DD277844A1 - METHOD FOR THE MULTI-STAGE DISCONTINUOUS SWITCHING TEST GRANULATION OF THERMOLABILER HYDROPHOIC SOLIDS, PREFERRED TO VOLULATION TOOLS - Google Patents

Abstract

The invention relates to a process for the multistage discontinuous fluidized bed spray granulation of thermolabile hydrophobic solids, preferably vulcanization auxiliaries. The process is preferably used for vulcanization aids, whose granules on the one hand must be low in dust and transport stable, but on the other hand, must decompose under the influence of a predetermined, relatively low mechanical pressure load in their Primaerpartikel. According to the invention, the starting amount of the filter-moisturizing vulcanization aid is divided in the ratio 99: 1 to 6: 1, the greater part pre-dried to a uniform humidity of 2 ... 12% and subsequently in a fluidized bed apparatus with the 0.2 to 1.8 times Mass, based on the pre-dried paste, sprays a base binder solution. The basic binder solution consists of an aqueous dispersion containing at least 55% of the smaller part of the filter-moist starting amount and an addition of 0.5% to 3% by weight of vulcanization-compatible binder. Following the basic granulation, the cover-binder solution is sprayed in the fluidized bed, which consists of an aqueous dispersion of the residual amount of the smaller part of the filter-moist starting material and a vulcanization-compatible binder, the mass fraction of 2% ... 6%.

Description

In DE-OS 412365 a method is described, the Kur production of non-dusting, easily wettable and rapidly soluble granulation leads. Another method for the production of non-stagnant, easily inert and rapidly soluble granulation is given in DD-PS 110770. In DD-PS 115047 "is shown in processes for the formation of agglomerated granules of hygroscopic fine powder, wherein a certain amount of wet particles of any intended insoluble material to which fine powder is added and the resulting mixture is thoroughly shaken with it this evenly mixed, which formed agglomerated granules! become. EP 0191396 describes a process for the production of free-flowing granules consisting of a pulverulent or fine-grained component containing the granules of the liquid component with up to 7 process steps, carried out in the mixed granulator alein or in the combination of mixed granulators and fluidized bed becomes. All four of these methods are suitable for easily wettable, rapidly soluble substances, but not for the question in question, in the dry state very hydrophobic vulcanization aids. In addition, in the penultimate method, the inadmissibility of admixing any insoluble material from the said grounds for refusal occurs. A frequently used method of granulation, which is technically to be controlled, is sintering granulation. EP 0 237 345 describes granulation and granulated product processes and apparatus employing meltable, powdery material supplied via a centrally located metering screw to a controllably wettable centrifugal dusting apparatus which may have a different geometric shape. The self-consolidation is achieved by molten and re-solidified shares. The vulcanization aids in general, but especially under the trade name Wobezit DM known Dibunzothiazyldisulfid lose their sintering operations their vulcanization-specific activities. When Wobezit DM occurs at too high thermal load, the quality damaging formation of sintered components as so-called "pointed grain on. Due to severe deterioration in quality, sintered granulation processes are in principle not applicable.

In the patents DD 203612, DD 223934, DD 228458 and EP 0163836 continuously operating methods of fluidized bed spray granulation are described, all of which sprühfähigon solutions or dispersions go out and give without additives or binder hard, transport stable granules. These processes have the disadvantage that they require a large amount of energy because of the high proportion of water in the solutions or dispersions. They lead to granules with relatively large diameters. However, all Varianton this Verfahrcinstypes lead to so hard granules that they do not disintegrate at low increase of the mechanical pressure load, so that these methods are not geeignot for the granulation of vulcanization aids.

One-step granulating processes also suffer from the disadvantage that they can not be optimally adapted to product properties. This applies in particular to the differentiated behavior of the products, according to which the transport stability must be ensured at low pressures, but, on the other hand, if the pressure is increased, the granules should spontaneously disintegrate into the dust-fine primary particles. The differentiated influence of the different vulcanization aids can only be taken into account to a limited extent.

From the analysis of the known technical methods it follows that no requirement-based methods exist. The reasons for this are very broad. First of all, the material properties of the vulcanization aids with their hydrophobic behavior pronounced in the dry state represent a problem that is difficult to control. A particular problem of a particular kind is the directly contradictory requirements for particle stability. Either hard, transport-stable, dust-free granules can be produced with the known methods, but then they are so hard that they can not disassemble into the dust-free primary particles necessary for the incorporation process into the rubber before vulcanization by simple crushing. Or soft, not transport-stable granules are produced, which strongly dust. -The third and equally significant disadvantage of the previous method is the unsolved problem of vulcanization-compatible binder. - A fourth disadvantage is the one-step granulation process in the restricted process control and the resulting limited Prozeßeripsssung.

Object of the invention

The object of the invention is a process for the multistage discontinuous fluidized bed spray sterilization of thermolabile hydrophobic solids, preferably of vulcanization aids, which avoids the disadvantages of the previous processes and ensures the differentiated granule structure, which guarantees both dust-free transport-stable structures and at the same time spontaneous decomposition with little increase in Druckbelnstung includes in the dust-free primary particles, whereby an optimized use-value behavior of the granules is achieved with less energy consumption.

Explanation of the essence of the invention

The object of the invention is to provide an energy-saving process for multistage batchwise fluidized spray granulation of thermolabile hydrophobic solids, preferably of vulcanization aids, with the -unter addition of only those substances that are useful in quality and quantity recordable vulcanization compatible in the specific sense recordable - The thermolabile, in the dry state pronounced hydrophobic properties of autweisenden solids are converted into non-dusting, transport-stable granules, but on the other hand dieso granules even at low above the occurring in TUL and dosing processes spontaneously disintegrate into their primary particles.

Invention sgemaß the object is achieved as follows, wherein the explanation of the Ahrenspnniips for thermolabile hydrophobic Solids are exemplified by vulcanization aids: The filter-moist paste of the vulcanization aids, which usually accumulates with water mass fractions between 40 and 75%,

is divided in the ratio 99: 1 to 6,00: 1 and the greater part of the filter-moist paste to a uniform moisture content of

Water mass fractions pre-dried at 2 to 12%. The granulation of the pre-dried vulcanization aid is used in multi-stage cyclic fluidized bed apparatus

carried out. With air, which arrives at incidental temperatures / between 20 and 80 ° C., it becomes, according to the invention, the predried one

Paste brought into the fluidized state and in a period of between δ and 30 minutes with the 0.2 to 1, pieces of mass,

based on the pre-dried paste, sprayed with a base binder solution.

Another crucial feature of the process according to the invention is that the binder solution can be prepared from the aqueous Dispersion of the smaller part of the filter-moisturizing vulcanization aid, with a water content addition between 76 and 95%

will be produced. It is shared in the ratio 80:20 to 55:45. - The greater part of the water dispersion of the filterfouchten

Vulkanisationshilfsmittels forms with an addition with Maspenanteilen of 0.5 to 3% of a usable value Binders, whereby, in the case of hydrophobic vulcanization auxiliary compositions, as a vulcanization-compatible binder latex, Carboxymethylcellulose, n-alkane-rich hydrocarbons in the Boreich C "to C, ₂ , higher alcohols in the range greater C ₁ . Emulsifiers of various chemical constitution and composition, as well as rubber-plasticizers or

the combination of which is used, the basic binding solution. - The smaller part of the water dispersiot? the filter moistening

Vulkanisationjhilfsmitiel forms with a percentage by weight addition between 2 and 6% of the binders already mentioned above

the deck binder solder.

According to the invention, subsequent to the basic granulation, likewise in the fluidized bed, but with up to 10K

lowered air inflow temperatures, a deck binder solution of 0.3 to 1, (make mass, based on the pre-dried paste, a Deckgranulation performed in a period between 8 and 20 minutes.

Immediately after the top granulation, the granules, also in the fluidized state, with air at Anströmtemperaturen between 20 and 140 ⁰ C, dried on Endfeu ^ hten with water mass fractions below 1%. Compared to previous methods are significant Vorteilet determine. Compared to the sintering process remains the full Effectiveness of vulcanization aids obtained. Compared to those with germ recirculation and those with the total

spraying active dispersion spraying processes has an important energetic effect as well as an overall effect; The required differentiated particle structure with dust-free granules on the one hand in the TUL and dosing processes and the spontaneous

Decay into the dust-free primary particles on the other hand achieved with little increase in compressive stress without

vulcanization-interfering additives are added.

Practice ;. abschenderweise resulted from the combination of base and top granulation particularly useful value Granules: Their tendency to form dust is significantly lower than that achievable with a uniform binder content Stability of the granules under the conditions of the TUL and dosing processes. On the other hand, two-stage continuous showed

produced granules improved bpu.itan-Zerf behaviors in the dust-free primary particles with small increases in the

Compressive stresses, such as occur during the incorporation of the vulcanization milksil in rubber. Exemplary embodiments The invention will be explained in more detail below on three AusfÜT approximately examples. The parameters according to the invention of the material composition and the process parameters in the process stages of Granulation and drying are shown in Tables 1; 2 and 3 summarized. The method was based on the two Characterisistischer vulcanization aids Wobezit DM (Dibenzut ^ iazyluisulfid) and Wobezit M (mecaptobenzthiazole) in combination with the binders latex and latex with 10% carboxymethylcellulose

tested.

All samples showed dust-free conditions under the conditions of the TUL and dosing processes. The necessary spontaneous Decay behavior of the granules in the dust-free primary particles with little increase in the pressure load on don Mixing processes of the vulcanization aids with the rubber was very pronounced. An adjustment H .'loktive

the decay behavior is thus realized by the parameters of the process to different products.

Table 1: Example 1 of the process for multi-stage discontinuous fluidized bed spray granulation of thermolabile hydrophobic fatty substances of hydrophobic vulcanization! help

1. FMTMTJON (F)

- Filter moisture flap Wobe / itDM

• Waster-Matson share Xwf /% 58.0

• Mette m »/% 62,3

• PattenTellungtrrWk.0 99.08 - 94.9 Ratio m <ji / kg 3.17 5.1

2. VortioekmmeiV)

• Air temperature U.vfC 140

- Pre-dried flap

• Waster-Maitenanteil X _W > V ^V * 5.2

• Masts m _tv / kg 26.10

3. Onmd <lramilatlon (QG)

- Basic Bleaching Agent

• Mat ratio rrWkg '18,26 »0,70

m _T ./kg 26.10 1

• Watter / utaU rwowo'kg 15.45

• Watt Ratio Mat Ratio X _{M Λ} / Ν 84.6

• Binder: latex

• Bonding agent X * .oo / N 1.6

- Basic granulationtnlMln 25

- Air temperature U oo ^ 'C 80

4. Dediormiletion (Da)

- Deck-Binder-Lotung

• Mat count moo / kg 7, W-0.30

nriry / kg 26.10 1

• Watter Ingredient m ^ oo ^ n β, 90

• Watter * uta-share * Xw do '* * 87.9

• Binder: latex

• binder content X »do / N 4.0

- Oeck granulation / ett oc '^ in 10

- Air temperature UWC

5. Final route (T)

Granulated Wobezite (DM)

• mat mt / kg 26.9

• Watter-Mattenariteil X «y i / S 0.6

• Oilding mat proportion X ₁ i / S 2.2

TabsMa ?: Example 2 of the process for multi-stage batch fluidized bed spray granulation of hydrophilic hydrophobic solids from hydrophobic curing agent

1st filtration (F) Xw. "/% Χ · .οο ^ Xsoo /% Whereby OM 52.0 Filter moisture paste m _f /% oo / min M / Min 59.0 • Wesser mass fraction nir.f / kg U ot / 'C 0.97 • Dimensions mo., / kg 57.26 " 12:03 • paste division VerMKnie tt.v / * C moe / kg m _T / kg 145 2. VortrodtmmeO /) miy / kg X * t /% • air temperature Xw.v /% Xif / S 3.7 - Pre-dried paste mr.v / kg Xw Ou '^ 28.50 • Water mass fraction • Binder: latex ♦ lOSCarboxymethyl / ellulose • Dimensions • Binder content 1. Qrund-OramilaHort (QO) mgo / hg · OeukGranulationwdit 0.45 - Basic binder solution mi.y / kg - Lultiomperatur 12.M = 1 • Masserc ratio nv.oo'kg B. Endcrowding (T) 28.50 11:58 Xwoo '% - Granulated Woboiit (DM) 90 2 • Water certificate / • Binder: Latex ♦ IQSCarboxymethycellulose • Dimensions • WasseriuMti-Mabsonanteil • binder mass fraction • Water mass fraction 1.5 - Basic granulation Bindemetal-Massonanioil 18 - air temperature 78 4. Decfc Orafwletion (DQ) - Oeck-binder solution • mass-selection 0.30 1 • water addition 28.55 7,55 • Water-to-mass ratio 88.3 3.4 12 65 29.0 0.65 1.7

Table T. Example 3 de "method for multi-stage discontinuous fluidized bed Spührgranulierung thermoiabiier hydrophobic solids of hydrophobic Vulkanlsationshilfsr Littel

1. FHtradon (F) X _wf /% WobezitOM , 42.9t-1.4 « Filter moisture paste m ^ /% 68.0 29.34 1 • Water mass fraction mj ^ y / kg 95.0 38.20 • Dimensions m _o .r / kg 2MO »94.0 88.9 • paste division 3.17 5.1 Verhiltni " ti, _v / ° C 1.2 2. pre-drying (V) 120 27 • air temperature Xw.v 70 - Pre-dried paste mr.v ^ kg 3.3 • Water mass fraction 29.34 • Dimensions 14.90 ° 0.51 3. GrurKt OrangeryOt) rHoo ^ kg 29.34 1 - Basic binder solution mi., / kg 12.74 • mass ratio mw.oo ^ kg 85.5 • Watching the water 5.0 • Wesseriusau mass appeal Xa.GO '^ 90 • Binder: latex cc / min 60 • binder mass antifungal W ¹ C - Basic granulation time - air temperature 31.7 4. Decfc-OranuhrtkmlDO) moo / kg 0.7 - Deck-binder solution MTV / kg 4.0 • mass ratio mw.oo / kg Xw.oo /% • Water additive • water toe mass fraction X _{| D0} /% • Binder: latex oo / min • Binder content tioo / "C - Oeck granulation time - air temperature S. Endtroefcnunfji (T) mf / kg - granulated Wobe / it U) M) Xw i /% • Dimensions χ, t /% • water mass flow • Binder material

claims:

Process for the multi-stage discontinuous fluidized-bed spray granulation of thermolabile hydrophobic solids, preferably vulcanization aids that tend to dust in the dry state, the granules are on the one hand low dust and transport stable, but on the other hand disintegrate under the influence of a predetermined pressure load in their primary particles, in multi-stage cyclic fluid bed apparatus characterized in that the filter moist thermolabile hydrophobic solids in the ratio 99: 1 to 6.00: 1 are divided, of which the greater part is pre-dried to a uniform moisture with water mass fractions of 2 to 12% and then in the fluidized bed granulator with air at Anströmtemperaturen 20 to 8O ⁰ C, is brought into the fluidized bed state and sprayed in a period of between 5 and 30 minutes with the 0.2 to 1.8 times the mass ratio of a base binder solution, based on the pre-dried paste sprayed is then sprayed at about 10K lowered air temperatures, also in the fluidized bed, in a period between 8 and 20 minutes, with the 0.2 to 1.0 times the mass flow ratio of a Deck-binder solution, also based on the pre-dried paste in which the entire binder solution is prepared from the aqueous dispersion of the minor portion of the filter-wet, thormolabile hydrophobic solids having an additional mass fraction of between 75 and 95% water, which is then divided in a ratio of 80:20 to 55:45 and forms a major portion of the water dispersion of the In the case of hydrophobic vulcanization aids, the vulcanization-compatible binders latex, carboxymethyl cellulose, n-alkane-rich hydrocarbons in the range C ₈ to C ₂₂ , higher alcohols in the range greater C ₈ , emulsifiers of various types chemical constitution and composition, as well as rubber-compatible plasticizers or their combination as the base binder solution, were added while adding to the smaller amount of water dispersion of the filter-wet thermolabile hydrophobic solid, 2.0 to 6% by mass, which forms the topping binder solution, and subsequently dio Deckgranulierung, also in the fluidized bed, at Luftanströmtemperaturen between 20 and 140 C, to final moisture mass fractions water is dried below 1%.

Field of application of the invention

Dio invention concerns! a process for the multi-stage discontinuous Wirbolschicht-Sprühgranulierung hydrophobic solids, preferably of Vulkammationhilismittoln that tend to dust / dust whose granules are both low dust and transport stable, but on the other hand decay under the influence of a predetermined, relatively low mechanical pressure load in their primary particles.

Characteristics of the known state of the art

The standard of production is mainly characterized in that which has as a paste in the filter resulting vulcanization a moisture content with water mass fractions between about 50 and 80 ° o and then is dried to a final moisture content with water mass fractions under 1 ^c o. Oa / u are preferably chamber or Pa :. used in a fluidized bed dryer. At the same time, the final product, which results in the presence of π particles on the inside of a 63 μιη test sieve fabric of ninom Massonantoil of at most 1 'character, coincides. However, this particle size distribution, which is necessary for the mechanical processing process of the vulcanization agents into the rubber, is disturbing in the preceding TUL and Dior processes, which favor dustbonding.

For the granulation of fine-grained, strongly dusting substance with a high fines content with a particle diameter of • ΙΟΟμιη there seems to be a wide range of methods.

The following and the simplest method Variant is there; Adding and mixing with suitable substances as a dust binder. In DD PS 119669, the binding of the dust content you I wetting with natural fats, especially such nut a) high content of oleic acid (WaIoI, goose or lard) proposed According dor DD PS 233531 dissolved as Styubverhindrndes agent for debris in aqueous ethanol dissolved distillation residue proposed from the acidic hydrogenation of Acctaldol. According to DEOS 930 18079, an aerosol is used to prepare a stauharmo preparation Dio Dt OS 22 & 040? proposes the addition of fibrillar ΡΤΓΕ by weight up to 20 ^c o. In DE PS 110770 general, not more closely defined additives in the form of binding, wetting and solubilizing agents, acids, bases or DiS (JOr gier medium η proposed

In DE-0512365 a seduction is described resulting in the production of non-dusting, easily wettable and rapidly soluble granulation. Another method for the preparation of non-dusting, easily wettable and soluble granulation is given in the OD-PS 110770. DD-PS 115047 discloses a process for the agglomerated granules of hygroscopic fine powder, wherein a certain amount of wet particles of any insoluble material provided to omcm, to which fine powder is added, and the resulting gum is thoroughly agitated, are therewith this uniformly mixed, whereby agg'omeriorte grains are aebi'dt't. EP 0191 396 describes a process for the production of free-flowing granules consisting of a pulverulent or fine-grained component containing the granules of the liquid component with up to 7 processing steps, in the mixed granulator alone or in the combination of mixed granulation site η and fluidized bed is performed. All four of the above-mentioned Verfahron are suitable for easily benotzbaro, rapidly soluble substances, but not for the question in question, in the dry state very hydrophobic Vulkanisationshilfsmittul. In the penultimate method, moreover, the inadmissibility of admixing any insoluble material with the abovementioned grounds for rejection also occurs. A frequently used for granulation, technically dominant process type is the sintering granulation. In EP 0237345 ancestors and apparatus for granulation and granulated products are described, which works with fusible, pudrigem material, which is supplied via a centrally arranged Dosiorschnecko a controlled heated Centrifu (j.zilzerstaubungsvorrichtur, g.di may have different geometric shape Self-stabilization is achieved by molten and re-solidified contents The vulcanization aids in general, but especially Dibi.nzothiazyldisulfide known under the trade name Wobe / it DM, lose their vulcanization-specific activities in sintering processes. The formation of Sintorantoil as so-called Spitzkorn due to these serious quality reductions are in principle not applicable to methods of Sintergramilation.

In the patents DD 20? 612, DD 223934, DD 228458 and EP 0163836 continuously operating methods of fluidized bed Spruhgranuliciung are boschrieben, dio all emanating from sprayable solutions or dispersions and without Zusatzo or Bindemitto! harto, transport stable yield granules. These methods have the disadvantage that they wcgon dos high water content in don solutions or dispersions require a lot of energy. They drove to granules with relatively large diameters. However, all the variants of this type of fermentation lead to such hard granules that they do not decompose with a slight increase in the mechanical pressure load, so that these processes are not suitable for the granulation of vulcanisation aids.

One-stage ancestors for granulating bosit / cn darube. addition, the disadvantage that they can not always be optimally adapted to the product properties. This concerns in particular the differentiated behavior of the products, according to which the transport stability must be ensured at low pressures, but with a slight increase in the pressure, the granules should spontaneously disintegrate into the dusty primary particles. The differentiated influence of the different vulcanization aids can only be taken into account to a limited extent

From the analysis of the known technical ancestors, it follows that there are co-existing methods of law. The Grundo are very broof. First of all, the material properties of the vulcanization aids with their hydrophobic contents expressed in the dry state are difficult to control. A particular problem of principle is the directly contradictory requirements for the particle stability. Either by don known methods harto, transportstdbilo, dust-free granulato can be produced, but then they are so hard that they can not be in the necessary for the incorporation process in the rubber before vulcanization dust-free primary particles by simply crushing zer. Odor os arise weicho, not transportstabilo granules, which strongly dust. - The third and equally significant disadvantage of the previous method is the ungoloston problem of vulkanisationsvcrtraglichen binder. The fourth disadvantage is the one-step process of granulation in the narrow process control and the consequent limited sample adaptation.

Object of the invention

Zir I of the invention is a Verfahron for mehrstu'-jen discontinuous fluidized bed-Spruhgranulierung thormolabile hydrophobic solids, preferably of vulcanization aids, the dio Nachtoilo the previous Verfahron avoids and secures the differentiated granule structure, which guarantees both dust-free transport stable structures and at the same boi low increase in Pressure Bclastation tion spontaneous decay into the dust-free primary particles, whereby boi lower energy consumption oin optimized Gobrauchswortverhalton the granulato is achieved.

Illustration of the essence of the invention

The object of the invention is to provide an oncrgicsparcncs process for mohrstufigen discontinuous fluidized-Spuhgrariuheriing thormolabile hydrophobic Foststoflo, preferably of Vulkanisationshillsmitteln, with dom with the addition of exclusively those substances which are in terms of quality and quantity gobrauchwortgorecht, bespiolsvteisc vulcanisationsvertrlich in the special sense - dio thormolabilon , in the dry state, pronounced hydrophobic properties have been converted into non-stubborn, transport-stable granules, but on the other hand, these granules spontaneously spontaneously burst into iluo f'nmarp particles even in the case of low ubor don boi TUL and dosing process.

According to the invention, the object is achieved as follows, the explanation of the process principle for thormolabilo hydrophobic solids using the example of vulcanization aids O'fo'gt:

The filter-filled paste of the vulcanization aid, which generally accumulates with water mass fractions / between 40 and 75 °, is divided in a ratio of 99: 1 to 6.00: 1 and the greater part of the filter moisture paste is combined with a uniform moisture of WfissorMassonanteilen 2 to 12% pre-dried.

The granulation of the predried vulcanization aid is carried out in a multi-stage cyclic fluidized bed apparatus. With air entering at streaming temperatures / between 20 and 80 ° C, according to the invention, the pre-dried paste is placed in the fluidized bed state and pre-dried in a period of between 5 and 30 minutes with 0.2 × to 1 × B Paste, sprayed a reason binder solution.

Another important feature of the method according to the invention is that the binder solution is prepared from the aqueous dispersion of the small particle fraction, the filter-moisturizing vulcanization aid, with an added water content of between 75 and 95 ° C. It is shared in the ratio 80:20 to 55:45. - The greater part of the water dispersion of the filter-moisturizing vulcanization aid bildot with an additive with mass fractions of 0.5 to 3 ° o a Nutzswartgurechten binder, wherein in hydrophobic Vuikanisationshilfsmitteln as vulkanisationsvertraglicho binder latex, carboxymethylcellulose, nalkanroicho hydrocarbons in the range C ₈ to C _!} , Higher Alcohols in the range of high C ₈ , emulsifiers of various chemical constitution. And composition have been used as well as rubbery plasticizers or their combination, the basic binder solution. - Dor smaller tail of the water dispersion dos filterfeuchten Vulkanisationshilfsmittels bildot with a proportion by mass between 2 and G ¹ O the above genannton binder dio DeckBindomittellosung.

According to the invention, there is then a base-bindery, but also in the fluidized bed, but reduced by up to 10K air flow temperatures, in ouierniü'röuiii / 8 and 20 minutes a cover-binder solution with dor 0.3 · to I.Ofachen In the immediate aftermath of the deoxyribonitration, the granules are dried, also in the fluidized bed / ustand, with air at an initial tonicity between 20 and 140 ° C, on final fume with a water mass fraction below 1 Ό Underhousing procedures are essential advantages to satisfy. In the context of the sintering process, the effectiveness of the vulcanization aids remains unchanged. An important energetic effect as well as the need for a differentiated particulate structure with dust-free granules on the one hand with don TUL- um) dosing per se and spontaneous decay in dio dust-free primary particles on the other hand at low compared to don with Keimrückfuhrung and working with dor total sprühfahigen dispersion Stoigorung animal Druckboanspruchung achieved without vulkanisationsstorondo additives have been added

Surprisingly, the combination of base and dock granulation resulted in granules which are particularly easy to process: Ii tendency to form dust! «Vcsc-nüich lower than the ml! The amount of binding agent achievable stability of the granules under the conditions of the TUL and Dosior processes Anderersoits showed two-stage continuously produced granules ·. ¹ oin improved spontaneous Zerfallvorhaiten in the dust-free at Piimarpartikol gpMigon dor increases compressive stresses as they I) ¹ I of incorporating dos Vulkanisat'onshilfsmitlels m dun rubber luft'oter.

Ausführungtbeispiele

The invention will be explained in more detail below on three Ausfuhrungsbeispiolon The orfindungsgemaßon parameters dor material composition and the Prozesspararneter in the process step dor granulation and drying are in dan tables 1; 2 and 3 summarized.

The ancestor was tested on Wobezit tion two characteristic Vuikanisationshilfsmitteln DM (Diben / othia / yl disulphide) and Wobozil M (Mecaptobenzthiazol) in combination with binders don latex sowio latex at 10 ° j Carbexymethylzollulose

The necessary spontaneous decay behavior of the granules in the dust-free primary particles with little disturbance during compression mixing with the vulcanization dor vulcanization aid with dibutyl rubber is pronouncedly pronounced Eino soloaktivt adjustment of the Zorfallvorhaltons is thus by dio parameters dos method to different products feasible.

Table 1: Example 1 of the process jur multistage discontinuous fluidized bed spray granulation of thermolabile hydrophobic solids of hydrophobic vulcanization aids

1st filtration (F) _Xn »/% - Filterfouchte paste m /% • Wassor massa style / I kg • Dimensions m _G , / kg Paste division relationship t _lv / -c 2. Predrying (V) • air temperature Y / C Λ _{Λ v} / O - Pre-drying photo pasto m _{T v} / kg • Water mass fraction - Dimensions 3. Basic granulation (GG) NWKG - ürund binder solution m _T , / kg • mass ratio

Water / usatf

Water content Masson content Binder: Laifix binder · Massonantoil

Λ ItCi '

- basic granulations / fit ,,,, / min - air temperature I ₁ o ,, / C 4. Deck granulation (DG) - Dock binder solution • mass ratio NWKG • Wassor supplement / m _rt rx, / kg • Water / usat / massant Χλ ik, / ° o • Binder: I atex • Bindomiltelanteil Oock-Grnniil ^ Linn / nit ... / min - air temperature ti t *; ' C 5. Final drying (T) - Granulioites Wobe / it (DM) • Dimensions mi / kg • Water mass Χλ ι '"" • binding agent! mass fraction X ₁ ,, / c

Wobe / itDM 58.0 62.3 94.9 B9.05 - 5.1 3.17 140 5.2 26.10 0.70 18.26 1 26.10 15,45 84.6 1.5 25 80 0.30 7.85 \ 26.10 6.90 87.9 4.0 10

26.9 0.6 2.2

Table 2: Beispiol 2 dos Vorfehrons for mohrstufigen discontinuous fluidized bed Spruhgranulierung thermolabile hydrophobic solids of hydrophobic vulcanization aids

1. Filtration (F) Xw if '' Xb οι, / "» Xn [x, / ° <> WobezitDM 52.0 FiltorfeuchtePasto m _f / ° o ,, (/ min ! "/ Min 59.0 • Masson water mi.f / kg ti <, ", / C I ₁ ι «, / C 0.97 • Dimensions moj / kg 57,26 - 12:03 • paste division · 1.80 relationship ti v / C moo / kg nii / kg 145 Second Pre-drying (V) m, _v / kg Χλ τ / ° ο • air temperature Xw v / ° » ηι _Λ ιχ -, / kg Xh i / ° o 3.7 - Vorgotrocknoto paste m _{T v} / kg Χλ (χ, / "» 28.50 • WaterMassonantcil • Bindi.Miilul Latex ♦ 10 ° oCarboxymethyl7elluloso • Dimensions • binder content 3 Reason Granuleilon (GG) moo / kg Dock granulation / express 0.45 - Base binder solution mi v / kg Lutttemperatiir 12.80 1 • Masser ¹ ratio πιλ f, o / kg Final drying (T) 28.50 11.58 Xw C ₁ J ⁰ O Granulated Wobe / it (DMI 90.2 • Wassor / usat / • Binder: Latex ♦ lO'OCarboxymethyl / ellulose • Dimensions • Water additive Masson proportion • Binder mass fraction • Water mass fraction 1.5 GrundGranulationsjoit • Binders M assonant οι Ι 18 air temperature 78 - Deck granulation (DG) - Deck · binder solution 4th • mass ratio 0.30 - 8:55 1 • WassorZusat / 28.55 7:55 • Water / usat / mass fraction 88.3 3.4 12 65 5 29.0 0.65 1.7

Table 3: Example 3 of the process; Mohrstufigen discontinuous fluidized bed Spuhrgranulierung thermolabile hydrophobic solids of hydrophobic Volkanisationshilfsmittel

1st filtration (F) Xw f / ^{O /} o Wobo / itom 6Ö.0 Filter moisture paste m, / 'i> 95.0 • Wassor massa style _mt / kg 94.0 • Dimensions m _or / kg 28.40 5.1 • Paste Tilling · 3.17 relationship Uv / C 120 2. Predrying (V) • Air Temporary Xa v 3.3 - Vorgotrocknele paste m, _v / kg 29.34 • Water mass fraction • Dimensions 3. Basic granulation (GG) 1:46 - Basic Bindery Solution m _t ./kg 42.96 1 • mass ratio "Yes, (o / kg 29.34 38.20 Xa <; c, / o 88.9 • Wassnr / usat / • Wassor / usat / mass fraction 1.2 • Binder: Latox ei / min 27 • Bindomittol-Masson content Ii < ;, / C 70 - basic granulation / egg Lufttemporatur 4. Dt »cU Granulation (DG) 0.51 - Dock Bindomittol Solution nii _v / kg 14.90 1 • Mass Preference _mrt CK, / kg 29.34 12.74 X _n cx, / o 85.5 • Wassor supplement / »Wassor / usat / mass fraction Xe iK, / °° 5.0 • binder: latox _IKl / min 9.0 • Bind share ti [", 'C 60 - DeckGranulatiodS / eit - Air Temporary S. final drying (T) mt / kg 31.7   Granulated wol) P / it (OM) * / O Λ _Λ \ l ο 0.7 • Dimensions Xbi / ° o 4.0 • Masson water Bindomittol mass fraction

Claims (1)

Process for the multistage discontinuous fluidized-bed spray granulation of thermolabile hydrophobic solids, preferably vulcanization aids that tend to dust in the dry state, fJöron granules are on the one hand low dust and transport stable, but on the other hand disintegrate under the influence of a predetermined pressure load in their primary particles, in multi-stage cyclically operating fluidized bed apparatus characterized in that the filter-moist thermally stable hydrophobic solids are divided in the ratio 99: 1 to 6.00: 1, of which the greater part is pre-dried to a uniform moisture with water mass fractions of 2 to 12% and then in the fluidized bed granulator with air at Anströmtemperaturen 20 to 8O ⁰ C, is brought into the fluidized bed state and thereby in a period of between 5 and 30 minutes with the 0.2 to 1.8 times the mass ratio of a base binder solution, based on the pre-dried paste besprü ht is, then at lowered to about 10K air temperatures, also in the fluidized bed, in a period between 8 and 20 minutes, with the 0.2 to 1, Ofachen mass flow ratio of a Deck 'binder solution, also based on the pre-dried paste, the entire binder solution is prepared from the aqueous dispersion of the smaller portion of the filter-wet thermolabile hydrophobic solids with an additional mass fraction of between 75 and 95% water, then divided in the ratio of 80:20 to 55:45 and the greater part of Water dispersion of the filter-moist, thermolabile hydrophobic solid Weight percentages of 0.5 to 3% of a binder suitable for use in the case of hydrophobic vulcanization auxiliary as vulcanization-compatible binder latex, carboxymethyl cellulose, n-alkane-rich hydrocarbons in the range C ₈ to C ₂₂ . higher alcohols in the range greater than C ₈ , emulsifiers of different chemical constitution and composition and rubber-compatible V.'eichmacher or their combination as a basic binder solution, added währe..d the smaller part of the water dispersion of the filtorfeuchten thermolabile hydrophobic solid mass proportions of 2.0 be added to 6%, which forms the top binder solution, and then to the top granulation, also in the fluidized bed, at air inflow temperatures between 20 and 14O ⁰ C, dried to final moisture mass fractions water below 1%. Field of application of the invention The invention relates to a process for multistage discontinuous fluidized bed spray granulation of hydrophobic solids, preferably vulcanization aids that tend to Stnuton in the dry state, the granules on the one hand low dust and transport stable, but on the other hand under the action of a predetermined, relatively low mechanical Oruckbelastung in ihro PrimSrpartikol zorfallon. Characteristic of the known state of the art The state of production is predominantly characterized in that the vulcanization aid obtained as a paste in the filter has a moisture content with water mass fractions of between about 50 and 80% and is subsequently dried to a final moisture content of less than 1% by weight. For this purpose, chamber or paste vortex layer dryers are preferably used. This results in a dusty end product whose primary particle size distribution is characterized by a residue on a t> J pm test sieve with a mass fraction of at most 1%. This particle size distribution, which is necessary for the mechanical incorporation process of the vulcanization agents into the rubber, interferes with the previous TUL and Dosiorpro / essen because of dust pollution Pur granulation of foaming, heavily dusting substances with a high fines content with a particle diameter of 100pm, there seems to be a wide range of Method. The closest and economically simplest process variant is the addition and mixing with suitable substances as a dust binder. In the DD PS 1186f θ the dio dust binding is suggested by wetting with natural fats, in particular those with a high content of acid (waiol, goose or lard). After we DDPS ^"4 proposed 233,531 as staubvorhinderndes funds for debris Good in aqueous ethanol dissolved distillation Stuck status from the acidic hydrogenation of acetaldol. According to DEOS 93018029, a low-dust preparation is produced with an aerosol. DEOS 2250402 prevents the addition of fibrillated PTFE by up to 20% by mass. In DEPS 110770, generally, not more closely defined additives in the form of binders, wetting agents and solubilizers, acids, bases or dispersants are proposed