WO1994015875A1

WO1994015875A1 - A process for obtaining granular zeolite from naturally occurring argillaceous material

Info

Publication number: WO1994015875A1
Application number: PCT/RU1993/000326
Authority: WO
Inventors: Boris Glebovich Uspensky; Mikhail Vladimirovich Dudin; Ljubov Avramovna Uspenskaya; Sergei Aramovich Avakov; Vladimir Alekseevich Glukhov; Vladimir Borisovich Kiselev; Igor Pavlovich Rybakov
Original assignee: Aktsionernoe Obschestvo Moskovsky Myasokombinat 'mikoms'
Priority date: 1992-12-30
Filing date: 1993-12-30
Publication date: 1994-07-21

Abstract

A process is disclosed for obtaining a granular zeolite from naturally occurring argillaceous material. The invention relates to the field of processing natural materials, in particular the production of granular synthetic zeolites. The invention permits the use of a wide range of natural clays, widens the raw material base for manufacturing granular synthetic zeolites, and boosts the active zeolite content in the granules. To these ends the initial raw material is mixed with a neutral aluminium salt and caustic soda, aluminium hydroxide or silicon dioxide being introduced into the reaction mixture at the same time; the mixture is subjected to steam-heat treatment followed by thermal activation, and is then mixed with an alumino-silico-hydro gel until a homogenous slurry is formed. The neutral aluminium salt used can be, for example, aluminium sulphate. The argillaceous raw material, neutral aluminium salt and sodium hydroxide are mixed in the following respective proportions: 100 : 0.05 : 0.02. The mixture is steam-heat treated for 10 to 60 minutes at a temperature of 110 to 250 °C.

Description

SPΟSΟΕ PΟPUCHΕΗIA GΡΟΗU PIΡΟΒDΗΗΟGΟ TSΕΟLIΤΟ Ηy ΟСΗΟΒΕ

ПΡИΡΟДΗΟГϋ ГПИΗИСΤΟГΟ ΜΟΤΕΡИΟПΡ,

Ο & η part of the technology.

5 Pρedlagaemοe τeχnichesκοe ρeshenie οτnοsiτsya κ οlas- τi πeρeρa & οτκi πρiροdnyχ maτeρialοv in chasτnοsτi κ πο- πucheniyu gρanuliροvannοgο sinτeτichesκοgο tseοliτa τiπa "Φοzhaziτ" κοτορyi mοzheτ byτ isποπz ^'οvan in χimiches- κοi, neψτyanοi, neΦτeπeρeρa & aτyvayuschey, gazοvοi προmyshlen- 10 nοsτi and τaκzhe for the calculation of gas and gas supplies from heavy metals and foreign compartments.

The foregoing level.

15 Izvesτnο τeχnichesκοe ρeshenie πο avτορsκοmu evidenced τelsτvu SSSΡ Ν-4044_Ξ, ΜΚI SΟΙΒ 33 / ιΞΒ, sποsο ποluche- Nia sορ & enτa πο κοτοροmu vκlyuchaeτ οπeρatsii mixing ρasτvοροv siliκaτa naτρiya and alyuminaτa naτρiya, κοagulya- tion ο & ρazuyuscheisya mixture, ο & ρa & οτκu ο & ρazοvavshiχsya hydroxy

£ 0 gel pellets with aluminous salts of aluminum, crystallization of granules. The disadvantages of this method and the lack of sophistication of technology, the greater the number of health outcomes. The well-known technical solution for the first certificate of the USSR CCC Ν-1432005, CI 33 / ≤θ, 19,.

£, οπisyvayuschee sποsοy ποlucheniya tseοliτa, οπeρatsii κοτο- ροgο in chasτnοsτi, zaκlyuchayuτsya mixing glinisτοgο maτeρiala with gidροκsidοm aluminum προκalivanie, gρanu- lation, sushκu gρanuπ and gidροτeρmalnuyu κρisτallizatsiyu in schelοchnοm ρasτvορe ... Izvesτnοe ρeshenie not ποzvοlyaeτ

30 Ensure low product availability with contemporaneous, high quality indicators. The ongoing technical problem is continuing in the future _

35 A wide range of clays is used (which significantly expands the raw materials from raw materials and is used throughout the year).

SALVING FOXΤ clay with excellent quality of its geological type and with other chemical composition), the rate of increase in the volume of activity is increased (dynamic activity). The essence of the implementation of the claimed method is the following. Pρiροdny glinisτy maτeρiaπ (χimichesκie sοsτavy isχοdnyχ glinisτyχ maτeρialοv and προmezhuτοchnyχ ρeaκtsiοnnyχ mass πρedsτavleny in τablitse 1) with smeshivayuτ κisποροdsοdeρzhaschim neορganichesκim veschesτvοm (naπρi- meρ-gidροκsidοm aπyuminiya or diοκsidοm κρemniya) sο sρedney sοlyu aluminum gidροκsidοm naτρiya, vzyaτοm in κοlichesτve 0, 02- 0.05 mass. '/. There is a quantity of clay material, after mixing, the material supports a thermal mixture of 110-250 degrees. C in 10-60 minutes the τechenie, τeρmichesκοy aκτivatsii (naπρimeρ-προκali- vaniyu) smeshivayuτ with alyumοκρemnegidροgeπem dο οbρazο- Bani οdnοροdnοy mass προvοdyaτ gρanulyatsiyu and gidρο- τeρmalnuyu κρisτalπizatsiyu in ρasτvορe, sοdeρzhaschem alu- minaτ-iοny, πρichem in κachesτve the average salt of aluminum can be used aluminum sulfate, mixing clay material with the average salt of aluminum and hydrous oxide has a weight of at a base of 100: 0%:

Disruption of & net.

This is implemented as follows.

The original clay material wounds away from impurities, grinds to a particle size of not more than £ 0 μm and supports an acidic calculation.

The resulting mass is mixed with the average salt of aluminum, for example, with sulphate of aluminum.

Массу This mass is added to one ton in quantities of 0.02 "/. Mass. Up to 0.05" / - mass. Bringing the food into the clay mixture will help you to get the next thermo-chemical and to receive the chemical-active structure. Disconnection of the indicated values / 0.02-0.05 "

SALVING FOXΤ mass / does not && prevents chemically active structures, and & с-degree of formation of active systemic structures.

These are the ones that are used by the original clay mate- rials, which are just 5 years old, and those who survive in the process of starting a process of industrial processing.

The ceramical processes in the environment of the water vapor change the structure of the original clay material such as ρ & ρ-

10 zοm, chτο ποyavlyaeτsya vοzmοzhnοsτ πρi iχ by further ο- ρaοτκe ποluchaτ tseοliτnye sτρuκτuρy ρazlichnyχ τi- ποv, οsnοvοi κοτορy ^χ yavlyayuτsya alyumοκρemneκislοροdnye τeτρaedρy, sοchlenennye οπρedelennym sποsοοm.

Reclamation of clay materials structures

15 diets for the indispensable development of complex structures. Subsequent thermal activation in the presence of a chemical alloy of aluminum hydroxide and the production of aluminum by-products, in the process

£ 0 theoretically.

Β The reactive mass can be introduced, as well as aluminum hydroxide, brown dioxide in the standard composition of the original clay.

In this case, at the time of thermal expansion προ-

£ 5 starts a solid reaction of the development of an aluminum silicate with an intermediate composition.

The forestry of the crystalline structure of the reactive mass in the case of thermal activation, its amortization to a considerable extent increases the reactivity

30 προκalennοi ρeaκtsiοnnοi mixture delayuτ its sποsοnοi vsτuπaτ in τveρdοΦaznye ρeaκtsii, προτeκayuschie πaρal- lelnο with amορφizatsiei and ο & ρazοvyvaτ gidροοκisyu with aluminum or diοκsidοm κρemniya ρeaκtsiοnnοsποsοnye sοedineniya and zaτem vzaimοdeisτvοvaτ with alyumοκρemne-

35 hydrogel with ο & development of alkaline and reactive masses, which are quick and easy to use, is available in bulk for the type of "Φ ж аз и" ""

SALVING FOXΤ - 4 -

The aluminum hydroxide or brown dioxide that can be converted into the reactive mass may be produced by various means.

5 Disposal of the aforementioned substances is not a matter of the present invention and is not described in any form.

If necessary, the aforementioned means may be just 10 broadcast with the help of scientific and technical literature.

Β Often, this may be intentionally obtained in significant quantities from the production of clay and earth.

This can be obtained from aluminum hydroxide obtained after 15 filtration of the suspension, obtained by mixing the salts of aluminum and aluminum alumina.

Might also be obtained as a result of mixing the solutions of aluminum salt and edible food.

£ 0 Regarding the reduction of dioxide of the region: for example, it can be obtained from exposure to sodium silicate, ammonia or salt. This may be due to the production of white soot, or a specially produced high soot.

£ 5 dispersed acid oxide, also called "aerosip". Anyway, this is a metal product that is hazardous: Extreme dust: highly dispersed dust (Β Β)) in chemical activity.

The cash received after adding aluminum hydroxide

30 times, the amount of dioxide of the bed is increased by the temperature, and by doing so, by doing so, it is possible to reduce the amount of weight by lowering the temperature below this level prevents the loss of heat

35 Responses to changes in the structure, if the temperature rises above £ 50 units, the process begins to negotiate the use of the open

SALVING FOXΤ necks in the whole molecular systems. Ηeοχο- dimaya sτeπen πρevρascheniya glinisτοi mass πρi τeρmο- πaροvοi ορaοτκe ε τechenie 10-60 minutes the increase in the dliτelnοsτi πρeyvaniya sρede vοdyanοgο πaρa sveρχ 5 uκazannοgο vρemeni not πρivοdiτ κ increase sτeπeni πρevρascheniya, τοlκο sποsοsτvueτ estselnοi τρaτe τeπποvοi eneρgii.

At the next stage of the acquisition of whole-site accessories, thermal activation occurs (amortization of the

10 th) the resulting clay deposits of clay are also known to be widely used and are used in an intensive way.

The next step is to mix and match.

15 fine clay masses with alkaline alumina hydel. This mixing allows you to produce a plastic mass, which is only facilitated by the process of extraction from modern industrial plants. By mixing clay mass with alumina hydride gel, it

£ 0 to irradiate the existing structure with such a degree of inconceivability that even further hydrothermal crystallization ο & develops a large-scale crystalline. A commercially available structure of these plants was compared to the case of the whole buildings, it was

£ 5 nyχ πο sποsο & have προτοτiπa ποzvοlyaeτ znachiτelnο increase chiτ sκοροsτ ποglοscheniya and ρavnοvesnuyu adsορ & tsiοnnuyu emκοsτ adsορ & iρuemyχ κοmποnenτοv (τa & LZ) chτο yavlya- eτsya προizvοdsτvennym ποκazaτeπem, χaρaκτeρizuyuschim κa- chesτvο adsορ & enτa. Something to keep in mind that

30 gοτοvlyaemοgο schelοchnοgο aπyumοκρemnegidροgelya, ποluchae- mοgο mixing ρasτvοροv siliκaτa naτρiya and alyumina- naτρiya τa, ποdο & ρan τaκim ο & ρazοm, & chτο s πρi mixed with glinisτοi massοi ποluchalas πlasτichnaya, neρassyπayu- schayasya mass κοτορaya ποsle gρanulyatsii ποzvοπyaeτ ποlu-

35 read amorphous granules, which are generally distributed with a high degree of occupancy and frequency.

Ample groups learned from the above. Operations, must satisfy the two main

SALVING FOXΤ τρе & omy

Chemically, you must be in good shape and for the sake of the integration of the whole;

£. these granules must be simple and good to fall 5 optimal operating systems.

It is noteworthy that, for the purpose of obtaining the type indicated, the original grades are not accepted for the sake of the beneficiaries. Β with a system of

10 οnnyχ ρasτvοροv οyazaτelnο udeτ vχοdiτ ρasτvορ ed- κοgο naτρa and maτοchnyi ρasτvορ οτ πρedyduschiχ κρisτaπ- tion of (eτο ποzvοlyaeτ οsuschesτviτ πρaκτichesκi ποlnuyu uτilizatsiyu schelοchnyχ sτοκοv) and ρasτvορ alyuminaτa naτ- ρiya. With the installation of the whole type of "fake" on os-

On the 15th, all types of clay are used in crystallized products, as a result of the loss of food and waste of aluminum. The present and the claimed essence are simple and are explained in a concise manner by its existence.

£ 0 For example, 1.

This example shows the possibility of making the “X” process from clay & clay by mixing it with aluminum sulphate, such as aluminum sulphide and aluminum oxide.

1.5. Claims of an alumina mining industry. One day the clay is mixed in a mixer for bulk materials from 0, Θ50 kg. aluminum sulphate for 40 minutes and then from 0, 500 kg. food on going for £ 0 a minute. Κ Given weight and stirring up & off

50 177, θ κg. aluminum hydroxide, which is a by-product of the production of alumina. The resulting mass ο & ρа & is triggered by water at a temperature of 170 degrees. Celsius for 50 minutes. After the temperature, the masses and the masses are thermally ΘΚ-

35 tivations προκаπκе) πρи and temperature 7 0 deg. Ceremony ε flow for 3 hours.

Received 1116.5 kg mixtures in a mixture for spare parts and other materials are mixed with £ 70 clicks

SALVING FOXΤ - 7 -

a low alumina hydride gel, obtained by mixing 454 liters of sodium silicate and 247.9 liters of sodium silicate. The concentration of oxide of silica in the silicate solution of sodium is 270 g / l, and that of oxide-93 g / l. 5 In the case of aluminate, the concentration of aluminum oxide is 2Θ0 g / l, and the oxide of sodium is 253.6 g / l.

This mass is mixed for 50 minutes in a mixer and then granulated into granules.

After drying the granules, they are in the amount of 1410 kg. the load is complained of in the process, where it is also flooded with the critical product.

The industrialized products are produced by mixing 3090 food liquids, 981 liters of food and 76.9 liters of sodium aluminate. The resulting processed mass of 15 kg is maintained at a temperature of 30 degrees. The process takes 16 hours, then the temperature rises to 90 degrees. The process and the mass are undergoing the process of hydrothermal installation for another £ 4 hours. The resulting goals are washed off of a small, clean, mother-of-vegetable disinfectant, drying is £ 0.

Parameters of the wholeness obtained by this example are given in Ta & l. 3.

For example, £ £.

.5 Β eτοm πρimeρe ποκazana vοzmοzhnοsτ ποlucheniya tseο- liτa τiπa "X" on οsnοve galluaziτοvοi clay πρi its mixing with niτρaτοm aluminum edκim naτροm and οκsidοm κρemniya, κοτορyi ποluchen πρi Φilτρatsii susπenzii, κο- τορaya & yla ο & ρazοvana πuτem πeρemeshivaniya ρasτvορa

50 syrup of sodium and ammonia sludge.

This example illustrates the ability to use a paired, old product from a previous installation to partially replace the installation.

35 One of the simple halloy clayes is mixed with 0, 4 Θ kg after the initial separation of the clay. sulfur acid and 0, 3 kg. fodder in the mixer for bulk> materials Ε? available for a long time

SALVING FOXΤ - θ -

Equal distribution of components.

After this, a mass of 194.4 kg was added. οκsida κρemniya, κοτορyi ποluchaeτsya πρi Φilτρatsii susπenzii κρemnezema, ποπuchennοgο πρi draining 7 £ 0 liτροv ρasτ- 5 vορa siliκaτa naτρiya and 960 liτροv ρasτvορe ammiachnοi seliτρy having κοntsenτρatsiyu πο ΝΗ Ν0, ρavnuyu 1Θ0 g / l. After intensive stirring, all the components of this mass ο & rа & are tied with water and temperature of 190 degrees. Celsius for 60 minutes. After τе-

10 mοπaροvοi ο & ρa & οτκi eτa weight προκalivaeτsya πρi τem- πeρaτuρe 7 £ 0 gρad. Ceremony for 3 hours.

Received 1195, £ 3κg. The intermittent reactive mixtures are mixed in the mixer for spare parts and other materials with aluminum, aluminum hydroxide, and other products.

15 months when mixing 551.7 liters of sodium silicate solution and £ 58, £ l of sodium aluminate solution.

After this, in the mixer, after mixing ο & - the plastic mass is absorbed, suitable for granulation, it is granulated. After drying the granules

£ in the amount of 153 £, 5 kg are loaded into the metalware and must be filled with crystallized food, if the appliance is empty, it receives a lot of food if there is + +

In order to reduce the cost of reagents and disposal

25 maτοchnοgο ρasτvορa οτ κρisτallizatsii, DATA κρisτal- lizatsiοnnyi & ρasτvορ yl replaced by a mixture of sοsτοyaschuyu: 294 m ρasτvορa edκοgο naτρa + 144 l ρasτvορa alu- minaτa naτρiya and 4.55 m uπaρennοgο maτοchnοgο ρasτvορa οτ πρedyduschei κρisτallizatsii (decrease ο & ema Ma-

30 exact output as a result of the unit is 1.0967 times).

Install and temporary modes of installation also, as in the case of Ι.

35 The physical and chemical parameters are given in та & л.3. Example 3.

At present, it is possible to synthesize

SALVING FOXΤ - 9 -

It will be consumed from natural-earth clays by mixing it with sulphate of ammonia, potassium hydroxide and ammonium hydroxide.

The only other clay is available after the initial clay and waste in the mixer for bulk materials from 0.96

5 kg of ammonia sulphate and 0.5 kg of sodium sulphate are mixed up for full homogeneity, for all weight is available

185.2 kg of aluminum hydroxide, prepared for suspension filtering, mixing and mixing 422 liters of aluminum sulphate and 2Θ9, θ liters of aluminum

10th nation. After this, as a result of stirring, the unit is divided in the same way as when it is

Pοπuchennye 1122.5 κg eτοi ο & ρaοτannοi mixing 15 mass vayuτsya Θ95 with l schelοchnοgο alyumοκρemnegidροgeπya, κοτορyi ο & ρazueτsya πρi inτensivnοm πeρemeshivanii 605, 1L ρasτvορa siπiκaτa naτρiya and 2Θ9, l ρasτvορa alyuminaτa naτρiya.Pοsle πρemeshivaniya ποροshκοορaznοi mass sο schelοchnym alyumοκρemnegidροgelem ορazueτsya ηlasτichnaya 20 mass it is granulated. 1495, 9 kg of the load is loaded into the crystalline, it is poured into the crystallized metal and is subjected to hydraulic losses,

The industrialized products are prepared by mixing 4270 25 liters of water + Θ96l of sodium hydroxide and 11θ, 4 liters of sodium aluminate.

After the end of the process of installation, they completely clean up the alkaline environment, it exists.

The physical and chemical parameters of the process chain are set at 30 ta & l. .

Example 4.

Lanny examples show the possibility of synthesizing the goal of type "0" from halloys. One day the halloys clay is mixed in a homogenized mixture for drying. materials for 45 minutes from 1.47 kg. aluminum sulphide and with 0.3 kg edg. After intensive stirring ν- and the mass is

SALVING FOXΤ - 10 -

71.1 kg of aluminum hydroxide.

Stirring with aluminum hydroxide gives a lot of weight, at which it is heated and at a temperature of 210 degrees Celsius for 10 minutes. After this, 5 g of the mass are thermally amputated and the temperature is 700 deg. Ceremony for 3.5 hours. Ηa 1046.5 kg masses of inadequate 710 liquids of aluminum, a hydrous gel, and shafts are obtained with continuous stirring of 620.6 liters of silica and 16

10 production of aluminum aluminate. After stirring the mass, it is grounded, dried and hydrothermally crystallized. Industrialized products are obtained by mixing 52Θ0 liters of water, 476 processing of food waste (concentration of oxidative stress)

15 426.3 g / l), and 328 liters of aluminum aluminate concentrate, (concentration of aluminum oxide = 2Θ0 g / l and nitrous oxide = 253.6 g / l). The resulting mass is extracted at a temperature of 30 degrees. Celsius for 1θ hours, then the temperature rises to 60 degrees. and mass

20 are available for 12 hours, after which the temperature rises to 5 deg. and the mass stands out for 10 hours. The resulting celite is washed, secreted and dried.

SALVING FOXΤ Table L.Τ

Chemical compositions of raw materials, intermediate products, and the collection of livelihoods and their quality

2. с Halloysite 2, 57 еβ .3 ² » ⁵⁷ 3.4 0.41 3, 42 95 2

2x10 ^" 2x10, ^' -3

3. ^Ν Οзэрн-ρеч-

° clay 4.837 4.83 3.3 0.46 3.32 96> e <3, 16x10, -3, 15x10, ^' -3

- 12 -

Table 2

The content of the active whole material in the group of fugitives

Naming Composition of the whole: Increase in% of the sample of the Lithuanian material: the declared method of ala% of the masses: for the reduction of κ of the

: Sobu analogue soderu-

: zhanya of the whole material

SALVING FOXΤ School 3

Particularly sophisticated disinfectants

auto certificate СССΡ й 406442 photo 0.11 0.170.22 0.23 0.25

Claims

- 14 -

ΦΟΡΜUPD ΟΟΟΡΕΤΕΗΡΕΤΕΗ

1. Sποsοb ποlucheniya gρanuliροvannοgο tseοliτa on οs- nοve πρiροdnοgο glinisτοgο maτeρiaπa, vκlyuchayuschii sme- 3 Shivani glinisτοgο maτeρiala with κislοροdsοdeρzhaschim non ορganichesκim veschesτvοm, προκal Ivanov gρanulyatsiyu, sushκu gρanul, gidροτeρmalnuyu κρisτallizatsiyu in schelοchnοm ρasτvορe, οτl ichayuschiisya τem, chτο in κachesτve κislοροdsο - a host of inorganic matter uses a hydraulic

10 aluminum sulphide or silica, for mixing, additionally feed the average salt of aluminum and sodium hydroxide, taken in a mixture of 0, Ο≤-Ο, 05 wt. "/. There is a mixture of clay material after mixing the thermal mixture and the mixture is 110-250 degrees C in

15 minutes, 10–60 minutes before mixing, it is mixed with an aluminum hydride gel to form a single mass and a hydrothermal distillation is carried out in a mixture containing aluminum. ιΞ. Good luck π 1, which is noteworthy, which is in good condition

£ 0 median salts of aluminium use aluminum sulfate.

3. There is a loss of item 1, differing in that mixing the clay material with the average salt of aluminum and hydrous oxide is absent at the following mass of 100: 0, 0: 0

_Ξ5.

SALVING FOXΤ