, the equilibrium conversion of strong exothermal reaction is increased with reaction temperature and is gradually dropped It is low, reaction need to be controlled as far as possible to be carried out at low temperature.Therefore, exploitation has the enlarged reaction unit gesture of strong heat exchange function must Row！

By taking synthesis gas methanation reaction as an example, shown in key reaction such as equation (1-3), it is seen that

CO + 3H2→ CH4 + H2O ΔH=-206.1 KJ/mol ..............................(1)

CO2 + 4H2→ CH4 + 2H2O ΔH =-165.0 KJ/mol ...........................(2)

2CO + 2H2→ CH4 + CO2 ΔH =-247.3 KJ/mol ............................(3)

Methanation reaction is strong exothermal reaction, while the surface fast reaction of the reaction or volume reduction.Currently, world wide Inside realized synthesis gas methanation production mature technology mainly include Luigi company design the neat methanation process in Shandong, The TREMP methanation process and DAVY methanation process of Topsoe.Above-mentioned three kinds of technics comparings are similar, are using 3-5 sections Fixed bed adiabatic methanator, first segment and second segment reactor use series and parallel structure, are high-temperature reactor, mixing Near 650 DEG C, the reaction that CO is converted into CH4 mainly carries out in the two reactors gas outlet temperature, is a large amount of methanations Reactor.Third and fourth section of reactor is low-temp reaction device, converts CH4 for unreacted CO in preceding two reactor, makes The methane content of synthetic natural gas reaches the level of needs, to supplement methane reactor.Whole process is steamed by by-product high pressure saturation Vapour recycles the heat that methanation reaction generates.

It is insulated multistage methanation reaction process and removes methanation reaction process using the means that segmentation conversion and segmentation move heat In a large amount of heat, this is allowed for, and reaction system is complicated, equipment investment is big, energy consumption is high, operating difficulties, cannot achieve short route methane Chemical industry skill.

The units such as Institutes Of Technology Of Taiyuan develop a kind of slurry bed system methanation device and technique (CN101979475B, CN101979476B, CN102952596B), catalyst is dispersed in inert fluid, and bed is close to isothermal operation.Slurry bed system Heat exchange efficiency is high, bed temperature is average, reaction condition temperature, overcome fixed bed reaction depth and it is strongly exothermic between contradiction.But Slurry bed system is limited by mass transfer between gas-liquid-solid three-phase, and combined coefficient is low, and slurry bed system methanation process cannot achieve continuously Operation, back-mixing is serious, and solid catalyst separates difficulty with atent solvent.

Process institute, the Chinese Academy of Sciences, Tsinghua University and Beijing low-carbon etc. exploitation based on conveying bed and fluidized bed methane chemical industry Skill (CN1960954A, CN101817716A, CN102040441A, CN101774876A, CN102180757A).Convey bed and stream Changing bed reaction has efficient gas solid transfer and heat transfer efficiency, and temperature and particle are uniformly distributed in reaction bed, can effectively be inhibited Bed overtemperature and temperature runaway phenomenon.But exploitation is suitable for high intensity, high-wearing feature catalyst and the catalyst carry-over loss of fluidized bed The problems such as there are no intact solutions.

The exploitation such as Beijing Hua Fu, Shanghai Chinese Xing Nengyuan and China Petroleum isothermal tubulation methanation process (CN102010284B, CN207362166U, CN103373887B).Catalyst loads in shell-and-tube reactor, and shell is cold by conduction oil or vapor etc. Matchmaker moves heat, is a major advantage that heat exchange area is big, but device fabrication is difficult, and equipment dependability is low.For methanation reaction, column There is thermal balance hardly possible in pipe reactor, be embodied in CO and CO2 concentration highest in the reactant for initially enter reaction unit, The reaction of catalyst bed upper layer is more violent, and heat release is the most serious, but conventional shell-and-tube reactor is uniform heat exchange, can not solution by no means The problem of homogeneous temperature field and field of flow are mutually matched.

Summary of the invention

The purpose of the present invention is to provide a kind of suitable for the concentric circles isothermal reactor of strong exothermal reaction and its technique side Method, reactor of the present invention are constructed using concentric circles, and every layer of concentric circles collet is relatively independent.Catalyst packing is in random layer collet Between, contacting with catalyst chuck layer is the refrigerants such as vapor or conduction oil；Reactor can ideally realize reaction bed temperature Spend the stability contorting of field gradient and non-equal field of flow.

The purpose of the present invention is what is be achieved through the following technical solutions:

A kind of concentric circles isothermal reactor suitable for strong exothermal reaction, the reactor include pressure-bearing shell, high pressure resistant collet, It is slidably connected, closed circuit water route, gas quadratic distribution partition；Reactor uses concentric design；Catalyst monolayers or multilayer filling It is refrigerant heat-transfer surface, the far unconventional shell-and-tube reactor of heat exchange area outside concentric circles chuck layer, collet；Every layer of collet phase of concentric circles To independence, each catalyst bed feed gas flow rates and refrigerant flow rate can be adjusted respectively；The most strongly exothermic amount of initial reaction stage is corresponding The minimum refrigerant of temperature, concentric circles periphery loaded catalyst maximum correspond to maximum heat exchange area；Reactor pressure-bearing shell and High pressure resistant collet is pressure-resistant material, and the pressure-resistant upper limit is 30MPa；It is the catalyst of single-layer or multi-layer filling in reactor jacket, folder Outer set is refrigerant collet；Reactor catalyst bed upper end or lower end are equipped with the quadratic distribution partition of regulating gas flow velocity.

A kind of concentric circles isothermal reactor suitable for strong exothermal reaction, the temperature reactor refrigerant chuck layer phase Mutually perforation, radial width are freely adjustable.

A kind of concentric circles isothermal reactor suitable for strong exothermal reaction, the catalyst in reactor are radial single Layer or multilayer filling, catalyst bed thickness can freely regulate and control.

A kind of concentric circles isothermal reactor suitable for strong exothermal reaction, the quadratic distribution partition hole shape It can be round, linear or irregular shape；The size and concentration in hole can the flow velocity tune according to needed for reaction and gas It is whole.

A kind of concentric circles isothermal reactor process suitable for strong exothermal reaction, the strong exothermal reaction of the technique, Including but not limited to various synthesis, hydrogenation reaction such as synthesize ammonia, methanation, methanol-fueled CLC, oxidation or nitration reaction；The reaction The stability contorting of device reaction bed temperature gradient and non-equal field of flow；Reactor jacket layer is that vapor or conduction oil etc. are cold Matchmaker, reactor feed gas enters catalyst bed by the top of concentric circles or bottom, so that the most strongly exothermic amount corresponding temperature of initial reaction stage Minimum refrigerant, concentric circles periphery loaded catalyst maximum correspond to maximum heat exchange area, and each chuck layer is done relatively independent Reaction compartment, be then discharged after the convergence of product gas from reactor bottom end or top；Liquid phase or gas phase heating agent include: water, Vapor, conduction oil, dense dissolved salt etc. are organic or inorganic can to pass hot medium.

A kind of concentric circles isothermal reactor process suitable for strong exothermal reaction, the methanol-fueled CLC are anti- It answers, the full bed temperature difference is lower than 5 DEG C.

A kind of concentric circles isothermal reactor process suitable for strong exothermal reaction, the methanation reaction, Its full bed temperature difference is lower than 5 DEG C.

The advantages and effects of the present invention are:

1. the present invention can not solve the problems, such as that non-uniform temperature field and field of flow are mutually matched shell-and-tube reactor, start A kind of isothermal reactor design method suitable for strong exothermal reaction, the reactor can ideally realize reaction bed temperature field The stability contorting of gradient and non-equal field of flow.

2. the Process of absorption or liberation of heat that the concentric circles isothermal reaction device of design method initiative of the present invention is not only applicable to common intensity is anti- It answers, is particularly suitable for strong exothermal reaction, such as: methanol-fueled CLC, preparing methane by synthetic gas and oxidation or nitration reaction, it can be timely The a large amount of reaction heat for removing generation avoid overtemperature and temperature runaway phenomenon from leading to sintering of catalyst and surface carbon deposit.

3. the multistage insulation that the concentric circles isothermal reactor of design method initiative of the present invention can replace original process complexity The integrated reaction system of fixed bed reactors, significantly reduces equipment investment cost, saves energy consumption.

Detailed description of the invention

Fig. 1 concentric circles isothermal reactor Catalyst packing sectional view；

Fig. 2 concentric circles isothermal reactor refrigerant flow section figure；

Fig. 3 secondary air distribution grid design drawing.

Specific embodiment

The present invention is described in detail for illustrated embodiment with reference to the accompanying drawing.

The present invention generally reactor is constructed using concentric circles, and every layer of concentric circles collet is relatively independent.Catalyst packing exists Among random layer collet, chuck layer is the refrigerants such as vapor or conduction oil.Reactor feed gas by the top of concentric circles or bottom into Enter catalyst bed, so that the minimum refrigerant of the most strongly exothermic amount corresponding temperature of initial reaction stage, concentric circles periphery catalyst dress The amount of filling out maximum corresponds to maximum heat exchange area, and each chuck layer can regard relatively independent reaction compartment as, and then product gas converges It is discharged after poly- from reactor bottom end or top.

Reactor of the present invention uses concentric design；2) catalyst monolayers or multilayer are seated among concentric circles collet, folder Jacket layer is refrigerant heat-transfer surface, the far unconventional shell-and-tube reactor of heat exchange area；3) every layer of collet of concentric circles is relatively independent, each catalysis Agent bed feed gas flow rates and refrigerant flow rate can be adjusted respectively；4) minimum cold of the most strongly exothermic amount corresponding temperature of initial reaction stage Matchmaker, concentric circles periphery loaded catalyst maximum correspond to maximum heat exchange area.

The concentric circles isothermal reactor includes pressure-bearing shell, high pressure resistant collet, is slidably connected, closed circuit water route, gas Quadratic distribution partition.

The concentric circles isothermal reactor pressure-bearing shell and high pressure resistant collet are pressure-resistant material, and the pressure-resistant upper limit is 30MPa.

It is the catalyst of single-layer or multi-layer filling between the concentric circles isothermal reactor collet, is refrigerant folder outside collet Set.

The liquid phase or gas phase heating agent includes: that water, vapor, conduction oil, dense dissolved salt etc. are organic or inorganic can Pass hot medium.

The concentric circles isothermal reactor refrigerant chuck layer is mutually communicated, and radial width is freely adjustable.

Catalyst radial direction single-layer or multi-layer loads in the concentric circles isothermal reactor, and catalyst bed thickness can be free Regulation.

The concentric circles isothermal reactor catalyst bed upper end or lower end are equipped with secondary point of regulating gas flow velocity Cloth partition.

The quadratic distribution partition hole shape can be round, linear or irregular shape；The size in hole and close Collection degree can the adjustment of the flow velocity according to needed for reaction and gas.

The concentric circles isothermal reactor includes but is not limited to various synthesis, hydrogenation reaction, such as synthesize ammonia, methanation, Methanol-fueled CLC, oxidation or nitration reaction etc..

The specific design scheme of reactor:

As shown in Figure 1, catalyst bed is alternately present with refrigerant bed, catalyst bed can for concentric circles isothermal reactor cross section It can also be loaded with single layer filling with multilayer.Each catalyst chuck layer is relatively independent.Refrigerant enters mode such as Fig. 2 institute of chuck layer Show, refrigerant can enter collet with section up, down, left and right side.Pressure-bearing shell maximum can bear 30.0MPa pressure.

Reactor feed gas enters catalyst bed by gas quadratic distribution partition, and gas quadratic distribution partition is using porous Hardened structure, as shown in Figure 3.Porous plate hole shape can be round, linear or irregular shape；The size and concentration in hole It can be adjusted according to reaction, general principle of design is that the smaller more loose aperture of area will lead to resistance to mass tranfer increase, can be subtracted Pass through the reaction gas bulk flow of catalyst bed less, but flow velocity is speeded；More bigger, more intensive aperture approximation does not have mass transfer to area It is smaller to play the role of quadratic distribution to gas for resistance.The size and arrangement mode of perforated area can be it is non-uniform, it is more The aperture mode of orifice plate for reactor feed gas in secondary or multiple adjustment reactor by catalyst bed the type of flow and Throughput influences the Temperature Distribution of reactor different zones catalyst bed indirectly.Catalyst radial direction bed in concentric circles collet Thickness can be adjusted freely, if every layer of catalyst is single layer filling, the catalyst for being equivalent to unit volume is corresponding Heat exchange area is approximately equal.If catalyst Multi-layers distributing, for strong exothermal reaction, design principle is closer to reactor wall Catalyst bed is thinner, and the catalyst bed closer to reactor center is thicker.The effect reached is reactor radial outer list Volume of catalyst corresponding heat exchange area in position is consistent with internal layer catalyst.The catalyst bed of quadratic distribution partition isolation can be 2 layers, it is also possible to multilayer, at most can achieve 20 individual catalytic beds.

Be passed through the heating agents such as water or conduction oil in concentric circles isothermal reactor collet, heating agent the type of flow can be it is enterprising Go out down, is also possible to bottom in and top out.Heating agent is injected by pressure liquid pump, spherical cavity outlet connects drum, and maximum 25 MPa of pressure-bearing is carried out After gas-liquid separation, steam is used directly for the steam turbine that generates electricity or drive, and steam pressure range is 4.0-20.0MPa, liquid Body is recycled in reactor after heat exchange is cooling through high-pressure pump.Once occurring overheating problem in reactor, directly reduces drum and go out Mouth pressure, or even emptying drum, gasify rapidly by heating agent and take away excessive heat in reactor, reach temperature of reactor and uniformly divide The purpose of cloth.

Embodiment 1

By taking synthesising gas systeming carbinol as an example, unstripped gas group becomes 69.92%H2,29.26%CO, 3.11%CO2,0.13%CH4,0.57% N2,0.004% methanol, 240 DEG C of reaction temperature, reaction pressure 6.0MPa, unstripped gas air speed 7500h-1, reaction gas recycle ratio is 3.86.Using concentric circles isothermal reactor, 20 kilograms of loaded catalyst, catalyst radial multilayer loads (4-5 layers radial), adopts Low temperature, low pressure methanol synthesis catalyst and the Al2O3 bead commercially produced with Shenyang University of Chemical Technology, filling mass ratio is 1: 1, the concentric circles isothermal reactor entrance and exit temperature difference is 1 DEG C.

Embodiment 2

By taking coke-stove gas methane as an example, unstripped gas group becomes 26.3%CH4,57.1%H2,7.7%CO, 2.7%CO2,3.2%N2, 0.5%O2,0.75%C2H6,1.75%C2H4,400 DEG C of reaction temperature, reaction pressure 1.5MPa, unstripped gas air speed 5500h-1, instead Should gas recycle ratio be 1.75.Using concentric circles isothermal reactor is used, 20 kilograms of loaded catalyst, catalyst radial multilayer is filled It fills out (4-5 layers radial), the Catalyst for Low-Temperature Methanation and Al2O3 bead that filling Chinese Academy of Sciences's process is commercially produced load matter Amount is than being 1:1；The concentric circles isothermal reactor entrance and exit temperature difference is 2 DEG C.

The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (7)

1. a kind of concentric circles isothermal reactor suitable for strong exothermal reaction, which is characterized in that the reactor includes pressure-bearing shell Body high pressure resistant collet, is slidably connected, closed circuit water route, gas quadratic distribution partition；Reactor uses concentric design；Catalyst Single-layer or multi-layer is seated in concentric circles chuck layer, is refrigerant heat-transfer surface, the far unconventional shell-and-tube reactor of heat exchange area outside collet；Together The heart every layer of collet of circle is relatively independent, and each catalyst bed feed gas flow rates and refrigerant flow rate can be adjusted respectively；Initial reaction stage The minimum refrigerant of most strongly exothermic amount corresponding temperature, concentric circles periphery loaded catalyst maximum correspond to maximum heat exchange area；Instead Answer device pressure-bearing shell and high pressure resistant collet for pressure-resistant material, the pressure-resistant upper limit is 30MPa；It is filled in reactor jacket for single-layer or multi-layer The catalyst filled out, collet are outside refrigerant collet；Reactor catalyst bed upper end or lower end are equipped with the two of regulating gas flow velocity Secondary distribution separator.

2. a kind of concentric circles isothermal reactor suitable for strong exothermal reaction according to claim 1, which is characterized in that institute It states warm reactor refrigerant chuck layer to be mutually communicated, radial width is freely adjustable.

3. a kind of concentric circles isothermal reactor suitable for strong exothermal reaction according to claim 1, which is characterized in that institute The filling of catalyst in reactor radial direction single-layer or multi-layer is stated, catalyst bed thickness can freely regulate and control.

4. a kind of concentric circles isothermal reactor suitable for strong exothermal reaction according to claim 1, which is characterized in that institute Stating quadratic distribution partition hole shape can be round, linear or irregular shape；The size and concentration in hole can roots It is adjusted according to flow velocity needed for reaction and gas.

5. a kind of concentric circles isothermal reactor process suitable for strong exothermal reaction, which is characterized in that the technique it is strong It is anti-such as to synthesize ammonia, methanation, methanol-fueled CLC, oxidation or nitrification for exothermic reaction, including but not limited to various synthesis, hydrogenation reaction It answers；The stability contorting of the reactor reaction bed temperature field gradient and non-equal field of flow；Reactor jacket layer be vapor or The refrigerants such as conduction oil, reactor feed gas enters catalyst bed by the top of concentric circles or bottom, so that initial reaction stage is most strongly exothermic The minimum refrigerant of corresponding temperature is measured, concentric circles periphery loaded catalyst maximum corresponds to maximum heat exchange area, each chuck layer Relatively independent reaction compartment is done, is then discharged after the convergence of product gas from reactor bottom end or top；Liquid phase or gas phase heat Matchmaker, which includes: that water, vapor, conduction oil, dense dissolved salt etc. are organic or inorganic, can pass hot medium.

6. a kind of concentric circles isothermal reactor process suitable for strong exothermal reaction according to claim 5, special Sign is that the methanol synthesis reaction, the full bed temperature difference is lower than 5 DEG C.

7. a kind of concentric circles isothermal reactor process suitable for strong exothermal reaction according to claim 5, special Sign is that the methanation reaction, the full bed temperature difference is lower than 5 DEG C.