JPH01500252A - Equipment for endothermic reactions, especially hydrogen generation reactions - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Apparatus for endothermic reactions, especially hydrogen evolution reactions An endothermic catalytic reaction that recovers heat and supplies energy internally among reactions between gas reactants. It relates to equipment for carrying out. The present invention further provides hydrogen-rich hydrogen using the present device. - Also related to processes that generate gas. The H2 gas obtained here is NHL and / or can be used for the synthesis of CllIOH.

The processes carried out in the apparatus of the invention are themselves well known.

In other words, this reaction involves a catalytic reaction between hydrocarbons and steam at a high temperature and pressure of 850°C or higher. ``Steam reforming'' is a process in which a gas mixture of hydrogen and carbon monoxide is created by This is a method called "

This reaction can generally be represented by the following formula.

CuHm + aHzO + bOz2 CH2 + dCo + eCoz 11 conversions The reaction is endothermic over a wide temperature and component range, thus achieving high yields. This is a reaction that requires external supply of thermal energy.

In the well-known steam reformer, a raw material is supplied to a tube filled with a catalyst. It is normal to The tubes are arranged in a furnace and are directly exposed to the flames from a number of burners. It has a heating structure.

It is unimaginable that heat can actually be recovered from reaction products to raw materials in a furnace. Well, even the well-known reformer mentioned above does not do this.

Steam reformers with electrical heating are also well known.

British Patent No. 866085 discloses hydrogen and carbon monoxide by adding water vapor to hydrocarbons. Discloses the process of disassembly. According to the British patent, external heat-generating The boiler (5) generates approximately 383 liters of Mizusawa air using the heat energy from the reactor. do. Next, the real water stalks are heated to about 673K in a heat exchanger, and hydrocarbon vapor at the same temperature is produced. Buy and/or mix with gas.

This mixture is then fed to the reactor (4) and is heated to a reaction temperature of approximately 1 Heat to 223K). The high temperature products produced are transferred to a special chamber outside the reactor (4). It is supplied to a special heat exchanger and used to generate the above M%.

As explained above, thermal energy is added at low temperature levels.

The apparatus for carrying out the above conversion reaction is composed of at least three types of apparatus. i.e. a reaction chamber (4) in which no heat exchange occurs from one reaction product to the feed compound; A boiler is used to evaporate water using the generated gas and heat this water vapor to approximately 383K. Ra (5) and - Heater (6) for heating the steam generated in the boiler (5) to a higher temperature That is.

Comparing this plant, which has different equipment located apart from each other, with equipment made as one piece. It is natural that the structure is extremely complex.

In the reformer of West German Published Specification No. 2809126, a high-temperature helium-cooled reactor (H Using the thermal energy of the cooling medium (THR) and electrical energy, It converts gaseous hydrocarbons and water vapor into hydrogen and carbon monoxide. The high temperature of this TL structure However, it is not suitable for high pressure (expansion compensator, catalyst exchange vessel).

European Patent Publication No. 0020358 discloses a tube with internal insulation and a tube containing a catalyst. He teaches conventional electric reformers. A heating element is placed in the same tube inside the catalyst. is passing through.

The clear technical differences between these reformers and the device of the present invention are as follows: The rehomer uses internal cooling to cool the container wall with the raw material, internal heat recovery, and further heat recovery. It is equipped with a catalyst arrangement and heating device that have many advantages from both mechanical and process engineering points of view. Ru. All these components can be housed in one pressure vessel, so As a result, the process can proceed under high pressure, a crucial requirement in the hydrogen industry. It will not meet your requirements. [I] The heating element is an electric heating device or a burner. can be used.

The process for obtaining hydrogen-rich gas performed with the device of the present invention can be performed using a wide range of raw materials. In other words, it is suitable for various hydrocarbons, air, air-oxygen mixtures, etc. Furthermore, control of different reactions can be easily carried out.

An endothermic reaction is carried out between gaseous reactants at high temperature and pressure, and the heat of the reaction product is used as raw material. Apparatus of the present invention comprising an internal heat recovery device for supplying to a substance, a catalyst and a heat supply facility - The raw material is transferred from the inlet between the pressure wall and the hull of the device. Inner shell (13) for heat insulation for transporting along the gap, and internal heat recovery inside the single shell. a bundled tube heat exchanger installed for the purpose of which the raw material flows outside the tubes of the heat exchanger; a catalyst located at the bottom of the single exchanger and/or downstream thereof; - at the final conversion reaction point; Thermal energy is supplied to a reactant, and the reaction products enter the tube through the interior of the tube. Feedstock material - ＼Heating material placed in the catalytic region to impart heat and reach the device outlet - locating all these parts in a pressure vessel.

To further explain the first special feature of the above device, the heating means is a burner. - into which oxygen-containing gas is fed from the outside and heated by heat exchange. The octopus gas reacts with a part of the reducing raw material and generates heat, and at this time there is a In this case, the burner is placed between the two blocks (15, 15').

To explain the features of the second implementation of the present invention, Mr. Q's device, the heating means is an electric heater. The heating element must be placed outside the tubes of the heat exchanger in the lower part containing the catalyst. It is to be placed in minutes.

- The third form of the IG-like device is characterized in that the heating means includes an electric heating element and a bar. device in which both elements operate separately and independently, with the main The heating means are arranged outside the tubes of the heat exchanger and at the bottom of the upper block of the catalyst. Ru.

All of these devices are fitted with metal and/or ceramic insulating shells and , attach a heat insulating layer to the outside of the pressure vessel.

In a first embodiment, the catalyst is divided into three parts, with one part placed outside the heat exchanger tubes. placed in layers in the basket, and another part placed in the path of the reactants after the burner. so that the reactants pass through both catalyst blocks and In the case of heat recovery, the oxygen-containing gas whose temperature has increased is mixed with a reducing gaseous reactant. Made into an injector type and reacts with oxygen-containing gas to raise the temperature. Allow material to enter the second block catalyst.

In the device of the second embodiment of the invention, the catalyst is placed in a basket outside the tubes of the heat exchanger. are arranged in a layered manner so that the raw material passes through this layer at least once, and The electric heating element is placed in the lower area of the basket containing the catalyst, but not in the bath. away from the heat exchanger tube so that it is on the outside of the heat exchanger tube.

In the case of the device of the third embodiment, the catalyst is divided into three parts, one part being the tube of the heat exchanger. Placed in layers in the outer basket of the burner and separate the passages for the reactants after the burner so that the reactants pass through both catalyst blocks, and the electrical The heating element is placed away from the lower hemisphere of the basket containing the catalyst for heat exchange. The burner is placed outside the exchanger tube, while the burner is heated to an oxygen-containing temperature due to heat recovery. Create an injector array that mixes the gas into a reducing gaseous reactant to Allow the reactant whose temperature has increased by reacting with the gas to enter the second block catalyst. .

To create a process for generating hydrogen-rich gas using the device of the present invention, water vapor is required. the required amount of raw materials in the form of air and hydrocarbons, electrical energy and/or raw materials; The need for a form of oxygen-containing gas to partially oxidize reducing components in a substance The hydrogen-rich reaction products are extracted by supplying thermal energy to this device. Ru. This process is used as a base for producing raw material gas for NH, IJ, and OR synthesis. It is useful.

The reactor of the present invention is illustrated using three specific embodiments: That is, Steam reformer with one burner (Figure 1) - Steam reformer with electric heater (Figure 1) Figure 2) - Steam reformer that combines a burner and an electric heater (Figure 3, 5, 4th to 6th The figure shows some important thermodynamic relationships for the process carried out in the reformer of the present invention. This is what is shown. These graphs should be read in relation to the following Tables 1 to 2.

FIG. 1 shows a special device of the invention according to dependent claim 2.6.

where (E) is the raw material, i.e. substantially gaseous and/or vaporized hydrocarbons; This is the inlet for a mixture of water vapor and water vapor in appropriate proportions. (E’) is an oxygen-containing gas i.e. the inlet of air or oxygen-enriched air, along with water vapor. can be put in. Gaseous reaction products are taken out from the outlet (A).

The entered raw material actually fills the gap between the container wall (11) and the internal heat insulating layer (13). It flows along the entire height of the building. Guided by the baffle W (14), the gaseous raw material It flows outside the tubes (19) of the heat exchanger (19'). star from a certain height This flow continues, but first flows inside the catalyst (first block) layer. gas has been heated (primarily from the preceding heat exchange) so that the reactants are not in contact with the catalyst. The reaction starts immediately. When the conversion has progressed to a certain extent, the gas becomes (1 Enters the 7B1 area, into which the oxygen-containing gas heated in the special tube (16) flows. . A predetermined amount of reducing species (species) in the raw material is combusted by the introduced oxygen. Upon baking, the gas reaction reaches its optimum reaction level. Element (15, 15' ), the reforming conversion reaction reaches equilibrium and the gaseous reaction The product is discharged via tube (19) and outlet (A). As a result, heat energy enters It is transmitted to the incoming reactants and (indirectly) to the incoming oxygen-containing gas. It becomes.

FIG. 2 shows a second special embodiment corresponding to claim 3.7.

In this case as well, (E) is the inlet of the supplied gaseous raw material, and (A) is the gaseous reaction product. It is an outlet for things. The components (21, 22, 23, 24, 29> are all ( 11, 12, 13, 14, 19), and (26) is fixed outside the tube and the catalyst An electric heating element separate from the The electric wire is indicated by (27).

Figure 3 shows a third special device of the invention as defined in claim 4.8. It is.

Here, (E) is the inlet of the raw material, and (E') is the oxygen-containing gas and water vapor if necessary. It is the entrance to something that has added. (A) is a gaseous reaction product, i.e. hydrogen-containing This is the gas outlet.

When the raw material enters, the container wall (31) (insulating layer (32) on the outside) and the internal It flows through the gap in the thermal layer (33) virtually over the entire height of the device. Guide with baffle plate (14) The gaseous raw material is passed around the outside of the tube (19) of the heat exchanger (19'). flows. This flow continues starting from a certain height, but in this case, first The gas (mainly due to the preceding heat exchange) passes through the catalyst bed (first block). Because the gas is heated, the reaction starts as soon as the reactants come into contact with the catalyst. Ru. After the conversion reaction has progressed to some extent, a wire (37') is attached. After being heated by the heating element (37), the gas flows into the region (17) (sic (16), into which the oxygen-containing gas heated in the special tube (16) enters. original A certain amount of the reducing species in the feed material is burned by the oxygen introduced here, and the gas reaction is at its peak. Increase to appropriate reaction level. A second contact consisting of elements (15, 15') When the reforming conversion reaction reaches equilibrium in the medium block, the gaseous substances produced are transferred to the pipe (19). and is discharged from the outlet (A). At that time, thermal energy is transferred to the reactant in which the product enters. It also provides (indirectly) thermal energy to the incoming oxygen-containing gas. will give.

Figures 4 to 6 show a process for producing hydrogen-rich gas using the steam reformer of the present invention. This shows the important thermodynamic relationships of Figure 4 shows the device shown in Figure 1 using air. , FIG. 5 shows the relationship when the same process is performed with oxygen. Figure 6 2 shows the process carried out using the apparatus shown in FIG.

Tables 1 to M listed below should be read in conjunction with Figures 4 to 6, and the meanings of the abbreviations. The taste is as follows.

T is the temperature axis (K) H is the enthalpy axis (KJ 1 mole) H3 is the enthalpy recovered by heat exchange H2 is the enthalpy recovered by heat exchange and conversion The enthalpy H1 recovered during internal heating is the enthalpy H2 recovered during internal heating. The thalpy △T is the temperature interval that is effective for heat exchange between both media, and A is the raw material with heat exchange only. Heating curve B of a substance is obtained by heat exchange and (endothermic) conversion reaction.Curve C is obtained by heat exchange and conversion reaction. The curve E obtained for the reaction and internal heating is the gas temperature and entrenchment when the chemical reaction reaches equilibrium. Isoquants showing the relationship between Rupees Table 1 below is the data on which Figure 4 (air) is based.

Table 1 1. Process along curve A Heating of raw material by heat recovery Unit: Inside the jurisdiction Outside the jurisdiction Reaction product raw material Inflow Outflow Inflow Outflow Fluid data Average molecular weight g/mol 17.4 17.4 17.7 17.7 Pressure ba r 30,05 30.0 31,4 31.3 Temperature K 850 625 5 60 800 Specific weight kg/m37, 38 12.8 8.38 Constant pressure heat capacity J /(mol K) 36,4 35,4 46,2 43.7 Kinematic viscosity -g/( s m) 33,9 25,6 19,8 28.8 Thermal conductivity mW/(K m ) 122 92,8 54,0 82,6 Prandtl number 0.581 0,5 63 0.958 0.860 Data regarding the flow of substances Mass velocity Kg/s O, 890,58 Volume velocity m’/s O, 1210,0 880,0450,069 heat flow kW 420 Conduction density kW/m” 16 1 l Inolds number 17200 22700 17800 12200 Pressure drop -ba r 50 100 2. Process along curve B Reforming with only heat addition through heat recovery Unit: Inside the jurisdiction Outside the jurisdiction Reaction product raw material Inflow Outflow Inflow Outflow Data between fluids Average molecular weight g/mo1 17.4 17.4 17.7 15.5 Pressure ba r 30.1 30.05 3L3 30.8 Temperature K 1228 850 8 00 950 specific weight kg/m' 5,10 7,38 8,38 6.05 constant Barothermal capacity J/(Ilol K) 39.4 36.4 43.7 41.2 Dynamic Viscosity -g/(s M) 45.2 33.9 28.8 35.1 Thermal conductivity mW/(K m) 166 122 82.8 144 Prandtl number 0.61 8 0,581 0,859 0.646 Data regarding the flow of substances Mass velocity Kg’s O, 890,58 Volume velocity -”/s O, 1750, 1 210,0690,096 heat flow 1 kW 730 Conduction density kW/m” 40 28 Reynolds number 12900 17200 12200 10000 Pressure drop mb ar　50　500 3. Process along curves A and B Heating air with heat recovery Unit: jurisdiction air Inflow Outflow Fluid data Average molecule 1 g/mol 28,85 28.85 Pressure bar 31,0 3 0,8 Temperature K 400 900 Specific weight kg/silver’ 27.2 11.9 Constant pressure heat capacity J/(mol K) 2 9,1 30.1 Kinematic viscosity -g/(s m) 23,0 40,1 Thermal conductivity m To W8 m) 32,9 60.2 Prandtl number 0.71 0.75 Data on material flow Mass velocity Kg/s O, 31 Volume velocity m”/s O, 0110,026 Heat flow rate kW 166 Conduction density kW/m wealth 14 Reynolds number 26300 15600 Pressure drop mbar 200 The following Table ① is the data on which Figure 5 (oxygen) is based.

Table ■ 1. Process along curve A Heating of raw material by heat recovery Unit: Inside the jurisdiction Outside the jurisdiction Reaction product raw material Inflow Outflow Inflow Outflow Fluid data Average molecule 1 g/mol 15.5 15.5 17.8 17.8 Pressure ba r 30,05 30.0 31,4 31.3 Temperature K 850 625 5 60 800 ratio IIT kg/+m36.60 9,11 12,8 8,52 Constant pressure heat capacity i J/(+eolK) 37,7 37,1 46,2 43,3 motion Viscosity mg/(s m) 32.5 23.9 19.9 28.9 Thermal conductivity mW/(K m) 133 99.2 53,1 81.3 Prandtl number -0 , 5940, 5760, 9750, 868 Data on the flow of substances Mass velocity Kg/s 0.75 0.68 Volume velocity m”/s O, 1120, 0810,0530,080 Heat flow 1 kW 407 Conduction density de/mχ 1712 Reynolds number -14900202002070024300 mbar under pressure R 50 100 2. Process along the curve Reforming with only heat addition through heat recovery Unit: Inside the jurisdiction Outside the jurisdiction Reaction product raw material Inflow Outflow Inflow Outflow Fluid data Average molecular weight g/mo1 15.5 15.5 17.8 15.6 Pressure bar 30,1 30,05 31,3 30.8 Temperature K 1263 850 8 00 950 ratio nt kg/n' 4,40 6,59 8,51 6,13 constant Pressure heat capacity J/(molK) 41.2 37.7 43.3 40.9 Kinematic viscosity Degree -g/(s fog) 45.2 32.5 28.9 35.2 Thermal conductivity m W/(M m) 188 133 81.4 142 Prandtl number -0,64 00,5940,8670,652 Data regarding the flow of substances Mass velocity Kg/s O, 75o, 68 Volume velocity m”/s O, 1670, 11 20,0800,112 heat flow!　k　W　765 Transmission rate kW/m250 35 Reynolds number -10600149001430011700 Pressure drop mbar 50 500 3. Process along curves A and B Heating oxygen by heat recovery (1) Oxygen Unit: jurisdiction oxygen Inflow Outflow Fluid data Average molecular weight g/meng. l 32 32 Pressure bar 31 30.8 Temperature K 400 900 Specific gravity Ikg/IB3 30.2 13.2 Constant pressure heat capacity it J/(mol K) 30.1 34.4 Viscosity mg/(s m) 25.8 44.7 Thermal conductivity mW/(K m) 34.2 66.11 runs) Le number 0.711 0.72 Data on the flow of three substances Mass velocity Kg/s 0.07 Volume velocity +*3/s O,0020,00S heat flow!　k　W　37 Conduction density k round/m” 2.0 Reynolds number 4900 2900 Pressure drop +mbar 200 The following Table (2) is the data on which Figure 6 (electric heating) is based.

Table m 1. Process along curve A Heating of raw material by heat recovery Unit: Inside the jurisdiction Outside the jurisdiction Reaction product raw material Inflow, outflow) Mass outflow Fluid data Average molecular weight g/mol 12.7 12.7 17.6 17.6 Pressure ba r　30.2　30,0　31,4　31. ．． 0 temperature K 870 650 5 60 800 Specific weight kg/m” 5,26 7,02 12,6 8,3 Constant pressure Heat capacity I J/(molK) 35,3 34,2 46,0 44,2 Kinematic viscosity Song g/(s m) 32,9 25,2 19,8 27.1 Thermal conductivity -W/ (K m) 180 140, 2 55, 9 80.7 Prandtl number 0.51 0 0.486 0,925 0.842 Data regarding the flow of substances Mass velocity Xg/30.58 0.58 Volume velocity m3/s O, 1100,0 B3 0,046 0.069 Heat flow rate k 350 Conduction density k1N 7 pieces 21.1 14.8 Reynolds number 11500 15 100 17700 12900 Pressure drop mbar 40 50 2. Process along curve B Reforming with only heat addition through heat recovery Unit: Inside the jurisdiction Outside the jurisdiction Reaction product raw material Inflow Outflow Inflow Outflow Fluid data Average molecule’pi g/mol 12,7 12,7 17,6 17.5 Pressure bar 30,3 30,2 31,0 30,0 Temperature K 940 870 800 870 Specific gravity 1 kg/m’ 4,88 5,26 8,33 7.57 Constant pressure heat capacity J/(mol K) 35.7 35.3 44.2 45.7 Dynamic Viscosity - g/(s so) 35.2 32.9 27.1 31.1 Thermal conductivity -1 bar K +s) 192 180 80,7 95.8 Prandtl number -0, 5170, 5100, 9860, 991 Data regarding the flow of substances Mass velocity Kg/s O, 580, 58 Volume velocity m3/s O, 1190, 1 100,0690,0? ? Heat flow! bw 116 Conduction density kMm” 21,0 14,7 Reynolds number -108001150 01290011300 Pressure drop s+bar 40 200 3. Process along curve C Reforming by heating with heat recovery and electric heating Unit: Inside the jurisdiction Outside the jurisdiction Reaction product raw material Inflow Outflow Inflow Outflow Fluid data Average molecular weight g/mo1 12.7 12.7 17.6 12.7 Pressure ba r 30,6 30,3 30,9 30.6 Temperature K 1285 940 8 70 1285 specific gravity 1 kg/m33,60 4,88 7,57 3,60 constant Pressure heat capacity J/(mol K) 38.2 35.7 45.7 38.2 Kinematic viscosity Degree B/(s m) 44.6 35.2 3L1 44.6 Thermal conductivity mW/ (X m) 248 192 95.8 248 Prandtl number 0.543 0 ．． 517 0,843 0.543 Data regarding the flow of substances Mass velocity Kg/s 0.58 0.58 Volume velocity +a3/s O, 1610 ,1190,0770,161 Heat flow kW 585 Conduction density kW/Kou 22B, 9 20.2 Reynolds number 8500 10800 11300 7900 pressure drop *bar 60 350 Based on the above method, data corresponding to the process performed with the device shown in Figure 3 was derived. This is easy for experts to do.

FIG.1 FIG.2 ↑ ↑ E FIG.4 Ding F I G, 5 , H2-1111 temperature engineering international search report ANNEX To 4HE INTERNAτl0NAL 5EARCHRE? ORτON

Claims (10)

[Claims] 1. A device for performing endothermic reactions between gaseous reactants at high temperatures and high pressures. , recovers internal heat from the reaction products and supplies it to the raw materials, and also recovers internal heat from the reaction products and In devices with stages, feed material is passed from the inlet along the gap between the pressure wall and the shell of the device. An internal uninterrupted shell (13) for transporting heat, and a built-in shell for internal heat recovery. a bundle tube heat exchanger arranged in such a manner that the feed material flows outside the tubes of the heat exchanger; a catalyst disposed in the lower part of the exchanger and/or downstream thereof; Thermal energy is supplied to the reactants at the final conversion point, while the reaction products pass through the tube. a heating means which supplies heat to the incoming raw material and then reaches the outlet of the apparatus; Consisting of An apparatus characterized in that all of the parts are housed in a pressure vessel. 2. The heating means is a burner, into which oxygen-containing gas is introduced from the outside, and this After the heat exchange, the gas reacts exothermically with a portion of the reducing feedstock material, during which time the burner is Patent claim: The equipment specified in item 1 of the scope of the request. 3. The heating means is an electric heater, and the heating element is placed outside the heat exchanger tube, and the catalyst Claim 1, characterized in that the area is located in a lower part of a certain area. Device. 4. The heating means is a device that combines an electric heating element and a burner, and this Both elements operate separately and independently, with the main heating means being connected to the lower part of the upper catalyst block. Claim 1, characterized in that the heat exchanger is placed outside the tubes of the heat exchanger. equipment. 5. The internal insulating shell is made of metal and/or ceramic and has a cutout on the outside of the pressure vessel. Claims 1, 2, 3 and/or 3, characterized in that a thermal layer is attached. Apparatus in Section 4. 6. Split the catalyst into two parts and place one part in a basket outside the heat exchanger tubes. The reactants are placed in layers and the other part is placed in the reactant passage after the burner. passes through the catalysts in both blocks, and the burner recovers heat to raise the temperature. An injector arrangement that mixes oxygen-containing gas into a reducing gaseous reactant. Thus, after the reactants are heated by an exothermic reaction with an oxygen-containing gas, the second catalyst The device according to claim 2, characterized in that it is adapted to be inserted into a block. . 7. The catalyst is packed in a layer in the basket on the outside of the heat exchanger tube, and the is passed through the feed compound one or more times, and the electric heating element is filled with catalyst. located outside the heat exchanger tubes, away from the basket, in the lower area of the The device according to claim 3, characterized in that: 8. Split the catalyst into two parts and place one part in a basket outside the heat exchanger tubes. The reactants are placed in layers and the other part is placed in the reactant passage after the burner. is passed through the catalyst in both blocks, and the electric heating element is filled with the catalyst. located outside the heat exchanger tubes, away from the basket, in the lower area of the The burner converts the oxygen-containing gas, whose temperature has risen due to heat recovery, into a reducing gas. An injector arrangement for mixing reactants with an oxygen-containing gas. After being heated by an exothermic reaction, it is introduced into the second catalyst block. The device according to claim 4, characterized in that: 9. Required amounts in the form of water vapor and hydrocarbons and electrical energy and/or raw materials Thermal energy in the form of oxygen-containing gas required for partial oxidation of reducing components in the material is A patent characterized by supplying a hydrogen-rich reactive product to a device and removing a hydrogen-rich reactive product from the device. A process for producing hydrogen-rich gas using the apparatus according to claims 2 to 4. 10. Claim 9 for producing raw material gas for NH3 and/or CH3OH synthesis term process.