JPS61247617A - Production of glauber's salt - Google Patents

Abstract

PURPOSE:To obtain Glauber's salt economically and favorably by roasting the mixture of iron sulfate and NaCl in the presence of O2 and steam, volatilizing the chlorine content, producing the water slurry of a roasted material, purifying and concentrating a mother liquor after filtering iron oxide. CONSTITUTION:After mixing or granulating iron sulfate and NaCl, the mixture is roasted at >=400 deg.C in the presence of O2 and steam to volatilize the chlorine content and a roasted material consisting essentially of iron oxide and Glauber's salt is obtained. Hydrochloric acid is recovered by cooling and absorbing the gas generated in the above-mentioned process. After the roasted material is treated with water or a Glauber salt aq. soln. to make the Glauber's salt aq. soln. slurry of iron oxide, the mother liquor of Glauber's salt is obtained by filtering and separating iron oxide and Glauber's salt is obtained by purifying the mother liquor, heating and concentrating or cooling it. Also iron oxide is recovered by washing and drying the separated iron oxide. By this method, Glauber's salt is obtained by using inexpensive NaCl and, also hydrochloric acid and iron oxide can be simultaneously produced.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to the economically advantageous production of sodium chloride using iron sulfate and sodium chloride as raw materials.

[Conventional technology]

Ferrous sulfate is produced in large amounts as ferrous sulfate from the sulfuric acid method titanium oxide manufacturing process and steel pickling process.
Used as a raw material for magnetic materials, shield materials, water treatment agents, etc.
ing. Furthermore, attempts have been made to produce Glauber's salt, which is in great demand, using such iron sulfate as a raw material. That is, ferrous sulfate is dissolved to make an aqueous solution, and then neutralized with sodium carbonate or carbonate, or after neutralization. , vapor oxidation, or oxidation using a NOx catalyst to produce iron hydroxide, iron carbonate, iron oxide, etc.4, which is separated to obtain a sodium sulfate solution, and after further purification, Methods for producing Glauber's salt by heat aggravation or cooling are known. Yes.

As mentioned above, these conventional methods use an expensive carbon powder or carbon powder, so they are not necessarily economically preferable.

[Problems to be solved by the invention and means thereof] The present inventor took into consideration the above-mentioned 1Iff, and conducted intensive research to solve the problems.
This led to the invention of a method for producing Glauber's salt using sodium chloride as a raw material.

That is, first, iron sulfate and sodium chloride are mixed or made into m-granules, and then roasted at 400'C in the presence of oxygen and water vapor. A roasted product is produced as a product. Next, this is mixed with water or a diluted sodium sulfate solution (1) to dissolve the sodium sulfate in the roasted product (2) to obtain a slurry of iron oxide in an aqueous sodium sulfate solution. From this slurry, iron oxide fr
: After filtration and separation, the obtained mirabilite mother liquor was heated to 1 kgL, heated to 1 kg, and the mirabilite was poured into a boat.

Hydrochloric acid-containing gas generated by roasting can be absorbed after cooling to recover 11-hydrochloric acid. In addition, iron oxide is recovered by filtration, washing, drying, and freezing.

According to the present invention, it is possible to economically produce hydrochloric acid and iron oxide for M using 1JIIa iron by-product and cheap rock salt as raw materials without using expensive hydrocarbon soda, and to produce hydrochloric acid and iron oxide, which are highly priced for M. As a method, it is extremely advantageous.

[Details of means]

The present invention will be explained in detail below.

First, the raw materials, iron sulfate and sodium chloride powder, are mixed as they are in a mixer such as a kneader, or if the raw materials are in the form of lumps, they are simultaneously pulverized and mixed in a hammer mill or the like.

Alternatively, the above-mentioned raw materials can be granulated using water, sodium sulfate, liquid, or sodium chloride solution, which is preferred because it facilitates handling.

Raw material iron sulfate salts include ferrous sulfate heptahydrate such as titanium oxide by-products and pickling by-products, heptahydrate gold dehydrated salts, pentahydrate salts, tetrahydrate salts, l-hydrate salts, anhydrous salts, and the like. Use a mixture of j and et al.

Of course, ferric sulfate and salts of iron sulfate and salt can also be used. Rock salt, industrial salt, etc. are used as sodium chloride.

The mixing ratio of the raw materials (Fe50./Na01) and the ratio are important because they affect the residual chlorine content of the roasted product obtained by roasting, as well as the quality and yield of Glauber's salt. That is, (FeS
O4/Na1l) The molar ratio is preferably 0.45 to 0.65.

If the above molar ratio is too small, 7 um will remain unreacted and the chlorine content of the mirabilite solution from which the roasted product has been leached will increase4, causing a decrease in the yield of mirabilite and deterioration of the quality. In addition, problems arise regarding the material of the crystal can.

On the other hand, if the amount is too high, the amount of sodium chloride used in the solution will increase, as there will be a large amount of unreacted iron sulfate in the sodium sulfate solution. Also, gas generation wrinkles in SO5 and E302-J increase, which causes deterioration in the quality of recovered hydrochloric acid.

Next, the mixture obtained in < L as described above is heated to 400° C. or higher and 700 to 750° C. in the presence of oxygen and water vapor, and roasted.

That is, the volatilization of salt accumulation begins at about 350°C, and the rate of volatilization increases as the temperature rises, becoming extremely rapid above 500°C. Industrially, it is preferable to raise the temperature to 700 to 750°C and roast and grind.

The overall reaction of such roasting is Fe804-1-H,0-1-Z NaOl+lAO
.

→1/12Fe 20s +Nag 804 + 2
``01''''Ill p, in the process, the following reactions (2) to (5) occur up to 350℃ 3 F13804 +3/402 → IkrLa2
03+Fe2(SQ,), 11 @ @ (2)
Fe, (So,), +6Na01-+2FeO1,+3
Na2SO, ee +31 or Fe50. +2NaO1-+Fe01□+NaR8o,
*@ef413 Fe01 t + 3/1
02 →”/2F” 20 g +2 F801
* @ @ @ (When it reaches 51350'CJul, the following (6) ~ (force reaction also begins.

2FeO1,+2i(2Q-1-1/20□-pFe,
O, +2HO1@ee(Q)2FeO1,+3/2H,
O→ffe O3+3HO15o-(71 as a whole is expressed by formula (1).

Oxygen can usually be supplied by combustion excess air of the fuel or secondary air vent, -C. The water vapor may be produced by combustion, or if it is insufficient, it may be supplied by mixing water or water vapor with the total combustion gas.

This field & oxygen violet and water vapor '1 are 2 to 3 of the tl1 formula theoretical quantity
More than twice as much is preferable. If there is a lot of water vapor, only hydrochloric acid will be produced8 and can be recovered. If there is no or little water vapor, chlorine will be generated, and some hydrochloric acid can also be recovered, but in this case, the reaction between iron sulfate and salt (IJum) will be slow, and the volatilization of chlorine will be suppressed, resulting in roasting. It is preferable because it increases the amount of residual Jif4 in the baked goods. <No.

This is because when the raw material is a hydrated material, the temperature increase rate during roasting is 200 to 200 b, which may cause the reactants to melt during roasting. This phenomenon is likely to occur when there is a large amount of water in the raw material mixture, such as when iron sulfate Ig is used as a 7-hydrate salt, or when a large amount of water is used for granulation. . In such cases, it is preferable to reduce the heating rate, or to first dehydrate the mixture at 300° C. or higher to partially or most of the water and crystallization water, and then roast it to a high temperature. . - When the crystallization water of iron sulfate is trihydrate or more, such a phenomenon almost never occurs and disappears.

Next, other causes are considered, and Feo
l, -Fe, Ol, -Na1l -Na25o,
Although the melting phenomenon is thought to be due to the formation of a eutectic, it is not a problem when the heating rate is 200~b. However, if the amount of melting is small, it will reduce and eliminate dust, which will have the effect of facilitating the recovery of hydrochloric acid. ``The thus improved roasted product is fed to a leaching tank which is supplied with water or diluted sulfur solution generated in the subsequent iron oxide separation step, without being cooled or pickled.

Glauber's salt in the roasted product dissolves easily, and the iron oxide makes it cloudy.

The resulting slurry becomes a sodium sulfate aqueous solution slurry, and the concentration of the sodium sulfate solution can be easily adjusted to 29-31 g.

Next, this slurry is filtered 9 to separate iron oxide and obtain a mirabilite mother liquor. The mirabilite mother liquor contains unreacted iron sulfate and low reactivity.
A sulfate, such as manogan sulfate, is dissolved. Taking one row of titanium oxide by-product sulfur e iron tl- raw material and L-, then, 80.265.3 Vt, Fe0.15 is tlMn
3.5 Vl 1? Melt. The mirabilite mother liquor described above was adjusted to pH 5 to 8 using a powder, etc., and then oxidized with air or with an oxidizing agent of 1 kO1!
By using and oxidizing yθ2+, Fe(0)i)3
It is removed as a precipitate, the pH is adjusted to 9 or higher, carbon dioxide gas or sodium carbonate is added thereto, and the solution is removed and recovered as carbonic acid.

Alternatively, simply pH 1 (IIc neutralization can remove iron hydroxide and hydroxide ma/ga/, and scouring can yield tomokinite mother liquor A/)
.

The mirabilite mother liquor obtained by the above-mentioned purification is heated and concentrated to a copper crystal slurry by a known method, and the crystals are separated using a centrifuge, washed, and dried to obtain product P: nitrate. .

On the other hand, iron oxide and m# separated from the nitric solution slurry
! The carbonic acid 1/gas/gas separated is washed, dried, and recovered.

[Implementation row]

Example 1 1 Iron sulfate by-product of the titanium oxide sea bream production process as a raw material for iron sulfate 1
ioy and... / Rock salt crushed with Marmil 43, 1 f
The mixture was dry-mixed in a kneader for 10 minutes. Mixing ratio (FeE
30. /Na01) mol was 0.54.

The composition and particle size of the raw materials used are as follows.

Analysis of titanium oxide by-product iron sulfate 1 Analytical value of straight rock salt The above mixture was dried in a dryer at 70°C for 1 hour, and Fe
16.9 jJ, 01 min 20.6% dry matter.

The water of crystallization of d-acid iron in the dried material is equivalent to the trihydrate salt and is of the order of magnitude.

This dried food is 100? It was placed in a retort with a gold inner diameter of 100mm and a volume of 300mm, and roasted by rotating it in an electric furnace. 200 co/min of air from one end of the retort.

Water vapor9. l f/hr while supplying 200
°C/hr (D.

? , Fe2, . 4.1chi, So, 43.2chi, OL
o, 6 at 05%. Another 1 recovered salt +1! Is Naodo 58? ) 1013.2.0chi, Fe20 ppm.

The roasted product is 60! Add lf to 89 rnl of water and heat to 60'C.
Stir for 11 hours.1. After dissolving mirabilite in the roasted product W4, filtration,
Cleaning 1. , So, 195 F//l, Fe O,1
3f/l, Mn 2.4 LVt Glauber's Salt I@l&1
Obtained 30rnl.

This glass solution'100m/50% strength soda 1.21
The pH was reduced to 0, and iron and magnesium were precipitated and removed as hydroxide products. Heat and evaporate the mother liquor to dryness 1
ml, anhydrous mirabilite crystal 28.8 P. This crystal 20.6? , Fe20. ．． It was 97.9 cm.

-j! Example 2 Take the sulfur d1 iron raw material, and first dehydrate the acid 1 hytetane by-product iron sulfate to 0.0% iron sulfate hydrate and 10.0% iron sulfate hydrate. OkIP and granular rock salt 6
, 09 rf were mixed and ground in a hammer mill to form a mixture 't-4. Mixed, proboscis (FeSO,/Na01)
The molar ratio V was 0.55. The analysis value of 1 water term used was 80.55.7 excellent, Re 30.8%, MnO
, 86% answered 6. The analysis value of rock salt is the same as in Example 1.

The above-mentioned mixture is a rotary furnace 1 with a metal diameter of 140 mm and a length of 1400 mm.
Continuously supplied at c450℃5/nr, maximum temperature 750℃
It was roasted. During cultivation, air was supplied at 200 HA/hr and water vapor at 150 f/hr. The composition of the roasted product is 80.44', 5%, Fe 23.0%, MnO,
I got 95 with 63 chips.

The bottom 7.5 kf of the roasted material was placed in a leaching tank containing 11.511 l of water, heated to 60°C, and stirred for 1 hour to dissolve the L4 nitrate. The generated iron oxide glass slurry +I-
kf', JAL, 1, e Nit6a1a, 05 Q (
xo, lt) 4) Friend. Composition is So, 265.3
f/l, Feo, 15′t/l, Mrl”V
t, pH (l) is 2.5, fco e iron cake is filtered and washed with water, so, 117 Vt washing solution 5.5
Excellent t. The Za cleaning solution is recycled from the leaching process of roasting and then reused. Almost all m of 804 in the roasted product is P
It was able to be eluted and contained in the washing solution and washing solution.

Iron oxide cake gold dry jA L, Fe69. l%, Mn
A 0.11 inch fine powder of α-FO1032,45q was obtained.

For a long time, I put 10 power and 76p on Akonguchi Shoyui,
Air oxidation at pa 7 to 8 causes 0, hydroxide ratio to mainly form iron,
This was separated by filtration. Next, stir the f solution and add 6
The temperature was raised to 0°C and carbon dioxide gas was added. The pH of the liquid was 9.3, and 7 tons of carbonic acid was precipitated. The entire slurry was filtered and washed to obtain mirabilite mother liquor and carbonate solution. The analysis value of manganese carbonate in dry story is un43.8 excellent, Fe1
It was of high quality with a rating of 00 pp+71.

The composition of the mirabilite mother liquor obtained by the above purification is Na, 80
．． 30.1%, and Mail 0.038%.

Put 1 oz of this mirabilite mother liquor into a steel/less container.
711 Heat compression to generate a crystal slurry, extract a part of the slurry, filter it, and separate the crystals L6, re,
Separate the crystals by returning them to the container.
L.i. C(1)j')lcL, tefi sulfur salt crystal 2.
Separated liquids of 785ff and 0.6 k7 were obtained.

The separated liquid was then heated and concentrated, and then crystals f and f were separated 1-. The mirabilite mother liquor of No. 307 was washed with Spray L.

The analytical values of 90i of mirabilite crystals that were excellent in the final stage were Ha, S
o, 99.8%, Na1l o, o 05%
Met.

The total anhydrous mirabilite crystal obtained was 2.875%, and its analytical values were Na, So, 99.8%, Mail 0.004
It was very high quality at 8%.

The crystallized barley separation liquid contains Na, 80.30% and 330y-
Met.

Procedural amendment document July 1985 I6 "1 1. Indication of the case 1985 Patent Application No. 85936 2. Name of the invention Method for manufacturing mirabilite 3. Person making the amendment Relationship to the case Patent applicant address Iwaki, Fukushima Prefecture 110-4, Shimoyoji 1, Ichiizumi-cho, Address of agent: 2-4-1-5, Marunouchi 2-chome, Chiyoda-ku, Tokyo, Detailed explanation of the invention in the specification to be amended, column 6, Contents of the amendment (1) Details Book No. 6, first line [Correct hydrochloric acid 1 to chlorine 1.

(2) Page 11, line 4 from the bottom to page 12, line 2 [1-% of the mixture described above]. 1 is corrected as follows.

1- The above mixture was continuously fed into a rotary furnace with a diameter of 140 mm and a length of 1400 mm at a rate of 450 g/hr, and the maximum temperature was 750 g/hr.
Roasted at °C. During roasting, air was supplied at 20ONσ/hr and water vapor at 1509ON/hr. The average amount of roasted products produced is 35
At 0g/hr, the composition is 80444.5%, Ii'e
24.5%, MnO, 63%. On the other hand, the H Cρ-containing gas generated from the rotary furnace is sucked into a double tube cooler,
Cooled indirectly.

Here, water vapor and IICQ in the gas were condensed and recovered. The temperature of the gas after recovery was 18-20°C. The average amount of hydrochloric acid produced is 261 g/hr, and the concentration is 32.1%.
,I (The yield of C12 was 85%).I (3) Lines 8 to 7 from just below No. 12 [The iron oxide cake was dried to obtain...'' was corrected as follows. do.

Claims (1)

[Claims] (a) After mixing or granulating iron sulfate and sodium chloride, roasting at 400°C or higher in the presence of oxygen and water vapor to volatilize the chlorine content, converting iron oxide and sodium sulfate into products. (b) A step of cooling and absorbing the gas generated in the above step to recover hydrochloric acid; (c) Treating the roasted product obtained in step (a) with water or an aqueous solution of Glauber's sulfate. After making a slurry of iron oxide in an aqueous solution of mirabilite, the iron oxide is separated to obtain a mirabilite mother liquor, from which mirabilite is obtained. (d) The iron oxide separated in step (c) is collected by filtering, washing, drying A method for simultaneously producing Glauber's salt, hydrochloric acid, and iron oxide.