JPS5921502A - Method for concentrating and separating hydrogen or helium - 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] - The material is a porous body, preferably a porous glass I
This is a method of concentrating and separating g, using L7 aqueous system or Q', mixing power containing helium, and hydrogen or helium.

In recent years, since the beginning of oil production, there has even been a shift towards steelworks that do not use oil72, and all-caucus operation has been implemented in blast furnaces. This is because the injection of heavy oil into the blast furnace is stopped and the blast furnace is operated by increasing the amount of coke used.

This will lead to an increase in the amount of iron-making gas generated in the iron-making LSR process, and it will become necessary to develop new uses for the iron-making gas, which are outside the conventional use of self-use fuel.

There are three types of steelmaking gas: coke oven gas, converter gas, and blast furnace gas. The main component of the corcus furnace gas is hydrogen, and the useful component of the converter scum and blast furnace gas is carbon oxide. -What about carbon oxide? It can be easily converted to hydrogen using the +l/nod inverse ratio. In order to use steel mill scraps for purposes other than fuel, it is important to find out how to economically, conserve, and precisely extract the target components in steel scraps.
That's the point. (＼Invention rJ, Hydrogen-shi, ＜ is 11L of hydrogen from the mixed scum that sinks helium ＜i'', -＼Use 4 economically and energy-savingly (a cuff that divides 11 times)
Regarding the second, there are the following: -J, -rotJ, next, j, ・LeeC.

That is, at least wholesale] pore size L[0-i (i fl
IY to i+1Ill 41. , ”,) If the pore diameter is 110 to 110, the diameter of the pores is 110 to 110. z',)-・out'n(+drink-・\/2-out and partitioned between the two glues i7-water -;7 I, L <
&. ↓ −＼ ri ・'7), of (η attack &
: Take 1 piece of outside meat (16 pieces).

The mixed gas f l', which sinks into the space of rJ (element (,Lghaheliuno・), is supplied) into the space of J and 1111 through the I hole Pf body 1-5p, -water + , Do:' L, < is-\Riuno, separate θ1 and bring out the Ridjikas, ・17)
7. The water temperature in the concentration separation device 6 is set to 11 (the lees!) and the mixed gas is turned off. (is the concentration separation method of '\RIUNO.

11;1 principle of the present invention Q1, porous body, desired, < (r
, l: Expand hydrogen using the pores of ζ
Separation 1 - ('-, dregs 0) The homogeneous self-height stroke is λ, the pore diameter is d and JZ, and λ,・d >>
In the region of
? '-1 Its molecule-velocity J-gl is compared to t+U) Principle::1lii is originally 4-. 1", that is, the curse molecule (flow 44) passing through the pore L1, '^J', passes through the hole 1 + lJ- to the flat knob root for the molecules of the gas, so it is 1
In the book by Min-R Ko [7 small hydrogen atoms, lr], the dregs component of 111A and the ryy separation are achieved by IIJ function.

)) Cause 11. ...Ill ability 19'a region tJ is strictly in the region of 2, /t:1, '>>J, and it is necessary to make the pore diameter extremely small in this region. [,
However, if the pore diameter is reduced (2O,), even if the ideal separation power is
The amount of gas permeating through is small, and f+:I is suitable for practical separation stability.
: It can't be. In other words, it is generally recognized that there is a relationship between the ability to separate and the ability to pass through. However, in reality,
Relationship Q between separation power and penetration power; 1 medium pure h' anti-relationship is l
rg, high standard of separation NIP-;
6 There are 0 suitable pore diameters. Porous material utilization 17% efficiency,
5.1 In addition to selecting the appropriate pore size, the concentration and separation device 6
The structure, 1i', i, and operating conditions are also vehicle-specific.

The present invention has developed a pore size range that shows the maximum likelihood separation ability based on the relationship between the overall pore size and separation capacity of a porous body. Confucius S-i T-t- also used poly-porous materials to efficiently conduct hydrogen. i, 1-
- This shows how to reduce and divide Ryuuno, -1
4th, I! ! The iron gradient is also 1-<, in order to obtain the market-level 1X1C ability, an iFi machine that concentrates hydrogen from the mixed scum that loses water like denatured steel scum, and separates it by η.
There are 113 forces θ, -C. IJ1] ＼゛Amei 6-1 It is preferable to coarsen the 145 degrees, as an example, using a hydrogen concentrating separation device consisting of a porous hole ↓ Q 1'; One of the IJ methods for separating hydrogen by condensation (+:, 'μ), 1 row of experiments, real/, 'i'ii I+IJL・'
, hihi 11 shi 1 tari ・I don't show it ＼ri 1 - Ming's 8Y
Itokawa was founded in 6th century;,)・ Figure 1 is used for experimental examples, implementation 1+11 results, and comparative examples.
This is the structure of the front end θ compression device. Outer diameter 5 I+++
X, I%h(1,J) Question, 1 (60o mm (
] Arrived at Koga Gasis on 19th day of the year. ing.?
Holes '11 (1 each at both ends 7i of the color bow-1 assembly)
3() 朋(・j-type banknote f4 glass 1゛; outer periphery ↓, yohi stainless steel j ``4 and (・porous glass; i7i: q
The gap between the knee volume and the sol agent (5 is filled with 71, χ
- Hole 'tji crow 9: ; Outer peripheral surface space of bond collector, 1 and porous "7"↓notsis'i'i 4 ↓ 11+ Jy of the volume
A space 26 communicating with both ends in the direction - outer periphery [1]. Water A9
zu11 mixed gas (f, 1 porous glass, i7; l, +
4. Building blocks f' (1) iMl + 111 to one no. 1 of the space 2 communicating with both ends in the force direction, () Flowing with pressurized Ql, the curved blade's -T'S o <・hole T1
The outer circumferential surface of the crow positive aggregate and the space between HL and 11-shaped near LH
(1+Return 7 (10#Im 8%) i'11
It is held and permeates through 4 holes of porous glass, /
This hydrogen-enriched gas flows into the outer peripheral surface space 7 of the porous glass tube assembly.
i6: Outflows from 5.

Example 4. In the pre-concentration device shown in Fig. 1, hold the yarn ((-1, space, 1
Reduce the pressure to 1'700 mra 19. A mixed gas (], : fl) of hydrogen and carbon dioxide gas was supplied to space 2. O, '4-2.8 K for the specified 1 toka between 2 and 2
4/cJ Changes in the jll12 range of G
゜)/(2-"i-",) , :, , : Nirua 1. Hydrogen lip scum water (・
2 words 1 boat 2: (Hydrogen concentration of the scum (- λ.: Not □h water oia of the scum) Obtained by Ijlj. As a result, the amount of gold was 21 ゛ 1.

In Experimental Example 1, #llI five layers due to desired element adsorption), 4i
d! 'I lr, i4 connection 1 ↓ - C) : tllll tithe 1 effect) I) ~ scarcity + I-1, A and wholesale 1 (L ff, l
10-i 6゜spread over 6-motsu ('hole゛C↓]
l lath was used. Experimental example (4):,: q) 1 qtl
l+Ijl conversion f￥, "S Q -50A and I111 hole diameter 80-110・＼ 1 go Yukini, '□); hole 'P
i crow wo/II l) 7'ko. Actually, experimental example:) -c
iyi 411 hole F-¥'30 ~5 I-j
tma and #lII fL iY' Sat 6 C
1-2 20・Ma Nibi Begging also used 2) I・Ko'tq crow. ko, 11, et al ()'g fl '('j i
j 5 Suno #II Hole 5) Cloth k 43 Figure I'-i
i<f. Porous 7 lenora"l'J,-'a2 [-)
-11゜o3S], 024 glass heat treated L-,,j-
h 41101. ! 4! , 'c・if: l2sa-
M - Ntr, 20 e, , o3 thread I U with acid r waste,
'l4-ru-2-J:11 Created 1. Ru. In this case, heat 'ILj'l! ('1.) riot I+j,
'l'1-1i: l ni,, J: ri-porous 35j cuff
Snow, 111tl pore size, L(')J: i'ill go'
T) I117 da ＼ redundant 1, :ノL? f: for iq,
(-Medium, 1llil hole IT 1. Sorting IJ. I, I will make a porous crow. , -, J-Nishi ('J '', +71-Porous crow wholesale J Hole ;)
7i+ is I! ! j '71'+, Niyama Beeri t most things are on.

, Nino 1. IJ, + ', ZS O 7' Tukaras state 1
Pore diameter 1Lo-, +6oXC・) t+a 41,? For the product 151″i′″ state 1 hole holding, ■1 ratio is Experiment 1 11-(1・, L , 1. :, :%, J, :, Experiment 1 series i + Jy□yohi Actually, in experiment 1 + 3, it's L.J.
) 11%, j, 2% is 7 chiru.

ノ<acid 7 nos 0 medium”:+ fl ii 1j about t:j
, chamber 1. XW - Mixed dregs) EF J0, 4-2.8
Kq/crdG (d 3 L 4λ−I L 6λ).

Using porous glass with a pore diameter of 350 to 50 z and a pore diameter of 80 to IJOλ, / C Experiment Example 2v, 1) It can be said that the uniform diameter is sufficiently small compared to the uniform free path of carbon dioxide gas. J hole diameter 30~ei Oλ and 1 hole diameter 10~160
Experimental Example 1 and iM No. 1 hole size 30-50λ, thread III
(L (-> 16←) ~ In experimental example 1'3 using porous crow with a peak at 220λ, 1j hole?l is q
I can't say that J is very small in the process of ``gyra''. In fact, Experimental Example Y shows the coefficient of the largest component of force.If the hole diameter becomes larger than Experimental Example 1, the Experimental Example's 3-fold Nt coefficient &J will be considerably larger. Low 1: Yes.

,=it is 1 of 0 11. ! J-th 14". According to the principle of separation, the highest part nlt N
F'6- This is the experimental example with the smallest pore diameter that is considered to have the smallest pore diameter, and it shows the lowest external factor 1 coefficient. This shows that the porous body is used to increase the maximum pore diameter of the nonporous glass (L in hydrogen concentration stage II).

Evening and Saturday, as we did in the experimental example, (-) the pores of the body are -/this hydrogen (Iμ reduction Afff device, All (1,t ￥・small Et and lI''? 1 minute N (because 1 ability is gill cuffed? -, j h-\゛, quite friendly wholesale 1-fL child is on the contrary high = lI + ig Tani: ", 1, toriil
vB (y:'+ &'1 empty porous body and L
-111-71rY-1,t ('i -i 60;
Niill 41. Something with a distribution peak )−
1: , bi11go1, ij3not o ~q, t)
o
'; The one that occupies two single bond anchors 1゛1' number J double 1 is optimal 1),;) #b fil K high l-, f K')
Is it possible to put NU (transmission coefficient) into practical use in the industry?
Go, (X, go.

1),), ,,,,f,!・') Cases 6 and 7 No. 1
Does it contain hydrogen as shown in the figure? h', inter)) The porous 7-glass 71 aggregate//no Tsukuda; in the direction! J in Y seat,
, lit , fl via 1iiJ 2 ni J Kiyosuke scum inflow r] 1 and outflow +13 Marishima], and in the same 11s, the outer circumference of the porous crow 71 collection 4, 11 body I/+j
Space 4 is brought into a state of ρ1 and ν pressures, and hydrogen is passed through the casing for 9:11 minutes.

'J', Figure 1 shows j, · ke 4] The device^'' is used, the gas flow is reversed, and 5/(~44. Outer peripheral surface of body 7 1iiJ 4
Mixing 1j and 5) while supplying t2 - Fig. 71<sit not outflow 11'', and not letting outflow same 1 (, 5 to both ends of the *l+ direction of the porous crow v′te 1 aggregate °I) The space 2 passing through ψ is 11. It is also possible to separate hydrogen under pressure conditions 1 to 1 and extract it from 1 and/or 3, thereby making it possible to separate hydrogen and helium with an efficiency close to that of Example 1.

In this case, it is preferable to construct the assembly so that a gap is created between the porous glass tubes (for example, by attaching a ring to the outer periphery of the porous glass tubes) to improve gas diffusion and flow.

Furthermore, it is also possible to use a device shown in FIG. 4 as an example for supplying a mixed gas to the outer peripheral surface space of the porous glass aggregate and extracting the separated hydrogen from one end in the axial direction of the porous glass aggregate. Ru.

The apparatus shown in Fig. 4 uses a porous glass tube assembly with both ends open (gt1); / This is an example of using a porous crow aggregate.

In this example, the porous crow positive aggregate 'I's sealed enclosing body 11'?
+: Supplying the mixed gas from 1 to the outer peripheral surface space 4 7. Outflow [Porous crow at the same time as outflow from J33! 1゛; Purple space 2't(
il, i pressure 1, "-" L-(, zJ(-141廿1
From rllll Lte 5) ly comes out, \ ・,
).

1. -(7)+4/IJ's 44.1. Place it on the stand to improve the diffusion and distribution of waste/chi'hole 7'■ Place it in the gap between the glass pipes! It: f+lLf't<Itt'M Ile, Zui], - is preferable. Furthermore, the first
FIG. ) to (S orgy in the glass?
9 angle t1 again (・:1, hollow board (1 history f'H- in shii
Jru, both are functional, 'F1. Z, 1 + t + IL), explanation [/ζyo-) (-★', porous body -7i1
1 [) τ hydrogen +: 'i'l' mixed i"i' kasu, 1
．． When hydrogen is concentrated Afl, the most refined iY- is rI:
Using a two-porous body that fis the optimal thin J'l body ('), III'r〉-7,j-(medium', water, +, i-';
i,,,'<Ui-\When separating lium, 1-
(Gammat, A degree of the negative gas) Both 11- ii + 'W adjustment (- gives a dividing effect (1 and 1'' towards -1 and 1-4 - (the longest point is 1. Do one thing yourself.

Example and if, l'z I=16-3j jl:,
L 2i: Full explanation.

('14. , i・yama I...li 1,・ ,1,
hi tl; 1:'<I'li),'11.1
ixl to 'J, L;4=zJ(NeiK fall5"j
In the Ml device 6'', two heaters are wound around the outer periphery of the hydrogen concentrator 6'', and the temperature of the scum flowing out of the hydrogen concentration separation device is 6 g'jll ('maintained at a constant temperature). 7, hydrogen 4 f), j) candy, pyroic acid gas 45]%, moisture and (, ;3% mixed gas H) o CC
In the state of 1135at, the porous glass material is introduced into the space 2 passing through 11 holes at both ends in the axial direction of the porous glass material assembly.
Space 1i-i on the outer periphery of the aggregate 5 u: Vacuum pump 1i-7
() Passes i through the porous glass 9, and the hydrogen gas flows out from Pf5. Hoda-Jj:
7th T′i is transmitted 11·%l, no unpermeated gas is lη1:
From 5, Ura comes out.
and the water concentration a of the hydrogen-rich gas, and the separation coefficient α□
~ seek/ko.

'In Example 1, the hydrogen-condensation device is used.

total 10%) 0~52 ”C, actual addition i 1ull
2, the hydrogen concentrated juice 1 unit was taken out from Ura 2, and the temperature was set at 15?~), and the IC7-1 comparative example was
Nonope and Akira 1-IJ-u leaking out of the Fu1 old separation device
6'-, held at 40 nc. Two sets of results are shown in the table.

, : l'l, 1 surface water (, (), 1. sweating; ill'Ib: +^°needle' city output power, supplying temperature I ship!I-,,4); The squirrel γ crystallinity l″λ1 is maintained, ;3 'ノ, the example is ゛ro 2~! Jijj30・)
Did you decide to use the device N to hire hydrogen? tC・'l” ;l-,
:, Kas T + 'Beg 1 Li / C 1 Co Ml
There is -C to Tsuno Sun.

1 (; lp,, IP+・1] (・)
-;・I don't like 2. Namely.

[・Bulk separation! -Supply the temperature of waste in the tray.
．． Mixed cass jli, 1', clear 1', ('',)
l'AA 1tJ- to 1 Song (4 then a high level separation official) <shii: +::I) 7 7 and j+h
There is a small -C.

1\Invention'↓, /l狽1ull k1 Hydrogen (It-Jσ, 'shows...7'Ha, 4\Invention is not only the reduction separation of hydrogen, but also one\su1: J 7. () Concentration 5) 厘1 (- is also 11.3 due to H' effect. 71... In the explanation, tit multi-purpose '1' ↓ body and L- (general ') 74 (/j Shirasu ( 1-1I (14 times (・), Pa J
謬Ill l,, lkoga, 夷・口'7' (Tsunojisu I
)-J, outer porous dug body (1 row 1.'J: ceramic thin) also front 1 (1) l-2/(, Jq IL gradient, 1 stage)
.

(2) The first one has a pore diameter of J1, and the second one has a 1" pore I+)" ↓ Similarly to Karakaku, J7- can be easily separated. Hollow prismatic hollow 1' provisional +4 is also ゞiYi''1., and the present invention is crow 1It-r- or -2) 7t.

6. It is clear that 1.a) there is no restriction to the porous ``ili aggregates''.

[Brief explanation of drawings]

Figure 1 C1 Example of the present invention
- 1 hit 1 + 1 hJ, Nina] 1. □X-one hydrogen concentration C) The structure of the skin is C. 7 Figure 2 d2 Mixed dregs in the experimental example 11 force and 6) 1ζffl (,?i
It is a diagram showing the relationship with numbers. Solid line ~ Experimental example 11
'-The relationship between the mixed scum pressure and the thickness separation 1f coefficient is...41. Dotted line (t'1.Experimental example 2'? Yohi Experimental example ts (July Soba 4 ts.. Nitrogen absorption of porous crow using Figure 53!'f?]
, 1-The pore size of the porous crow's pongee (1) used in 1- )) 'rli k・, dashed line 1
and OJ dotted line 2 &; No. 41zl? ,,1, The ability of the song of the present invention flj 1+
lJ device 6 small - 1 ". Mixed gas flow chamber 1"2; - Porous glass tube nest; ! 'i'f outer peripheral surface space 5 Permeated gas outflow [j()-'-noL agent,
Fu...Porous glass tube nest 8/Sfoonless steel wall
Bond figure 1 噸竿2 figure Kikutei 04 θ(9/, ;' /, 62°θ 24 z, θ
ytL, '=Likanu, pressure 9-/cm 2Q 3rd
Figure ``-: 1, 4th-Achi 14E supplementary iJF, i!
J:5! JR No. 8 □ Benefits of the invention, hydrogen or lqi helium concentration separation method, Nusode 11-
6-Relationship with person 1+ fi 11-! License applicant 1 location
East U1L Miyakochiyo [1-1 Ward Hitote-cho 2J-6-33 Name (hO,'y) Yu 1'' Wooden J. 15 electric (5 () Chang M8
'77f4J91 1-Nishishinbashi, Minato-ku, Tokyo. 12-
1 Daiichi Mori Building 8th floor 01111II glue 1 unit,!
Specification ■Detailed description of the invention. The rii Qj lung sea light column of the drawing, and the υ frog. 1 Ryo・1 Drunken Pass・No (1) In the details of the copper box, page 2, line 6. It says, ``...new for purposes other than purpose.'' [...new use other than use] and [J pressure]. (2) On page 6, line 4 of the specification. ``Example''. Correct it to "experimental example." (3) On page 10, line 3 of the specification, it says "Example". (-Continues with Actual 1v1 Example 14. (4) Attached to Specification, page 13, lines 10 to 9 from the bottom. 1-... Supply gas temperature is below. Comparative example...
・Nizuginai. ” it says. "...The fractionation coefficient of the comparative example where the temperature is below the supply gas temperature is 2.
．． I don't like 2. ” and corrected him. (5) Light a + trace, page 15, line 2: At 2, it says ``Both ends in the axial direction.'' Corrected 1E to read ``One end in the axial direction.'' (6) Clear 1 yen Figure 2 attached to supplement 11'), 1
2nd Eye 4 Togesu Mannaru Pq Procedural Amendment 1980, Lj Month/Day Kazuo Wakasugi, Commissioner of the Japan Patent Office 1. Indication of the Case 1982 Patent H No. 113988 2. Name of the Invention Hydrogen or Helium Related to the case involving the person who applied the concentration separation method Sleeve 1E Patent applicant address 2-6-6 Otemachi, Chiyoda-ku, Tokyo Name (665) Takeshi Nagisa, Representative of Nippon Steel Corporation 1)
4TS4 representative person 〒105 Tlri [Pa50
3) 4877 Address Tokyo Minato 1 person Nishishinkyo 1-12-
14N1 Mori Building 81 Item 7 Contents of the amendment (]) 't4iγ1 The scope of the claim should be ￥il as stated below.
i Correct. I', l) < J: also has a pore size of 110 to 160X (1i peak or a pore size of 110 to 16
A porous body in which the pore volume of 111 - When supplying a mixed gas containing hydrogen or . 1iii) A method for concentrating and separating hydrogen or helium, characterized in that the gas crystallinity in the concentrating and separating device is maintained at a level lower than that of the supplied mixed gas.-1 (2) In line 102 of the specification, "1 majority" is corrected to J-50RILl. (3) In the same line 7LA7, [...shown in Figure 3]. Insert the following sentence after ``. , [--Pore distribution by nitrogen adsorption method] In the measurement, adsorption, etc. (K obtained from the black line) (1 hole separation and persuasion, etc.) is considerably more obvious than the pore distribution obtained from the YAA line. 3. The pore size shown here is determined from the desorption isotherm without fat., I (4) Ibid. No. 907
In the line ``Majority - 1'' is 150% J and old i, E. Hydrogen (previously defined as seismic intensity 1. (6) On page 6, line 19 of the same book, insert the following sentence after ``calculated by 1.'' This 1 combination, 1-1: Force of Increase and self-reduction ((-4 permeated gas)); or increase in FIE force ((both supply gas), the ratio of permeated gas amount to 11 permeated gas amount is 1:2 luck. I adjusted ζ so that it becomes -1 (7) 12th
In line 10 of Sada, [-unpermeable gas] is corrected [-non-permeable gas-IJ-. (8) On page 12, line 11, correct [-non-permeated gas-1] to [-non-permeated gas-1 by nJ. (9) In line 1407 of the same, [Clarify. Insert the following sentence after -1. Example B shows an example of the present invention using a porous body other than porous glass. (Example 6 and Comparison Il+lJ) A silicon nitride tube with an outer diameter of 10 mm, an inner diameter of 3 mm, and a length of 5 Q mm having pores with a uniform pore diameter of 1000X was placed in a vacuum deposition chamber, and A4 was deposited at a vacuum degree of 10-'mjnHg. did. The pore distribution measurement results of this AA vapor-deposited silicon nitride tube by the nitrogen adsorption method showed that the pore volume with pore diameters of 110 to 160X accounted for 51% of the total pore volume. This porous tube is placed on the inner tube, and a steel tube is placed on the outer tube to create a double tube. was supplied under pressure.A ribbon heater was wrapped around the double tube, and the sound intensity of the non-permeable gas was maintained at 28 to 30°C by applying electricity. The space between them was depressurized to -7Q[]mmmm1j to determine the separation coefficient αm.In this case, the amount of gas supplied was adjusted so that the ratio of the amount of permeated gas to the amount of non-permeated gas was 1:2. In addition, in the comparative example, the outer tube of the double tube was particularly heated (the same 25°C mixed gas as in the example was supplied under pressure to the inner tube, and the space between the porous tube and the steel tube was 700 mm x 11 g). The separation coefficient αm was determined in the same manner as in Example J when the pressure was reduced.The results are shown in Table 2.Table 2 [1fl] On page 13, lines 18 to 20,
- So, in the explanation, I have only explained an example of an aggregate of porous glass tubes as a porous body. "Did you explain about the aggregate?" I corrected myself. 01) In line 11m, line 19, "(Example and Comparative Example)" is replaced with 1-(Example 1)
, 2 and comparative example).

Claims (1)

[Claims] At least 1 (1, 1, has a total 1 pore distribution peak in the diameter 110-160λ, t5 or pore diameter 110-h6oX, a polymorphous body that accounts for more than half of the total volume of 18I11 pores) -\te-C into the space of knee 9. If the gas mixture is 1-1f [l],
, ”, this hydrogen permeates through the porous body into the space of jj.
, ' L < is - Riuno, Noritsuchi gas is separated into one stream, and 17. Supplying the dregs temperature in the concentration ON# device d71. RU/I11 Hold more than 10 minutes.
)' Features - J-6 Mizuki Moshi 2 or Heliuno
11 separation methods for concentrated water.