JPS58501816A - Fluidized bed process for the production of sulfides - 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] Fluidized molten bed for sulfide production The present invention (1) comprises a method for producing an alkali metal compound, -I]χ-,=(:,IJlte,,)(Arsenal compound, -f, i.e., alkali metal , acids and sulfur-containing compounds, such as subsalts of alkali metals or sulfur. Regarding the above method by reducing with a solid carbonaceous reducing agent such as an acid salt, do. In one of its more specific aspects, is this invention an anti-disaster, a thing? Introducing The rock melt forms in a flowing layer along the periphery of the reaction zone. Regarding the method.

2. Conventional technology The production of alkali metal sulfides is extremely difficult. industrial chemicals Alkali metal sulfides as products have a wide variety of end uses. The others are sulfur Combustion of fuel contained in the flue gas (・ζ) It is also frequently used as an intermediate in the sulfur process and other industrial processes.

The production process of alkali metal sulfides removes various forces, especially (oxidation/sulfur compounds) U.S. Pat. In the method described in this issue, molten sulfuric acid is used) Sodium sulfide is produced. − The method described in U.S. Pat. No. 1,212,702 is Or by reducing sulfuric acid and sodium sulfuric acid and converting it into sodium sulfide in a Yaft furnace. , by controlling/supplying this amount of air in the furnace to produce small pieces of coal or coke. 2 "(Material trade 4 table and reducer [)h keep begging.

(p; Charcoal, lumber, and salt - egg heat carbonaceous material" 2 at a temperature of about 100 degrees Celsius Melt and reduce at 30°C.

United States (hj i+-specification-L No. 6,867.251 is a horizontal combustion The evaporated aluminum produced in the 16 chambers (obtained from pulp production) From the caustic cooking liquid to the alkaline alkali metal carbonate or hydrogen sulfide, (~ and approx. Alkali metal compounds are formed at a temperature of 900°C. , second area C (second area ( -1, combustion gas (1 tangentially injected/ζ oxygen-containing gas approximately 1100° from the Oxidized at temperatures between 1200°C and 1200°C.

U.S. Pat. A bifurcated method for reducing sodium sulfate that accumulates in iτ is disclosed. 1st stage C Reducing atmosphere 't': (mN) Provided at a temperature higher than the melting point of I-hysodium. , sled) Result melt @temporized sodium It collects as a melt at In the second stage, discrimination C: the concentrated reducing agent and the inert exhaust When gas is added to the molten material, sodium sulfate is added to the molten material. A large amount of thorium sulfide is produced from the gas. - Sodium sulfide (bent oxide with C-G Contrary to this, sodium hydroxide may be formed in the spinning bath.

The conversion of oxysulfur compounds into sulfides is produced by combustion of fossils and fossil fuels. A second field designed to remove sulfur oxides from the flue gas of electrical power plants. This is particularly important.

Molten carbonate e! described in U.S. Pat. No. 3,468,728Q! In that case, Sulfurized impurities are removed from the hot combustion gases at temperatures of at least about 350'C. contact with a molten salt mixture containing an alkali metal carbonate as an absorbent; Remove by. Sulfur-based compounds absorbed primarily as alkali metal sulfites The molten absorbent solution contains a reducing agent gas containing hydrogen, carbon oxide or a mixture thereof. It is convenient to form a sulfide mixture at a temperature of at least about 400°C. Treatment under reaction conditions absorbs sulfur valuables (modified by alkali metal sulfide Q). I can do it. Thereafter, the bath molten salt containing the alkali metal sulfide is heated to a vapor and carbon dioxide content. with a gaseous mixture containing 30% or more at a temperature below about 450°C to produce an alkali metal carbonate. 1~Moreover, the alkali metal imitation 1 substance can be sulfur or 241 Flea -CD, w Feed 1 I L ko) ζ -) -2:5- Pig,' ! -6.

The sulfide/＼0) reduction of the alkali metal oxide/sulfur compound is f-y Merica Electric Power Conference Report (Le-, DC’: eL’+l+i): q(’, j’jl’ ieA: i, e) l+-anp617-IC (ear 11':,■・;!1t)6 ),: 1977, 39 He Bela Ro 19 Donkey 1 Gia "Trinona (To Do Bow 1'' Ji 1 (only = CP) and Richard Day Ordef force / Pu (Tota, Go 11), o: 顛・１し、〕ear)C から f　=　=, -I for York County Public Utilities QQ-1v Tatami 2nd generation SO, - removal demonstration tQ (A 10Q - M'N 5ec aca Ger+Liu a"uxo+.

S (Bow RemC','a 1 5:i C1p l;Ocho≦)Go,:O- r　Pear+”b　for　Ne+;t+　YorkSt(l↑, e　Ult ,]i,i↑IP)-1) It is a part. In this case, remove the flue gas using an aqueous solution of sodium carbonate. Sulfur dioxide is a valuable material from the gas. During the absorption process, at step 1, the @liquid is carbonated with an uncured core. There are two oxysulfur compounds, namely sodium sulfite and sodium sulfite. and sodium sulfate, dry spent man's salt (Sp e n t21", )・, changes.

Sodium sulfide (oxygen/sulfur compound) Hydrogen sulfide gas is reduced and then reacted with brittle sodified water and carbon dioxide. According to this citation, it is necessary to have 4 nights of storage of sulfur and thorium carbonate. , the reduction process is kept at approximately 1000°C; It is completed. Use Y41 Bamboo salt is a solid substance such as petroleum coke or coal. Together with the base agent (τ reactor (B) is supplied.Air (1) below the surface of the bath melt, (2’ti : + Near dI V nozzle? ,<,',-,'EHl-teI'/,-11, 3 H The primary combustion gas that provides heat to the system (serves as a source of oxygen) For example, if carbon monoxide or carbon dioxide is used, a water vapor-like substance will be generated. is blown into the molten salt pool together with nitrogen from the supply air. Original reaction ℃, (Gas produced by the process (':L P'Saki'1: Many gases) Work, Mixing The gas flow is the generated gas, and the anti-L1-benefit separation! 7ru. One errand done! Meshio Uchiri) Oki/ The carbon present in sulfur compounds (-170- Give back. Sodium sulfide product, plus a small amount of sodium carbonate from the original feed The molten salt containing unreacted carbon and oxy/sulfur compounds is removed from the molten pool. It is pulled out with overflow force 2〇. Gas is at the top and close to ζ Discharge boat 2 After that, it comes out of the container.

The method described in f in this reference (-i is an effective way to remove sulfur dioxide from flue gas. Although it provides many advantages over the above conventional technology, it also has some disadvantages. However, this is not to say that there are no major issues regarding reactor design. The small dimensions, which are large and therefore expensive, do not allow excessive amounts of vortex gas to flow. Transferring a liquid (C or hydrodynamically unstable bath molten salt) to make a fluorite: ・A pool of air and the generated gas liquid (resulting from the blowing of air and air.Practical) The objective (C is a surface gas velocity of approximately 2 feet per second or It was found that the maximum speed of the vote octopus was given by the reductor capacity. Determine the required container diameter 2.

A second problem with this type of reactor design is the difficulty of maintaining a constant melt discharge rate. 2 For example, a slight increase in air velocity will increase the height of the melt and the number of bubbles in it. Let it increase in order to increase. Kneading has a large immediate melt overflow rate. It causes a significant increase in temperature and, as a sequence, provides a safety standard for subsequent melt quenching. ((Operation problem 2 can be played with.

Alkali gold oxides are produced from the corresponding oxy/sulfur compounds with high yields. It is an object of the present invention to provide a method.

Another object of the present invention A mixture of sulfates and sulfates or alkali metal sulfides (methods reduced with We would like to provide a method that can reduce sulfide by using a sulfite bottle. .

Another object of the present invention is to utilize molten salt without the need for prior art molten salt pools. The purpose of the present invention is to provide a reduction method that can be used.

A further object of the present invention is to provide a method that can be carried out with relatively simple equipment. It is to provide law.

Other objects and harmonies of the present invention will become apparent during the course of the detailed description.

In accordance with the broad aspects of the invention, the alkali metal θ) oxy/sulfur compounds are Alkali gold @ sulfide π, alkali metal oxy/sulfur compound and solid carbonaceous oxide The ox/sulfur compound and the reducing agent are introduced into the reaction zone; In the reaction, the oxygen/sulfur compound is melted by heating the region and the oxygen/sulfur compound is melted. The alkali metal sulfide is produced by reacting the alkali compound with the reducing agent; Distilled alkali metal sulfide, unreacted oxy/sulfur compound and unreacted reducing agent 2 The unreacted liquid is passed through the reaction area 7 containing the molten liquid and along the periphery of the bar. A method characterized by the recovery of oxygen/sulfur compounds and sulfur compounds. is converted. In a ready-to-use embodiment, reduction with oxy/sulfur compounds Far-IL-force agents and at least one of the oxy/sulfur compounds and the gas flow This is caused by tangential injection of the transferred solid carbonaceous reducing agent.

Brief description of the drawing FIG. 1 shows an embodiment of an apparatus that can be used to carry out the method of the present invention. Schematic representation of a partial π cross-section, where the product gas and product melt flow through a single nozzle. +Ni can be used directly in various tanks containing water.

Figure 2 is a partial diagram of another embodiment of an appropriate device for use in the invention. Schematic diagram of section C, where most of the produced gas is centered near the top of the reactor. The discharging boat provided discharges the resulting molten material into a quenching tank near the bottom of the reactor. It is discharged through two nozzles.

The figure shows a partial cross-sectional diagram of a sixth embodiment of the device that can be used in the present invention. is a schematic diagram in which the produced melt and produced gas solidify into the produced molten granular product. A cooling area designed to reduce

FIG. 4 is a cross-section taken along line 4--4 of the drawing.

Description of embodiment that immediately f″ In the present invention, a low-cost solid carbon material such as coal or petroleum coke is used as a reducing agent. Oxygen/sulfur compounds using a simple reactor containing materials and simple setup. provides a continuous method to reduce

The reduction reaction that occurs in the method of the present invention may be represented by the following formula: IJ2S04 ↓ 2 M2 S → -2CO2 (1) M2SO4+ 4 C-M2S + 4CO (2) 2M2S○3 + Ro C2 2ht2s Yoro CO2 (3) Artificial 2S 3 + 3C = M, SJ - Yoro CO (4) M2SO4 + 8 H2 B, 42S + 4H20 (5) Sa, I2303 -1-6 , H2 MyoS + 3H0O (6) 4M2S○3 26M2SO4+ M2S (7) here 1ν1 (alkali gold), z), 81.2, ro, and 4 In carrying out the method (invented by the present invention), the most common oxy/sulfur compounds encountered are Some reductions (-4->3・0 Equations 5 and 6 are Paired with the carbon in the reduced body carbonaceous substance!・All no) 5 indicates reduction by hydrogen 0 Formula 7 shows that the alkali metal sulfite in the reaction stream is one of the above formulas, 4, or In addition, the alkali metal sulfur is removed, which is therefore disproportionated rather than reduced. Formation of acid salt 2 Disproportionation reaction that occurs, ? Illustrate. 10,000 - Disproportionate sword, if it occurs , the resulting alkali metal sulfate (alkali metal sulfate according to equation 1.2 or 5) Compound π can be reduced.

In order to carry out the desired reduction reaction 7, the reaction exemplified above must be carried out with a small amount flowing down the inner wall of the reactor. A simple reactor is used which allows at least partial C to occur within the bath melt layer. reactor is heated, and the heated reactant mixture is melted in the bath by centrifugal force (applying to the reactor wall soil). Let it form. In a preferred embodiment of the invention, the torpor-thermal reactant (d at least A part of the reactor with a circular cross section (in the tangential direction ( Apply a centrifugal force of 5. In this method G (in which the heated oxy/sulfur compound is @3 fl, downward spiral θ in the reactor] As per the orbit and under the influence of centrifugal force in the reactor ζ) along the wall C′ξ of carbonaceous reducing agent U) along with unreacted particles c? ：Precipitation Do it. The reaction between the oxy/sulfur compound and the solid carbonaceous reducing agent is progressing. During the time ((, get) 41 ”+’r　V-1 bite,’,”T’(’ ) ') with the lower blade (・-moving, female τ] 7th layer; j anti-ls, X'?: 7r4 Contact with the cooling gas (from the force) or water tj+, e cold bath It's cooler than the plane 7 when someone hits it).

I-Ba, 1/Nioki/'9 Lunoa one compound fqr water V [skin cold soluble quasi-L/ζ soluble-C It's okay if you have 4 or so, or 2 to 1 lj. l, -even, +nj cold l- 2nd bath melt f! :'Iris-tj' (2) You can collect the alkaline metal from the bath. ・ζ, Ri, L2 Netsuyu l, etc., [I4 (Kiss Den Monster (・Bosaku::+ VC% Ri 1~ So, I'm going to reduce it'\Goki/Saltzer compound: So, I'm going to enter the inn 81. Carbonates of alkali metals that can be used or (d-carbonate regeneration [- may also be used.

Ouchinosulfur compound (. At (-I1, the temperature at which the reactor is heated is 1,000) or θ) may be lower than that when an anneat salt is involved.

I1 is removed from the reactor and treated with τ and π to increase the price. You may collect items. An example is -acid11. It burns the carbon component and gives heat. Addition [1's double carbon t] may be formed using carbon dioxide acid 7), rj liquid missing θ) foul・(・σ Therefore, hydrogen sulfide 7 can be extracted′, ?8=2 (ゝ0,8→-2+, J, (one one 2p, :plC○3+Itan, 5(8)2:2 +3+ C○, +H,, O-\42 C03+ Toni, s (9) 4Hiii water Ne is 7) Release 7 and Klaus (Cl-1...,) Koyo and sulfur C for a sword that exceeds 9) , 1. , Rui (1 wax acid production (may be used). Produced gas 1'□; 15 , vessel 0') Jjj, F, (,;Q・1−)μ, at best, 11.4・shiri・ I wish (5) B4, together with Bifu (remove from the bottom of the anti-W profit) It's okay.

The heat of the river is a foul, and the vessel; 5) Rui (・JLf X agent) -, -E5j, 'min θ) Oxidation may be caused by The reduction reaction is high, I'i 71 degrees, 1 trace j-ladder 90 mouth'-□~1400'C range. range, and preferably in the range of about 950'' to 1150'' (3V). Ru.

0) One of the major disadvantages of the present invention is that the reaction and vessel y) External heat is unnecessary. . Rather, the 7 JD heat to produce the required bath melt temperature 7 The amount of D oxidizing gas obtained in the field is two g) Useful for the purpose π i.e., heating the reaction zone and burning the fuel used in C. The liquid melts and the resulting bath molten reaction, ':fA failure), causes the layer of liquid on the periphery to flow. The method is to deflect and push the helical orbital π reactant particle 7 within the region.

The flowing melt layer thus formed is 1. If the reactants or such flowing melt The layer does not change; the time period is longer than that which reacted only during the ζ interview (with the flow of oxidizing gas). Reactant? Can be touched.

The inventor of the present invention has a variety of other ideas/! lI-rufer compound wick alkali metal Waxed substance, change this; (It is not necessary to use it. Compound)) Some of them are lithium sulfite, sodium sulfate 8, and sulfate chloride x 　l　　　+′-1hi,('Albus ffl genus scolding, ゛acid acid and C'J・ TI Acid' Tsume Ashi, For sulfo/acid (-I4 to light/fire) ◇T is still (Vi1L product 1.: [I, Kotono, Tezakan].

Yu ° basket [existence] and 1, non-exit (J Tae's same shape 1 to thread? L se 41-□'s chair) 1 Also, both legs can be used. Other 0) Form ()) j element 'Mi substance moxibustion, shop 1 Tesha) 6゜For example, asphalt , beet, lignite, or wood may be used.

Oki/Saltzer compounds and carbonaceous materials (in addition to τ, other salts can be added to θ) Shiojiri mixture Tsu) Melting point - Ox Q) -1 fl　i・C Therefore, the form of the bath melt is inevitable. In order to learn (・Ko Cun L1, benefit j/), raw one t1tt-:, I want to have a passion that won't happen. σSomething like that, 7f must be seen). For this purpose, alkali gold Forehead/・Ride,/Kotoe is sodium chloride L) Rum-like compound S”?J is Al Carbonates of all kinds of potash (・1 bicarbonate, for example, thorium carbonate and 0・bicarbonate) I found out that something special, like sodium, is very satisfying. Sowara (- Oxysulfur compounds may be used in amounts of up to 50 ml.

Reaction, begging reactor (input i% ζ): Use carrier gas, □-Dingba Tomi gas, the analogy is that of a touch wheel. ) Rui tenon:? i id indoor heat ≦ or (1・Ajido Gas Cpa) Yo (xT:, Ya i 'l gas may be used, 7 ft. Alkali Kinmakioki/Sulfur Compound ゛A very busy aircraft. - Dojinmoto L3-j Bosai...ke transfer (use in sufficient amount. If oxidizing gas is used) If the 1 movement of one person Z・1～ is enough to give both workers Ge, itl must be done. Warp, : τ) 3 and used as reduction chamber 1j t'l one sound In order to oxidize the 17th part of the oxidizer, Tj is required. carbon I9 The oxidation of a substance hθ) produces a large amount of heat 0) (-7) 57z reaction is There was one cow with emergency C and fever. Melt raw quinosulfur compound in heat bath Not only does it keep the adult compound in a molten state, but also the endothermic reaction that takes place inside the vessel. However, it is also necessary to perform the It is undesirable to get exposed to oxidation gas due to excessive heating than the door that needs to be heated. Excess oxidizing gas causes reaction, oxidizing part of the sulfide produced in the vessel, and This is because the overall yield of sulfides may be reduced.

In some cases the reactor (with respect to the tangential force or the axial force (with respect to the other) may be It may be preferable to use a burner to provide the necessary heat. However, Therefore, the history of such an auxiliary burner cannot be provided with a book n old. Why oxidation (of a portion of the carbonaceous reducing agent in one reactor). 　　　　　　　　　　　　　　　　　　 　 - Provides a sufficient amount of sound and is oxidized, such as air or diluted metal, Part of the carbonaceous material is used as a carrier gas and part of the oxidation is transferred to the gas. It may be desirable to supply the quality even with oxidation.

Oxygen/sulfur compounds used in the present invention include, for example, alkaline Starting materials that may also be included in potash metal carbonates and other alkali metal salts can be obtained from industrial methods such as glazes. The analogy is Oki/Sulfurization The usefulness of this compound is that it is used to desulfurize flue gas from factories that burn fossil furnace materials. Used absorbent from process, from paper mill (pal-e'-no,lls) Used sulfite "black liquor".

11qucr) J or magnetohydrodynamic (h+HD) power plant Used "/-de (5eed) In this case, the main oxy/sulfur compounds produced are Fi Potassium carbonate, which is exposed to burning gas, also absorbs sulfur compounds in the gas. The gas generated is potassium sulfate. -C Therefore, oxy/sulfur compounds have many This can be obtained from the process flow. The oxosulfur compound was prepared using the aqueous carbonate method (A CP) π, the premix is suitable for use in the method of the invention. It is desirable to form a combined oxy/sulfur compound-carbonaceous material feed. There is no possibility. In the dough, 1 part water, 1 part raw charcoal, and 2 parts from the flue gas to be treated. A master craftsman's skill in mixing carbonate and carbonaceous substances, which are used to absorb sulfur oxides. Omotesho 58-50181Ei (6) to be completed. While carbonaceous substances are dissolved in carbonate, When the dry reducing agent and the dry used absorbent should not be removed, A homogeneous (L!’i 7], rr:a, “+%) mixture is obtained.Charcoal Each small amount of sodium chloride and sulfur dioxide are absorbed and dried. 5: The presence of a reducing agent will prevent the oxidation of sulfite to sulfate. use Before drying (5') (with a reducing agent of 7. For example, sewage sludge or coal slurry may be used. sodium carbonate , the mixture of reducing agent and water is then thermally converted into a sulfur-containing gas in the usual manner. The rice is blown out, so that effective contact between the small liquid and the gas is obtained, and the sulfur dioxide may be Both sodium and reducing agent? The dry powder containing sulfur dioxide absorption in the Δ, Cp method Obtained as a product of the collection-drying process. This technology involves reacting and mixing substances in a reactor. so that you don't have to.

amount of solid carbonaceous material, burner fuel, and a given amount of alkali metal sulfite. The nature of the feed of the oxidizing gas and the necessary oxidizing gas are The rate of conversion required depends on the reactor design, and other factors in mind. For example, also The carbonaceous material is carbon, and the ox/sulfur compound is pure sodium sulfate. If it is, then at least 2 moles of carbon or 0 moles of salt are added to the supply. She is definitely a must-have woman. The fuel and oxidizing gases are either burned or fed salts. To bathe and melt (・night cry, na @]) -j-I'm going to have Hong Tsumugi, suck it, reduce it, and use it. Tsunotsutsu? Then, raise the temperature of the object to the exhaust temperature of the object, and then the temperature of the object may be increased from the system. A sufficient amount is required to account for any heat loss Vζ. All the fuel you need Alternatively, a portion may be in the form of a solid carbonaceous material. Solid carbonaceous reducing agent and combustion Reactions and total amount of carbon and hydrogen in both sintered fuels and sulfurization All of the compounds and oxidizing gases (T) necessary for the conversion of oxygen into carbon and water must be in excess of the stoichiometric amount.

Anti-engraving results can be obtained in many different ways, depending on the results and the type of starting material used. The most desirable form is the combustion mixture and Mixture of oxygen/sulfur compounds, carrier gas in reduced It's like going back and introducing the previous steps. In particular, for example, oki/sulfurization A mixture of carbonaceous substances and a carrier gas is used as a fuel; A specially designed burner boat, e.g. The vortex J burner located at the center top of the reactor It is desirable to introduce gas in the tangential direction (at the same time as oxidizing the gas through the . This combination of gas flows (d reactants) only creates the necessary helical orbitals. is also a result of implementing appropriate heating conditions with respect to the reactant streams.

In a special embodiment C of the invention, air is present in the carrier As both (El j Tsueshi, coal or reducing agent jj Yohi oxidizable/P It is used as a carbonaceous material that acts as both sodium sulfite and breaker. A mixture of thorium and sodium carbonate is a salt compound. In this embodiment, If there is coal and air on almost three sides, the combustion products, and the vortex? give burner Fuel [7 stratified, vessel; (concentrically arranged in one tangential direction). Is the reactant a reactor because the result of Chron action is π? Spiral trajectory: Proceed along IM , the formation of the desired melt can only occur in place as it moves up the reactor and redeems the helical trajectory. The molten material precipitates on the walls of the reactor and flows down the walls as the reaction progresses.

In the process of the present invention, the oxy/sulfur compound is fed into the reactor. [The sulfide Gτ is reduced. For example, if the feed is sodium sulfite and sulfuric acid Sodium sulfide is formed where sodium is present.

Since the reaction takes place in a fluidized bed of melt, one yield of raw sulfide, one melt, is obtained.

Opening during residence of melt in reactor: speed of reactant flow in reactor, temperature and reactor can vary over a wide range depending on the pressure and the length of the reaction zone within the reactor. − A bath melt retention time of about 2 minutes and preferably about 5 to 60 seconds is used.

At the time of Wakudome, the reactor (Kojin I); at least about 80% of the hydrogen oxide/sulfur compound 0% is sulfide, please reduce it by 4, sure (・rubbing・-7) (with 15 or more) When: ll　,, 1 Sanda Seiko Ln 2) 5, anti”; 1.’d: #・’teya〕ru life Molten material (-cooled to produce 11.1 yield of butterfly) Total, I'm going to have a good time) (・I'm going to have a good time with my own weight) -) C) Not. The purpose of this is to avoid contact with cold gas. may be convenient, but other methods may be used if desired. 5ζv in case of water contact 1. Contact ≦f with a common melting water bath tτ flow t7 included or a liquid water jet S) ′+ru. Two-party relationship: /ζ, ii'' (, ((a aqueous solution t' may also be used.) ! For the removal of the products present in the material, make equipment. The liquid is then quenched and extracted from the liquid [7, moreover, by a known method: therefore, compared with the bath liquid Pure alkali gold, including the cuff 47.　j desa You can also shade it with f.

1 ~ Alkali metal corrosion and recovery in solid form instead of water-based liquids If necessary, a gas post-catalyzer device such as Kotogo Keo, side 11 pieces) 1, carp 1'', life paraboloid disturbed bath melt, ・-1 anti 1] At the discharge nozzle knee 52 at the bottom of the S vessel, the t formed by C during the reaction that takes place inside the vessel. ] gas (blown away from τ and formed by a small neap tide. Ij 7 horizontal beads or prills (H) As a result of contact with relatively cold gas in the rig tower, It's a long time since I've been in the middle of a long time. My hands and nose become sore after cooling down. Alkali gold @ sulfide special table Showa 58-5018 16 (7) geinc, -', prill (-ding) 0 lirinoku tower horn J 戊1:'iT (-sai,? -) Only 1, tower top) Rui is another cheap container θ)・8-) ST or IC O: J-ru Floor > (collection, zo) Heneru. Carbon dioxide and water vapor are transmitted through the melting of salt. 1 degree, moreover, 1' thicker, 250" to 650℃ J・range, the floor can be used] 4-ru. Alkali gold/sibase compound is expressed by formula 80) Rui l’j　91 according to 7 The first step is to convert alkali metal salts or carbonates.

Total or part of the gas produced in the reduction (for the reaction of 1 kneading) carbon dioxide As pointed out above, this gas, which is preferably 1f'' as an elementary source, is in sufficient supply. Add 3 liters of carbon dioxide and water vapor, if necessary, add liquid water. can be enriched by injecting water vapor. Because of the special shape of Nanano 1 and others; ・C, prills are permeable and do not allow gas flow to stagnate or become clogged in the contact area. A porous high surface area filled bed that does not dry out.

Solid alkali metal sulfides are recovered from the reduction reactor (using a prilling tower) Things to do & i:! ”-D supply regeneration and M HD combustor; Regenerated zolyl (which is advantageous in i). element σ) / - de (5e rad) (・te4 The ash compound produced by the ζ reducer is MHD combustion. in a high temperature vessel (decomposed from A slightly smaller amount is used in the flow; it is redistributed and reappears in the . This method: The ash in the coal ash is mainly used for coal ash passing through the channel. After passing through the discharge point and eventually leaving the CC, i4) circulates and r.)J- j Small note: Tesaru, flue gas removal 14i 17) Recycling of used salt; (When used, the ash content can be removed and it can be produced in the form of an aqueous solution of l-kamono raw carbonate.) is desirable. Ko]? In performing G, the prill is dissolved in superhydrous water or else Otherwise, it will separate and produce a sodium chloride solution and an ash cake.

” - Extracting the recovery power of the Purring tower (1 gas 7・'Riera as a dog of particle contact legend') f'lru. Fluidized bed rotary kiln, lubricate (-other gases) It's a monkey to get a result like "Riichi".

The product of the process (of this invention) is the melt mentioned in Looking at the chain-linked substances, there is no increase in the amount of dust, and there are many reactions that are being started in the reactor. The resulting gas also contains. The gas in the corn is carbon monoxide, carbon dioxide, and water. vapor? include. The production of a gaseous product having a CC,:CO ratio of at least about 11 Desirable 7. Realized! At this ratio, carbonaceous materials can be practically used in IC reactors [historically dasa)]ru.

In the gaseous products: the amount of carbon dioxide present For the cow again! It can be used in

Among the main advantages of the present invention, τ(・Machi), the above-mentioned advantages(JD) and carbonaceous materials are Since the carbon is used up in the reactor, there is almost no carbon that contaminates the produced chemical products. 5. Another advantage (1) Conventional -7+molten salt pull reducer; ), l: Rimo has always achieved a large gas velocity τ of 41″; It is possible to use a small container and save a lot of money. ;・, look at - (Tau sweat part 2) Is it necessary to eliminate the 7 nozzle blockage problems? Eliminate the palace. ,already One advantage is that there is a very small amount of ash content - molten homogeneous phase η - production, i.e. Ash-melt interaction to form silicate (1 reaction, vessel)) Residence time or short ) Equilibrium: There is not enough time to reach it. reduction 3H,z) downstream silicate contamination; Attribution results) IJum's failure and method problems (1. I will. Another O・1 point 1-41-paper There is no need to control the liquid level of the molten salt pool.

FIG. Toe is a metal θ) Sealed container (...ko, JANY EP-T) 14 yen melting casting a It is a container with a circular cross section lined with a lumina block. reaction, The vessel 10 has a tangential nozzle 16 located near the top of the vessel (near the top of the vessel) It has 18 discharge nozzles located at the bottom 5. Oki/zulfur compounds and Flour! F♂j (fz carbonaceous reducing agent, for example, coal, mixed with salt The reactor 10 (introduced through the tangential inlet nozzle 16 after a life of 20 Ru. Air (after 11 rai / 22 lbs. supplying boundary-coal mixture? Transfer-J-O reaction, The top of the container 10 (with 24 burners installed, that's it!) is the nozzle 2 in the bag direction "b". 6 and axial entry ['' nozzle 28? include.

The air passes through 30 lines and enters the inlet nozzle with 26 inlet nozzles. Tsumeen, After 32 lives, the soul stone is supplied by an axial inlet nozzle 2EN. burner 2 In addition, the subsection of the reactor 10 was exposed to 34 flames. Ra-shaped locus 36 represents the path followed by the mixture 6 of salt and reducing agent coal, and fl is the tangential direction. It is introduced with a carrier air stream through the inlet nozzle 16. Inside the reactor 10 The melt 38 shown along wall 46 is formed as molten salt particles and is associated with reducing agent. The particles are thrown onto the wall 40c by the action of centrifugal force. Bath melt 38 is foul, vessel 10 The layer moving along the inner wall 40 travels downward and, together with the generated gas, exits the discharge nozzle 1. It exits the reactor 10 through 8 tubes. an aqueous quench bath liquid that is a mixture of melt and product gases Enter 42, including 44. The outlet nozzle 46 is provided in the cooling chamber 42, and the Exhaust gas is removed through line 48. The product salt is recovered from the quenching solution 44. collected and further processed as required.

The embodiment of FIG. 2 differs from that of FIG. 1 mainly in the method of removing the generated gas. Ru. In this embodiment C, a, the reactor 100 has a circular cross section and is made of metal. is lined with a corrosion-resistant refractory 102 in a sealed container 104. at the top of the reactor Moreover, located in the center is a gas exhaust nozzle 108 covered with a refractory material 110. .

The gas discharge nozzle 108 minimizes the amount of particulate matter being discharged together with the gas. It has a structure like this. In this embodiment, the product gas can be removed at high temperature; 1971-501816 (8) A yield of 114 liters of heat can be achieved, which improves steam efficiency. melting The material is passed through a discharge nozzle 112 at the bottom of the reactor 100 into an aqueous quench bath liquid 116 and High-pressure water or water vapor is discharged from the quenching tack 114π, including the quenching machine 118. Air is injected through nozzle 120 to form a stream of melt that falls from discharge nozzle 112. It is divided into 1q1JK when it comes into contact with a cold solution 116. 1a cold tank 114 is equipped with a quenching solution supply nozzle 122 and supplies the aqueous quenching solution through the 7 holes. 4V to the quenching tank 114; equipped with a quenching and melt discharge nozzle 126; Through this, the water bath liquid containing quenched molten water is discharged after 1 liter/128v; The line is equipped with an outlet nozzle 130 through which the generated gas from the quenching tank 114 flows into the line. 132 and is discharged.

Referring to FIGS. 3 and 4, reactor 200 is cut into a metal enclosure 206. Corrosion resistant refractory 202 surrounded by thermal castable refractory 204, e.g. It is a circular cross-section reactor lined with something like a fused-cast alumina block. . The reactor 200 has two tangential feed nozzles 208x and A discharge nozzle 210 is provided at the bottom of the pipe. The supply bomber 212 is oki/sulfur - Compounds and powdered solid carbonaceous reducing agents? Salt feed mixture containing 214 Bi, Life 2 16, through which a pneumatic gas is applied to at least one of the supply nozzles 208. Transported by carrier gas, the electric current (distributed and supplied) is [Thank you for your understanding. Carrier gas is passed through Inno 218 and Prower 220 which are supplied together. Enter. Another burner 222 has its own fuel life 224 and air supply line. 226.

Discharge nozzle 21CH: Sufficiently increases the velocity of the exhaust gas so that its force is within the anti-bleaching unit 200. Designed to cause a breakup of the formed bath melt. It will be done.

The melt flows downward along the inner wall 228 of the reactor 200 and mixes with the product gas. The melt solidification chamber 230c is also discharged through the nozzle 210v. Gas pipe is continuously removed from the chamber after a life of 232 hours in a heat exchanger 234. Cooled by heat recovery fluid and passed through line 236 to chamber 2. +Crv Return f'l. Gas circulation is forcibly carried out by a blower 238 and A quantity of produced gas equal to the net quantity of gas produced in is continuously passed from the system through line 240. removed. Solid particulate products are removed by valve 242. Cha/Bar 230 Cooling is achieved by simple contact of the falling droplet with an ascending stream of cold gas. style Other cooling techniques such as moving bed or rotary granulators may be employed within the scope of the present invention. good.

Please refer to the following examples to demonstrate the present invention's practical aspects of the method of the present invention. Although it is better understood, it should not be considered as limiting the scope of the invention.

Excerpt 111 A structural unit (d. Jr.,) having the general structure of the reaction, vessel and fuel system shown in Figure 6. )? Assembled. Sorimachi, the upper part of the vessel (size ID 51! 1. Height 8 inches, cylinder) there were. Below this, I had a 61n, a high iron 2 lrr, and an ID discharge boat. There was a conical part. Structure J Ebisu unit (7 units Near the abutment of the cylinder part, there are two tangential Equipped with 7 supply nozzles. Nominal composition Na, CO3 30%, Nb, 2S0.2 b　O%　, Na2SO4-20%2 feed salt escapes one of the nozzles and becomes powder It was supplied mixed with petroleum coke. Ordinary gas/air burner with 7 second nozzles and burned it. The product melt and gas were discharged through the bottom nozzle. typical The results are salt supply 13.21b/hr 5.21b/hr coke supply 2 ．． 81hi 1r-r 2.2 ib/br natural gas to burner 421 ports 08C fr = 43.0Oscfrr: Total air supply 9.69sci’m 9.8ro sc erosion produced gas composition Internal reactor temperature 972° CI 021°C Reduction to sulfide 85% 95% Test reactor No. 1: A simple cylinder with the general shape and structure of the structure shown in . It is assembled with a similar design. The inner diameter is 1ti.

The internal height is about 6ft. The constituent unit is the apex π) Inlet and central burner population? I had it.

The coal is fed with air through the central burner at F4 and F12, and the f-O salt is fed through the central burner. When the powdered coal and Beg and supply. Salt 17) Two tests with nominal composition vi6H'r (・ In this case, the typical test results were as follows: Ntλ2'J: 03 15.0% 1ro, 5% 1勅2SO320,0%口 Na2SO465-0% 8 filtration, 1 candy feed coal'chloride 0.25 Lb/ l○　0. Ro81hi, -3 supply law Coal-geothermal mixture 250 lb, /’br 4141b/’l-to Ir burner Coal 80 Lb/hr 1051 b/hr Total air 150 scf; h 214 scfm lower crystallinity 1186℃ 1100℃ Sulfide/\l)) Change rate 85% 87% Q chain H total 8-501816 (9) Reaction region I) Structure 1-3 Yohiyo no) Anti-[1-condition, Cn i 10 (1'j) Execution of <　0・Variation method 20 shots-↓” (The baking soda shown here) -・,-) It goes without saying that ff-1 may be within the parameter control limit. , don't understand. Therefore, if this invention is exemplified by a certain tide, , feeding method, (3), temperature, and other reaction conditions. The best truth is that the name is not listed and the name is not listed. On the other hand, the present invention (1J, as is obvious to those skilled in the art) - τ, which may be implemented in other ways within the scope of the teachings presented. Therefore, this invention Isn't this an illustrative and specific implementation of f'lK that cannot be limited by everyone? Its scope (1) is the scope of the claims regarding t'l (C, therefore, there are many things to be determined).

Submission of translation of written amendment J) City 1. 'Law Article 181-72 of 1972!+: June 25th Commissioner of the Patent Office ], Patent application indication paT/us821014602, Title of invention Sulfide Fluidized Bed Process for Manufacturing 3.1 Patent Applicant Shintemachi Bilderek 331 Telephone: (211) 3651 (Representative) Name: (6669) Asamura Hako 5. Date of submission of Supplement + I3: March 21, 1982 6. List of attached documents: Supplement Translation of the book (1 copy) Scope of claim 1 Alkali gold / sulfur compound, corresponding alkali gold side sulfide / sulfur compound C loading method, comprising alkali metal oxy/sulfur compound and solid carbon. Introducing the evaporator into the reaction zone: The oxy/sulfur compound and the reducing agent are subjected to centrifugal force, and the oxysulfur The compound and the reducing agent are depleted in a downward spiral trajectory through the reaction region, and Can be thrown around the reactor; Heating the reaction zone melts the oxysulfur compound and melts the oxysulfur compound. ・Alkali metal sulfide is produced by reacting the argon compound and the reducing agent.

The alkali gold compound, unreacted oxy/sulfur compound and unreacted reduction A melt containing the agent is flowed through and around the reaction zone to remove the unreacted oxygen. / sulfur compound and the unreacted reducing agent are reacted to add alkali gold of 71[1] sulfides are produced and introduced into the reaction zone through the bath melt IJ''-the reaction zone. At least about 80% of the alkali metal oxy/sulfur compounds recovered do A method characterized by:

2. Is the nuclear oxysulfur compound proboscis and the reducing agent the oxy/sulfur compound? l and applying a centrifugal force to the reducing agent by a gas flow applied to the reducing agent. c. How to follow.

6 the gas stream is related to at least one of the oxysulfur compound and the reducing agent; 2. The method according to claim 2, comprising a carrier gas comprising:

4. Those according to claim J, paragraph 6, in which the carrier gas consists of an oxygen-containing gas. Law.

5. The oxygen-containing gas comprises the reducing agent ((related carrier) and the reaction region is At least a portion of the heating heat is generated by a threshold reaction between the reducing agent and the oxygen-containing gas. A method according to claim 4.

6. The method according to claim 1, wherein the reaction region consists of a section of real Japanese cedar.

7. According to claim 3, wherein the carrier gas enters the reaction zone in a sliding direction. Method.

8. Those according to claim 2, where the gas flow is generated by a vortex burner. Law.

9. Converting alkali metal oxy/sulfur compounds to the corresponding alkali metal sulfides In this method, a gas is placed near the reaction area with a substantially circular cross section. Solid carbon-faced snails and alkali metal oxy/sulfur separated by Flow (C transferred sentence reduction 1) Combine the mixture with the compound in a spiral shape downwards through the reaction area. ! In addition, a method of rubbing is introduced so that it can be thrown around the reaction area. .

Add the reaction area and bathe the oxygen/sulfur compound. / Nalpha compound and the alkali metal Sulfuric acid proboscis and gaseous life 5 older brothers 10 years old.

Suebun Oogi/Sulfur compound proboscis, Kyoso proboscis and 11-, byX proboscis alkaline rei 10,000 ↓It is 5'Z downward from the bottom (・C the flowing melt layer is around the circumference of the reaction area) surrounding and thereby forming the unreacted carbon/fluorophore fE proboscis and carbon R+' During the reaction, the alkali 4. Fluid and gaseous chemical products are transferred to the reaction region (・(-alkali introduced). Rimetal Oxide/Sulfur Compound, Boo) At least about 80 articles are alkali metal compound. The snout,... - the speed of the reduction, the cow, and moreover. Formation of alkali metals, melts and gaseous substances @? Exclude from the reaction give out How to feel confident about something.

10 Alka; Nokin, 4 Oki/'Tsurtur compound proboscis 1 Sodium bistoite, 'i R Sodium, forget ad Potassium, B selected from the father's liver, B Also purchase from the V. The method according to paragraph 9 for the so-called Bo's skewer α.

11. Alkali metal oxy/sulfur compound and solid carbon member divided into imitation thin strips +) rJ type mixed proboscis h) alkali metal oxy/sulfur compound and carbon direct proboscis There is a form of solid particle C which separately contains both A and J, and the solid particle is 8-501816 (11) Aqueous slurry containing alkaline liquid/sulfur compound and carbon haze substance The method according to Section 9 of the claim is to evaporate the water.

12 The melt, molten material, J reaction region, 1) -, q gas discharge, 'li, and the gas Opposite of that: 1. Those who comply with the scope of claim 9, who are called and issued. Law.

16 The melting-! ! IJ is discharged from the two bottoms of the reaction head region, which produces gaseous gas. 5M of gas, @molten alkali metal%'n (separately) /] A method according to claim 9, in which f′ rose in the dark: f et al.: C.

14. The yoke of claim 1, which is cooled after being discharged from the melting and reaction area. Method according to Section 9.

15 The claimed @melt is directly cooled in an aqueous solution after being discharged from the warped core extinguisher. Method according to Scope No. 9.

16 In general, the proboscis is converted into a solid particle and through which carbon dioxide and water Steam) is then melted to remove the alkali gold and sulfides present in the melt with alkali metal charcoal. The process according to claim 19 (wherein 'p;' of the bed converted into an acid salt is collected.

17. The method in which the gas source is X

18 The gas! A moves from inert gas to TJZ, so-called range of transport, shameful item 9;・Follow. Method.

19 The reaction of the mixture consisting of the /XX territory Unjuku Karyotakeka and the gas Area: By entering in the direction of Kobata, fYL-)YL'J,,L'i　艮') Ii 1. ’JJ’A9”Ai second obedience, no.

2 [] Aya・Zu response; Uta ζ branch Ha no 11 Father-in-law 1) Mixed proboscis, ``3: Rebellion, Shintoki, and often lacrimal sword [1ka, 2] From Hitorerokohiji 11) Shouti-), jl'igo〈の・Usuiyoukun9　;)(;-亦 Gone.

21 Ii!・T-+U・9. 7 boar dogs Kasumi ru A'j) consisting of a part of the river For ships □ Section 19 or a, Section 20, following the departure, 22, the waterfall is 'T N (su..., Ztsu 1-)]・Also, the addition of the Izu 1 core jouki is also part 1 (Koika char- So, I decided to sing part of the first part and f. 1:9 6 and tbri 11, So, I looked at the sand and saw the waves/compounds. 1 Sky ← 'Koma, Z "T" -2, 鴬, top 2 graduates Right, 7 hits and no) Gla / for 2 Kita 9 I ｉ シ ノ ノ ノ ノ〕〕〕〕〕

23, d'TI-(c,]0m,w;・Niyukishi, dog iM(;z'J2 ! Also, two? j　;　　;　H, q diagonal, 5- is also played, 1γn ha goes. ・11boq-1) 1, ^7 for 100 :) tl　i,? 2 J shell :′(2 1.5 left.

international search report

Claims (1)

[Claims] 1 Alkali metal oxide/sulfur compound proboscis, Z-pairing alkali metal sulfur scolding 1 °C - Soft force removal, alkaline needle [-X, sulfur compounds and solid charcoal] So N Hiro Jakui 1 and Osu area, ・Koriki 2 people. Greetings / sulfur compound proboscis and the temple's removal 2 distance, power foot, ka', su. The reaction mixture is heated and the oxidized/sulfur compound is melted in a bath. A compound? The alkali metal i (produced in arsenic and Contains alkali metal sulfides, unreacted oxy/sulfur compounds and unreacted heat exchangers The unreacted ox/salt is removed by flowing the molten metal through and around the reaction area. A timely method of reacting the fur compound proboscis and the reducing agent. 2 The ox/sulfur compound f7IJ and the reduced 411 The compound and the reduction 'TIJL/c acting gas flow ν1-therefore ・Yes, so-called Mizu no Kankanshima 1st paragraph: ζ Obedience. 6. At least one of the gas flowing, the oxygen/sulfur compound, and the selection material. 7c, consisting of a carrier gas according to paragraph 2 of the soaking water range. 4. A method according to claim 6, wherein the carrier gas comprises an oxygen-containing gas. 5 The oxygen-containing gas comprises a carrier for the oxidant and the reaction region - at least a portion of the heat generated (due to the reaction between the reducing agent and the oxygen-containing gas); The range of X that occurs in section 4 (the direction that follows is wide 6) The reaction area is published by Yamagata Arata. An act of relaxation that consists of a song and falls within the scope of clause 1 of the claim. Z. The carrier gas enters the reaction zone tangentially, according to paragraph 3 for display category 1. How to do it. 8. The gas (produced by the t6 portex burner, the range of display according to paragraph 2) How to do it. 9 Alkali metal sulfide foot change corresponding to alkali U gold 4 oxysulfur compound A method in which a gas flow is placed near the top of a reaction region having substantially a shaded surface. 1 isomorphic carbon surface divided into imitative thin lines and alkali metal oxy/sulfur compound Mixing with things? D"5 (, the mixed proboscis/form reaction song, the attack is downward 1 (spiral trajectory) 4 people passing through and in such a way as to be able to surround the reaction area. Heating the reaction zone bath-melts the oxy/sulfur compound a and melts the oxysulfur compound a. A-1 is called one by one, and the J carbon 5 oath is turned against L6, and the alkali plexus manga is turned into the proboscis and the gas. Producing a solid product: Compound with unreacted oxysulfur r, carbon 1-r71 and forming alkali metal A downward flowing molten mass consisting of sulfide forms around the reaction zone, which: ( Therefore, the 1-core oxysulfur compound, -1111+6 and the carbon 1 substance react. The alkali metal sulfides and produced with gaseous products; Exhaust the bath gas containing alkali metal sulfides and the gaseous Iff products from the reaction zone. give out A method characterized by: 10 Alkali metal oxy/sulfur compounds contain sodium sulfite and sodium sulfur. The claimed invention consists of an ingredient selected from the group consisting of Method according to Box 9. 11. Alkali metal oxy/sulfur compound and finely divided solid carbonaceous material The quality mixture contains both the alkali metal oxy/sulfur compound and the carbon page A. It is in the form of solid particles containing separately, and the solid particles contain alkali metal oxide/sulfur. obtained by evaporating water from an aqueous slurry containing carbonaceous compound 2 and a carbonaceous substance. A method according to claim #1111. 12. The melt is excavated from one end of the reaction area and is the gaseous artifact. A method of covering the 9th term of the range of display, which is discharged from the opposite end of the n. 13. The melt and gaseous formation b) Low specificity of yield reaction region 1981-50181 G(2) This is discharged from the gaseous alkali metal column 41 (J). A method according to claim 1, in which the droplets f7c are dispersed. 14 The claim is cooled after being discharged from the @Jjj object dichromatic reaction region, For use, how to follow Section 9 Proof. 15. Commonly used, tactile proboscis tsu' = yield reaction area 0, water soluble after excretion, g. A method according to claim 9, wherein the medium is tinted. 16 The solution is converted into solid particles, through which carbon dioxide and Water vapor passes through the bath, and the alkali metal carbonate is present in the alkali metal carbonate. A method according to claim 1, in which the salt is converted into urine and placed in the urine. 1Z A method according to claim 9, wherein the gas stream is not an oxidizing gas. 18. A method according to paragraph 9 of the present invention, in which the gas stream is comprised of an inert gas. 19. Is the heating of the reaction zone a mixture of fuel and oxidizing gas? The reaction area: axis The method according to the so-called range 9th term 1τ is performed by entering the direction 1. 20 Heating the reaction zone causes the mixture consisting of 8 families and nt 10,000,000 according to claim 9, which is performed by inserting in the sliding direction. 21. Paragraph 19 of the scope of the request, which consists of a part of the ceremonial oath. Alternatively, follow Section 20, C. 22 The accent is made of air, and the reaction head is sweaty.'1. ’: + Part of the boar's proboscis? By dredging and by external claim, which is achieved by introducing a mixture consisting of gas and air into the reaction zone. Scope No. 9: Method according to TTC. 23 Air introduced into the cough reaction area together with the carbon direct substance and with the combustion The method according to claim @4.22.5, wherein the amounts of are approximately equal.