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ADD-Vantage Formulations [Intermediaries /addivites for fertilizers]

A product range of

Global Speciality Chemicals Company Product brochure

Contact: Firas T. Mandahawi General Manager, Global Specialty Chemicals Co. Group Dammam, Saudi Arabia Tel: +966 (3) 8184899 Fax:+966 (3) 8188987 Cell: +966 5 66549105

www.gs-chemical.com

http://www.gs-chemical.com/

ADD-Vantage™ Formulation for life

Global Speciality Chemicals Co

Add-Vantage 1 Formulation for life

Table of content:

Sr. Topic Page #

1. The problem with fertilizers – opportunity for GSC 2

2. Introduction 3

3. Anti-caking agent 5

4. Coloring agents 7

5. Anti-foaming agents 9

6. Anti-floating aid /softening agent Curing aid for SSP fertilizer

10

7. Multi-functional additives for UREA prills [granulating aids, anti-caking, de-dusting, prill toughening agent]

12

8. Anti-caking agent for UREA 14




In recent years, the

ushering of the global

Green Revolution has

given agriculture the

much needed impetus

and has contributed in

registering a steady

growth rate.

Global agriculture is on

the threshold of

becoming more

competitive and is in a

position to make major

gains in the export

market. The global price

of food grain has

attained a level which

has enabled the country

to export large volumes

of it.

In order to keep food

grains competitive, it

has been necessary to

upgrade the quality of

fertilizer supplied to the

agrarian.

GSC is playing a vital

role in this area. GSC

has been studing the

problem areas and

working towards its

elimination --

successfully

The problem with fertilizers Caking: One of the most troublesome properties of crystalline material is their tendency to bind together, or cake on storage. This not only destroys the free flowing nature of the product but it also necessitates some crushing operation, either manually or mechanically - before it can be used. The cause has been found to vary for different materials. It could depend on the size, shape, moisture content, pressure under which the product is stored, plus the temperature and humidity variations during storage - all of which can contribute to the compression of a granular crystalline product into a solid lump. In general, it has been discovered that caking is caused by crystal surface becoming damp in a number of ways. The product may contain traces of moisture left behind due to inefficient drying, or the moisture may come from external sources. This causes the solution which is formed to evaporate later and unite adjacent crystals with the cement of recrystallized solid. This problem was discovered to have been with any fertilizer product that is water soluble. lf partial pressure of water vapour in the atmosphere is greater than the vapour pressure that would be exerted by the saturated aqueous solution of the pure substance at that temperature, water will be absorbed by the crystals. If later the atmospheric moisture content is reduced to give a partial pressure below the vapour pressure of the saturated solution the crystals will dry out and bind together. Small fluctuations in atmospheric temperature and humidity are sufficient, to bring about these changes, which can occur several times in one day. Commercial crystalline salts frequently exhibit hygroscopy at atmospheric pressures lower than those given for pure salts. Caking can generally be minimised by reducing the area of contacts between the crystals. This can be achieved by producing granules of a uniform size. The size of the granule should be as large as possible; the smaller they are the larger will be the exposed surface area per unit mass. The shape and uniformity in size are extremely important factors affecting caking. Shape and uniformity of the particles affect the behaviour of the product under storage. If the crystals are packed in bags and stacked on the top of one another the pressure in the bags near the bottom of the pile tends to force the crystals into closer contact. With non-uniform crystals, the compression may be quite severe and in extreme cases many of the crystals may be crushed. If the solubility of the salt increase with an increase in pressure, traces of solution may be formed under high local pressure at the points of contact. The solution will then tend to flow into the voids, where pressure is lower and crystallise.




Introduction: Some finely divided solids, whether powdered, granulated or prilled may cake under certain conditions, losing their fluidity and forming hard blocks or lumps. This phenomenon is called “caking” and effects at solids with very diverse chemical constitution. The following table shows us some common characteristics of these products:

Characteristics Examples

Physical appearance Powder, crystals, granules Powdered cocoa, powdered milk

Physical properties Water solubility, hygroscopicity, sensitivity moisture, pressure and temperature variations

Soluble coffee, starch, sugar, metallic powders , plastic powders , plastic resins

Chemical properties Oxygen or water reaction. Reactions of decomposition

Mineral salts Common salt Fertilizers

The caking phenomenon occurs during the storage, handling or transport operations of the material. Recently caking and its inhabitation have received great attention, due to its importance in the fertilizer industry, owing to:

Return of lumps or caked products to the manufacturer.

Reconditioning of rejected products.

Extra transport, handling and packing costs.

Physio-chemistry of caking phenomenon A caking phenomenon can be defined essentially as a superficial process of recrystallization which occurs in two stages: 1. Humidification The surface of the solid is covered with a thin water layer which can be produced either by:

Absorption of relative humidity

Movement towards the surface of the water accluded in the particles, or

Both phenomenon at the same time.

2. Desiccations When the humidity of the air alternately rises and falls, or as the material undergoes changes in temperature, the absorbed water re-evaporates, and

the "liquid bridges" of saturated solution become "crystalline solid bridges” which cause the crystals to stick together

Main factors inducing a caked condition Chemical composition When the chemical nature of fertilizer (formula, concentration, impurities, etc.) changes their hygroscopicity and their tendency to cake can be modified. Specific surface area Caking tendency of fertilizer closely depend on the particle size and shape of the material.

a) Particle size

When the particle size increases, the specific surface area decrease, causing a reduction of the forces of attraction and the points of contact between adjacent particles and lowering their tendency to cake.

b) Particle Shape

If particle surface is smooth and well formed the caking will be delayed due to the limitation of contact points between the particles.




Humidity

a) Initial moisture content Relatively small changes in moisture content have marked effect on the caking of fertilizer. A high initial moisture content favour the atmospherical moisture absorption and consequently the formation of liquid bridges. Below an initial moisture content of 0.S%, products do not show any tendency to cake under the pressure applied in storage, therefore a careful control of humidity is specially recommended in the fertilizer industry. b) Relative atmospherical humidity Caking depends closely on atmospherical relative humidity variations. Every salt or mixture of salts has a definitive critical relative humidity. Above it, we will have moisture absorption, and below it, moisture evaporation. Relative humidity changes are usually more dangerous than a higher constant hygrometric level. 3. Temperature The effect of temperature is an important one. If the product undergoes high temperatures or sudden thermic variations, it tends to cake badly due to:

Water re-evaporation (recrystallization and establishment of crystalline bridges)

Development of internal reactions (double decomposition reactions)

Crystal-habit changes (e.g. ammonium nitrate as a structure change at 32.3°C)

4. Pressure Pressure tends to increase the number of points of contact between particles, including stored material to cake. 5. Time of storage

The time of storage has a great effect on caking, which increases rapidly in the first fifteen days, going on slightly for 6 to 8 weeks, and finally reaching an almost constant value.

UNIQUE BREAKTHROUGH The group Companies are the leading manufacturers of anti-foaming agent, anti-caking agent, colouring- cum-anti-caking agent, granualating aid-cum- dedusting agent, body colouring-cum-dedusting agent, antifoaming / softing agent and colouring aid a range of products with proprietary chemical additive developed specially for the use in fertiliser industry. This surfactant formulation exerts powerful crystal inhibition effect by strong interaction between the anti-caking agent and the surface of the fertiliser granules. This interaction is promoted by the specific property of these agents to spread readily over the crystal surfaces. As a result, the bridging between the individual fertiliser granules is effectively inhibited.

SALIENT FEATURES: Addition of anti-caking agent on fertiliser granules keeps them in free flowing form. Handling, packaging and many other operations are all made easier if the granules maintain their original shape and size. Sometimes the fertilisers have to be stored in silos for long duration due to various reasons. The caking of these products due to long exposure to varying humidity conditions and under high pressure due to storage makes handling of these products very difficult and necessitates the use of bull-dozers and other mechanical means which cuts into profits by reducing product appeal and creates second grade product stocks. The Anti-caking agent prevents caking and maintains free flowing properties of straight, mixed and complex fertilisers in granules or crystalline form. The range of anti-caking agents are safe to use, provide excellent anti-caking effects on urea and NPK products respectively which can hardly be expected from any other conventional anti-caking agents. In addition to crystal modifying property, the product has a surface activity which furnishes adequate anti-caking effects on them. These properties of the ‘anti-caking agent’ range of products enables crystal, prilled and granulated products to be handled, transported and stored easily without having caking problems in bulk or as packed.




ANTI-CAKING AGENT

RECENT DEVELOPMENTS IN ANTI-CAKING The use of habit modification, as a means of minimising crystal caking is quite common abroad. Should the crystals cake at some later stage, the cement of crystalline material now consisting of the modified habit, will be very weak and will easily break down on handling. These anti-caking agents can be incorporated on the fertiliser with higher degree of effectiveness at levels as low as 0.05% to 0.1% . The exact amount to be dosed; however depends upon moisture, temperature, storage pressure and surface area factors that vary, from one product to another, as well as, from one plant facility to another. Additionally, these anti-caking agents also considerably reduce troublesome dust formation when fertilizers are handled.

Untreated fertilizer

TECHNICAL DATA SHEET Trade name CAKEFREE™ Function To reduce the caking tendency of the CAN, ANP

and NPK fertilizer Action It modifies the crystallization habits, promotes

free flow properties, helps in retaining the granular integrity of the fertilizer by forming a thin film on the granule

Treated fertilizer Composition It is blend of selected amines, dispersants, sequestrante, crystal habit modifiers, hydrophobic agents in a petroleum oil vehicle

Form Brown coloured liquid

Viscosity In the gravity flow range Flow characteristics Free flowing liquid pumpable through metering

pumps at 600 C. Density 0.95 to 0.99 +/- 0.05 gms/cc Flash point > 1700 C. Recommended dosage As per requirement. 0.06 – 0.08% max. By

weight of the fertilizer i.e. 0.6 kg – 0.8 kg per M.T of fertilizers

Storage Air tight containers, store in cool dry place

Handling Eye protection and gloves recommended while handling




Comparative Performance of Coated & Uncoated

FERTILISER (17:17:17) Accelerated caking tests were conducted on NPK Fertiliser

(17:l7:17) coated with 0.06% of CAKEFREE™ and compared with

untreated NPK fertiliser and their caking characteristics were

studied under varying humidity conditions for extended time

period and the observations were as follows.

1. Untreated NPK Fertiliser showed several times more tendency

to absorb moisture, at relative humidity of 45% and higher,

than the NPK fertiliser treated with 10.06% CAKEFREE ™.

2. The bonding strength of the crystal bridges formed between

the untreated granules were much higher than those formed

between the treated fertilizer granules. Further the granule

integrity retention rate in the treated fertilizer was much

higher.

Dosing system layout for CAKEFREE ™ Anti caking agent




COLOURING AGENTS 1. Body Colouring Agent

The Company with its expertise in the field of speciality chemicals has developed exclusive de-dusting & colouring Agents for DAP Fertilizer. These products are free flowing liquids at ambient temperatures and can be easily dosed through any metering /gear pump. Colour is dispersed across the entire body of the fertiliser and thus offers a permanent colour to it. It does not, in any way, interfere with the physical properties of the fertilizer. It is effective at the dosage rate of just 1000 ppm. It offers a distinct brand identity to the fertilizer. Its better binding properties ensure less dust formation at the time of granulation. No toxic effects, safe to handle. It gives a dark grey body colour to DAP fertilizer, as well as, it works as granulating aid, so that dust formation can be reduced to a great extent in the granulizer. When granules are of uniform size and powdering has less available exposed open area for moisture, absorption is also less. So, good granule automatically protects itself from moisture absorption and hence ADDCA-BxxTM indirectly works as an anti-caking agent cum granulating aid.

TECHNICAL DATA SHEET Product name ADDCA-BxxTM [range].

Application Granulating aid cum body colouring agent for DAP fertilizer. Appearance Homogeneous liquid.

Composition Blend of colouring aids, dispersants, binders and crystal bonding agent in a water thin-able medium.

Viscosity In the gravity flow range Density 1.05 +/- 0.1 gms/cc

Recommended dosage level 0.15-0.25 % by weight of DAP Recommended dosage point At the pre-neutralizer

Compatibility with DAP fertilizer The formulation is compatible and does not in any way interfere with the physico-chemical properties of the fertilizer.

Safety and handling Normal procedures of handling any plant liquid can be adopted Flammability Non-flammable




2. Surface Colouring Agent

Surface colouring-cum-anti-caking ADDCA-SxxTM [range] gives attractive colour for separate identity to fertilizer with improved anti-caking property. It can be sprayed at dryer or scrubber, at 0.08 to 0.12% by weight level by spray nozzles. Colour of output fertilizer will be same and uniform irrespective of change in colour of raw material input with different source. Highly concentrated liquid will help to stop the use of powder an anti-caking cum colouring agent. Powder creates pollution problem for surrounding plants and area.

TECHNICAL DATA SHEET

Product name ADDCA-SxxTM [range] Application Colouring cum anti caking agent for NPK fertilizer Appearance Dark, thick, homogenous liquid Composition Blend of colouring aids, dispersants, binders and

crystal bonding agent in a suitable solvent medium

Viscosity Free flowing at 70o C

Density 0.98 +/-0.1 gms/cc

Recommended dosage level 0.08-0.12 % by weight of fertilizer Recommended dosage point At the colour /coater Compatibility with fertilizer The formulation is compatible and does not in Safety and handling Non-toxic, non-hazardous, environment friendly Flammability Non flammable




ANTIFOAMING AGENTS Antifoaming agents are the right choice as they are superior in many ways to the conventional types. ADD-DAF™ series:

Provide high efficiency

Cover a broad spectrum of applications.

Are largely chemically inert; i.e. they do not interfere with the chemical process.

Are added in small quantities only and do not reduce or hinder product efficacy. These antifoaming agents spread over the foam. The active ingredient displaces the surfactant and thins out the lamellae, leading to destabilization and eventual foam collapse. SALIENT FEATURES

Better dispersing properties.

Long term action in the reactive media.

Better Compatibility.

High temperature stability.

They are stable to cold and heat and can be stored without a problem

Storage at room temperature is recommended.

ADD-DAF™ Used to supress extensive foaming during rock phosphate reactions with acids, otherwise it can go out of control and can burn the persons working around the vessel . It is highly effective to suppress the foam in stipulated time frame

TECHNICAL DATA SHEET Trade name ADD-DAF™ Function Antifoaming agent for DAP, NPK process Density 1.05 +/- 0.1 gms/cc Flow characteristics Free flowing liquid at ambient temperature Recommended Addition point Scrubber /neutralizer Storage Air tight containers, store in cool dry place Handling Eye protection and gloves recommended while handling Flash point > 150o C Dosage As required generally less than 200 ppm Note Spillages can be slippery




Anti floating aid / softening agent for NPK /NP fertilizer In combination with potash, local filler used during the manufacturing process becomes hard due to process water evaporation at high process temperature, the granules do not become soft in required residual time, remain hard and insoluble after 10 to 15 minutes, which creates desolution problem for it. This phenomenon is generally observed in NPK group, for NP fertilizer, filler desolves and gets separated from P2O5; N2 structure of fertilizer and starts floating on top of water. The floating structure is looks like the granule itself, but it is not granule, it is like pieces of sponge. The common man will think it is fertilizer that is floating. In both the cases, we require some softening agent which accelerate sthe desolution of granules completely in specified time limit. The chemical is UN-Float™.

TECHNICAL DATA SHEET Product name

UN-Float™

Function Anti-floating / softening agent for NPK/NP fertilizer Appearance Free flowing colourless liquid Composition Surface active Agents, crystal habit modifiers, softening agent and

emulsifiers mixed on aqueous vehicle. Viscosity <100 cps max. at 25oC Density 0.98+/-0.05 gms/cc at 25oC Recommended dosage level 0.90 to 1.6 kgs. max. per MT of NPK/NP depending upon the

hardness of it and required dissolving time.

Flow characteristics Pump-able and spray-able through metering dosing pump. Storage Cool dry locations, eye protection and hand gloves recommended

for handling. Safety and handling Normal procedures of handling any plant liquid Can be adopted . Flammability Non-flammable, Flash point > 300°C Performance Data Easy mixing, uniform and non- lumpy output, increases water

solubility of product and drastic reduction in curing time.

CURING AID FOR SSP FERTILIZER – UN-Float™ 1. It is a normal practice in many plants to use about 7-10%

excess sulphuric acid compared to the norms of 100 Kgs. of 71 % sulphuric acid 125 Kgs. of rock (33% P2O5). Curing Aid user will get the benefit of using the above stoichiometric ratio and will avoid acid excesses while still maintaining relatively rapid curing rates and relatively higher conversion to water content in the finished Super Phosphate, will have to re-adjust the water content in the acid feed.




2. Even if it is not contemplated to reduce the level of the excess acid,

under identical condition use of Curing Aid will give following results: a. The den mixing is superior. b. The den out-put is uniform and non-lumpy. c. The Super Phosphate consistently shows at least a 0.5% increase in

the available water soluble P205. d. A plant which typically has a curing period of 15 days to get a

minimum of 16% water soluble P205 without curing aid, can look forward to almost half the curing period for getting the same water soluble P205.

e. In plant, we have to judiciously adjust the excess acid in combination with the finished Super Phosphate can be kept quite low thereby making the fertilizer more useful to the farmer.

TECHNICAL DATA SHEET Product name UN-Float™ Function Curing aid for single super phosphate fertilizer Appearance Free flowing colourless liquid Composition Surface active Agents, crystal habit modifiers, softening agent and

emulsifiers mixed on aqueous vehicle. Viscosity < 100 cps max. at 25°C Density 1.031005 gms/cc at 25°C Recommended dosage level 0.05% max. based on weight of SSp fertilizer. Dosage point Curing Aid should be mixed in the mixer before the den, the dosing point

should be adjacent to the point where Sulphuric Acid is being fed. Flow characteristics Pump-able and spray-able through metering dosing pump. Storage Cool dry locations Safety and Handling Eye protection and hand gloves recommended for handling. Flammability Non-flammable, Flash point > 300°C

Performance data Easy mixing, uniform and non- lumpy output, increases water solubility of

product and drastic reduction in curing time.




Multi-functional additive for Urea prills: URE-GAD™ works simultaneously as:

1. Granulating aid 2. Anti – caking agent 3. Dedusting agent 4. Prill toughening agent GRANULATING AIDS: URE-GAD™works as a distinct granulating aid in Urea production, as seen from comparative position given below:

Without URE-GAD™ Addition of URE-GAD™ (1-1.4%)

Powder formation 10-12 % Less than 3 %

Granule size of prills +0.25mm to +2.00 mm

75-80 % 96-97%

ANTI-CAKING AGENT URE-GAD™ works also as Anti-caking agent. Consequent to very low production of powder, because of the use of URE-GAD™, moisture absorption in urea prills is greatly reduced. The prills become solid without any porosity and thus become much more resistant to moisture absorption, than the prills produced without the additive. DEDUSTING AGENT Nothing is visible inside a prilling tower when the prilling process is on because of dense cloud of urea dust. But use of the additive URE-GAD™ removes the dust cloud altogether and the visibility is so good that even the conveyor belt at the bottom of the tower can be seen with the naked eye from the top of the tower. Then the cloud of the urea coming out from the air exhaust system fitted on top of the prilling tower, causing panic in the environment by its ammonia smell is eliminated by the use of URE-GAD™ additive. At the same time, it saves urea going out daily in the air as powder. This saving alone is enough to cover full cost of the additives.




Caked urea prill

Another positive and cost-saving effect of dust elimination by URE-GAD™ is reduction in lump formation on or around the walls of the prilling tower which in turn means less loss of material and saving in recycling cost. PRILL TOUGHENING AGENT Urea prills without additives easily become powder even on little pressure or rubbing. With the use of URE-GAD™, they become tough and resistance to breaking into powder at pressures encountered in loading, transit, storage at the factory and distribution centres.


Coated urea prill

Product name URE-GAD™ Application Binding additive for improving strength of urea

prills. Dedusting agent in Prilling Tower. Appearance Homogenous liquid Composition Proprietary blend of dispersants, blinders and

crystal bonding agents in a suitable solvent medium

Viscosity In the gravity flow range Density 1.05+/- 0.1 gms/cc

Recommended dosage level

0.05-0.1% by weight of urea

Hard and uniform Urea prill

Recommended dosage point

In the urea solution tank

Compatibility with Urea Fertilizer

The formulation is compatible and does not in any way interfere with the physic-chemical properties of the fertilizer.

Safety and Handling Normal procedures of handling any plant liquid can be adopted.

Safety and Handling Non-flammable Flammability Non-flammable

Dosing system layout for URE-GAD™ binding additive




Urea Prills

ANTI-CAKING AGENT FOR UREA World over, the practice in Urea conditioning has been limited to formaldehyde products, either as UF solutions or as HMTA (HEXA METHYLENE TETRAMINE). As compared to carcinogenic properties associated with presence of free formaldehyde inevitable in use of UF solution or HMTA, UN-CAKE™ is completely free of such hazardous materials its composition and hence this unique formulation is the No. 1 safety option for Urea conditioning. Field tests simultaneously conducted on stacked bags and heaped urea over long storages on Freeflow and HMTA as conditioning agents showed much improved results in prevention of caking while using fertiflow conditioner, at much lower cost inputs. This is why UN-CAKE™ is the No. 1 economic option for Urea conditioning. RELAX on your Urea conditioning problems; once you are on to UN-CAKE™ the product has a proven performance in India and the Middle-East. UN-CAKE™ SALIENT FEATURES

UN-CAKE™ can be used on all grades of Urea intended for agricultural and technical use.

While the conventional additives such as formaldehyde, HMTA are prill strength improvers only and can hardly be called anti-caking agents, UN-CAKE™ imparts pronounced and very definite anti-caking properties to urea.

UN-CAKE™ does not call for any process modification in Urea plant and is wholly belt spray-able. It has no reactivity that is likely to cause damage to the rubber belting.

A mere spraying and limited homogenization by rankig (by use of rakers made out of rubber/plastic materials) on the belt is adequate for UN-CAKE™ application on urea. This is due to a remarkable and unique self-spreading and migrating property of UN-CAKE™.

UN-CAKE™ toxicity data indicates that it is safe for agricultural and animal use as a coating on urea.

Never before has handling and transport of urea been made so simple whether in bulk or in bagged condition.

Recrystallization of Urea - uncoated

Reorganization of Urea coated with UN-CAKE™





Trade name UN-CAKE™ Function Anti-caking agent for Urea Prills

Composition Surfactants and crystal habit modifiers on aqueous vehicle. Form Free flowing colourless /pale yellow liquid. Density 1.0 +/- 0.05 g/cc at25°C Flow characteristics Pump-able and spray-able at 25-30°C Viscosity < 100 cps max. at 25° C Flammability Flash point > 200° C Storage and handling Cool dry locations for storage; eye protection and hand gloves recommended

for handling. Suggested dosage 0.05 - 0.08% max. based on weight of urea prills. Typical performance data Reduction of 70% and above in Prills caking of urea fertiliser over long storages.

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