JPS58208102A - Apparatus for concentrating and separating hydrogen or helium by means of porous glass film - Google Patents

Abstract

PURPOSE:To concentrate and separate H2 or He efficiently from a gaseous mixture contg. H2 or He by means of porous glass films by specifying the pore size distribution of the porous glass films. CONSTITUTION:Many porous glass tubes 7 are put in a stainless steel pipe 8, and both ends are sealed with a sealer 6. A gaseous mixture contg. H2 or He is fed from one inlet 1 of the pipe 8 under pressure. At the same time, the space 4 between the pipe 8 and the assembly of the porous glass tubes 7 is evacuated. Gaseous H2 or He in the gaseous mixture is diffused in the space 4 through the pores in the tubes 7, separated as concd. gaseous H2 or He, and taken out of the outlet 5. At this time, the pore size distribution of the tubes 7 is regulated so that the peak is set at 110-160Angstrom pore size. The separation factor of H2 or He is enhanced, and H2 or He can be concentrated and separated efficiently.

Description

[Detailed description of the invention]

The present invention utilizes a porous glass membrane to generate hydrogen or
・Hydrogen or ・＼11 +
') 1. Regarding equipment for concentrating and separating
5ru. In recent years, since the oil shock, there has been a shift toward steel mills that do not use oil, and all-coke operation in blast furnaces has become a reality.
ing. I, j', <furnace ＼0) Stop injection of heavy oil, start coke 1 history tl+'”:+-1'n1'g), and start tI, furnace 11'g milk. Ding-)+)ノ), stab a
, the production that occurs in the place '+J, Ga--〇)Se1L1person5zu-
・The conventional method is 7 degrees Celsius.) 1. The traditional method of in-house combustion is 1!/) Manufacturing Chichiriki・-So') Iff 笥: 1.. 1. I wonder if there is a need to develop new uses for frogs. Steel manufacturing There are three types of gas: sludge furnace gas, converter power, /, and blast furnace scum. The main component of the gas, d'h・Unonosu)i, is carbon monoxide. -・Carbon oxide can be easily converted to hydrogen by conventional technology through /ft reaction 4+A
Teshiro. '9A To provide iron gas for purposes other than fuel'
- Inappropriate: This is the key point to concentrate and separate. The present invention is for concentrating and separating hydrogen in an economical and cost-saving manner. (9) Regarding equipment, the following points are as follows. That is, (1) Porous glass All? , V
<, - A mixed gas containing utilized hydrogen or helium, i) In an apparatus for concentrating and separating hydrogen, hydrogen, < is helium, the power to have an outer pore heat in a pore diameter of at least 110 to 160X. L, Qft thin rL diameter 110-16
Hydrogen using a 74-filtration porous cuff membrane, each formula (-7 Kuha・
121 .11:H: Open the ends. an outer circumferential surface space configured to be air-filled and integrated with the porous glass tube nest 18;
A bundle of glass tubes + a carrier is separated into a space extending 1 m from both ends of the glass tube bundle, and the outer periphery of the perforated lath tube assembly is connected to the space (or to both directions). Hydrogen or ＼ on either side of sky 11]
11. The scope of claim 1 is to provide a means for supplying a mixed gas containing 11, t, and 11, and a depressurizing means is provided in the space in which the mixed gas supply module is provided, and in the space in the other space (j). Device described in the 1st generation k0 1.31 - A porous hole 'V with a closed end and the other end as a closed end
Gaffs * bond body p7) The outer circumferential surface and the demolition matter m are arranged 1
1. The outer circumferential surface including the closed end of the porous glass tube assembly is open 111.
1, and a means for supplying a mixed gas containing water 7 (2, or (t. Moni s t
jj+: 4t, porous glass management structure) Axial own 1
i1x' : 1': connected; +++ , r z, a pressure reducing means is provided in the space (, f t, Patent No. 61'1)
ith l. J'1'4 i'! l: Equipment listed. It is. The basic structure of the present invention is 1 ull i, with a pore 't4 (although it is assumed that hydrogen is diffused and separated by using a Karaska pore 4', θ), the mean free path of the gas is λ, and the pore diameter is d, then λ-/ ′
d) In the region of 1, gas molecules passing through 4.111 holes 0)
11 which is proportional to the molecular speed of the liquid! It makes sense. That is, the flow of gas molecules passing through the pore is calculated by the square root j of the gas molecules molecule i and the counterpressure f+! Since the molecular weight of water is relatively small, it is separated from other gas components.5) - Separate mouth ■
The functional region is strictly a region where λ/'d:>1, and for this purpose it is necessary to enlarge and reduce the pore diameter. It is a good idea to make the pore diameter too small.
Even if the ideal separation capacity is obtained (7), the amount of gas permeating through the pores is small and it cannot be used as a practical separation device.

[The present invention shows the maximum resolution in the relationship between the pore diameter and separation power of porous glass. The existence of a hydrogen C4 condensation separation device was discovered and the effectiveness of using porous glass was determined. Porous glass is Na20-++20I-S i 0
2 yarn crow 4 - heat treatment to cause phase separation phenomenon, Na2
Prepared by acid bathing the phase of O13203 yarn.1. Ru. In this case, the distribution of the a pore size of the porous crow differs depending on the sub-IW of the thermal processing station 1 ri and 1 hour;
．． Using this method, we can create a porous crow with a 5-pore distribution with five pore diameters. Obtained in this way: 1. The pore distribution of porous glass gel usually has two peaks. While showing a comparative example for one example, 4:
Detailed description of the invention. Figure 1 shows the structure of the hydrogen condensing device used in the center/Alf column with a ratio of 4.41 to 0. Cut J 5' mm, thickness 0.5 mm, length 600
19 RNM porous guff tubes were bundled into a porous glass tube (4 = 7 to 1). Porous" 1)
jlj part X30mm is a porous colored glass tube U) outside 1r, J
j'il(t; !, H A -r 'y' l-i of the steel pipe and the porous glass tube bundle, 111 (J) Sky-9
A space 4 on the outer circumferential surface of the porous glass tube assembly (!: porous glass tube assembly) is separated into a space 2 communicating with both ends in the axial direction. A (+The mixed gas is connected to both ends of the porous glass tube and the volume 7σ) 4-The force σ of the space 2 flows in from the population 1 in a pressurized state. It flows out from the other outlet 3. The outer periphery of the porous glass tube assembly [1 (1 space, 1 is Fl, The concentrated hydrogen gas exits the space 1 on the outer circumferential surface of the porous glass tube assembly from the space 2 in the space 2 at room temperature. The pressure was maintained at a predetermined v) JJI+ ++> state, the pressure in space 4 was reduced to -700 mm IIg, and a mixed gas of hydrogen and carbon dioxide (1:],) was supplied to space 2. The predetermined pressure in space 2 was varied in the range of 0.4 to 2.8 Kp/crlO, the hydrogen gas +41 of the outflow gas from 3 and 5 was measured, and the separation mooring under each condition was determined. The results are shown in Figure 2. For example, the results of pore distribution measurement using the nitrogen adsorption method showed that porous glass with a molded pore size of 30 to 50 x and a peak of pore size of 1 to 160 x was used. .In Comparative Example 1, 1ltl pore diameter 3O-50xc!: Fine diameter 80-110.:% to 1-
A porous glass with a single layer was used. Comparative Example 2 A porous glass having a pore size of 30 to 5° C. and a) pore size of 160 to 220° C. were used. The third factor is the pore distribution of the porous glass. ,・The ratio of the pore volume of the pore diameter 110 to 160X of the porous glass to the total pore volume was 52 in the implementation f+lJ, and in Comparative Example 1 and Comparative Example 2. So'l'
7.14 section. This is Section 12. Mean free path of carbon dioxide gas (room temperature, mixed gas 1-1: force o, 1-2.8 Kp/caO is 314X-116X. Pore:! 30-50X Poor pore diameter 80-11
Comparative Example 1 using porous glass with peaks at 0 and X
can be said to be a sufficiently small pore diameter compared to the mean free path of carbon dioxide; t”
Unexploded 11J-1 example using 1 crow and pore size 30-5f) 'i, , -111,14H pore i, 1
In Comparative Example 2 using a porous glass having one peak at 60-220X, the pore diameter cannot be said to be smaller than the mean free path. Monika\Waraden, 4. Fully open U) 夾/A example has the largest separation coefficient 4-・Bo 1-7. Unexploded 1iJ
When the pore diameter becomes larger than the example of j, the ratio 4 i't fa
ll 20) The separation coefficient is kana 6) Low. Koi 1. corresponds to the 14P principle of separation. Based on the principle of 11, Comparative Example 1, which has the smallest pore diameter and is considered to have the highest separation ability, shows the lowest separation coefficient. This '-IS- uses porous glass '4-I L,
In hydrogen condensation separation, the appropriate pore size M of the porous glass or the existence A
- indicates that Although this cannot be explained from the principle of separation, it can be imagined as follows from the method of producing porous glass. That is, the smaller pores of the porous glass are Na20-
[It is formed when the 32o3 phase cannot be completely extracted and remains in large quantities, and this strongly adsorbs impurity gas components other than hydrogen, such as carbon gas, and is separated by the surface diffusion effect. This is thought to be due to a decline in performance. Hereinafter, I have shown examples and comparative examples.)
In addition, in a hydrogen concentration separation device that utilizes the pores of porous glass, the IVal pore diameter of the porous tube glass is small and 0 means high separation performance, but rather the pore size is quite large and the separation performance is high. η-6 Pore diameter 11 (1 to 1
The optimal one is one that has a pore distribution peak in 6FIX, or one that accounts for a pore volume of 110 to 160 X or a majority of the total pore f area. C) It also has a high level of permeability (permeability coefficient), which makes it suitable for industrial practical use. 0) In the embodiment, as shown in FIG. 1, a mixed gas containing hydrogen is supplied from the mixed gas inlet 1 to the space 2 of the porous glass tube assembly 7 through which it passes at both speeds in the Jl+ direction, and the mixed gas is supplied to the outlet 3. Let it leak more. At the same time, the outer circumferential surface space 4 of the porous straight glass arm body is brought into a reduced pressure state L7 to separate hydrogen, which is then discharged from the permeated gas outlet 5. Using the apparatus shown in Fig. 1, the gas (1) flow A1 is transferred to the
1° [Body 70] A mixed gas is supplied from 5 to the outer surface 4 between 4 and 5, .
Space 2 that communicates with both ends of the direction is pressurized to 11 □ and hydrogen is separated. i L, <
It is possible to separate ha・\su・'/ l. In this case, a gap is created between the porous glass tubes to improve diffusion and circulation (for example, a link is attached to the outer periphery of the porous glass tube) to form an aggregate.
That's preferable. Furthermore, a mixed gas is supplied to the outer circumferential space of the porous glass tube assembly, and the hydrogen separated from one end of the porous glass tube assembly in the axial direction θ) is expelled using the apparatus shown in Figure 4. - You can also. The device shown in FIG. 4 uses a porous glass tube assembly with both ends open, as opposed to the device shown in FIG.
This is an example of using a porous glass tube assembly with the other end open. In this example, the sealing of the porous glass tube assembly 7-7: T1
! When the mixed gas is supplied from 1 to the outer peripheral surface space 4 and is allowed to flow out through the outlet 3, the space 2 communicating with the open end in the axial direction of the porous lath tube assembly 7 is formed into a castle IF shape. T!
In addition, it is possible to separate hydrogen from 2 and start defeating from 5. Example: In order to improve the diffusion and distribution of gas, it is preferable to configure the Kanto bond body so that gaps are created between the porous glass tubes. The fruit of the present invention is that 0191 shows the agricultural contraction separation of hydrogen.The present invention is not limited to the agricultural contraction separation of hydrogen.
It is also effective for condensation separation.

[Brief explanation of the drawing]

FIG. 1 shows the structure of a hydrogen concentrating and separating apparatus showing the embodiment 191 of the present invention and a comparative example. FIG. 2 shows Example and Comparative Example 1. 1 shows the relationship between the mixed gas pressure and the separation coefficient in Comparative Example 2. The solid line represents the relationship between the mixed gas pressure and the separation coefficient in the example of the present invention.
Broken lines and dotted lines (showing those of Comparative Example I and Comparative Example 2). Figure 3 shows the narrowing and narrowing distribution training by the nitrogen absorption 7?A method into the used porous hole + t + 1 hole. Figure 3 below, RO.'-J3E 1. The porous 'r7f crow used in the example; ) shows the pore distribution. 41 yen] is implementation of 1112 of the present invention j + 1 yen:? 't
Not shown. 1. Mixed gas pipe inlet, 2. Space connected to both axial directions of the seedling crow and aggregate 1. 3. Mixed residue outflow 0.4. Porous [E] collar = 4 tubes Outer peripheral surface space of the aggregate, 5. Permeated gas Mi outlet, 6. Seal cutting, 7.
・Porous glass tube assembly, 8・Stainless steel, 1114 pipe rod/Fig.

Claims (1)

[Claims] +11 In an apparatus for concentrating and separating hydrogen or .\RIU l-1 from a mixed gas containing hydrogen or .\RIU l using a porous glass membrane, A porous glass tube aggregate having a pore distribution peak in the range of 110 to 160 mm, or having a pore diameter of 110 to 160 mm or more than half of the total MIIH pore volume. A C4 sardine separation device for hydrogen or helium using a high quality glass membrane. (2) Both ends of the outer circumferential surface of the porous glass tube assembly with both ends open are airtight (9), and the outer circumferential surface of the porous glass tube aggregate is airtight and the outer circumferential surface of the porous glass tube aggregate is airtight. 11f1' (separated into a space connected to both ends in the axial direction, the above-mentioned porous space; a space U connected to the outer peripheral surface of the straight glass tube assembly, or a space U connected to both ends in the axial direction), hydrogen in one side, or... I.J.
Providing means for supplying a Ti mixed gas containing r'Tsum 6
- both of the above-mentioned mixing gaskets, 11 of the space provided with the supply means;
1! 2. The apparatus according to claim 1, wherein said space is provided with a pressure reducing means. +, '((The outer peripheral surface and the open end surface of the porous glass tube aggregate with one end sealed and the other end open are configured airtight7, and the outer periphery including the sealed end of the old porous glass tube aggregate Axial release of surface space and porous glass tube assembly q; connected to 11'1
A means is provided for supplying a mixed gas containing hydrogen or . ! 11. The apparatus according to claim 1, further comprising an IE reducing means provided in the space communicating with the open end 1 in the 11-direction.